Inorganic Chemistry Book2

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UNIT – 1
LESSON – 1
CONTENTS
1.0 AIMS AND OBJECTIVES
1.1 INTRODUCTION
1.2 INORGANIC – R IN GS – CHA IN S – C AGE S
1.2.1 HETERO CATENATIONS
1.2.2 ISOPOLY AND HETEROPOLY ANOINS
1.2.3 CAGES
1.3 Let us Sum Up
1.4 Points for Discussion
1.5 References
The aims and objectives of this lesson are to learn and to discuss the
structural features of different types of inorganic chains and cage structures.
1.1 INTRODUCTION
S o m e n o n - metals have the tendency to resemble carbon in certain

properties. This chapter discusses one such property of nonmetals. Nonmetals
other than carbon have also the tendency to form chains, rings and cages.
Most metals show less tendency to form compounds of this type, and the
length of the chains and size of the rings thus formed are restricted.
However, the ease with which both metals and nonmetals and combinations of
the two form clusters has only been recognized in the last decade. This
branch of chemistry has seen a rapid growth.
Carbon has the tendency to form extensive stable chains and hence we
study the organic chemistry, as a separate branch. This phenomenon is not
common in the remainder of the periodic table. Silicon and related nonmetals
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have the tendency of form chains, to a limited extent. There is no

thermodynamic barrier to the formation of long chain silanes, Si( n ) H ( 2 n + 2 ) .
Their synthesis ad characterizations are difficult tasks. Si- Si bonds are
weaker than C- C bonds. Silanes are very highly reactive. At 400o C , S i 2 H6
decomposes much faster than C2 H6 .
2 S i 2 H 6 + 7O2 4 SiO2 + 6 H2 O. This reaction is kinetically

favoured. Compounds of silanes from n=1 to n=8 have been isolated,
including both straight chain and branched-chain compounds. A number of
Polysilane polymers have been isolated. The chemistry of germanes is similar
t o s i l a nes. Nitrogen, phosphorous and Sulphur form chains. Chain length up
to 8 atoms of nitrogen are known. They are highly explosive. In the case of
sulphanes, chains up to 8 sulphur atoms have been obtained. P2 H6 is well
known P 3 H5 is well characterized. Oxygen forms no chains longer than three
a t o m s , O 3 and its anion O3 and a few compounds are known, for e.g., bis
(perfluoroalkyl) trioxides such as F3 C000C F3 . Allotropes of both 'S' and
'Se', are known in which helical chains of great length are present. Sulphur
chains are instable with respect to S8 (Cyclic). The chain form of 'Se' is
stable. Red 'P' is polymeric and is thought to have chains of pyramidal 'P'
atoms. Polyhalide ions are stable, for e.g., I 3 .
1.2.1 HETERO CATENATION:
The phenomenon of hetero catenation or chains built up of alternating

atoms of different elements, is well known. Silicons, (R2 SiO) n a n d
polyphosphazenes (PN(OR) 2 ) n are hetero catenated polymers, having wide
application. The simplest hetero catenated compounds are those formed by
the dehydration of acids or their salts. Simple acid phosphate salts on heating
give rise to pyrophosphates, for e.g., (P2 O 7 ) - 4 . The general formula of
(n+2)-
polyphosphate may be given as : (Pn O 3 n + 1 ) ; n=2, it is known as
diphosphat e, n=3- triphosphate etc.,
melt/100l
5 N a 3 P O 4 + P4 O 1 0 3 Na5 P 3O10
condensed poly phosphates such as sodium triphosphates, are largely used as

detergents.
Silicate Minerals
Silicon forms a very large number of compounds containing

heterocatenated anions. The silicates make up of various minerals. About
three fourths of the earth crust is silicon and oxygen. The majority of silicate
minerals are insoluble, because they have an infinite ionic structure and
because of the Si-O bond. Silicate structures have been solved by X- ray
crystallographic methods:
i) The electro negatively difference between 'Si' and 'O' is equal to 1.7.
This suggests that the bonds are 50% ionic and 50% covalent.
ii) The structure may be considered both by ionic and covalent methods.
The radius ratio of Si+ 4 : O - 2 is 0.29, which suggests that 'Si' is four co
ordinate. It is surrounded by four oxygen atoms at the corners of a
tetrahedron. 'Si' in (Si O4 ) - 4 may be assumed to be SP3 hybridized (3s
and three 3P orbitals) and hence silicates are based on (si O4 ) - 4
tetrahedral units.
iii) The S iO 4 tetrahedra may exists as discrete units or may polymerize into
larger units by sharing corners, i.e., by sharing oxygen atoms.
iv) The 'O' atoms are often close packed or nearly close packed. Close
packed structures have tetrahedral and octahedral holes and metal ions
can occupy either tetrahedral or octahedral sites depending on their
si ze. Al 3 + can fit into either octahedral or tetrahedral site. Thus Al can
replace either octahedral or tetrahedral site. Thus Al can replace either
a metal in one of the holes or a silicon atom in the lattice. This is
particularly important in the aluminosilicates.
4
Classification of Silicates
i) Or tho Silicate s: A wide variety of minerals contain discrete (SiO4 ) 4 -

tetrahedra. They have the general formula M2 ( S i O 4 ) (M=Be, Mg, Fe,
Mn or Zn). M(SiO4 ) M- Zr. These silicates share no cormers.
I n Z n 2 SiO 4 (Willemite) and Be2 S i O 4 (Phenacite) Zn and Be have a

'CN' of 4; Zn and Be occupy tetrahedral holes. In Mg2 S i O 4 , Mg has a
CN of 6 and occupies octahedral holes. Zr SiO4 is a gem stone. Zr has a
CN of 8. The structure is not close packed. The garnents are minerals
with discrete tetrahedra; are used as red gem stones. Its formula is
M 3 M 2 ( S i O 4 ) 3 M(II) = Mg, Ca or Fe (II); Me(III) may be Fe(III), Cr or
Al. These are 8 coordinate.
ii) Pyrosilicates
Two tetrahedral units are joined by sharing the 'O' at one corner and
6-
the unit is (Si2 O 7 ) . This is the simplest of the condensed silicate
ions. The name pyro comes from the similarity in structure with
pyrophosphates like Na4 P 2 O 7 .
Pyrosilicates are rare, for e.g., Thortveitite (Sc2 ( S i 2 O 7 ) S i - O-S i b o n d

angle is 180o in this compound and it changes upto 133o .
The co ordination number of the metal changes from 6 to 7 and then to

8, with increase in size of the metal. Structural studies show no
difference in the lengths of the bridging and terminal Si-O bon ds.
Cyclic Silicat es
If two oxygen atoms per tetrahedron are shared, ring structures of

formula (Si O3 )n 2 n - may be formed. Rings containing, three, four, six and
eight tetrahedral units are known. But those with three and six are the most.
The cyclic ion Si3 O 9 6 - occurs in wollastonite, Ca3 ( S i 3 O 9 ). The Si6 O 1 8 1 2 -
occurs in beryl, Be3 A l 2 ( S i 6 O 1 8 ). In beryl the Si6 O 1 8 units are aligned one
above the other, leaving channels. Na+ , L i + and Cs+ are commonly found in
these channels, and because of the channels the mineral is permeable to gases
consisting of small atoms or molecules e.g., helium. Beryl and emerald are
gemstones. Beryl is found with granite and usually forms pale green crystals,
w h i c h a r e six sided prisms. Emerald has the same formula as beryl, but it
contains 1- 2%Cr, which gives it a strong green colour.
Chains Silicates:
Pyroxenes are simple chain silicates. These are formed by the sharing
of oxygen atoms on two corners of each tetrahedron, with other tetrahedra.
This gives the formula (Si O3 ) n 2 n - . A large number of important minerals form
chains, but there are a variety of different structures formed because the
arrangement of tetrahedra in space may vary and thus affect the repeat
distance along the chain. The most common arrangement repeats after every
second tetrahedron for e.g., in spodumene, Li Al [(Si O3 ) 2 ], enstatite
Mg2 [(Si O3 ) 2 ] and diopsite, Ca Mg [(Si O3 ) 2 ] . C a 3 [(Si O3 ) 3 ] has a repeat of
three, and others are known with repeat units 4,5,6,7,9 and 12.
Double chains can be formed when two simple chains are joined
together by shared oxygens. These minerals are amphiboles. They have
different formulae, due to several ways of forming double chains, for e.g.,
[(Si 2 O 5 ) n 2 n - , [ ( S i 4 O 1 1 ) n 6 n - , [( S i 6 O 1 7 ) n 1 0 n - etc., Asbestos minerals are the best
known amphiboles . These have the structural units (Si4 O 1 1 ) n 6 n - . Amphi bol es
a lway s c onta in – OH groups, which are attached to the metal ions. The Si-O
bonds in the chains are strong and directional. Adjacent chains are held
together by metal ions present. Pyroxenes and amphiboles cleave readily
parallel to the chains, forming fibres. For this reason, they are called fibrous
minerals. The cleavage angles for pyroxenes and amphiboles are different.
Example are tremolite Ca2 M g 5 ( [ ( S i 4 O 1 1 ) 2 ] (OH) 2 and crocidolite Na2 F e 3
Fe 2 ([(Si 4 O 1 1 ) 2 ] (OH) 2 (. (blue asbestos).
The mineral chrysatile Mg3 ( O H ) 4 ( S i 2 O 5 ) is white asbestos and is a

sheet silicate. Asbestos causes lung cancer.
Sheet Silicates
W hen S iO 4 units share three corners the structure formed is an infinite

two dimensional sheet of empirical formula (Si2 O 5 ) n 2 n - within the Si- O s h e e t
bonds are strong but much weaker forces hold each sheet to the next one.
These sheets cleave into thin sheets. These consist of two or three layers
joined together. Examples are
(i) Clay minerals (Kaolinite)

(ii) White asbestos
(iii) Micas (Muscovite)
(iv) Montmorillonites (fullers earth, bentonite).
consider the formation of a two layer structure. If a Si2 O 5 layer is placed

along side a layer of Al(OH)3 , then many of the 'O' atoms will coincide. The
'OH' groups in Al(OH)3 can be removed and an electrically neutral two layer
structure is formed. These double layers stacked parallel give the mineral
kaolinite, which has the formula Al2 (OH) 4 ( S i 2 O 5 ). It is a white solid and
formed by the decomposition of granite.
Al (OH)3 Sheet
Silicate Sheet
(Two Layer Structure)
Three Dimensional Silicates
Sharing all four corners of a Si O4 tetrahedron results in a three

dimensional lattice of formula Si O2 (quartz, tridymite, cristobalite etc.,).
These contain no metal ions, but three dimensional silicate structures in
which some of the Si + 4 ions are replaced by Al3 + , plus an additional metal
ion. This gives an infinite three dimensional lattice and the additional cations
occupy holes in the laltice. The cations are usually the larger metal ions like
K + , N a + , C a + 2 or Ba+ 2 . The smaller ions Fe 3 + , C r 3+ and Mn2 + which are
common in chain and sheet silicates do not occur in three dimensional
silicates because the cavities in the lattice are too large. Replacement of one
quarter or one half of the 'Si' atoms are quite common. These give structures,
M [ A l S i 3 O 8) and M[Al2 S i 2 O 8 ). Such replacements gives rise to the
minerals.
i) Feldspars
ii) Zeolites
iii) Ultramarines
Granite is made up of feldspars. We have orthoclase feldspars:

a) Orthoclase K[Al Si3 O 8 )
b) Celsian Ba[Al 2 Si 2 O 8 )
Plagio Clase:
a) Albite Na[Al Si3 O 8 ]
b) Anorthite Ca [Al2 S i 2 O 8 ].
The ortho clases are more symmetrical than are Plagio Clases. K+ a n d B a 2 +
are just the right size to fit into the lattice while Na+ & Ca2+ being smaller,
cause distortion.
Zeolites:
Zeolites have a much more open structure, than the feldspars. The
anion skeleton is penetrated by channels, giving a honeycomb like structure.
These channels are large enough to allow them to exchange certain ions.
They can also absorb or lose water, and other small molecules without the
structure being broken. Zeolities are often used as ion- exchange materials
and as molecular sieves. Natr o lite , N a 2 [Al 2 S i 3 O 1 0 ] 2 H 2 O is a natural ion
exchanger. Permutit water softeners use sodium zeolites. Zeolites take Ca2 +
from water and replace them by Na+ . Zeolites can absorb CO2 , N H 3 and Et
OH, Zeolites have been employed to separate branched chain hydrocarbons
from straight chain hydrocarbons.
The mineral lapis lazuli has a fine blue colour. It contains ultramarine
Na8 [(Al Si O4 )6]S 2 , in which the colour is produced by the polysulphide ion.
Ultra marines do not contain water.
The ultramarines are now produced synthetically is obtained by heating

kaolinite, Na 2 C O 3 and S in the absence of air.
1.2.2 ISOPOLY AND HETEROPOLYANIONS
Transition metals in their higher oxidation states are similar to

nonmetals with corresponding group numbers. For e.g., V and P in VO3 - 4 a n d
PO 3 - 4 , C r O 2 - 4 and SO2 - 4 , M n O 4 - and ClO4 - . The analogy may be extended to
poly anions, such as Cr2 O 2 - 7 . P o l ym e n s a t i on of some metal anions occurs
spontaneously, upon acidification. At low P1+ CrO4 - is converted into
Cr 2 O 2 - 7 . When Cr2 O 2 - 7 is treated with concentrated sulphuric acid red
chromium (VI) oxide, chromium acid is formed.
n 2- n
Cr2 O + nH + (CrO 3 ) n + H2 O
2 7 2
The structure of CrO3 consists of infinite linear chains of Cr O4 tetrahedra.

The vanadate ion, VO3 - 4 exists in extremely basic solution. Under dilution
+
and low pH, protonation yields monomers (VO 2 ). When solutions are more
c o n c e n t r a t e d ( V 2 O 7 )4 - and higher vanadates are obtained. The
polymerization of vanadate, molybdate and tungstates ions forming isopoly
anions have been extensively studied. In the condensation process, the
coordination number changes from 4 to 6 and the basic building block in the
polymerization process becomes an octahedron of six oxygen atoms,
surrounding each metal atom. The resulting octahedra may link either by
sharing an apex or edge (rarely a face) due to the relaxation of electrostatic
10
repulsion, in the larger octahedra. As a result, the structures tend to be small

clusters of octahedra, in the discrete poly anions, culminating in infinite
structures in the oxides. When the edge sharing occurs, the structure may be
stabilized, if some distortion occurs such that the metal ions move away from
each other. It might be expected that the smaller the metal ion, the less the
repulsion and the larger the number of edge sharing octahedra per unit. This
is found to be true V5+ (68pm), Mo6 + (73pm), W6+ (74 pm), Nb5+ (78pm) Ta5 +
(78pm) and the most common edge shared poly anions are, (V1 0 O 2 8 ) 6 - ,
(Mo 7 O 2 4 ) 6 - , (Mo 8 O 2 6 ) 4 - ( W 6 O 1 9 ) 2 - , (W 7 O 2 4 ) 6 - , (Nb 6 O 1 9 ) 8 - and (Ta6 O 1 9 ) 8 - . To
form larger polyanions such as (W12 O 4 2 ) 1 2 - edge sharing must give to rise to
apex s haring.
The isopoly an ions may be considered to be portions of a closest

packed array of oxide ions with metal ions occupying the oc t ah e d r a h ol es .
6-
The edge sharing array found in (V1 0 O 28) consists of ten octahedral
stacked. This is the largest stacked octahedra isopoly anion cluster
compatible with metal- metal repulsions, and the remaining edge shaped
structures represent portions of this unit.
Elements other than V, Nb, Ta, Mo and W do not form isopoly anions.
Al 3 + , G a 3 + , I 7+ may have appropriate radii for isopoly anion formation. But
they form, sheets or three dimensional frame works. The reason given is as
follows. The terminal oxygen atom in the isopoly anion is strongly Õ b o n d e d
to a transition metal such as Mo(VI) or W(VI). The metal ion is displaced in
the direction of the terminal oxygen; due to this effect. Metal ions such as
Al 3 + and Ga3 + a r e p oor Õ acceptors. Thus their terminal oxygen atoms are not
stabilized, and this leads to chain structures. Due to Õ bonding the terminal
oxygen atoms of the transition metal polyanions are stabilized and have less
affinity for adjacent metal units.
In aprotic media, new poly anions have been obtained for e.g., When
[(n- Bu) 4 N] OH and [(n- Bu) 4 N ] [ H 3 V 1 0 O 2 8 ] are mixed in acetonitrile, a new
isopoly vanadate, [V5 O 1 4 ] 3 - is formed. It is the first example of a poly
11
oxoanion cage that is built from corner shared tetrahedra. When [n- Bu 4 N]
[H 2 V1 0 O 2 8 ] is refluxed in acetonitrile, CH3 CN is found to be suspended in a
(V 1 2 O 3 2 ) - 4 basket.
Heteropolyanions
It has been found that there is a cavity in the center of a metatungstate

ion. This cavity is surrounded by a tetrahedron of four oxygen atoms. This
cavity is sufficiently large to accommodate a relatively small atom like P(v),
As(V), Si (IV), Ge(IV), Sn (IV) or Zr (IV). The 12- tungs to heteropoly anions
are of general formula [Xn + W 1 2 O 4 0 ] ( 8 - n ) - similar molybdo heteropoly anions
are also known. For e.g., when a solution containing phosphate and
molybdate is acidified, the ion (PMo1 2 O 4 0 ) 3 - is formed P- O b o n d s are not
broken in this process. The product anion contains the PO3 - 4 in the MO1 2 O 3 6
cage. Between 35 and 40 hetero atoms are known to form heteropoly anions
and their corresponding acids. Large hetero atoms such as Ce (IV) and Th
(IV) are found icosahedrally coordinated in salts such as (NH4 ) 2 H6 Ce Mo1 2
O 4 2 . It is unique in as much as pairs of MoO6 octahedra share faces to form
Mo 2 O 9 groups which are corner connected to each other 6 molybdo
heteropoly acids form with hetero atoms Te(VI), I(VII) and tri p o s i t i ve m et a l
ions such as Rh(III). All these heteroatoms prefer an octahedral coordination
sphere, which can be provided by a ring of six Mo O 6 octahedral. The isopoly
and heteropoly anions may be considered small chunks of metal oxide lattice.
F o r s e l ective oxidation of organic molecules, these may be used as catalysts.
As anions they show very low surface charge densities and low basicities.
Hence molybdate (-2) ion and 12- tungsto phosphate (-3) ion have lower
2+
basicities than perchlorate ion. Mn b i n ds weakly to a terminal oxygen atom
6-
of (H 2 W1 2 O 40) and the anion functions as a monodentate ligand.
C o in [(Si W1 1 O 3 9 ) Co (H2 O)] 6 - is 6 coordinate, the heteropoly anion

functions as a pentadentate ligand. (W6 O 1 9 ) 2 - has been studied using O1 7
N M R s p e c troscopy. The spectm gives three signals corresponding to twelve
bridging oxygen atoms, one signal for encapsulated oxygen and one for
terminal oxygens.
12
Fig.1.2(a) and (b) Bonding and structure of tetraborane, B4H10. (From

Mutterties, E.L. The Chemistry of Boron and Its compound; Wiley: New
York, 1967. Reproduced with permission.]
1.2.3 CAGES
The bonding and structures of boranes are of great interest. They are
different from all other hydrides. These compounds are electron deficient.
Di bo r a n e (B 2 H6 ) h a s 12 valency electrons (3 from B and 6 from H atoms).
Electron diffraction studies indicate that the compound has B- H- B b r i d g e s .
The two bridging H- atoms are in a plane perpendicular to the rest of the
molecule, and prevent rotation between the two 'B' atoms. Specific heat
measurements confirm that the rotation is hindered. Four of the H- a t o ms a r e
in a different environment than the other two. This is confirmed by Raman
spectra and by the fact that diborane cannot be methylated beyond Me4 B2
H2 , without breaking the molecule into B Me3 . The terminal B- H d i st a nc e s
are the same. These are assumed to be normal covelant bonds. These are (2C-
2e) two centre- two electron bonds. The structure is shoen in fig 1. Each of
the bridging B- H- B linkages then involves a delocalised three centre bonds.
Each 'B' is SP3 hybridised.
The appropriate combinations of three orbital wave functions, j B1 , j B2 ( S P 3

hybrid orbitals) and j H ('s' orbitals), give rise to three molecular orbitals
(M O )
13
1 1 1
Yb = j B1 + j B2 + j H
2 2 Ö2
1 1
Yn = j B1 - j B2
Ö2 Ö2
1 1 1
Ya = j B1 + j B2 + j H
2 2 Ö2
Y b= bonding Mo, Y a = antibonding MO and Y n = nonbonding. Each bridging

bond thus consists of a bonding Mo containing two electrons. Thus all the
twelve electrons in B2 H 6 have been accounted for fig,1.1(a) and (b) give
qualitative description of atomic orbitals and three centre Mo orbitals
r e sp e c tiv e l y B10 H 14 is quite stable in air. B4 H 10 is formed by slow
decomposition of B2 H 6 . In addition to terminal and bridging of B- H b o n d s
B4 H1 0 contains a direct B- B bond. Tetraborane undergoes both symmetric
and unsymmetric cleavage. Fig 1.2(a) and (b). Fig 1.3 gives bonding and
structure of B4 H1 0 . Larger bases spit off BH3 groups:
B4 H 1 0 + 2 Me3 N Me 3 N B 3 H 7 + Me3 N BH3 .

small hard Lewis bases (NH3 ) – result in unsymmetr i c al c l e a va ge – splits of
BH 2 +
14
+
B4 H 1 0 + 2 NH3 [H 2 B(NH 3 )2 ] + [B3 H 8 ] -
Fig 1.2 Symmetric (a) and Unsymmetric (b) Cleavage of Tetraborane
[B 1 2 H1 2 ] 2 - is a highly symmetric borohydride. It is obtained from B3 H8 - ion .
5[B 3 H8 ] - [B 1 2 H1 2 ] 2 - + 3[BH4 ]- + 8H2
T h e [ B 1 2 H 1 2 ] 2 - is a regular icosahedron of atoms, each of the twenty

faces being an equilateral triangle. All of the H atoms are external to the
boron icosahedron and are attached by terminal B- H bonds. The structure
involves several canonical forms. Both two electron, two centre B- B a n d
two electron, three centre B-B- B bondings are involved. Several boranes may
be considered as fragments of a B1 2 icosahedron (or of the [B1 2 H1 2 ] 2 - ion) in
15
which extra hydrogen atoms are used to "sew up" the unused valences around
the edge of the fragment. For e.g., decaborane (B10 H1 4 ), may be considered
as a B1 2 H 1 2 frame work from which B1 and B6 have been removed, leaving
"dangling" three centre bonds that are completed with hydrogen atoms to
f o r m B - H- B bridges. (B6 H1 0 (hexaborane) is a pentagonal prism.
Experimental work has shown that the icosahedrons of [B1 2 H 1 2 ] 2 - is merely
the upper limit of a series of deltahedra (Bn Hn)2 - (from n=4 to n=12). If all
the vertices of the deltahedron are occupied, as in the [BnHn]2 - series, the
structure is called a 'closo' (closed structure). The number of vertices in the
deltahedron will be one less than the number of bonding pairs in the
framework. This theory is called 'wades rules'. For the closo series the
number of frame work electrons equals 2n+2. Consider (B1 2 H 1 2 ) 2 - to count
framework electrons. Each 'B' has one of its valence electrons tied up with
the 'exo' B- 4 bond and it has thus two to contribute to the framework, giving
a total of 2n (in this case 24 electrons) from the 'B' atoms. No neutral Bn Hn
species are known, but an array of dianions, obeying the 2n+2 are known.
The 26 electrons (2 x 12 + 2) are just the number required to fill all the
bonding molecular orbitals in [B1 2 H 1 2 ) 2 - and this corresponds to 13 (n+1,
n=12) electron pairs as expected for an icosahedrons. If a B atom is removed
from a vertex of the closo structure, a cup- like or nest like structure remains.
Such structures are called 'nido' (nest). The nido structures obey the
framework formula 2n+4. Consider B5 H9 .
Five exo B-H groups will contribute two electrons each, and the four
extra 'H' atoms will contribute 4 electrons and thus the total will be 10+4=14
electrons (2n+4, n=5). This corresponds to 7 pairs (n+2) and the geometry
will be derived from an octahedron (n- 1 vertices). The structure is thus a
square pyramid nido form derived from the closo octahedron. If two vertices
are missing, the resulting framework is called "arachno" (spiders web). these
obey the formula 2n+6 (n+3 electron pair). B5 H 1 1 (ponta borane) has arachno
structure. In arachno series the extra H atoms form endo B- H bonds. In hypho
(net) series the rule is 2n+8. Some borane derivatives, fit it into this scheme.
For a regular deltahedron having 'n' vertices there will be n+1 bonding
16
molecular orbitals. The number of electrons that can occupy these Mos will
be 2n+2. This gives the highly symmetric closo structure.
Carboranes:
The systems C2 B1 0 H1 2 is isoelectronic with [B1 2 H 1 2 ) 2 - and can be

synthesized from decarborane and alkynes using diethyl sulphide as solvent.
B1 0 H 1 4 + R-C X C - R R2 C 2 B 1 0 H1 0 + 2H2
The acetylene may be unsubstituted or substituted, in which case, the

compound is known as 1,2 – dicarba-closo-dodeca borane or orthocarborane
and is isoelectronic and iso structural with [B1 2 H 1 2 ) 2 - . It is stable to both
heat and air, but it isomerises at high temperatures to the 1,7 (meta or 'neo'
isomer) and the 1,12 (Para isomer). The mono carboranes are known in closo,
nido and arachno structures.
Thus
closo – C 2 B 9 H1 1 + 2e [nido – C 2 B 9 H1 1 ) 2 -
[nido – C 2 B 9 H1 1 ] 2 - [closo – C 2 B 9 H 1 1 ) + 2e
In the anion [C2 B 9 H 1 1 ] 2 - , each of the three 'B' atoms and the two
carbon atoms on the open face of the cage directs an orbital (SP3 ) toward the
apical position occupied formerly by the 12th boron atom. Further these
orbitals contain a total of six electrons.
Hence this anion [C2 B9 H1 1 ] 2 - has a resemblence to

cyclopentadiendeanion. This anion could be considered isoelectronic with
C 5 H5 - and should be capable of acting as aP ligand in metallocene
compounds. Hawthorne succeeded in synthesizing metalla carboranes.
2[C 2 B 9 H 1 1 ] 2 - + Fecl 2 [(C 2 B 9 H1 1 ) 2 F e ] 2 - + 2cl-
This has structure similar to ferrocene.

17
Self Check Exercise m- 1
1) What is heterocatenation?
b) Discuss the different types of silicates and their structures.
2) Describe with examples, the isopoly anions.
Self Check Exercise – 2
1) Discuss the structures of molybdates and tungstates

2) Elucidate the structure of diborane
3) Discuss in detail the structures of boranes and explain the terms, closo,
nido and arachno with examples.
1.3 Let us Sum Up

Heterocatenations, like heteropoly and isopoly anions and their
structures are discussed various types of silicate minerals and how SO4
tetrahdra could form different types of structure sare indicated. Boron
cage compounds, wades rules and cloro nido and arachno spieces are
also described.
1.4 Points for Discussions
i) Silicates ad their structures

ii) Isopoly and heteropoly anions – structures and uses
iii) Boranes – Closo nido & arachno species the different formulae as
2n+2, 2n+4, 2n+6 and 2n+8
1.5 References
Concise Inorganic chemistry – V edition – J . D . L e e – B l a c k w e l l .

Publishing – No i da - D el h i – 20 05 .
18
LESSON –2
CONTENTS
2.1 INTRODUCTION
2.2 METAL CLUSTERS
2.2.1 TYPES OF METAL CLUSTERS
2.2.2 ORGANOMETALLIC CLUSTERS
2.3 Let us Sum Up
2.5 References
The aims and objectives of this lesson are to learn about the different
types of metal clusters and their structures.
2.1 INTRODUCTION
Compounds containing metal- metal bonds are as old as chemistry

itself. Calomel was known to chemists of India as early as 12th century. The
dimeric nature of mercurous ion was confirmed only later. It was only some
30- 35 years ago that the study of other metal- metal bonds began in earnest;
yet this branch of inorganic chemistry has grown at a phenomenal rate.
M e t a l c l u s ter compounds can be conveniently classified into two

classes:
i) Polynuclear carbonyls, nitrosyls and related compounds
ii) Halide and oxide complexes
The second class will be discussed here. The two classes have un
related chemistry. Metal atoms in class.
19
i) Have formal oxidation states –1 to +1, while those in

ii) are found in higher formal oxidation states, +2 to +3.
The transition metals (late transition metals) typically form class

i) Clusters, while those on the right side of the periodic table ( e a r l y
second and third row transition metals) tend to form class II clusters. Atoms
having large energies of atomization (hence very high m-pts and b- p t s ) f o r m
metal clusters. Thus the most refractory metals (Zr, Nb, Mo, Tc, Ru, Rh, Hf,
Ta, W, Os, Ir and Pt) have the greatest tendency to form metal clusters.
Effective overlap of d- orbitals appears necessary for stabilizing metal
clusters. Excessive contraction of the 'd' orbitals will destabilize the metal
clusters. Hence large charges (very high oxidation states) on the metal atoms
are unfavourable for the formation of metal clusters. In first row transition
metals, the 'd' orbitals are relatively small and metal cluster formation is not
favoured.
i) Dinuclear Compounds
The best studied compound is (Re2 x 8)2 - ion; obtained by reducing

Hx
x-
Perrhenate with H3 Po 2 in the presence of 2 ReO4 (Re 2 x 8)2 - ;
H3 Po 2
x= cl, Br, I, NCS.
It has two unusual features. Re- Re bond distance is 224pm compared

with an average of 275pm in rhenium metal, and 248pm in Re3 Cl 9 . T h e
unexpected features in this ion is the eclipsed configuration of the chlorine
atoms. But chlorine atoms are expected to lie at distances of 330pm, i.e., the
staggered configuration would be preferred. According to Cotton, the Z- axis
of the ion is taken a the line joining the two Re atoms. Each Re atom is
bonded to four 'Cl' atoms in a square planar array. We may consider the Re-
Cl bonds to involve dSP2 hybrids on each metal (using dx2 - y2 orbitals). The
m e t al d Z 2 and PZ orbitals lie along the bond axis and may be hybridized to
form one orbital directed toward the other rhenium atom and a second orbital
20
directed in the opposite direction. The former can overlap with the similar
orbital on the second 'Re' atom to form a 's ' bond, the second dZ2 - p z hy br i d
orbital forms an approximately a nonbonding orbital. The dxZ and dyz
orbitals of each rhenium atom can overlap to form two P bonds. The dxy
orbitals on each Re atom can overlap "sideways" forming a 'd ' bond (delta).
overlap of the dxy orbitals can only occur if the chlorine atoms are eclipsed.
If the chlorine atoms are staggered, the dxy orbitals do not overlap. The eig ht
d electrons (Re3+ , d 4 ) from two 'Re' atoms occupy s bonding (2), two P
bonds (4) and delta bond (2) ing orbitals to from the quadruple bond; hence
the complex is diamagnetic. The model accounts for the strength of the bond,
the short Re- Re distance and the eclipsed configuration.
The isoelectronic (Mo2 C l 8 ) 2 - is known. Both Re (III) and Mo(III) form

a large series of carboxylate complexes of formula Re2 (RCo 2 ) 2 x 4 etc, and
Mo 2 (R C O 2 ) 4 . Structurally these are related to (Re2 x 8 ) 2 - .
[Re 2 C l 8 ] 2 - (having qudruple bond) has all its bonding Mos filled up i.e
s2 P 4
d 2 (bond order = 4). d a nd d * are nearly nonbonding.
Tungsten forms a series of compounds W2 C l 4 ( O R ) 4 R 2 (R=Me, Et),

with a W=W double bond. These ditungsten compounds have bond orders 4,
3, 2 and 1 Cu(II) and Cr (II) in the 1st transition series form acetate
complexes. These are diamagnetic. Cu-Cu bond in Cu (II) acetate is only a
weak single bond resulting from pairing the odd electron in each copper
at om. Cr -Cr bond in its acetate complex, is stronger than Cu- Cu bond. Cr –
C r distance is shorter in the complex than in the metal. These suggest that the
Cr complex has a qudruple bonds (weak). But the lengths of the qudruple
bonds in Mo- Mo and W- W are uniform.
(RO) 6 M2 e.g. W2 ( OR) 6 are known. WXW i s found in these complexes

(s 2 P 4 ). This undergoes addition reactions with halogens (Cl2 , B r 2 , I 2 ) . W 2
(O- I- Pr) 6 dimerises to W4 (o- i-Pr) 1 2 – analogous to cyclobutadiene – a
fluxional molecule.
21
Trinuclear Clusters:
[(ReCl 3 ) 3 contains three metal atoms. Each rhenium atom is bonded to

other two 'Re' atoms directly by metal- metal bonds, and indirectly by a
binding halogen ligand. In addition each, rhenium atom in the triangular
array is coordinated by two more halide ligands above and below the plane
defined by the three rhenium atoms. Each Re (III) has d4 configuration which
would lead to a paramagnetic complex, if only metal- metal single bonds were
present. The complexes are diamagnetic, however which implies that each Re
atom is doubly bonded to its Re neighbour. Re3 cluster is persistent in many
chemical transformations.
Tetra Nuclear Clusters :
W 4 (OR) 1 2 is a tetra nuclear cluster which is formed by the dimerisation

o f W 2 (OR) 6 . The tetrameri c W 4 (OR) 1 6 has also been synthesised. W4 (OR) 16
is saturated, containing W- W single bonds. Qudruply bonded dinuclear
compounds can also dimerise to give tetrameric molecules
(R 3 P)
2K 4 Mo 2 cl 8 Mo 4 ( R 3 P) 4 c l 8 + Kcl.
Four member ring containing Mo is formed. The resulting four membered

ring is not square. Bond length measurements indicate, that there are
alternating single and triple Mo – Mo bonds. Tetranuclear cluster units
( rh o m b oh e d r a l M o 4 ), connected by oxygen atoms and forming infinite
chains, are found in Ba1.1 4 M o 8 O 1 6 .
Hexa Nuclear Clusters
Clusters of six, Mo, Nb or Ta atoms are known. There are two types. In
the first an octahedron of six metal atoms is coordinated by eight chloride
22
ligands, one on each face of the octahedran. This is found in "Molybdenum

dichloride ", Mo 6 , C l 1 2 , better formulated as [Mo6 cl 8 ] C l 4 . Each Mo (II) atom
can use its four electrons to form four bonds with adjacent Mo atoms and can
4- 4-
form dative bonds from the four chlide ligands (Mo2 c l 8 ) a nd (Mo6 cl8 )
have a cubicarrangement of chloride ions, Nb and Ta form hexanuclear
clusters. These have octahedron of metal atoms, but they are coordinated by
twelve halide ligands, along the edges. The structures are complicated. The
metal atoms are surrounded by a distorted square prism of four metal and
four helogen atoms. These compounds are electron deficient (as boranes) –
there are fewer pairs of electrons than orbitals to receive than orbitals and so
fractional bond orders of 2 / 3 are obtained.
Che vr el P h ase s
Ternary molybdenum chalcogenides, Mx Mo6 x 8, are called chevrel

phases and are polynuclear clusters having unusual structures. Thes have
interesting electrical and magnetic properties Pb Mo6 S 8 is a super conductor
below 13.3k. This has a octahedral cluster of Mo atoms, surrounded by a
cubic cluster of S atoms, which in turn is currounded by a cubic lattice of
lead at oms.
2.2.2 Organoi Metallic Clusters
Poly nuclear carbonyls such as B3 H7 [Fe(Co) 3 ] 2 and complexes of the

t yp e Rh 6 (Co) 1 6 m a y be classified as organo metallic clusters. The structures
of these cages or clusters can be predicted by 'Wades' rules' (Closo, nido or
arachno) using 2n+2, 2n+4 and 2n+6 formulae.
Consider the Molecule:
B 3 H 7 [ F e ( C o ) 3 ] 2 , for which n=5. The three BH units and the two

Fe(Co) 3 units contribute 2 electrons each and the four extra H atoms
contribute 1 electron each (total 14 electrons).
23
2 Fe (Co)3 = 2 x 2 = 4
3 BH = 3 x 2 = 6
4H = 4 x 1 = 4
14
Since n=5, there are 2n+4 frame work electrons and We predict a nido
structure for the same. Molecule has a square pyramidal structure. This
results from the substitution of 2 BH units by 2Fe (Co)3 units in B5 H9 .
C o n s i d e r R h 6 (Co) 6 : n=6. Each of the six Rh(Co)2 contributes 'I'

electron to the frame work, 4Co molecules provide 8 electrons.
6 Rh (Co)2 = 6 x 1 = 6
4 Co = 4 x 2 = 8
14
We have 14 framework electrons in 2n+2 formula (n=6; 2 x 6+2=14).

Hence the complex has a close structure. There are two terminal CO groups
per 'Rh' and four bridging 'CO' groups. Which span alternate triangular faces
[p-(cymene) 3 - R m3 S 2 ] 2 + has 48e- s closo structure. This can be reduced to a
nido structure (50e- s).
1. What are closo, nido and arachno structures? and explain wade's mles
with examples .
2. Discuss in detail the different types of clusters.

24
1) Show how wades mles can be applied to organo metallic clusters.

Compare with 18e rule for carbonyls.
2.3 Let us Sum Up

Motal clusters of different types such as tetra nuclear and polynuclear
structures are discussed in detail. The application of wades rules to
metal clusters is indicated organo metallic clusters such as Rh6 (CO) 6
and the application of 2n+2 rule is also discussed.
2.4 Points for Discussion:
1. Metal clusters – types and structures

2. Wade's mles
3. Organo metallic clusters.
2.5 References:
1. Concise Inorganic chemistry – J.D.Lee 5th edition

2. Inorganic chemistry – Huhecy et al Pearson Education – A si a .
25
UNIT – II
LESSON – 3
BORAZINES – PHOSPHONITRILIC COMPOUNDS
CONTENTS
3.1 INTRODUCTION
3.2 BORAZINES
3.2.1 SYNTHESIS OF BORAZINES
3.2.2 STRUCTURE AND PROPERTIES OF BORAZINES
3.3 PHOSPHONITRIC COMPOUNDS
3.3.1 SYNTHESIS OF PHOSPHAZENES
3.3.2 STRUCTURAL STUDIES
3.3.3 PHOSPHAZENE POLYMERS
3.4 Let us Sum Up
3.6 References
In this Lesson the Synthesis of Borazines and the synthesis of

phosphazenes are discussed. The structures of borazines and phosphazenes
are also discussed.
After going through this lesson you should able to compare the
structure of Borazines and Phosphazenes with benzene and other ring
systems.
· Understand the 'd' orbital participation in the phosphozenes structure.
· Develop interest in doing research in the fields of Phosphazenes and
their applications.
3.1 INTRODUCTION
The most important ring system of organic chemistry is the benzene

ring, either as a separate entity or in polynuclear hydrocarbons such as
26
naphthalene, anthracene and phenanthrene. Inorganic chemistry has two

analogues of benzene B3 N 3 R6 and trimeric cyclop h o sp ha z en e c o mp o un ds,
P 3 N 3 X6 . Alfred Stock synthesised borazine early in this century. He was the
first to study compounds such as boranes, silanes and other similar nonmetal
compounds. He perfected vacuum line techniques for the handling of air and
moisture sensitive compounds invaluable to the modern inorganic chemist.
3.2 BORAZINES
3.2.1 SYNTHESIS OF BORAZINES
Stock synthesized borazine by heating the adduct of diborane with

ammonia.
3B 2 H6 +6NH 3 3 (BH 2 ( N H 3 ) 2 ) ( BH 4 ) D 2 B3 N 3 H6 +12H 2 - (1)
More efficient of syntheses are:

NaBH4
NH 4 Cl + Bcl3 Cl3 B 3 N 3 H 3 B3 N 3 H 6 – (2)
NH 4 Cl + NaBH4 B3 N 3 H6 +H 2 + NaCl – (3)

27
N or B substituted borazines may be made by appropriate substitution on the

starting materials prior to the synthesis of the ring
NaBH4
(R NH 3 ) cl + BCl3 Cl3 B 3 N 3 R 3 H3 B3 N 3 R3 – (4)
or substitution after the ring has formed
Cl 3 B3 N 3 R 3 +3LiR' R3 ' B3 N 3 R 3 + 3LiCl - (5)
Borazine is isoelectronic with benzene, as B=N is with C=C (Fig 1.1).
Physical properties of borazine and benzene are similar. The physical
properties of alkyl- substituted derivatives of benzene and borazine a r e
remarkably similar. For example the ratio of the absolute boiling points of
the substituted borazines to those of similarly substituted benzene is
constant. This similarity led to a labeling of borazine as "Inorganic
Benzene". This is a misnomer because the chemical properties of borazine
and benzene are different.
3.2.2 STRUCTURE AND PROPERTIES OF BORAZINE
In both benzene and borazine the P electrons are delocalized over all
of the ring atoms. Because of the electro negativity difference between Boron
and Nitrogen, more electron density is located on the nitrogen atoms. Due to
this partial localization, the P b o n ding is weakened in the ring. Each
nitrogen receives more s - electron density from the neighboring boron than it
gives away as a P - donor.
The net effect is that the charge density on the nitrogen i n c r e a s e s .

Besides nitrogen retains its basicity and boron its acidity. Borazine is more
reactive than benzene and undergoes addition reactions. Benzene does not
undergo addition reaction with
HC'l, B 3 N 3 H6 + 3H X (H2 N-B H X 3 ) ; (X =Cl,OH,OR) – (6)
C6H6+Hcl no reaction.
28
One can compare the reactions of borazine and benzene with bromine.
It is of interest to note that borazine resembles benzene in forming

arene – metal complexes, thus the hexa methyl borazine complex- B 3 N 3
(CH 3 ) 6 Cr (CO)3 has been reported and closely resembles, C6 (CH 3 ) 6 C r ( C O ) 3
but is thermally less stable.
The ring metal dissociation energy of the borazine complex is about

one half that of the arene complex.
29
Self Check Exercise – I
Note: Please do not proceed unless you attempt the question, and write your
answer in the space below.
1. How are the following systhesised?

(a) Borazine and benzene (b) Bromo Derivatives of borazine and
benzene.
Borazine analogues of naphthalene and related hydrocarbons have been

made by pyrolyzing borazine or by passing it through a silent discharge.
1 1
Related four membered rings R2 B2 M 2 R2 a n d R 4 B4 M 4 R4 are also known
b o r o n n i t r i de ceramics has been synthesized from borazine derivative
(CH 2 = C H ) B 3 N 3 H 5 , which is polymarised and decomposed to give boron
nitride
Borazine 1000o C
CH 2 =C H B 3 N 3 H5 CH2 - CH- B3 N 3 H5 BN - (9)
o
125 C n NH3
Benzene may be hydrogenated to give cyclohexane. But hydrogenation

of borazine results in polymeric materials of indefinite composition.
Cycloborazine B 3 N 3 H 1 2 is obtained by the reduction of the chloro derivative.
6NaBH4
2 B 3 N 3 H6 +6Hcl 2cl3 B3 N 3 H9 2B3 N 3 H1 2 + 3 B 2 H 6 +6Nacl - 10)
B or a xine , H 3 B3 O 3 is isoelectronic with borazine. (Prepared by the explosive
oxidation of B2 H6 ). Boraxine is planar and has even less P d el o ca l i z a t i o n
than borazine B3 P 3 (Ph) 3 has also been prepared 'B' and 'P' have similar
electro negativities compared to B and N and therefore polarization is less
extensive in this compound than borazine and is considerably aromatic.
30
a) Compare the properties of borazine and benzene, on the basis of their

structures.
(b) How would B3 P 3 ( P h ) 3 react with Br2 ?

Please do not proceed till you attempt the above questions. The space
below in for your answer.
3.3 PHOSPHO NITRILIC COMPOUNDS

3.3.1 SYNTHESIS OF PHOSPHAZENES
The Phosphazenes are cyclic or chain compounds that contain

alternating phosphorus and nitrogen atoms with two substituents on each
phosphorus atom. The three main structural types are cyclic trimer (Fig 1.2),
cyclic tetramer (Fig 1.3) and the oligomer or high polymer (Fig 1.4). A few
cyclic pentamers and hexamers are also known. The alternating single and
double bouds in the figures are written for convenience but should not be
taken literally.
Fig. 1.2, 1.3, 1.4
Hexachlorocyclotriphosphazene (NPCl2 ) 3 , is a key intermediate in the

synthesis of many other phosphazenes and is manufactured commercially on
either a large or a small scale, it is readily prepared by the reaction
31
in C2 H 2 c l 4
nPcl5 + nNH4 cl (N PCl2)n + 4n Hcl – (1 1)
This reaction produces a mixture of (NPcl2 )n species with n = 3,4,5 and

low polymeric linear species. Favorable conditions give 90% yields of the
n=3 or 4 species, which can be separated easily.
The compound (NP Cl2 ) 3 undergoes substitution reactions with groups

l i k e , O H , O R , N R 2 ,NHR, or R, to give fully or partially substituted
derivatives.
(NP cl 2 ) 3 + 6Na OR (NP(OR)2 ) 3 + 6Nacl - 1 2)

(NP cl 2 ) 3 + 6Na SCN (NP(NCS)2 ) 3 + 6Nacl - 13 )
(NP F2) 3 + 6Ph Li (NP Ph2 ) 3 + 6Li F - 14 )
The mechanisms of these reactions are not fully understood, but in

general they appear to involve SN2 attack on 'P' by an anion.
Bromo compounds may be prepared in the same manner.
NH4 B r
P Br5 (N PBr2 ) 3 – (15 )
Excess Br 2
The fluoride may be prepared indirectly by fluorination of the chloride.

(NPCl 2 ) 3 + 6 NaF (NPF2 ) 3 + 6Nacl – ( 1 6 )
1. How are different types of phosphazenes syntherised?

2. Why excess bromine is added in reaction (15)
Please do not proceed till you attempt the above questions.
32
Fig. 1.5 (a) & (b)
3.3.2 STRUCTURE STUDIES
The halide trimers consist of planar six membered rings. The bond
2
angles are consistent with SP hybridization of the nitrogen and
approximately SP 3 hybridization of the phosphorous. Two of the SP2 o r b i t a l
of nitrogen, containing one electron each, are used for 's ' bonding and the
third contains a lone pair of electron. This leaves one electron for the
unhybridised P Z orbita l.
The four SP3 hybrid orbital (containing four electrons) of phosphorous

are used for 's ' bonding leaving a fifth electron to occupy a 'd' orbital.
Resonance structures can be drawn like benzene ring indicating aromaticity
(Fig 1.5a). The Planarity of the ring, the equal P- N bond distances and the
shortness of the P-N b o n ds, and the stability of the compounds suggest
delocalisation. All phosphazenes are not planar. This does not make them less
stable. Phosphazenes are much more difficult to reduce. Unlike in benzene II-
bonding in cyclophosphazenes involves d and p orbitals Craig and Paddock
suggested the following model. The dxz orbital of the phosphorous atom
overlaps with the pz orbital of the nitrogen atom adjacent to it (Fig 1.6a). As
a result of the ‘g’ symmetry of the ‘d’ orbitals an inevitable mismatch in the
signs of the wave functions occur on the trimer, resulting in a node which
reduces the stability of the dolocalished molecular orbital. The dyz orbital
33
which is perpendicular to the dxz, can also overlap with the pz orbital of
nitrogen, but in this case no nodal surface results (Fig 1.6b). There may be in
–plane – P bonding between the sp2 non bonding orbital of nitrogen and the
dxy and for dx2 – y2 orbital of the phosphorous (fig 1.6c and 1.6d).
The structure of tetrameric phosphoazenes is more flexible than these

of the trimers. The structure of (NPF2 ) 4 is planar, but others are found in a
variety of conformations (tub, boat, chair, crown, saddle and structures in
between). Inter molecular forces play a major role in these structures. The
use of ‘d’ orbital removes the restrictions of the Huckel rule (4n+2) II
electrons for aromaticity. Thus the model due to Craig predicts that the
tetramer is stabilized by delocalisation unlike cyclo, octatetraene)
Self Check Exercise 4
1.(a) Discuse the structures of phosphazenes on the basis of ‘d’ orbital

participation of the ‘P’ atom.
1.(b) is delocalisation possible in the trimer? Please do no proceed till you
attempt the above questions. The space below in for your answers.
34
3.3.3 PHOSPHAZENE POLYMERS
Phosphozenes can be polymerized. Their polymers have advantages

o v e r c a r b o n - b a s e d p o l y m e rs polyolefin’s and polyesters. However
commercial application is not well developed as silicones (R2 SiO) n . Trim eric-
chloro phosphazenes can be polymerized thermally.
D cl
(NPcl 2 )3 p = N - -- (17)
cl n
If this is done carefully, extensive cross linking does not take place
and the polymer (n=15,000) remains stable in organic solvents, similarly:
(PNcl 2 ) n + 2n NaOR [PN(OR)2 ] n + 2Nacl --- (18)

(PNcl 2 ) n + 2n R2 NH [PN(NR2 ) 2 ] n + 2n Hcl --- (19)
can be obtained. By varying the nature of the side chain ‘R’ various
elastomers, Plastics, films and fibres have been obtained. They are fle xi b l e a t
low temperatures and water and fire resistant. Some R groups like R=CH2 CF 3
in OR group in the above reactions are water repellant and do not interact
with living and promise to be useful in fabrications of artificial blood vessels
and prost hetic devices.
Self Check exercise –5

1. How are phosphazene polymers obtained? Indicate their uses.
Space for answers
3.4 Let us Sum Up

(i) The synthesis of brazine is indicated.
(ii) The planarity of benzene is compared with that of borazone.
(iii) The synthesis of phosphazenes and their structures are discussed.
(iv) The importance of dp - pp bonding in phosphazenes is discussed.
(v) polymeric phosphazenes and their uses are also indicated.
35
3.5 Points for discussion.
I (i) In the case of borazines compare its synthesis with benzene (ii)
Planarity of benzene ring to the compared with that of borazine (iii)
Compare the properties especially using electronogativities of B and
N.
II (i) In the case of Phosphazenes, the ’d’ orbital participation of ‘P’

atom in forming dII-PII bonding decides its aromaticity (ii) The
synthesis of polymeric phosphozenes and their uses to be discussed.
3.6 References
1. Advanced Inorganic Chemistry, A compre h e n s i v e T e x t - F , A l b e r t

Cotton and G.Wilkinsonwiley Eastern Limited – New Delhi- 3 r d
Edition1972.
th
2. I n o r a g n i c C h e m i s t r y – 4 Ed James E, Huheey, Ellen. A. Keiter
Richard L. Keiter – pearson Education Asia 4t h Ed, Reprint, 2002.
36
LESSON – 4
SULPHUR – NITROGENRING COMPOUNDS
CONTENTS
4.0Aims and objectives
4.1 Introduction
4.2 Sulphur – Nitrogen Compounds
4.2.1 Synthesis of S- N Compounds
4.2.2 Structural studies
4.2.3 One – Dimentional conductors
In this lesson the synthesis, of sulphur- nitrogen compounds and the

Syntheses of some derivatives of sulphur - nitrogen compounds are discussed.
After studying this lesson you would be able to understand the bonding in
S- N Compounds. Learn the application of S4 N 4 in forming (SN)x which
behaves like a super conductor.
4.1 INTRODUCTION
Compounds which contain sulphur- nitrogen rings were known in t h e

last century, but many new ones have been prepared in the last decade. It is
currently an area of considerable interest.
4.2 SULPHUR NITROGEN COMPOUNDS

4.2.1 Synthesis of S4 N 4 :
The ammonolysis of S2 cl 2 , either in solution or in an inert solvent or

heated over solid ammonium chloride yields tetrasulphur, tetra- nitride.
NH 3
S2cl 2 S4 N 4 +S 8 + NH4 cl – (1)
The product is a bright orange solid insoluble in water but soluble in

some organic solvents. The crystals are reasonable stable to attack by air,
37
they are explosively sensitive to shock or friction. Reduction of S4 N 4 w i t h

metallic potassium or sodium oxide gives S3 N 3 (Fig 2.1a).
Reduction of S4 N 4 with Sn (II) chloride produces tetrasulphur

tetraimide isoelectronic with S8 . When S4 N 4 is heated under pressure in a
solution of CS2, containing sulphur S4 N 2 is formed.
38
4.2.2 STRUCTURAL STUDIES OF S-N CO MPOU NDS
It is impossible to write a simple Lewis structure for S4 N 4 . A cage

structure for S4 N 4 has been suggested. This structure contains two pairs of
nonbonding sulphur atoms at a distance of about only 258pm, considerably
shorter than the sum of the vanderwall’s radii (360pm). All of the S- N b o n d
distances within the ring are approximately equal (162pm) and has 12 P
electrons and this indicates considerable delocalisation. The molecule S4 N 2
h a s h a l f - chair conformation. The molecule S3 N - 3 has a planar six membered
ring. It has 10II electrons instead of six (Fig 2.1b). Still the Huckel rule is
obeyed (4n+2) rule and the system is expected to be aromatic. Four of the P
electrons occupy antibonding orbitals.
and this weakens the S-N b ond.
Sulphur – nitrogen compounds have often unpredictable structures, for

example the compound Ph SN =S=NSPh is considered to have resonance
structures (Fig 2.2). This is based on the fact that the separation between end
sulphur atoms is only 329pm (compared to vanderwal’s sum of 360pm).
4.2.3 ONE DIMENSIONAL CONDUCTOR
Polymeric sulphur nitride (also called polythiazyl), (SN)x has some

physical properties of a metal. It is prepared from S4 N 4 .
39
Ag
S4 N4 S2 N 2 (SN) x . The S4 N 4 is pumped in a
o
vacuum line over silver wool at 220 C, where it polymerize slowly to a
lustrous golden material. It has a conductivity near that of mercury at room
temperature and it becomes a super conductor at low temperatures below
(O.26K). X- rays studies indicate that the SN chains have the structure shown
in Fig (2.3a). This chain can be generated from adjacent square planar S2 N 2
molecules. The S-N bonds in this starting material have a bond length of
165.4pm, intermediate between single (174pm) and double (154 pm) S-N
bonds.
For the (SN)x chain many resonance structures can be drawn. The
single structure (Fig 2.3 b) has single bond double bond resonance system,
with nine electrons on each sulphur atom. Every S- N unit has thus one
*
antibonding P electron. The half filled over lapping P * orbitals will combine
to form a half- filled conduction band in much the same way as half- f i l l e d 2 s
orbitals on a mole of Lithium atoms, form a conduction band. This
conduction band lies only along the direction of the (SN)x fibres, the polymer
is thus a one dimensional conductor.
40
1. Give the synthesis of S4 N 4 and S3 N 3 .

2. All of the S-N bond distances within the ring are equal and what does
it indicate?
3. How does (SN)x behave like a one dimensional conductor?
Model answer for Self – Check exercise – 1
1. S 4 N 4 is obtained from S2 cl 2 by ammonolysi s.

2. S- N bond distances (162pm) are equal and it has 12- II electrons, obeys
Huckel rule- aromatic.
*
3. P h a l f - filled orbitals overlap forming conduction band in one
dimension.
4.3 Let Us Sum Up

The synthesis of S4 N 4 is discussed. The molecule S3N3 has a planar
structure and obeys Huckels rules. (SN)x behaves like a one
dimensional conductor the conduction is expl ai ned .
(i) The molecule S3 N 3 has a planar six membered ring structure and has
10II electrons. The system obeys Huckel’s rule.
*
(ii) The over lapping of P orbital (half– filled) in (SN)x l e a d s to one
dimensional conduction.
4.5 References
1. Advanced Inorganic Chemistry – A comprehensive Text (3r d E d ) .

F.A.cotton and G.Wilkinson Wiley Eastern Limited - New Delhi
(1972).
2. Inorganic chemistry (4t h Ed) Re print – 2002 J.E. Huheey, E.A.Keitar

and R.L.Keiter Pearson education – A si a .
41
LESSON – 5
CONTENTS
5.1 INTRODUCTION
5.2 METALLIC STATE
5.2.1 FREE ELECTRON THEORY
5.2.2 BAND THEORY
5.3 LET US SUM UP
5.4 POINTS FOR DISCUSSION
5.5 REFERENCES
In this lesson the conductivity of metals can be understood on the basis

of free electron theory and band theory.
The behavour of semi conductors is discussed on the basis of band
theory.
After going through this lesson you would be able to
· Understand the electrical properties of metals.
· The electrical conductivity of semiconductors can be understood.
5.1 INTRODUCTION
Metals have the following characteristics properties (1) high

reflectivity (2) high electrical conductance, decreasing with increasing
temperature (3) high thermal conductance (4) Mechanical properties such as
strength and ductility. An explanation for these properties, and for their
variations from one metal to the other, must be derived from the structural
and electronic nature of metal. The electrical conductivities of
semiconductors can be understood on the basis of band theories.
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5.2.1 FREE ELECTRON THEORY
At the beginning of the twentieth century, a bold guess was made by

Drude regarding the electronic structures of metals. The resulting free
electron theory was made by Lorentz a few years later and is known as
Drude- Lorentz theory of metals. The basic assumption of this theory is that a
metal crystal consists of positive metal ions whose velance electrons are free
to m ove between the ions as if they constituted an electron gas. The crystal is
than pictured to be held together by electrostatic forces of attraction between
the positively charged ions and the negatively charged electron gas. It is
further assumed that the electrons are free to move throughout the entire
crystal subject only to the laws of classical mechanics. The mutual repulsion
between negative electrons is ignored in this theory and the potential field
due to the positive ions is assumed to be completely uniform. Thus the
electrons can move from place to place in the crystal without change in their
energy. The electrons collide occasionally with the atoms and have velocities
determined at constant temperature according to the Maxwall- B o l t z m a n n
distribution laws. This model of a metal is highly successful in explaining
many properties of metals. For example if an external electric field is applied
to metal, the negatively charged electrons are accelerated towards the
positive pole of the field. The resulting current is limited by electron atom
collisions and is proportional to the applied voltage gradient according to
Ohm’s law. The opaqueness of metals for all wavelengths of light is
explained by the ability of a free electron to oscillate in the electromagnetic
field of the incident light beam regardless of its frequency. Similarly a free
electron once excited to a higher energy by the absorption of energy, can
return to its former energy by reemitting light of the same frequency in all
direct ions .
Because only light rays directed towards the surface can get out of the
crystal, this interaction appears as a reflection of the incident light and
accounts for the so called metallic luster.
Success of the Free Electron Theory

1. It is used to verify Ohm’s law .
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2. It is used to explain the electrical and thermal conductivities of metals.

3. It is used to explain the optical properties of metals.
Breakdown of classical theory

1. From the classical free electron theory the value of specific heat of
metal is given by 4.5 x R, where R is the gas constant. But experimental
value is nearly equal to 3R. According to classical free electron theory, the
value of electronic specific heat is equal to 3/2R. But actually it is0 . 0 1 R
only.
2. We cannot explain the electrical conductivity of semi conductors or

insulators using this model.
3. Ferromagnetism cannot be explained by this theory.
4. The photo electric effect, compton effect and the black body radiation
cannot be explained by the classical free electron theory.
Self-Check Exercise – 1
1. As the temperature increases the electrical resistance of a metal

increases – explain.
2. Indicate the failures of the classical free electron theory.
Please do not proceed until you attempt the above questions. The space below
for your answer.
Special features of quantum free electron theory.
1. Quantum concepts are followed. That is, the distribution of electrons in

a solid is determined by Femi- Dirac distribution.
2. The wave nature of electrons is taken into account.

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3. The physical properties of solids depend on the number of free

electrons available at the fermi energy level. Thus the fermi level
electrons play an important role in determining the various properties
of a solid.
4. The correct values of electrical conductivity, thermal conductivity,

specific heat, optical absorption, ferromagnetic susceptibility are
determined by quantum free electron theory of solids.
5. Quantum free electron theory is not only applicable for metals

(conductors) but also for semiconductors and insulators.
6. Thus the correct pictures of atoms and molecules and their electron
distributions and bonds are identified only from the quantum free
electron theory of solids.
Electron in a Metal
Consider problem for a three dimensional metal in which the electrons

move in all directions so that three quantum numbers nx ,n y , and nz a r e
needed, corresponding to the resolution of the motion into components along
three perpendicular axes x, y, and z. For simplicity we will take the potential
energy of the electron to be zero inside the metal and infinite outside. So that
the problem is just an extension of the one dimensional problem. Therefore
with a cubically shaped block of metal of sides ‘a’ the permitted energy
levels can be written as
h2
En = (n x 2 + ny 2 + nz 2 ) ….. (A)
8ma2
where nx ,n y , and nz can each take any number from the set 1,2,3,…. etc.,
irrespective of what numbers the others take.
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Similarly the wave function
8 nx p x ny p y nz p z
y nx ,n y ,n z = Ö sin sin sin ….. (B )
a3 a a a
The three quantum numbers nx , n y and nz are required to specify

completely each stationary state. It should be noted that the energy E depends
only on the sum of the squares of nx , n y and nz .
Consequently there will be in general several different wave functions

having the same energy. For example the three independent stationary states
having quantum numbers
(2,1,1,), (1,2,1) and (1,1,2) for nx , n y and nz have the same energy
6h 2 /8ma 2 such states and energy levels are said to be degenerate and the
corresponding wave functions are Y 2 1 1 ' Y 1 2 1 Y 1 1 2 .
On the other hand if there is only one wave function corresponding to a

certain energy, the state and the energy level are said to be non–
degenerate. For example,
The ground state with quantum numbers (1,1,1) has the energy
3h 2 /8ma 2 and no other state has this energy.
The degeneracy breaks down on applying a magnetic field or electric

field to the system.
Electron Energies in metals and fermi energy
The expression for the energy values given in equation (A) corresponds
to the permissible energy values that the valence electrons in a me t a l m a y
have, but it is essential to know what energies the electrons actually possess.
For a piece of metal of macroscopic dimensions, say a centimeter cube, the
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energy of the ground state (nx = ny = n z = 1) is of the order of 10- 1 5 eV and

hence may be taken to be zero for all practical purposes.
Also the maximum spacing between consecutive energy levels is less

than 10- 6 eV. So the distribution of energy levels may be regarded as a
continuum.
If a plot is made for a large range of energy values such that the
individual En values are so close together that they can be shown as a
continuum and the number of states per interval of energy, N(E) increases
parabolically with increasing E as shown in figure (3.1(a)).
The dashed line shows the nature of the change in electron energies
that occurs on heating to room temperature.
Fig 5.1
Fi gure 5.1 (a) The distribution of energy states as a function of energy E

(b) Filling of energy levels by electrons at 0 K
(a). Fermi energy
The valence electrons tend to occupy the lowest available energy

states. However because of the mutual interactions among all the electrons
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that form the electron gas, it is necessary to consider that all the electrons
are in a single system and that the Pauli Exclusion Principal applies.
According to Pauli exclusion Principle only two electrons can occupy a

given state specified by the three quantum numbers (nx , n y and nz ), one with
spin up and other with spin down (i.e., with opposite spins).
As a result of this principle, at0 K the electrons fill all the states upto
a certain maximum energy level, Em a x called the fermi level or fermi energy
‘E’. All quantum states in the energy levels above EF are empty (figure
3.1(b). Thus the fermi level is a boundary line which separates all the filled
states and empty states at 0 K in a metal.
Thus in a metal the energy of the highest filled state at 0 K is called

the fermi energy ‘EF ’ or fermilevel. The magnitude of EF dependson how
many free electrons there are. AT 0 K all states upto EF are full and states
above are EF are empty.
5.2.2 Band or Zone theory of Solids
Energy bands in solids (quantitative treatment)

In an isolated atom, the electrons are tightly bound and have discrete
sharp energy levels. When two identical atoms are brought together the
energy levels of each atom which are initially the same are split in to two,
one higher and one lower than the corresponding levels of the separated
atoms.
The splitting only becomes appreciable when the wave functions of the
electrons on different atoms begin to overlap considerably; at a given
distance it is therefore greatest for the outermost electrons and least for the
inner electrons.
If more atoms are brought together more levels are formed and for a
solid of 'N' atoms, each of the energy level of an atom splits into N levels of
48
energy. The levels are close together that they form an almost continuous
band.
The width of this band depends on the degree of overlap of electrons

on adjacent atoms and is again largest for the outermost atomic electrons.
The bands appear only when the distance between two atoms is very small.
That is the bands are formed in solid only.
For example, when the distance between two sodium atoms is about 5Å
the splitting of energy levels is maximum and bands appear. But when the
distance between sodium atoms is about 20Å the splitting of energy levels is
minimum and there is no band formation and hence there is no solid
formation.
The electrons can take only the energy values which are in the band.
The gap between two allowed band is called forbidden energy gap (or)
band gap since the electron cannot take the values of energy which are in t h e
forbidden energy gap. Normally we are interested in the valence (outermost
energy) band, formed by valence electrons since these are responsible for
electrical, thermal and optical properties of solids. Above the valence band
there is conduction band which has no electrons at 0 K.
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Fi g. 5.2
Figure 5.2. Energy levels of an isolated atom and the energy bands in
the solid.
Figure 3.2 shows the energy levels of an isolated atom and solid which
is the collection of N atoms. We can see that the allowed bands and the
energy gap between the allowed bands. Thus the bands are formed in solids
only and are due to overlapping of wave functions of different states and the
consequent energy level splitting.
Distinguish between conductors, semiconductors and insulators on the

basis of band theory of solids.
In a solid the outermost allowed band formed by valence electrons is

called the valence band and is fully or partially filled. Since the valence
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electrons are alone determining the properties of the material, the remaining
lower allowed bands consisting of bound electrons are not considered.
The band that is above the valence band and empty at 0K is called the
conduction band and is partially filled by free electrons which ar e g e n e r a l l y
unbound valence electrons generated by thermal excitation or electric field.
The band gap or forbidden gap is the energy interval between the
maximum energy of the valence band and the minimum energy of the
conduction band. In conductors, there is no meaning for band gap. But in
insulators and semiconductors, the value of band gap plays an important role
in determining the carrier concentration or electrical conductivity of different
materials.
Solids can be classified on the basis of their band structure as

conductors, semiconductors and insulators.
Fig. 5.3 Schematic band structure of conductors
Conductors are those solids which have vacant electron energy states
immediately above the highest filled level of the valence band. This can
happen in two ways. In the first case, the valence band is only partially filled
as in figure 5.3 (a). The electrons here can respond to an externally applied
field by acquiring extra velocity and moving into higher energy states. In the
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second case, a full valence band overlaps the conduction band as shown in
figure 3.3(b) so that the forbidden gap is zero. Monovalent metals such as the
alkali metals have one electron per atom in the outer most shell and the outer
m o s t e n e rgy bands are half filled in these metals. Divalent metals such as
magnesium have overlapping conduction and valence bands. Therefore they
can also conduct even if the valence band is full. The band structure of
trivalent metals such as Aluminium is similar to that of monovalent metals.
Thus there is no meaning for band gap in conductors.
Semiconductors are those materials which have an energy gap of about

2 to 3 eV or less. When the energy gap is 2eV or less an appreciable number
of electrons can be excited across the gap at room temperature. So
semiconductors conduct much better than insulators at room temperatures but
still orders of magnitude poorer than metals which have no forbidden gap. By
adding impurities or by thermal excitation we can increase the electrical
conductivity in semiconductors. Figure 5.4 (a) shows the band structure of
silicon.
Insulators are those materials which have an energy gap more than
3eV. It has been estimated that millions of volt/m of electrical potential
would be necessary to accelerate an electrons sufficiently to jump the
forbidden gap. The other possibility for a transition is that electrons cross the
gap by thermal excitation. At room temperature the number of electrons that
can be thermally excitedacross the gap in insulators such as Diamond turns
out to be extremely small. Figure 3.4 (b) shows the band structure of
diamond.
So the conductors are the materials having enormous electr ical

conduction; the insulators are the materials in which practically there is no
electrical conduction and the semiconductors are the materials in which the
electrical conduction is in between the electrical conduction of conductor and
insulator.
Electron in a periodic potential (Origin of band gap and effective mass of

electrons)
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While the Sommerfeld theory discussed earlier accounts satisfactorily

for electrical conductivity in most metals, it failed to explain why other
substances that also contain free electrons have virtually no conductivity and
are considered to be excellent insulators. A solution to this problem is given
by the Zone theory or Band theory of solids. The effect of the periodic lattice
field on the motion of the electrons leads to the zone or band theory of
solids, which is of the greatest importance for understanding the structures
and properties of metals, alloys and non- metallic solids.
Figure 5.4 band structures of semiconductor and insulator
Fig.5.5 One dimensional periodic potential

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According to zone theory, the electrons move in a periodic field

provided by the lattice. The potential of the solid varies periodically with the
periodicity of space lattice and the potential energy of the electron is zero
near the nucleus of the +ve ion in the lattice and maximum when it is half
way between the adjacent nuclei which are separated by the interatomic
spacing distance 'a' (Figure.3.5). This model was first postulated by Kronig
and penny. So taking this model and solving the Schroedinger equation for
this case, we can find the existence of energy gap between the allowed values
of energy of electron.
So if we use classical theory, we can get a parabola when we plot the

curve between the electron's energy and its momentum. In the figure.3.6 (a)
instead of momentum 'P'
h 2p h
the wave vector k is used since P = hk = . Thus the 'k'
2p l l
is directly proportional to momentum 'P'. Since the curve is a parabola, we
can infer that the energy varies continuously.
But by Kronig- Penny model, we can get a parabola with some

discontinuities in it as shown in figure3.6(b). Thus we have allowed bands
and forbidden energy gap between the allowed bands.
Figure 5.6 Energy Vs momentum curve

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Self check exercise –2
1. How does the band theory explain the conductivity of semi conductors?
What are intrinsic semi conductors?
Self check exercise - 2

Model Answer:
(i) Ge and SI are intrinsic semi conductors. Their band gaps are low and
hence even at ordinary temperatures free electrons are present in the
conduction band and has appreciable conductivity compared to insulators.
5.3 Let us Sum Up

(i) The free electron theory and band theory of metals and their applications
are discussed. (ii) Quantum free electron theory is discussed. (iii) Fermi
energy is explained (iv) The conductors, semiconductors and insulators are
compared using band theory (v) Kroning- Penny model is indicated.
5.4 Points for discussion:
1. The free electron theory of metals as suggested by Drude and Lorentz

successfully explained properties of metals such as electrical
conductivity, increase of electrical resistance with temperature and
metallic luster.
2. It failed to explain the values of specific heats of solids
3. The modified quantum free electron theory gives the correct values of
electrical conductivity, thermal conductivity, specific heats of metals.
4. The quantum free electron theory can be applied to metals as well as

semiconductors and insulators.
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5.5 References
(1972).

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LESSON - 6
CONTENTS
6.0 Aims and Objectives
6.1 Introduction
6.2 CRYSTAL IMPERFECTIONS
6.2.1 Point defects (Zero dimensional defects)
6.2.2 Line defects (One dimensional defects)
6.2.3 Surface defects (Two dimensional defects)
a) Volume defects (Three dimensional defects)
b) Non- St occhiometry
6.3 Let us Sum Up
6.5 References
The study of imperfections has a two fold purpose, namely

(i) A better understanding of them and how they affect material
properties
(ii) Exploration of possibilities of minimizing or eliminating these
defects.
The term imperfection or defect is generally used to describe any

deviation from the perfect periodic array of atoms in the crystal.
6.1 INTRODUCTION
In an ideal crystal, the atomic arrangement is perfectly regular and

continuous throughout. But real crystals are never perfect; lattice distortion
and various imperfections, irregularities or defects are generally present in
them. The mechanical, electrical and magnetic properties of crystalline
solids, particularly metals and alloys are profoundly affected by the
imperfections in the crystals.
57
6.2 .1 Point Defects
1. Point imperfections are also called zero dimensional imperfections.

One or two atomic diameters is the typical size of a point imperfection.
2. In a crystal lattice, point defect is one which is completely local in its

effect, e.g., a vacant lattice site.
3. The introduction of point defect into a crystal increases its internal

energy as compared to that of the perfect crystal. Further they produce
distortions inside the crystal structure.
4. They change the electrical resistance of a crystal.
5. If a point defect is a vacancy, then there is no bonding. Hence the

value of the mechanical strength at that point is reduced.
6. Similarly if an impurity atom is present instead of the original atom, in

the lattice, there must be some strain due to the different size of the
impurity atom.
7. Point defects are created during crystal growth and application of

thermal energy, mechanical stress or electric field. Further they are
created by irradiating the crystal by x rays, microwaves and light.
Different types of point imperfection are described below:
a. V acan cies
A vacancy or vacant site implies an unoccupied atom position within
the crystal lattice. In other words, vacancies are simplify empty atom sites.
Vacancies may be single, two or more of them may condense into a divacancy
or tri- vacancy.
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It may be shown by thermodynamic reasoning that lattice vacancies are

a stable feature of metals at all temperatures above absolute zero. Vacancies
exist in a certain proportion in a crystal in thermal equilibrium leading to an
increase in the randomness of the structure.
The every day industrial processes of annealing, homogenization,

precipitation, sintering, surface hardening, oxidation and creep, all involve to
varying degrees, the transport of atoms through the lattice with the help of
vacancies.
Vacancies may occur as a result of imperfect packing during the

original crystallization or they may arise from thermal vibrations of atoms at
elevated temperatures, because as thermal energy is increased there is a
higher probability that individual atoms will jump out of their position of
lowest energy.
The atoms surrounding a vacancy tend to be closer together, thereby

distorting the lattice planes.
Schottky defect
1. Ion vacanciesare called Schottky defects.
2. A pair of one cation and one anion can be missing from an ionic
crystal. The valency of the missing pair of ions should be equal to
maintain the electrical neutrality. So these are normally generated in
equal numbers of anion and cation vacancies in a crystal.
3. When vacancies are created by movements of an anoin and one cation

from positions inside the crystal to positions on the surface of the
srystal, a schottky defect is said to have been formed.
4. This type of point defect is dominant in alkali halides.

59
b. Interstitial Defect
1. An interstitial defect arises when an atom occupies a definite position
in the lattice that is not normally occupied in the perfect crystal.
2. In interstitialcies, atoms occupy vacant positions between the atoms of

the ideal crystal. The interstitial atom may be lodged within the crystal
structure, particularly if the density of packing (or) packing fraction is
low.
3. Interstitialcy produces atomic distortion or strain because interstitial

atom tends to push the surrounding atoms further apart, unless the
interstitial atom is smaller than the rest of the atoms in the crystal.
4. By giving enormous stress (or) compressive force to a crystal, some of

the parent atoms dislodge from their lattice sites and occupy the voids
or interstitials present in the lattice. These type of imperfecti o n s a r e
called self interstitial imperfections.
Frenkel defect
1. In the case of ionic crystals, an ion displayed from the lattice into an
interstitial site is called a Frenkle defect.
2. As cations are generally the smaller ions, it is possible for them to get
displaced into the void space present in the lattice. Anions do not get
displaced like this, as the void space is just too small for their size.
3. A Frenkel imperfection does not change the overall electrical neutrality

of the crystal. The point imperfections in silver halides and calcium
fluoride are of the Frenkel type.
4. Frenkel and Schottky defects together are called 'Intrinsic defects'.

60
c. Impurities
1. Impurities give rise to compositional defects.
2. A controlled addition of impurity to a very pure semiconductor crystal

is the basis of producing many electronic devices like diodes and
transistors. Addition of pentavalent and tetravalent impurity atoms in
silicon or germanium crystal increases its electrical conductivity.
3. Foreign atoms generally have atomic radii and electronic structures

differing from those of the host atoms and therefore act as centers of
distortion.
4. Basically there are two types of impurity defects.

A subst itutional impurity refers to a foreign atom that substitutes for
or replaces a parent atom in the lattice as shown in fog. 4.1(a).
5. In the case of semiconductor technology aluminium and phosphorous

doped in silicon are substitutional impurities in the crystal. Further
during the production of Brass alloy, the zinc atoms are doped in
copper lattice. Here the zinc atoms are called substitutional impurities.
In ionic solids, for example in sodium chloride, the substitution of Na+
by Li + produces a substitutional impurity.
Fig. 6.1 (a) Substitutional Impurity (b) Interstitial Impurity

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An interstitial impurity is a small sized atom occupying the void space

in the parent crystal, without dislodging any of the parent atoms from their
sites as shown in figure 4.1 (b). An atom can enter the interstitial or void
space only when it is substantially smaller than the parent atom. For example
in FCC iron, the atomic radius of iron atom is equal to 2.25Å. The carbon
atoms with atomic radius equal to 0.777 Å can occupy the octahedra l v o i d
spaces in FCC lattice as interstitial impurities, But the carbon atom radius is
greater than the radius of the void and so a strain is produced there. Addition
of carbon atom upto 1.7% in Iron increases its mechanical strength.
d. Electronic defects
1. Electronic defects are the result of errors in charge distribution in

solids. These defects are free to move in the crystal under the influence
of an electrical field, there by accounting for some electronic
conductivity of certain solids and their increased reactivity.
2. For example if we take zinc oxide, the zinc ions can occupy
interstitials and this leads to a large number of positive charges at that
place.
3. In some places if zinc ions are missing, then in that places there is a
gain of negative charges due to loss of positive charges.
4. Thus a vacancy or an interstitial impurity may produce the excess or

the deficit of positive or negative charges.
Applications of point defects
1. Doped atoms or impurities in Si or Ge crystal increase its electric al

conductivity.
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2. The interstitial impurity carbon atoms in iron lattice increase the

strength of iron.
3. Addition of copper atoms in gold increase the ductility of gold so that

it can be drawn into wires
4. in copper lattice, the substitutional impurity atoms of tin increases the

bearing properties of copper.
6.2.2 Line defects
1. Line defects are called dislocation. These are one- dimensional

imperfections in the geometrical sense.
2. A dislocation may be defined as a disturbed region between two

substantially perfects parts of a crystal. It is a line defect in a crystal
structure whereby a partplane of atoms is displaced from its
symmetrically stable positions in the array.
3. The dislocation is responsible for the phenomenon of slip by which

most metals deform plastically.
4. One may conclude that dislocation is the region of localized lattice

disturbance separating the slipped and unslipped regions of a crystal.
5. Burgers vector marks the magnitude and direction of the strain

component of dislocation.
6. Dislocations arise in crystals as a result of

i. Growth accidents
ii. Thermal stresses
ii i. External stresses causing plastic flow
iv. Phase transformations
v. Segregation of solute atoms causing mismat ches , et c.
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7. The two basic types of dislocations are:

a. Edge dislocation and
b. Screw dislocation
a. Edge dislocation
v An edge dislocation is created in the crystal by introducing an extra

half plane or (any extra plane that does not extend up to the base of the
crystal).
v The bond lengths have been compressed to smaller than the equilibrium
value. Just below the edge of the extra plane the atoms are pulled apart
and are in a state of tension.
v Here the bond lengths have been stretched to above the normal values.
v This distorted configuration extends all along the edge into the crystal.
There is an extra energy due to the distortion in the region immediately
surrounding the edge of the incomplete plane.
v As the region of the maximum distortion is centred around the edge of

the incomplete plane, this distortion represents a line imperfection and
is called an edge dislocation.
v The edge dislocation is said to be negative, denoted by T, when the

insertion of the extra plane is from the bottom of the crystal.
v ^ denotes + ve edge dislocation in which the insertion of extra plane

from the top of it.
v Let us see something about the Burgers circuit. Take a point P Starting
from P, move x times the atomic distance in the positive x direction
and then move 'y' times the atomic distance in the positive y direction
and then move x times the atomic distance in the negatively x
direction and then move y times the y direction. After this movement
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we can arrive at the original starting point 'P'. The circuit is a closed
one and this type of circuit is called Burger s c ircuit.
v We draw the burgers circuit as explained above and if the circuit could
not be completed then Immediately one can infer that there is a
dislocation in the circuit.
v From the end point, if we want to arrive the starting point then we must
move an extra distance 'b'. Therefore the vector b connecting the end
point with the starting point is the burgers vector of the dislocation.
b. Screw dislocation
v Screw dislocation results from a displacement of the atoms in one
part of a crystal relative to the rest of the crystal, forming a spiral
ramp around the dislocation line.
v Figure 4.2 shows what happens when one part of the crystal is
displaced relative to the rest of the crystal and the displacement
terminals within the crystal. The row of atoms marking the
termination of the displacement is the screw dislocation.
v By means of burgers vector as shown in the figure 4.2 one can

determine the magnitude and direction of the screw dislocation.
v In the figure EF indicates the dislocation line.
v Normally the real dislocations which occur in the crystals are the
mixtures of edge and screw dislocations.
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Fig. 6.2 Screw Dislocation

6.2.3 Sur face Defects
v Surface imperfections which are two dimensional in the m a t h e m a t i c a l

sense refer to regions of distortions that lie about a surface having a
thickness of a few atomic diameters. These are also called plane
defects.
v We can classify these defects into two main types which are external
surface imperfections and internal surface imperfections.
a. External surface imperfections.

v The external surface of a crystal is an imperfection in itself, as the
atomic bonds do not extend beyond the surface. Although we may
visualize an external surface simplify a terminus of the crystal
structure, the atoms on that surface cannot be compared with the atoms
within the crystal.
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v Because the external surface atoms have neighbours on one side only,
while atoms inside the crystal have neighbors on either side of them.
Si nc e t he external surface atoms are not entirely surrounded by others
they possess higher energy than that of internal atoms.
b. Internal surface imperfections
v Internal surface imperfections arise from a change in the stacking of

atomic planes across a boundary. The change may be one of the
orientation or of the stacking sequence of the planes.
v Some important internal surface imperfections are given below:

i. Grain Boundaries
ii. Tilt boundaries and twist boundaries
ii i. Twin boundaries
iv. Stacking faults and
v. Ferromagnetic domain walls
i. Grain boundaries
v The grain boundaries are those surface imperfections, which separate

crystals of different orientations in a polycrystalline aggregate.
v During solidification or during recrystallization of polycrystalline

crystals, new crystals are randomly oriented with respect to one
another. They grow by the addition of atoms from the adjacent regions
a nd e ve nt u a l ly impinge on each other. When two crystals impinge in
this manner, the atoms that are caught in between the two crystals are
being pulled by each of the two crystals to join its own configuration.
v They can join neither crystal due to the opposing forces and therefore
take up a compromise position. The thickness of this region is only a
few atomic diameters, because the opposing forces from neighboring
67
crystals are felt by the intervening atoms only at such short distances.
The boundary region is called a crystal boundary or a grain boundary.
v The crystal orientation changes sharply at the grain boundary, as shown

in figure 4.3(a).
v It is obvious from this that the grain boundary forms a discontinuity in

the periodicity of the lattice of crystallite or grain and is therefore a
type of lattice imperfection called grain boundary.
ii. Tilt boundaries and twist boundaries
v Tilt boundary is another type of surface imperfection and it may be

regarded as an array of edge dislocations (^ )
v It is also a class of low angle boundaries
v By rotation of an axis in the boundary it is possible to bring the axis of

two bordering grains into coincidence, i.e. a tilt boundary, (figure
4.3(b). In this figure 'h' is the distance between two neighbouring
dislocations and 'q' is the angle of tilt, 'b' is the Burgers Vector.
v Twist boundaries are the second class of low angle boundaries result
from the set of screw dislocations. In twist boundary the r o t a t i o n i s
about an axis normal to the boundary.
6.3 (a) High angle grain boundaries (b) Tilt boundary

68
iii. Twin boundaries
v Surface imperfections which separate two orientations that are mirror

images of one another are called twin boundaries
v Twin boundaries occur in pairs, such that the orientation change

introduced by one boundary is restored by the other as shown in figure
(4.4).
Fig. 6.4 (a) Twin Boundaries (b) Stacking fault
iv. Stacking faults
v A stacking fault is a surface imperfections that results from the

stacking of one atomic plane out of sequence on another, while the
lattice on either side of the fault is perfect. The stacking fault is a
discrepancy in the packing sequence of the layers of atoms (although
all the lattice sites are occupies).
v For example in the case of close packed FCC structure the stacking
sequence can be written as ABC ABC … In that sequence it i s possi ble
in one atom layer 'A' the atoms are not positioned properly in a small
region and hence deviates from the sequence, relative to the atoms of
the layers above and below giving a defect, since now there is a
69
sequence of …BCBC… which belongs to HCP structure instead of …

ABC ABC…
v Figure 4.4(b) shows the stacking fault in a FCC metal. So on may

conclude that stacking fault may arise when there is only small
dissimilarity (electrostatically) between the stacking sequences of
close-packed planes in FCC and HCP metals.
v Stacking faults are more frequently found in deformed metals than in

annealed metals.
6.2 Volume defects
v Volume defects such as cracks may arise when there is only small
electrostatic dissimilarity between the stacking of closed p a c k e d
planes in metals.
v Further when clusters of atoms are missing, a large vacancy or void

result which is also a volume imperfection.
v Foreign particle inclusions, large voids or non crystalline regions

which have the dimensions of at last 10 to 30 Å are also called volume
imperfections.
Effect of Crystal imperfections

1. The addition of impurities in the case of semiconductors increases the
electrical conductivity; but in the case of metals, it decreases the
electrical conductivity.
2. The impurity atoms in the lattice give characteristic colours to the

crystals. These are called colour centers. If we take pure copper
sulphate crystal it is colourless. but due to addition of water molecules,
it turns out to be blue in colour. Similarly in the aliminium oxide
lattice the addition of chromium atoms gives the red colour to it.
70
6.2.(b) Non- Stoichiometry
A defect like schottky defect, leaves the stoichiometry of the ionic

crystal unaffected. For example there are equal number of Na+ and cl
- +2
vacancies in Nacl. These are 2cl vacancies per ca vacancy in cacl2 . But in
certain transition metal compounds, especially oxides and sulphides, non-
stoichiometric defect occurs. This is because of the ability of the metal to
exist in more than one oxidation state. A well known case is "FeO" which
consists of a 'CCP' array of oxide ions with all octahedral holes filled by
+2 +3
Fe ions. Actually some of these sites are vacant, while others – contain fe
ions, sufficient to maintain electroneutality. Thus the stoichiometry is
commonly about Fe0 . 9 5 O. Ti O can be obtained with compositions ranging
f r o m T i 0 . 7 4 O to Ti1 . 6 7 O depending on the pressure of oxygen gas while
preparing the material.
CdO loses oxygen when heated to give yellow to black solids of
compos i t io n. C d 1 +rO similarly when Nacl is trwated with sodium vapour, it
absorbs sodium to give blue solid of composition Na1 + r cl. An appropriate
number (nr) of anion vacancies are created. These anion vacancies are
occupied by electrons. These cavities are 'F' centers (fairbe).
1. What are point defects?

2. How are Frenkel and schottky defects created.
Please attempt (1) and (2) before you proceed further
1. Discuss the different types of dislocations please attempt (1) before

you proceed further.
Self Check Exercise - 3
1. What are non stoichiometric defects? Does schottky defect lead to non-
stoichiometry.
71
2. How are colour centers produced?

Model Answer:
Exercise – 3
2. Colour centers are produced due to anion vacancies and trapped

electrons cdo
D
CdO Cd 1 + r O
6.3 Let us Sum Up

Crystal imperfections such as i) point defects, ii) line defects, iii)
surface defects and iv) volume defects are discussed in detail. Effect of
crystal imperfections is indicated the different types of boundaries are
discussed.

1. Transition metal oxides and sulphides can have non- stoichiometry,
since these metals have variable oxidation states.
2. Anion vacancies can be created due to excess metal atoms.
3. Zno, on heating loses oxygen creating oxide ion vacancies, thus zno is
yellow when hot white when cold (F- centre formation).
6.5 References

(1972).

72
UNIT – III
LESSON –7
CONTENTS
7.0. Aims and Objectives
7.1 I ntroduction
7.2 Electrical Properties o f Solids
7.2.1 Conductivity in metals

7.2.2 Super conductors
7.3 Let us Sum Up
7.5 References
The aim of this lesson is to understand the electrical conductivity or

electrical properties of solids in general and electrical properties of metals in
particular.
After going through this lesson you would be able to
i) understand the electrical conductivity of metals and insulators
ii) understand the super conducting behaviour of certain materials
and the applications of super conducting materials
7.1 INTRODUCTION
The conductivity of metals can be explained on the basis of free

electron theory. The quantum free electron theory successfully explains the
conducting properties of metals and the decrease in electrical conductivity of
metals with the increase in temperature can be explained on the basis of
collisions of electrons with metal ions. Super conductors are zero resistivity
materials. The superconductivity is explained by means of Cooper pair. The
super conductivity depends on the critical temperature.
73
7.2. ELECTRICAL PROPERTIES
7.2.1 Conductors and nonconductors :
One of the successes of the zone theory is its ability to distinguish

conductors of electricity from nonconductors. Consider a Brillouin zone that
is only partly filled, as shown in Fig 1.1. In the absence of an external
0electric field, each electron moves with a velocity determined by its energy;
however, no net movement occurs, since for each electron with an energy
determined by k there is a symmetrically located electron at – k moving in
the opposite direction. When an external field is applied, the distribution can
be displaced in the direction of the electric field by moving the electrons into
adjacent quantum states in the same zone, as indicated in Fig 1.1 by the
dashed circle. Obviously, only the electrons occupying energy levels lying
near the Fermi surface can move into the higher energy states. Nevertheless,
a net displacement of the electrons produces a net current, and a crystal with
a partially filled zone is a conductor. As this process continues, it is possible
that an electron ultimately occupies a quantum state on the Brillouin- zone
boundary. At this point, it cannot mover farther in the same direction
without crossing the boundary, that is without a transition to a quantum state
lying in the next zone. Such a transition is highly improbable so that th e
electron's velocity normal to the zone boundary is zero in this state.
Physically, the electron can be pictured as being totally reflected by the
crystallographic planes parallel to the zone boundary at this point. In terms
of the zone model, the reflected electron "reappears" in the zone at a
translation- equivalent point on the opposite zone boundary. Such a
successive occupation of available quantum states in the Brillouin zone is
shown schematically in Fig 1.2, where q 0 shows the initial quantum sta t e o f
the electron, when an external field is applied; q R is the quantum state of the
electron when reflection occurs; and q F is the final state when the external
field is removed.
74
When the zone structure Figof a1.1crystal

& 1.2 is such that the energy values in
two adjacent zones overlap, it is not possible to complete the filling of one
zone without also occupying the lower-energy quantum states in the zone.
This means, of course, that such a crystal must have at least one partially
filled zone and that it is a conductor of electricity. An interesting situation
arises when one of the zones is very nearly filled while the next zone is only
partly occupied. The relative energy of the 4s states is slightly lower th an
that of the 3d states for the first transition series in the periodic table of
elements. The partial occupation of these states by the outer electrons of
transition metals means that the corresponding Brillouin zones are also party
filled. For example, it can be shown that the 3d zone of nickel is 94 percent
filled, whereas the 4s zone is 70 percent empty. Furthermore, it is believed
that conductivity in these metals takes place by transitions in the 4s zone.
Now, when a 4s electron undergoes a transition from a quantum state on the
zone boundary to an empty state it can be either "reflected back" in to the
same zone or "scattered" into the 3d zone because there are quantum states of
equal energy present in both zones. Such scattering decreases the n umb e r o f
electrons contributing to the current and is believed to be responsible for the
lower conductivity observed in the transition metals.
In case the Brillouin zones in a crystal are completely filled or

completely empty and separated by a forbidden- energy region, the electrons
cannot undergo transitions to adjacent quantum states and the crystal is an
insulator. There are special cases of insulators in which one zone is very
75
nearly filled and the next zone almost but not quite empty. This situation
occurs in semiconductors and also leads to conductivity. By comparison with
metals, however, the currents in semiconductors are many orders of
magnitude smaller.
Conductivity in pure metals :
The conductivity of most metals can be explained without recourse to

the zone theory. According to the free-electron theory, electrons can undergo
transitions from one quantum state near the Fermi surface to another adjacent
and unoccupied state under the influence of an external field. If this process
were allowed to continue without end, the electrons would continue to occupy
ever- increasing energy states, a situation that is contrary to the observed
steady- state current, which is proportional to the applied field. The fact that
the electrons cannot continuously increase their energy is explained by their
collisions with the metal ions, which occupy most of the space in a metal.
These collisions are elastic so that the electrons transfer both energy and
momentum in the process. Because of the much larger mass of the ions, an
electron loses most of its newly gained energy and momentum so that its
velocity, averaged over a period of time, is altered only slightly. There is,
nevertheless, a small but finite increase in the velocity component parallel to
the applied field. Thus, even though the electron follows an erratic path,
bouncing from atom to atom in all directions, it does undergo a net
displacement in a direction determined by the applied field. The increase in
its velocity component parallel to the applied field direction is called its drift
velocity.
The average distance that an electron travels between collisions is

called the mean free path l. The electron's acceleration due to the field is
proportional to its charge e and inversely proportional to its mass m. The
conductivity s or its reciprocal, the resistivity r , is thus given by
1 mv
r = -- - = - - - - …. ( 1)
s nc e 2 l
76
where n c is the number of conduction electrons a n d v is the average velocity

as determined by their average kinetic energy E v .
The vibration of
theFig ions
1.3 &in 1.4a crystal increases with increasing
temperature. This has the effect of increasing the probability of an electron-
ion collision or of decreasing the mean free path. Conversely, as the
temperature decreases, the mean free path should increase. This is actually
the case, as is shown in Fig 1.3. Note that the mean free path tends to
infinity as the temperature approaches zero. According to (1) this implies
that the resistivity of a metal should tend toward zero as the temperature
approaches zero. This conclusion is borne out by experiment, as shown by
the curve of resistivity plotted as a function of temperature in Fig 1.4. Note
that for all temperature above a certain low temperature the resistivity is
directly proportional to the temperature.
Quantitative calculations of the mean free path have been made for
certain metals, using quantum mechanics. These calculations have led to
results that are in good agreement with experimental values, particularly for
the simpler metals such as the alkalis. The conductivities (expressed in
o
millions of mhos per meter) of several metals at 20 C are compared with
calculated values below.
77
Fe Na Al Cu
Observed s 10 22 35 59 x 10 6 m hos/ m
Calculated s .. 22 .. 161 x 10 6 m hos/ m
In crystals belonging to the cubic system, the conductivity is

independent of direction. The conductivity (or its reciprocal, the resistivity)
does depend on direction in crystals of lower symmetry. In the case of
crystals possessing one unique axis, that is in the hexagonal and tetragonal
systems, the resistivity is different for current flow parallel to the unique
axis and normal to it.
Conductivity in alloys :
The mean free path of an electron decreases in an alloy for two
reasons. The first is an increase in the number of scattering centers caused
by local inhomogeneities in the crystal structure produced by the difference
in the sizes of the different atoms. This effect is particularly noticeable in
the case of solid-solution alloys. In the unannealed or random solid solution,
the resistivity reaches a maximum at the 50- 50 composition, since this
corresponds to the maximum possible distortion of the structure, and drops
rapidly at both ends as the pure metals are approached. The increase in the
resistivity is due to a discontinuity in the periodic potential encountered by
the electrons in the vicinity of the solute atoms. At the compositions of the
ordered alloys Cu3 A u a n d CuAu, the curve exhibits definite minima,
corresponding to the increased mean free path of the electrons due to
ordering, which restores a periodicity to the alloy. In practice, it turns out
that annealing serves to decrease the resistivity also because it removes other
imperfections present which may also act as scattering centers for electrons.
In a solid solution, the increased resistivity, due to the introduction of

solute atoms, does not disappear at the absolute zero. The resistance that
remains is usually called the residual resistance. The residual resistance is
independent of temperature in dilute alloys but varies with changes in the
composition of an alloy. According to Matthiessen's rule, the resistivity of
78
an ideal alloy can be expressed as the sum of the residual resistance and a
resistivity term which varies with temperature in the same linear manner as
the resistivity of a pure metal.
1. If kentic energies and mean free paths are assumed to be equal for Na
an d Al, what would be the ratio of the free electrons nN a ¸ nA l ?
2. Discuss the variation of resistivity with the compositions of cu- Au
alloy.
Please answer the above before you proceed further. The space below is for
your answer.
7.2.2 Zero resistivity materials (Superconductors)
The ability of certain ultra cold substances to conduct electricity

without resistance is called superconductivity. Substances having this
property are called superconductors.
Thus a superconductor is a conductor having almost zero resistivity

and also behaves as diamagnetic below its superconducting transition
temperature.
Fi g 7.5
79
The superconducting transition temperature 'Tc ' of a material is defined

as a critical temperature at which the resistivity of the material is suddenly
changed to zero as shown in fig. 7.5. Thus at that temperature a material is
ch an ged from normal material to superconductor. In the figure the transition
region is of finite width AB and depends upon the presence of impurities and
internal stresses in the sample. In chemically pure crystal which is also free
from lattice defects, the width of the transition region is very very narrow.
The temperature 'Tc ' of pure metals range from 0.35 K (Hafnium) to 9.22 K
(Niobium) and of semiconductors from 0.3K (Ge Te) to 1.25 K (NbO).
Commonly alloys have higher transition temperatures. Particularly Niobium
compounds such as Nb3 Sn (Tc = 1.81 K) and Nb3 Ge (Tc = 22.65 K) have
higher transition temperatures and so they are technically important
superconductors.
At the transition temperature, the following physical changes are
observed.
1. The el ectr ical resistivity drops to zero
2. The magnetic flux lines are excluded from the material
3. There is a discontinuous change in specific heat.
4. Further there are also small changes in thermal conductivity and the
volume of the material.
Explanations for the occurrence of superconductivity
1. At the extremely low temperatures, vibrations of the nuclei of certain

atoms slow down so much and they synchronise with passing waves of
electrons in a flow of electric current. When this happens resistance to
electric current disappears.
80
2. BARDEEN COOPER AND SCHRIEFFER THEORY

According to that, superconductivity occurs when there is a formation
of cooper pair of electrons (or) bound electron pair. These two
electrons with opposite spins and momenta form a pair through electron
– electron interaction via the lattice deformation or phonon field. This
type of interaction can occur only at very low temperatures. Thus
during the transition from normal state to super conducting state
electrons of opposite spin couple with each other via the vibrations of
the lattice that the material's atoms form. One electron in the
communicating pair distorts the lattice which can then take up energy
from the second electron and immediately they from a bound electron
pair or Cooper pair.
Fig 7.6
As shown in figure 1.6, one electron with wave vector k distorts the
lattice emitting a phonon of wave vector q. The other electron with wave
vector k takes up the energy down the lattice and its wave vector changes
into k + q. Thus these two electrons with wave vectors k – q and k + q form
a cooper pair and superconductivity occurs.
3. RVB Theory :
The conventional BCS theory accounts for superconductivity only at

low temperatures. At higher temperatures thermal degradation breaks the
cooper pairs leading to ordinary electrical conductivity. Thus it is unable to
explain the formation of high temperature superconductivity having high
Tc ( » 80 K)
81
Many theories have been suggested, but none is satisfactory. One of

the promising one is the Resonating Valence Bond (RVB) state theory
initiated by P.W. Anderson and the Princeton university group. According to
that intense electron pairing needed to explain hot superconductivity may be
brought about through an attractive correlation quite similart o t h a t
responsible for bonding hydrogen atoms in a molecule. Further it is based on
the idea that it is the short range repulsion between electrons in a narrow
band which gives rise to superconductivity.
A key element of RVB theory is that electron pairs can exist in a

material that is not superconducting. Superconductivity occurs when the
material is doped to create holes in it. The holes then form pairs and undergo
Bose Condensation, making superconductivity possible. These high
temperature superconductors are normally called p type superconductors
since the charge carriers are holes.
Recently 'n' type superconductors (Ln2 - x C e x C u O 4 - y ) where Ln = Pr,

Nd and Sm have been prepared but the transition temperature for this system
are very low (» 20K).
General properties of superconductors
1. Electrical resistance
The electrical resistivity drops to zero at the transition temperature.

One can conclude that superconductors have virtually zero electrical
resistance and they can conduct electricity without resistance.
2. Diamagnetic property
The superconductor is a perfect diamagnet. As the material which is

placed in an uniform magnetic field (whose value is smaller than the c r i t i c a l
magnetic field Hc ), is cooled below 'Tc ' the magnetic flux inside the
82
material is excluded from the material (fig 1.7). This is called MEISSNER
EFFECT.
Thus a material can behave as a superconductor only when

i) the resistivity of the material should be zero and
ii) the magnetic induction in the material should be zero when it is
placed in an uniform magnetic field.
Fi g 7.7
Both the conditions are independent to each other and to get

superconducting state, these two conditions should simultaneously exist in
the material.
83
3. Effect of magnetic field
Below Tc superconductivity can be destroyed by the application of

strong magnetic field. At any temperature, the minimum field required to
destroy superconductivity is called critical field (Hc ) of the material. Thus
the value of the critical field depends upon the temperature of the
superconducting material.
T2
Hc = Ho 1 - -- - --
T2 c
W here H o = critical field 0 K.
Fi g 7.8
From the fig. 7.8 one can know that when the temperature of the
material increases, the value of the critical magnetic field decreases
correspondingly. The value of the field will be different for different
materials.
84
Tabl e 1. 1 SUPERCONDUCTORS AND THEIR CRITICAL FIELD
Material Ho ampere/metre X 103 Material Ho ampere/metre X 103

Al 7.9 Sn 24.5
Co 2.4 Ba Bi 3 59.0
Hg 33.0 Ca Si 2 1.4
Pb 64.0 Nb 3 Sn 18.1
4. Effect of heavy current
T h e s u per conductive properties of conductors disappear when a

sufficiently heavy current is passed through them. Since when current flows
through a conductor it will set up the magnetic field which destroys the
superconducting state. According to Silsbee's rule, for a superconducting
wire.
I c = 2p rH c
Where I c is the critical current and 'r' is the radius of the wire.
5. Effect of pressure
By applying very high pressure, we can bring Tc of a material nearer to

room temperature i.e. if we increase the pressure on the material, Tc a l s o
increases. Tc is directly proportional to pressure at very high pressures.
Researches are going on to get superconducting state at room temperatures by
applying very high pressures.
6. Isotope effect
Maxwell found that the transition temperatures are inversely
proportional to the square roots of the atomic weights of the isotopes of a
single superconductor. Thus,
a
M Tc = a constant
85
Where a is a constant and it is approximately equal to 0.5. For example the

atomic weights of isotopes of mercury are from 199.5 to 203.4 atomic mass
units. Therefore their transition temperatures are also from 4.185 K to 4.146
K respectively.
Types of superconductors
Based on the value of superconducting transition temperature we have

1. High temperature superconductors
2. Low temperature superconductors
High Temperature superconductors Low Temperature superconductors
1 It has high super conducting 1 It has low superconducting transition
transition temperature (> 100K) temperature (<20K)
2 Super conductivity is obtained by the 2 Superconductivity is obtained by the
hole states. Dislocations also increase formation of cooper pair having two
the value of transition temperature. electrons with equal and opposite
spins and momenta.
3 It does not obey B.C.S. theory. High 3 It can be explained only from BCS
temperature superconductivity can be theory.
explained from resonance valence
bond (RVB) theory only.
4 It is very useful for commercial and 4 It is not so useful, due to
other applications because these have maintaining of ultra low temperature
high superconducting transition (20 K)
temperatures and are hard super
conductors which can produce strong
magnetic fields.
5 It is called p- type super conductor 5 It is called n- t y p e s u p e r c o n d u c t o r
due to the formation of due to the formation of
superconductivity from holes. superconductivity from cooper pairs
or electron pairs.
Based on critical magnetic field, there are two types of superconductors

i. Type I (soft) superconductors
86
ii. Type II (hard) superconductors
Type I Superconductors
1. Type I superconductor is the one which exhibits a complete Meissner

effect or perfect diamagnetism. i.e., above the critical field Hc , the specimen
is a normal conductor. Below the critical field, the specimen excludes all the
magnetic lines of force inside the specimen or it will become a diamagnetic
material
2. These are also called soft superconductors

3. The values of Hc , are always too low for these materials.
4. Example: A1, Zn, Ga.
Fig 7.9 (a) & (b)
In the Figure 1.9 Ha - applied external magnetic field and

Hb - Magnetic filed produced by the induced
superconducting currents when an external field is applied.
Type II Superconductors
87
1. Type II Superconductors are the superconductors in which the magnetic

flux starts to penetrate the specimen at a field Hc 1 which is lower than
critical field Hc . The specimen is in a mixed state between Hc 1 and Hc2 a n d i t
has superconducting electrical properties upto Hc 2 . Above Hc 2 the specimen is
a normal conductor (fugure 1.9 (b).
2. Type II superconductors are called hard superconductors which have a

large amount of magnetic hysteresis induced by mechanical treatment.
Solenoids wound with wire of a hard superconductors can produce field over
100 kilo tesla.
3. So type II superconductors can carry high super current densities in

high magnetic fields and are of great commercial importance.
4. Incomplete Meissner effect occurs in the region between Hc 1 a n d H c 2

and this region is called vortex region. In this region the magnetic flux lines
gradually penetrate the specimen as the magnetic field is increased beyond
Hc 1 .
5. H e a v y c o l d - worked and recovery annealed materials having high

dislocation density and fine grains are used for making type II
superconductors.
6. Examples : Zr, Nb, 60% Nb – 40 % Ti alloy.
High Temperature superconductors
Sodium tungsten bronzes and barium lead bismuth oxides are important
intermetallic compounds with high superconducting transition temperatures
(20K). In Bell Laboratory, during the end of 1986, it was detected that a
crystalline complex of lanthanum, strontinum and copper grown in an
atmosphere of oxygen has the highest superconducting transition temperature,
3 7 K . F o llowing the Bell Laboratory discovery , the Chinese group of
88
scientists has found a superconducting state in an octahedral crystalline

complex of lead, lanthanum, copper and oxygen at 77K.
After that C.W. Chu and his collaborators of university of Housto n,

U.S.A. found stable superconductivity at 90K in yttrium barium-c opp er o xi de
compounds. Detection of super conductivity especially in yttrium complexes
at operating temperature much above 130 K has been performed recently.
Now the stable and reproducing superconducting state is observed at a high
transition temperature around 165K. Researches are going on to get the
superconducting state at room temperature conditions.
Some of the high temperature (Tc > 100K) superconductors are given
below:
T1 2 Ba 2 Ca 2 Cu 3 O y , L a 2 - x Sr x CuO 4 , Y B a 2 Cu 3 O 7 - y and Bi2 (CaSr) 3 Cu 2 O y .

Here the value of x is less than 0.2. Further the value of y is a variable one
and depends upon the stability of the system. The rare earth oxide systems,
l i k e L a - Sr=Cu=O and Y- Ba-Cu- O have so far been found to have stable
superconducting transition temperatures in the range 80-100K range.
Recently T. Ogushi and his associates from Japan have reported in La-
Sr- Nb- O system (without copper) that shows superconductivity upto
255K.Some scientists believe that this copperless Y- Sr- Nb- O or La- Sr- Nb-O
system may lead to the real room temperature superconductors.
New oxide superconductors having Tc>90K without rare earth element
New oxide superconductors with above 90K transition temperatures

have been discovered in 1998. The newer compounds are still layered copper
oxide materials, but they do not contain rare earth elements. In place of
yttrium or other rare earths, the compounds contain metals like bismuth or
thallium. Thus they contain four metallic elements instead of three. For
89
e x a m p l e , t h a l l i u m - barium- calcium- copper oxide superconductor contains

three copper oxygen layers and it becomes superconductor at 120K.
Similarly bismuth- strontium – calcium- copper oxide has the

superconducting transition temperature around 120K.
Preparation and characteristic of high temperature ceramics

superconductors
The new ceramic oxide superconductors like yttium barium copper

oxide, Lanthenam barium copper oxide, Neodymium barium copper oxide and
T h a l i u m b a r i u m copper oxide are all types II superconductors which have
higher critical fields and hence are used to manufacture superconducting
magnets having higher strengths.
Let us see the preparation of yttrium barium copper oxide

superconductors by the 'Shake and Bake' method. This method involves a
four step process: 1.Mixing the chemicals 2. Calcination (initial firing) 3.
The intermediate firing (oxygen annealing) and 4. The final oxygen
annealing.
1. Mixing the Chemicals

The powders of yttrium oxide, barium carbonate and cupric oxide are
taken such that 11.29 gram of Y2 O 3 , 39.47 gram of BaCO3 and 28.86 gram
CuO so that the atomic ratios of yttrium, barium and copper are 1:2:3. A
mortar with pestle is used to grind down any lumps or large particles in the
powders. Then the powder mixture is shaken vigorously in a capped jar or
stoppered flask for several minutes.
2. Calcination
90
After the powders are thoroughly mixed, they are kept in an alumina
crucible and heated in a furnace of about 950o C for about 18 hours. The
following chemical reaction takes place.
0.5Y 2 O 3 + 2 Ba CO 3 +3 CuO Y Ba2 C u 3 O 6 . 5 + 2CO2

This initial heat treatment is called calcinations and results in a porous
dark gray or black clump and the basic crystal structure is developed. T h e
material formed will be shrinked and becomes much denser than the original
powder mix.
3. Intermediate Firing
The porous black clump is ground into a fine powder and placed in the
furnace. After the furnace temperature reaches about 500o C, a slow flow of
oxygen into the furnace is maintained. This heat treatment under oxygen flow
is called oxygen annealing. The oxygen flow should be maintained in a
constantrate for 18 hours at 950o C. The maximum temperature of 950o C
should be reached in an hour. After this firing, the cooling rate must be no
more than 100o C per hour upto 400o C and the oxygen flow is also maintained.
By this manner the oxygen content of each crystal unit is increased from 6.5
atoms to 7 atoms and the chemical formula for the material becomes YBa2 ,
Cu 3 O 7 . At 400o C, the supply of oxygen is cutoff and the rate of cooling can
be increased to 200o C per hour. Once again the material should be thoroughly
reground in a mortar and pestle.
4. The final oxygen annealing

The reground black powder is placed back in the alumina crucible. The
powder should be as finely ground and as densely evenly packed. Now heat
the sample between 950o C and 1000o C for about 18 hours. The cooling takes
place in a very slow manner with adequate oxygen flow. The rate of cooling
must be less than 100o C per hour upto 400o C. After that the rate of cooling
can be increased.
Pervoskite superconductivity
91
It is found that ceramic superconductors have the unit cell such that
one atom of a rare earth metal, two barium atoms, three copper atoms and
seven oxygen atoms. In the superconductors the metallic atoms are in the
ratio 1:2:3. Thus these new kind of superconductors are called 1- 2-3
superconductors. The electrical conductivity of 1- 2- 3 superconductors is
based on the presence of oxygen atoms in their unit cell. The oxygen atoms
have more vacancies and so they can accommodate electrons from other
atoms. It is found that electricity flows through the material by allowing thse
holes to move from atom to atom in the c rystal.
The unit cell of YBa2 C u 3 O 9 is a stack of alternating cubic pervoskite

structures (figures 1.11 (a) (BaCuO3 ) : (Y Cu O3 ): (Ba Cu O3 ). But is not a
superconductor. The unit cell of YBa2 C u 3 O 7 which is superconductor when
Ta = 90K is a stack of alternating oxygen defieicient (or defect) cubic
pervoskite structures in the idealized sequence noted, arrows. The chains of
alternating Ba:Y: Ba atoms which characterize the Y Ba2 C u 3 O 7 lattice are
perpendicular to Cu-O planes with alternating oxygen defects (Vacancies) as
shown in figure 1.11(b).
So the oxygen defects induce superconductivity in the pervoskite
structures.
92
Applications of superconductors
1. Electric generators
Superconducting generators are smaller in size and weight when we

compare with conventional generators. These generators consume very low
energy and so we can save more energy. The superconducting d.c. generators
are available which have electrical power of 2500kW having very high
current and very low voltage. These are in small size with superconducting
windings. The low loss superconducting coil is rotated in an extremely strong
magnetic field. Similarly there are d.c. superconducting motors which are
used in ship propulsion and large mills where very high torques are necessary
even at low speeds.
2. Electric Power Transmission lines
Electric power companies look forward to superconducting

transmission systems that would save most of the energy now being lost from
conventional power lines in the form of useless radiation and heat (I2 R Joule
heat losses). The electric cables are designed with superconducting wires.
Portable superconducting transformers with low loss are available for step up
or step down a.c. voltages.
3. Magnetic Levitation
In Japan, superconducting magnets have been used to levitate an

experimental train above its rails and drive it at great speed with minimal
expenditure of energy. A similar magnetic propelsion system may be used to
launch satellites in to orbit directly from the earth without the use of rockets.
Principal of Magnetic levitation
The diamagnetic property of a superconductor is the basis of magnetic

levitation. A sheet of superconductors in the superconducting state is kept
below the horizontal bar magnet suspended from a flexible chain and then
93
lowered over the superconductor. As the magnet approaches the

superconductor, the supporting chain becomes limp and eventually dropped
down in a loop below the magnet which floats horizontally above the
superconductor. The magnetic field due to the approaching magnet induces
current in the surface of the superconductor. Since the resistance of the
superconductor is zero, the current persists in the superconductor and a
magnetic field due to this induced current repels that the bar magnet. When a
superconductor levitates a magnet, a magnetic mirror image is formed in the
superconductor such that there is always a north pole induced in the
superconductor directly below the north pole of the levitating magnet and a
south pole is induced in the superconductor directly below the south pole of
the levitating magnet. The mirror image moves with the magnet as the magnet
moves so that the disk magnet can be given a rapid spin without aff ect i ng its
levitation. In fact the magnet may continue to spin for quite a long time
because its spinning encounters no friction other than the friction of air
resistance. When the surrounding air pressure is reduced, the levitating
magnet rises higher.
Instead of a permanent magnet, the supporting field is provided by

superconducting solenoid earring a current. The repulsion between the
supporting magnetic field and superconducting surface having persistant
current is the basis for magnetic levitation of trains and other machines.
4. Ore Separation
High efficiency ore- separating machines may be built using
superconducting magnets which are also used to separate tumour cells from
healthy ells by high Gradient Magnetic separation method.
1. Explain the BSC theory and RVB Theory

2. What are type I and type II superconductors
3. Explain the term meissner effect
4. Give a few applications of superconductors
94
Source : 1) Introduction to solids – Az a r af f

TMH – EdN - New Delhi – 19 60.
Model Answers
Self check Exercise – 2
2. Type I super conductors exhibits a complete meissner effect or perfect

diamagnetism Hc (Critical field is too low)
(eg) Al, Zn, Ga
Type II Can carry high super current densities in high magnetic fields.
(eg.Zr, Nb etc.)
7.3 Let us Sum Up

Conductivity in metals and alloys is discussed on the basis of zone
theory. Different types of super conductors, their synthesis and theories of
super conductors such as BCS theory and RVB are discussed in detail
Magnetic levitation is explained.

i) The variation of electrical conductivity with 'T' in the case of metals
and semiconductors are different
ii) Resistivity of a metal at a given temperature is a 1
Carrier concentration
iii) Cooper Pair concept explains the low temperature super conductivity
7.5 References
(1972).

95
LESSON – 8
CONTENTS
8.1 INTRODUCTION
8.2 MAGNETIC PROPERTIES
8.2.1 DIAMAGNETISM, PARAMAGNETISM & FERROMAGNETISM
8.2.2 DOMAIN STRUCTURE
8.3 LET US SUM UP
8.4 POINTS FOR DISCUSSED
8.5 REFERENCES
8.0. AIMS AND OBJECTIVES
The aim of the lesson is to study in detail, the magnetic pro p e r t i e s o f

materials. After going through this lesson you would understand the
fundamental theories of magnetism. The knowledge of the theories of
magnetic properties is important for selecting different types of magnetic
materials for various applications.
8.1 INTRODUCTION
When a substance is placed in an inhomogeneous magnetic field, it is

either attracted toward the strong part of the field or repelled toward the
weaker part. If it is attracted by the field, it is said to be paramagnetic, if
repelled it is said to be diamagnetic. A Ferromagnetic solid is one that can
have a permanent magnetization, after the magnetic field is removed.
8.2.1 MAGNETIC PROPERTIES
Diamagnetism: when a substance is placed in an inhomogeneous

magnetic field, it is either attracted toward the strong part of the field or
repelled toward the weaker part. If it is attracted by the field, it is said to be
paramagnetic, if repelled, it is said to be diamagnetic. The force F with
96
which a diamagnetic substance is repelled when placed in a field of strength

H and gradient dH/dx is determined by
dH
F = x VH
dx
Where x is called the magnetic susceptibility and V is the volume of

the substance. The magnetic susceptibility is a measure of the change in the
magnetic moment of the atoms caused by an applied field. It is usual to speak
of the atomic susceptibility x A which is determined according to Langevin's
equation.
N0e2
xA = Σ r2
2
6mc
= - 2 .8 3 x 1 0 1 0 Σ r 2 ….(2)
where N0 is Avogadro's number; e, m, c have their usual meaning for an

electron; and r is the average radius of the orbits of the electrons. Note that
the right side of (2) is negative, which indicates that the force in (1) is
negative. This is in agreement with Lenz's law that t h e m a g n e t i c flux
produced by an induced current opposes the change in the magnetic field
which produces it.
In quantum mechanics, The Langevin equation is valid provided that

the electron distribution is spherically symmetrical. Thus it is quite useful
when dealing with inert gases, ions, and neutral atoms. The value of r is
determined by the wave function, and since the susceptibility is proportional
t o r 2 , it follows that the outer electrons make the largest contribution. The
v a l u e o f x A , ca l cul a te d using quantum mechanics, is in good agreement with
the values found experimentally. For most elements, including Cu, Zn, Ga,
Ge, As, Se, Br, Ag, Cd, Te, and the inert gases, the magnitude of the atomic
susceptibility lies in the range 10- 6 to 10- 5 , w h e r e as for Sb , Au, Hg, TI, Pb,
and Bi it is greater than 10- 5 . Bismuth is exceptional in this regard; x A = -
1.35 x 10- 4 in MKS units.
97
Paramagnetism: It is possible for an atom to have a net magnetic

moment resulting from a particular combination of the orbit a l m a g n e t i c
moments and the spin magnetic moments of its electron. The unit for
measuring the spin magnetic moment of an electron is the Bohr magneton.
eh
β = = 9.27 x 10- 2 1 erg/gauss. …..(3)
4p mc
If an external magnetic field is applied, the spin moments can line up

either parallel to the field or antiparallel to the field.
The magnetic properties of many materials were first studied

systematically by P.Curie before the end of the nineteenth century. He found
that the paramagnetic susceptibility xp was inversely proportional to the
absolute temperature.
C
xP = ….(4)
T
Where C is the Curie constant and is characteristics of the material

Langevin later applied classical mechanics to paramagnetism in gases and
found that the Curie constant could be expressed theoretically
N 0 m2
C = ….(5)
3k
where N0 is Avogadro's number

k is Boltzmann's constant
m is a average magnetic moment per molecule
It also follows from classical mechanics that, for free electrons in a metal,
the Curie constant can be written
2
nβ
C = ….(6)
k
98
where n is the number of free electrons per unit volume. By substituting (6)
in (4) it is possible to calculate the paramagnetic susceptibility of any metal.
The value obtained in this way is approximately 100 times larger than the
values obtained experimentally. This is one of the properties of metals,
therefore, that the classical free- electron theory cannot explain correctly.
The total magnetization M is defined as the magnetic moment per unit

volume and is given by
M = XP H
2
nβ
M = H.
kT
Now, according to the Curie law (4), the susceptibility and, hence, the
magnetization should vary with the temperature. Again, this is not the
Fig 8.1
case for many metals. The observedx weak and temperature- independent
paramagnetism can be explained by applying Fermi- Dirac statistics to this
problem.
99
The distribution of electrons in a metal at the absolute zero of

termperature is shown in Fig.2.1 by plotting the parabola- s h a p e d f un c t i o n
representing the density of states as a function of energy. In the absence of
an external magnetic field, the electrons occupy all the available states
having energies less than the Fermi energy E 0 . They are shown divided into
two groups, in Fig.2.1A, accordingly as their spins are plus are minus. When
an external field is applied, the magnetic moments due to the spins line up
either parallel or antiparallel to the field. Assuming that a plus denotes
electrons which have antiparallel moments, these electrons undergo a shift in
e n e r g y + βH, as shown in Fig. 2.1. This situation is not stable, and at
equilibrium, some of the electrons in the antiparallel states undergo
transitions to the lower energy parallel states. This leads to the situation
shown in Fig.2.1C. The magnitude of the energy shift, even due to a fairly
strong field, H = 105 gauses, is very small, β H ~ 1 0 - 3 e V , so that, at room
temperature, the thermal energy, kT ~0.03 eV, is sufficiently greater to keep
the numer of electrons having parallel ands antiparallel moments very nearly
equal. Not only does this explain the very small value of the observed
susceptibility but also why the susceptibility is virtually independent of
reasonable changes in temperatures.
8.2.1 Ferromagnetism. It has been assumed, in the above discussion, that

the magnetic moment of the atoms was due entirely to the electron spin. This
i s a fairly accurate picture for such metals as Li, Na, Mg, AI, and K. In these
metals, the valence electrons are quite free to migrate through the crystals so
that they contribute primarily spin moments, whereas the inner shells are
filled and contribute only weak diamagnetism. On the other hand, if an atom
has incomplete inner shells, then it is possible that not only the spin moments
but also the orbital moments can contribute to the magnetic moment of the
atom. This normally leads to large paramagnetic susceptibility in accord with
the Curie law. Such relatively large susceptibilities are found among the rare
earths and the platinum and palladium- group metals. An anomalous behaviour
is encountered in the case of Fe, Co, and Ni, which are paramagnetic at
elevated temperatures but become ferromagnetic below a transition
temperature called the Curie point. A ferromagnetic solid is one that can
100
have a permanent magnetization after the external magnetic field is removed.

This permanent magnetization was first explained by P.J. Weiss in 1907 as
being due to a parallel orientation of the permanent magnetic moments of the
constituent atoms. The paramagnetic ferromagnetic transition can be
likened, therefore, to the disorder order transition. Above the Curie
temperature, thermal agitation is responsible for keeping the magnetic
moments randomly oriented, whereas below the Curie point the energy
favours an ordered arrangement in which more magnetic moments are
aligned in one direction than in another. In order to explain why an excess of
magnetic moments along one direction is more stable than a uniform,
distribution, Weiss proposed that a molecular field exists in the crystal and
favors such an alignment.
Heisenberg was the first to propose an explanation of this molecular

field based on the principals of quantum mechanics. He treated the problem
similarly to the Heitler- Londom treatment of the hydrogen molecule. In this
treatment, an exchange interaction between electrons in different quantum
states is shown to lead to a lower energy for a molecule than that obtained by
a mere superposition of the wave functions of each atom. Experiments have
proven that the magnetic moment, due to the electron spins rather than the
orbital moments, contributes to the permanent magnetic moment of the iron-
group atoms. The exchange forces, therefore, are necessary in order to
explain why, in certain metals, the atoms have electrons with parallel
magnetic moments. It is reasonable to expect that such exchange forces are
negligible unless the atoms are brought closely together. It can be shown
that, as two atoms approach each other, the electron spins of unpaired
electrons in each atom assume parallel orientations. As they are brought
closer together, the spin moments are maintained parallel by increasing
forces. As the interatomic distance is decreased still further, however, these
exchange forces decrease until finally they pass through zero and an
antiparallel spin orientation is favored. It has been shown by Bethe that, for
the iron group, the conditions favoring parallel orientations occur when the
ratio between one- half the interatomic distance in a crystal and the average
101
radius of the 3d shell is greater than 1.5. Some typical values of this ratio
for these metals are
Mn Fe Co Ni
Ratio 1.47 1.63 1.82 1.98
As can be seen, the ratio for manganese is lightly less than 1.5, which
explains why magnese crystals are not ferromagnetic whereas compounds
containing manganese atoms spaced farther apart are. Notable examples are
the Heusler alloys Cu2 MnSn and Cu2 MnAl. (Note that these ferromagnetic
alloys contain neither Fe, Co, or Ni)
According to the zone theory, two factors determine the energy of a

crystal. The first is the Fermi energy, which makes a positive contribution to
the total energy, and the second comes from the exchange integral and makes
a negative contribution. A crystal then is ferromagnetic when the negative
energy due to the exchange integral is greater than the positive- e n e r g y t e r m
due to the kinetic (Fermi) energy of the electrons, which tends to randomize
the spin directions. The exchange integral used in this calculation is
somewhat different from the one proposed by Heisenberg in that it is based
on the electrostatic interaction between one electron and the electrons in an
identical fictitious crystal having a hole in place of this electron. It turns out
that this exchange integral is independent of interatomic distance and does
not vary too much from atom to atom in the metal. In order to explain
ferromagnetism, therefore, it is necessary to compare the Fermi energies of
different metals. Although only nickel has been examined in detail, the
r e s u l t s c a n be extended to show that the Fermi energy is smaller than the
exchange energy in Fe, Co, and Ni. As expected, it is somewhat greater in the
case of Mn. It should be noted that a small Fermi energy denotes a narrow
energy zone, that is , a larger number of electrons having very closely spaced
energies. Thus this calculation supports the earlier conclusions that narrow,
partially filled d zones, which do not overlap in neighboring atoms to any
appreciable extent, are necessary and sufficient for ferromagnetism to occur.
102
More recently, Zener has proposed a different explanation for the

occurrence of ferromagnetism. The exchange integral, as calculated in the
Heitler- London model for the bonding of two atoms, is negative. Heisenberg,
therefore, was forced to postulate that the exchange integral was negative
obly when the atoms were brought very closely together and became positive
when the unfilled d shells did not overlap appreciably. It has never been
proven, however, that such a reversal in the sign of the exchange integral
actually occurs. Zener has suggested that the exchange integral always
remains negative and that ferromagnetism is due to an interaction between
electrons occupying quantum states in the partially filled d and s zones. The
propo s ed i nteraction, which accounts for the exess of parallel spin moments
of one kind, similar to the interaction (Hund's rule) that causes unpaired
electrons in different orbitals to have parallel spins. According to this model,
a n o v e r- all decrease in the energy is obtained when the electrons occupying
states in the d zones have parallel spin moments and the s- z on e e l e ct r o ns
contribute a small moment in the same direction. Because of the approximate
nature of the calculations used to support the above stated competin g
theories, it is not possible to decide, at present which one describes most
correctly the interactions responsible for ferromagnetism.
On an atomic scale, the reason for the permanent magnetic moment of

Fe, Co, and Ni atoms is best understood by considering their electronic
structures. Each atom has two 4s electrons and an incomplete 3d shell.
Fe 3d 6 4 s 2
Co 3d 7 4 s 2
Ni 3d 8 4 s 2
The atomic moments of these metals should be, respectively, four, three and
two Bohr magnetons. The actual values turn out to b e
Fe Co Ni
Atomic m om ent 2.22 1.70 0.61 Bohr magnetons
103
The no integral number of electron spins per atom determined from

saturization magnetization measurements given above is explained by making
use of the zone theory as follows: The 3d 4s zones of these metals overlap,
as shown for the case of nickel in Fig.2.2. Since the relative occupation of
these two zones is determined by the Fermi energy E0 , it is assumed that 0.6
electron occupies states in the 4s zone and 9.4 electrons in the 3d zo n e . O f
these, five must have one kind of spin and 4.4 the other, leaving 0.6 spin of
the same kind per atom. The accuracy of this model can be readily checked
by alloying nickel with copper or zinc. The substitution of a copper atom for
a nickel atom introduces one additional electron in the crystal, whereas zinc
introduces.
Two additional electrons. It is reasonable to expect that these electrons
will prefer the lower- lying 3d states of nickel and therefore, as more copper
(or zinc) is added, the magnetic susceptibility should decrease. It has been
shown from saturization magnetization measurements that this is indeed the
case; the magnetization becomes virtually zero when 60 per cent Cu or 30 per
ent Zn is added, that is, when enough electrons are added to fill completely
the 3d zone of nickel.
8.2.2 D o m a in S tr u c t u re . The above discussion has explained why iron,

cobalt, and nickel are ferromagnetic, but it has not accounted for such
physical properties of magnets as, for example, the well- kn o w n h y s t e re s i s
loop, relating the amount of magnetization to the strength of the applied
field. Even before the atomic mechanism of ferromagnetism was clearly
understood, Weiss assumed that a single crystal of iron consists of small
regions or domains, within each of which the electrons have all their spins
parallel, but that the spins of neighboring domains are not parallel.
104
Fig. 8.2
Fig. 8.2 Schematic representation of overlapping 3d and 4s states of nickel.

On an average, 9.4 of the 10 available 3d states and 0.6 of the 2 available 4s
states are occupied (After Slater).
When an external field is applied, the domains that have net moments
parallel to the directions of the field have their energy reduced, whereas
those domains that do not have their energy increased. The crystal's energy,
obviously, can be lowered if all the domains align themselves parallel to the
field. This can be accomplished in either of two ways. Either the direction of
magnetization of an entire domain changes at once, or a domain that is
favorably oriented grows in size at the expense of a less favorably oriented
domain. When the external field is reversed in direction, all the domains must
be reoriented, and , owing to several causes discussed below, this requires an
additional field to overcome the factors opposing such reorientation so that a
hysteresis loop results.
In turns out that magnetization is an anisotropic property in crystals.

for example, it is easier to magnetize iron (body-centered cubic) along (100)
than along any other directions, and most difficult along (111). It is common
105
practise to refer to these as easy and hard directions of magnetizatio n,

respectively. To show that this is a structure – sensitive property, the easy
directions in nickel are (111) (normal to the closest packed layers) and the
hard directions are (100). Similarly, the easy direction in the hexagonal
closest packing of cobalt is normal to the hexagonal closest-p a c ke d l a ye r s .
The magnetization of single crystals along certain directions is invariably
accompanied by changes in their physical dimensions. For example, iron
crystals expand along the direction of magnetization and contract at right
angles to it so that the total volume tends to remain the same. In a nickel
crystal, the dimensional changes are reversed; it contracts along the
magnetization direction and expands in directions normal to it. Thus the
magnetization of ferromagnetic crystals depends on the way that the structure
is strained, a phenomenon called magnetostriction. As might be expected,
magnetostriction is related to the elastic properties of the crystal and can be
used to explain the formation of magnetic domains in crystals. With six (100)
directions equally easy, it is natural that a single crystal of iron has domains
containing magnetic moments aligned parallel to each of these six directions.
Obviously, the domains must be separated by boundaries in which t h e
magnetic moments undergo a gradual transformation from one orientation to
the other. The exchange energy favoring parallel alignment of all moments
prefers thick boundaries. It is opposed by the magnetic anisotropy, which
favors a minimum deviation from the easy directions of magnetization. A
compromise between these opposing forces is reached, and it turns out that
the boundaries have thicknesses of the order of hundreds of atoms in actual
crystals. The domains themselves can have various sizes, determined
primarily by the free energy of the boundaries, whose contribution to the
crystal's energy decreases with increasing domain size, since the ratio of
boundary area to domain volume decreases. Lest it be deduced from this that
a single crystal consisting of a single domain has the lowest possible energy,
it should be realized that such a crystal is a permanent magnet whose
magnetic field contains magnetic energy. Thus the domain structure proposed
by Weiss serves to lower the overall energy, thereby ne u t r a l i z i n g t h e
individual permanent magnets.
106
When a weak magnetic field is applied parallel to an easy direction of

a crystal, the domains having lower energies, because of their more
favorable orientation, grow in size owing to the reorientation of the m o m e n t s
in the boundaries . The resulting movement of boundaries can actually be
observed by sprinkling a fine powder of Fe2 O 3 on a polished crystal surface.
The powder particles align themselves along the domain boundaries and a so-
called bitter pattern is obtained. Several domains can be seen in the Bitter
pattern of a single crystal of iron shown in Fig.2.3. It has been observed that
the movement of domain boundaries is impeded by imperfections and
proceeds in jumps. These jumps can be made audible by su r r o u n di n g t h e
crystal with an induction coil connected to an amplifier. This so- called
Barkhausen effect is even more noticeable if the domains change their
magnetization directions by rotation. The latter effect becomes more
prominent when the strength of the field is increased.

Fig 8. 3
107
In a polyerystalline material, magnetization is impeded by the random

orientation of the grains. Consequently only some of the grains have their
easy directions parallel to the direction of the applied field. More over
magnetostriction in these crystallites produces strains in their neighbors
which, In turn, affect the ease of magnetization in a more complicated way.
Thus, if a material that is easily magnetized is desired say, for transformers,
it is necessary to find one having little magnetic anisotropy or
magnetostriction. Such a material does not necessarily have higher
saturation magnetization, it simply reaches saturation more rapidly. On the
hand, if a permanent magnet is desired, the strong magnetostriction is an
asset. This is so because, once such a material is magnetized along a given
direction, it is more difficult to change its magnetization direction.
Self Check Exercise - 1

1. Using Langevin's equation, calculate the value of the constant in the
equation.
2. Calculate β from β=eh/4p mc
3. If xp = 1.732, calculate, curie constant at 300 K.

1. Discuss the ferromagnetism of Fe, Co, Ni
2. Write a note on domain theory
Model Answer
Exercise – I
2. b = exh = 4.8 x 10- 1 0 x 6.627 x 10- 2 7
4p x m x c 4 x 3.14 x 9.1 x 10- 2 8 x 3 x 101 0
= 9.27 c 10- 2 1 erg/gauss

3. xp = C
T
C = xp x T
= 1.732 x 300
= 5.19 x 102
= 5.19 x 102
108
8.3 Let us Sum Up

Langevin equation is discussed paramagnetism and Carie’s law are
explained. Theories of ferromagnetism (for e.g., Zener’s theory are
discussed in detail).
8.4 Point for Discussion

1. The curie constant is characteristics of the material.
2. The Paramagnetic susceptibility is a 1 / T
3. Zener's theory to explain ferromagnetism the exchange integral is
always negative and that ferromagnetism is due to an interaction
between electrons occupying quantum states in the partially filled 'd'
and 's' zones.
8.5 Referen ce:

1. Introduction to Solids – Azaroff TMH – Edn- New Del hi - 1960
109
LESSON – 9
CONTENTS
9.1 INTRODUCTION
9.2 THERMOELECTRIC PROPERTIES
9.2. 1 GENERAL PRINCIPLES AND THEORETICAL CXONSIDERATION
9.2.2 MATERIAL PREPARATION AND THERMOELECTRIC MATERIALS
9.2.3 APPLICATIONS
9.3 LET US SUM UP
9.5 REFERENCES
The aim of this lesson is to study the phenomenon of thermoelectricity

and to learn the several applications of thermoelectric materials, such as
thermoelectric generations and thermo electric refrigeration. After studying
this lesson you would be able to
i) Understand the Phenomena of Thermoelectricity

ii) Know about the synthesis and applications of thermoelectric materials
like lead telluride, bismuth telluride.
9.1 INTRODUCTION
In Several space crafts the source of electric power, is the
thermoelectric material like RTG (Radio Isotope thermoelectric geberator).
The thermoelectric material uses the Seebeck effect and the reverse
phenomenon, the Peltier effect. The Seebeck effect converts the heat from a
radioactive heat source directly into electrical energy. The Seebeck effect
and the Peltier effect are the principal elements of thermoelectrics- t h e
science and technology associated with thermoelectric generation and
refrigeration.
110
9.2.1 GENERAL PRINCIPLES AND THEORETICAL CONSIDERATION
An electric potential (Voltage) is generated with any isolated

conducting material that is subject a temperature gradient, this is the absolute
Seebeck effect, (ASE). The absolute Seebeck coefficient (ASC) is defined as
the instantaneous rate of changes of the ASE with respect to temperature at a
given temperature. ASC = d(ASE

dT T
The simple example of the way in which this phenomenon is used is to

form a thermocouple composed of two dissimilar conductors, or
thermoelements, by electrically joining one set of their ends. The application
of a temperature difference or gradient, between the ends of the device will
produce a voltage across its unpaired terminals that is a function of the
temperature distribution. The resulting voltage is the relative seebeck emf,
'RSE"/ It results only from the difference between the internal potentials or
ASE, within the individual conductors of which it is composed. Relative
seebeck coefficient is the variation of relative seebwck emf with temperature,
i.e.
RSC = [d(RSE)/dT)]T . The seebeck effect is not affected by Thomson

or Peltier effects. Thomson and Peltier effects are present only when current
flows in a thermoelectric circuit. But seebeck effect exists as long as
temperature gradient is maintained, regardless of whether current flows in the
circuit or not . The greatest application of the seebeck effect is in thermal
electric thermometry. This results from the fact that thermoelectric circuits
convert thermal energy into electrical energy. The open circuit emf obtained
this means is the RSE, which can be used to measure temperature. Thermo
couples composed of standardized metallic conductors are widely used for the
accurate sensitive, and reliable instrument and /or control of temperature.
111
P el t ier showed that heat is liberated or absorbed when a current crosses

an interface between two different conductors. The peltier coefficient, p AB i s
the change in the reversible heat content at the junction of conductors A and
B w he n unit current flows across it in unit time.
p AB = p A + p B. p A a n d p B are the absolute Peltier coefficients of the

conductors. The direction in which current flows across a junction and the
values p A a n d p B determine whether heat is liberated or absorbed. The
peltier effect is a result of the change in the entropy of the electrical charge
carriers as they cross the junction. It is not an emf inspite of the fact that
p AB can be expressed in energy units involving volts.
For a constant current the peltier effect is proportional to RSC, and at

any fixed junction temperature, it is proportional to the current. These
reversible effects are independent of the shape or dimensions of the junction.
This is different from joule heating which is a function of dimensions, does
not require a junction and is irreversible.
The Thomson effect is the reversible change of heat content within any
single homogeneous conductor in a temperature gradient when an electrical
current passes through it.
T h i s m a y occur in any non- isothermal segment of a conductor. The

Thomson coefficient is the reversible change of heat content within a single
conductor per unit temperature gradient per unit current flow. Thomson
termed it the "Specific heat of Electricity".
The Thomson effect is not a voltage. But it can be expressed in energy

unit involving volts. Let the relative Seebeck emf generated by the
temperature difference be EA B . For a unit current flow in a thermoelectric
circuit.
EA B = d EA B
∆T (1)
dT
112
The other energy factors in a closed thermoelectric circuit are Peltier

effects and Thomson effects.
Peltier effect at the junctions. Heat absorbed at the hotter junction

= p AB (T + ∆T)
Heat liberated at the colder junction = - p AB (T)
Thomson effect within the conductors; Heat absorbed in conductor

B = β B (∆T)
Heat liberated in conductor A = β A (∆T)
p a n d β are peltier and Thomson coefficient, respectively. It is possible to
show that for a unit current flow:
dE A B dp AB
+ ( β B – βA ) --(2)
dT dT
This is the fundamental thermodynamics theorem for c l o s e d

thermoelectric circuits. It shows the relation between electrical seebeck
effect and the thermal Peltier and Thomson effects.
By a rigorous analysis it is possible to show that p AB ~ dEA B T …(3)

dT
This equation is helpful in understanding the operation of peltier

devices. This shows why combination of thermoelements with large peltier
effects must be used for power generation or refrigeration.
9.2.2 MATERIAL PREPARATION AND THERMOELECTRIC

MATERIALS
Compounds like, Bimuth Telluride, antimony telluride, lead Telluride

and alloys have been synthesized and studied for their thermoelectric
properties. The deviation in stoichiometry of the compound bismuth Telluride
113
accounts for its usefulness as a thermoelectric device. Bismuth telluride has a

hexagonal cell, which is formed by the stacking of layers as;
(1)
Te – Bi - Te ( 2 ) – B i – T e (1)
(1)
The T e - Te ( 1 ) bonds are of vanderwaals type while Te ( 1 ) – Bi and
Bi – Te ( 2 ) bonds are of ionic – covalent type. The energy gap for Bi2 T e 3
was found to be 0.16eV at 300k and 0.18eV at Ok. For example binary
compounds of Bi2 T e 3 and Sb2 T3 have been obtained by travelling
heatermethod. In this method a molten zone passes through a polycrystalline
ingot (source ingot) in a quartz ampoule sealed under high vacuum. The
source ingot is prepared by the synthesis of high purity components with the
stoichiometric composition of the compound to be prepared (Bi2 T e 3 , S b 2 T e 3 )
. This method allows single crystals to be prepared at a temperature lower
than the melting temperature and consequently of high quality. The transfer
of the zone through the source ingot improves the purity of the material by a
zone melting process. Single crystals of n and p type were grown by the
traveling heater method, at different temperatures. In this preparation, the
carrier concentrations on the p- t yp e (~ 10 2 0 / cm3 ) are greater than the n- type.
It is found that the change in type occurs at about 583o C. The concentration
of charge carriers is directly related to the concentration of inherent defects.
These defects are responsible for deviation from stoichiometry. Sb2 T e 3
prepared by the above method shows p-type conduction. Bi2 T e 3 is a more
useful than S b 2 T 3 as a thermoelectric material. Thermoelectric figure of
merit is given by the relation.
Z= a 2 / ( l p), where 'a ' is the seeback coefficient l = thermal conductivity and
P = electrical resistivity.
Z is a common measure of the effectiveness of a material to function in

a thermoelectric couple for heating or cooling applications various types of
'Z' meters have been developed for the measurement of figure of merit of
thermoelectric materials. By measuring a , l and P, one can calculate 'Z' for
any material. For example Bi2 T e 3 ( P - type) has a 'Z' value of Z. 10- 3 = 2.2 at
114
582 o C . ' Z' has been found to be anisotropic. Along the 'C' axis Sb2 T e 3 has a
Z value of 1.6 x 10- 3 K - 1 .
At present solid solutions of the compounds Bi2 , T e 3 , S b 2 T e 3 and Bi2 ,

Se 3 have the highest thermoelectric figures of merit in the tenperature range
around room temperature. Lead telluride and alloys of Pb-Sn- Te have also
been studied for thermoelectric characteristics.
9.2.3 APPLICATIONS
1. THERMOELECTRIC POWER GENERATION
Thermoelectric power generations have been employed for generating

power from milli- microwatts generated in miniature thermocouple arrays
integrated into a semiconductor microelectronic chip) to the multikilowatt
nuclear reactor powered generators.
As detectors and sensors miniature thermocouple arrays (thermopiles) have
found wide applications as pyrometers and as sensor elements used in the
measurement of magnetic, radiation, chemical and mechanical signals.
Thermoelectric generator consists of a large number of thermocouples

connected electrically inseries to form a module the module is the basic
building block of the generator.
Heat from a variety of sources is applied to one surface of the module

(referred to as the hold side) and rejected at a lower temperature from the
opposite surface (Cold side/Heat sink). Provided a temperature difference is
maintained across the module, electrical power would be delivered to an
external load. The power output from a thermocouple is approximately
proportional to area and inversely proportional to the length.
The best known medical application of a miniature thermoelectric

batteries is in the cardiac pacemaker thin film thermo elements, deposited on
glass slides (Bi2 T e 3 + Bi2 S e 3 and Bi2 T e 3 + S b 2 T e 3 ) have been employed for
power generation.
115
All of the currently available generators that operate on gaseous fuels

(Propane or natural gas) are intended for stationary out door application. The
output of these generators is fixed. The generators produce a constant amount
of power. The thermoelectric converters used in commercial ther mo e l e c t r i c
generators use either lead telluride or bismuth telluride.
The heat sinks are usually a series of aluminium fins. The most
important applications of thermoelectric generators are cathodic protection,
data gathering and telecommunication. The generators usually used for
cathodic protection have out puts of 60W are higher. Thermoelectric
refrigerators (Peltier Cooling) are silent and have neither moving parts nor,
gases to leak away. Thermoelectric refrigerators do not pollute the
a t m os p he re a s conventional refrigerator. If the thermoelectric generator is
operated under conditions of maximum cooling power, the coefficient of
performance is high.
Self Check Exercise -1
1. Explain Seeback effect

2. How are peltier and Thomson effects are different from seeback effect?
1. Give the fundamental thermodynamic theorem for closed

thermoelectric circuits?
2. Explain the term 'Z'? How can it increase?
9.3 Let us Sum Up

See back, Peltier and Thomson effects are explained. Thermoelectric
material synthesis is indicated. Thermoelectric figure of merit ‘Z’ is
defined. Applications of thermoelectric materials are indicated.
116
Model Answers:
2) The seeback effect is not affected by Thomson or peltier effects. T h e

latter are present only when current flows in a thermoelectric circuit.
But seeback effect exists as long as temperature gradient is maintained,
regardless of whether current flows in the circuit or not.
i) Absolute seeback coefficient, thermal conductivity and electrical

resistivity would decide the figure of merit of a thermoelectric
materials.
ii) The utility of thermoelectric materials in power generation and
applications have to be discussed.
9.5 References
1. Introduction to solids - Azaroft
TMH – Edition- Publisher – Tata Mc Grahi – Hi l l – New Delhi – 2 7
- New Delhi – 2 7
2. CRC Hand Book of Thermoelectrics – Edited by D.M.Rowe Ph.D,
D.Sc- CRC P re ss – N.Y, London, Tokyo – 199 5.
117
UNIT – I V
LESSON – 1 0
CONTENTS

10.1 INTRODUCTION
10.2 N- P- RATIOS DIFFERENT TYPES OF NUCLEAR FORCES
10.2.1 NEUTRON PROTON RATIO
10.2.2 NUCLEAR FORCES
10.3 LET US SUM UP
10.5 REFERENCES
To learn, how neutron/proton ratio helps in the understanding of

nuclear stability and to understand the basic nature of the forces that bind
nucleons together
10.1 INTRODUCTION:
The packing fraction is an important concept in understanding the

stabilities of nuclei. A negative packing fraction implies exceptional stability
of the nucleus and a positive packing fraction suggests that the nucleus is
somewhat less stable. This chapter describes the other important concepts
like n/p ratio and binding energy, in understanding nuclear stability.
10.2.1 NEUTRON PROTON RATIO
A review of the nuclear compositions and masses of various nuclides

has revealed a number of general rules concerning the stability or instability
118
of atomic nuclei. Consider the variation with increase in mass number, the
ratio of neutrons to protons in the stable nuclides. The results are plotted
with the number of protons (z) on the x-axis and the number of neutron s ( A -
Z) on the Y- axis. A line is drawn at an angle of 45o , so that points lying on
this line represent nuclei containing equal numbers of protons and neutrons.
For elements of low mass numbers the neutron – t o – proton ratio is equal to
unity for stable nuclei of the 18 nuclides with mass numbers through 20,
there are equal numbers of neutrons and protons in eight and a difference of
only one in nine others. This exact equality is to be expected from the
similarity of (P- P ) . ( n - n) and (n- p) forces. To maintain stability the number
of neutrons must exceed the number of protons. For the heaviest stable
206 209
nuclides, such as Pb and Bi, the ratio of neutron to proton is slightly
82 83
greater than 1.5. Each proton repels and is repelled by, all others present in
the nucleus. As a result the electrostatic repulsive force grows rapidly with
increase in atomic number. The total repulsive energy in a nucleus is roughly
proportional to Z2 /R, Z is the number of protons and R is the radius of the
nucleus. R varies as A1 / 3 (A=mass number). Hence electro static repulsion is
determined by (Z2 /A 1 / 3 ). For e.g., the repulsion energy of protons in
209
Bi, is about ten times as great as that of 40 Ca (N/P = 1).
83
To attain stability, the heavier elements should contain larger proportion of
neutrons. The additional (n- n) and (n-p) attractive forces then compensate for
the growing p- p re pul sio n.
Nuclei containing even numbers of both protons and neutrons are much
mo r e c omm on than any others. Nuclei containing odd number of protons and
even number of neutrons and vice versa are equally common. But those
containing odd numbers of both protons and neutrons are rare. Stable nuclei
contain even numbers of both neutrons and protons. Those containing both
16 24 28 28 40
odd numbers are very unstable. Thus six nuclides O, Mg, Mg, Si, Ca,
48 56
Ti, Fe, constitute about 80% of the earths crust. Thus a pair of neutrons
and of neutrons may be regarded as constituting a sub- shell, leading to
119
greater stability than would be the case for incomplete sub- hell i.e., with odd
numbers of nucleons.
4
He is highly stable (2P and 2n). But 5 He and 5 Li which contain one
2
neutron and one proton more than 4 He respectively, almost instantaneously
e xpel t he extra nucleon 9 Be, 13
C and 17
O, with one excess neutron are stable
nuc li de s. But 9 B, 13
N and 17
F with one excess proton are not. There are only
four nuclides of the odd- odd type =
2 10 6
14
D B and N. The stability of 2 D, has been attributed to the
Li
1 3 5 7
attraction of neutron and proton, having the same spacial co- o r d i n a t e s a nd
parallel spins. In the other three stable odd- odd nuclides, the numbers of
neutrons and protons are equal, so that the extra, unpaired neutron and proton
probably have the same spatial coordinates. In
19 2723
F Na Al, the one extra neutron, causes stability in these nuclides
9 11 13
Sn(Z=50) is the only element with stable isotopes (115, 117 and 119).
If the atomic number is odd, the element has few stable isotopes, never
more than two. In general regardless of its atomic number no element (with
exception of Sn), has more than two stable isotopes of odd mass number.
Isobars and b -decay
If there are two isobars of adjacent elements, with atomic masses

which differ by a small amount, the one with the larger atomic mass will tend
to disintegrate by b - d e c a y c o n s i d e r 3 T a n d 3
He. The atomic masses are
3.016049 and 3.016029 amu, respectively; the mass difference is thus only
0.00002 amu, equivalent to 0.018MeV. But tritium is radioactive, since it has
the higher atomic mass, decaying to form 3 He, with the emission of
b -particle, having a maximum energy of 0.018MeV. Consider for e.g., Cd- 113
120
a n d I n – 113 and Sb- 123 and Te- 123. These pairs differ by 1 unit of atomic
number. These pairs appear to be quite stable. The reason given for the
stability is probably that the beta transitions are highly for bidden because of
the large differences of nuclear spins. For e.g., the nuclear spin of Cd- 1 1 3 i n
the ground state is ½ , Whereas that of 1 1 3 In is 9/2 and the energy difference
is small. It may be noted, however the negative b - decay of a 'metastable'
(isomeric state) of 1 1 3 Cd with an estimated nuclear spin of 7 / 2 , has been
observed to the ground state of In- 113. It would appear therefore that Cd- 113
is beta active. In the pair Sb-123 and Te-123 also a similar situation exists.
Te- 123 decays by orbital electron capture with a half- life of 1.2 x 101 3 ye ars.
10.2.2 NUCLEAR FORCES

i) Packing Fraction:
It is defined as :
Packing fraction = Atomic mass – mass number x 104
Mass number
The following observation can be made when packing fraction is

plotted against mass number. The packing fraction is high for elements of
low mass number, apart from (He- 4) , C - 12 and 0- 16), but it decreases rapidly
w i t h m ass number. Then after passing through a flat minimum, the packing
fraction begins to increase slowly but steadily. Negative packing fraction
implies exceptional nuclear stability. On the other hand a positive packing
fraction suggests that the nucleus is somewhat less stable. Nuclides He- 4 , C -
12 and 0- 16are very stable. Elements of high mass numbers having positive
packing fractions are unstable and radioactive.
Determination of Binding Energies
Binding energy is a more important concept in understanding n u c l e a r

stabilities. True mass defect is obtained as follows:
True Mass defect = (ZmH + (A-Z)m n )- M
121
Zm H is the mass of the protons and (A- Z)m n gives the mass of neutrons. M is
the experimentally determined atomic mass. The mass defect may be regarded
as the loss of mass or more correctly the mass which would be converted into
energy, if a particular atom were to be assembled from a given numbers of
electrons, protons and neutrons. The same amount of energy would be
required to break up the atom into its constituent particles. Therefore the
energy equivalent of true mass defect is taken as a measure of 'binding
energy'.
Hence binding energy in MeV, is given by=

Binding energy = 931.4[ZmH + (A- Z)m n -M]-MeV.
The masses of the proton and of the neutron are respectively 1.007825 and
1.008665, amu. the atomic mass of
20
Ne, is 19.992440amu. A is 20 and Z=10. Therefore the binding
10
energy is = 931.4[(10 x 1.007825) + (10 x 1.008665) – 19.992440]
= 160.6 MeV . 160.6/20 =- 8.0 (B.E per nucleon)

Calculate the binding energy for 209
Bi,using the same values of
83
masses for protons and neutrons. The atomic mass of this isotope is 208.9804
and also the B.E per nucleon.
122
The binding energies of some of the lighter nuclides such as 2 D a n d

3
He are very low, but over a very considerable range of mass numbers, the
binding energy per nucleon is close to 8MeV. As mass number increases, the
bi nd i ng e nergy decreases to 7.6MeVper nucleon (say for Uranium). It is this
diminution in binding energy which is the fundamental cause of the release of
energy in the fission of nuclei of high mass number. Calculation of mean
binding energy per nucleon indicate that µ - decay is common among elements
with mass numbers exceeding 210.
Nucleon – Nucleon Forces:
We have to understand the nature of forces which bind together the

protons and neutrons in the nucleus. These forces are fundamental l y d if fer ent
from the more familiar gravitational and electrostatic forces of attraction as
well as from weak interactions involved in beta decay. The nucleon forces are
known as short range forces, operating over very short distances only, of the
order o f 1 0 - 1 3 cm. The binding energy is approximately proportional to the
number of nucleons. This is attributed to the saturation character of the
forces between nucleons that is to say each nucleon attracts those in its
immediate neighbourhood, but is relatively indifferent to the others. Thus the
nucleus may be compared to a liquid drop.
Each molecule in the drop attracts those with which it is in contact but
has no influence on the more distant molecules. As a result, the total energy
and volume of a liquid drop are proportional to the number of molecules it
contains. The same is true of atomic nuclei; the binding energy and volume
are related to the mass number, i.e., the number of nucleons in the nucleus.
The existence of (p- n ) , ( p - p) and (n- n) forces of attraction can be proved by
consideration of a few simple nuclei. The relative stability of the deuteron
made up of one proton and one neutron shows that the (p- n) force has
appreciable magnitude. Tritium contains an extra neutron. Its binding energy
increases partly due to (n- n) forces. He-3 contains
2 1 3
D+ H He
123
1 1 2
contains an extra proton and its binding energy increases due to (p- p) forc es.
The binding energy of 3 T is greater that that of 3 He. It would appear that
(n- n) forces are larger than (p- p) forces. The interaction between two protons
always involves a force of electrostatics repulsion. It looks as though that the
attractive nuclear forces between two neutrons and two protons is essentially,
identical. This result is referred to as the charge symmetry of the inter
nucleon forces. The scattering of protons and neutrons by protons is studied
with targets of hydrogenous materials. Such scattering studies indicate that
(n-p) , ( p- p) and (n- n) forces are equal.
This principle is known as the 'charge independence' of the nucleon

force. Comparison of binding energies of certain isobaric nuclides e.g.,
Be- 1 0 , B - 10 and C-10 confirms that nuclear forces are charge independent.
I n B -10 however, the number of (n-p) forces is different from that in other
two nuclides. Theoretical considerations indicate that if the nucleon forces
are charge independent, there should be an excited state of B- 10 with the
same binding energy, apart from electrostatic effects, as the other nuclei in
their ground states. There is evidence that such an excited state of 1 0 B ex ist s.
The remarkable constancy of nuclear densities is also in agreement with
charge independent principle.
Characteristics of Nucleon Forces:
There is undoubtedly an attractive central force between nucleons.

There is a force of attraction acting along the line joining the nucleons, that
depends on their distance apart. This force is independent of charge, on the
nucleons and is the same for all three types of nucleon pairs, namely (n- n)
(n-p) and (p- p). It is a short range force that decreases sharply at distances
greater than 10- 1 3 cm. Its magnitude depends on the directions of the spins of
nucleons. Deuteron having a nuclear spin of 'One' (I=1) i.e., the proton and
neutron have parallel spins, is stable.
124
But diproton and dineutron, in which, the nucleons would have

anti-parallel spins do not exist.
The magnetic properties of the deuteron can be accounted for only by

postulating the existence of a 'tensor force' between the proton and neutron.
The magnitude of this force depends on the directions of spin axes of the
nucleons with respects to the line joining the particles; but unlike the central
force, it does not necessarily act along this line.
Another type of inter- nucleon force to be considered results from the

interaction of the spin and orbital angular moments. Evidence for the spin-
orbit force comes from the scattering of protons by protons. The possibility
o f s p i n - orbit interaction is also indicated by the success achieved in
arranging the nucleons in various groups or shells, in a nuclei. Nucleon–
Nucleon repulsive force also has to be taken into account. If the forces
between the nucleons were only attractive, with no repulsive forces , n e i t h e r
the binding energy nor the nuclear volume would be proportional to the
number of nucleons. If the nucleus were to be stable, then there should be a
repulsive force operating over a shorter range than the attractive force.
The Meson Field Theory of Nucleon Forces:
H.Yukawa proposed a theory of nucleon forces, based on an analogy

with electromagnetic forces. The photon is referred to as the field particle of
the electromagnetic field. Yukawa proposed that the (Strong) interaction
between nucleons might be accounted for in a similar manner by postulating
an appropriate 'field particle'. He showed that the field particle could have a
mass roughly 200 times the mass of an electron. Such a particle was
discovered in cosmic rays and is known as muon. But another particle heavier
than muon was discovered in cosmic rays. This particle is known as pion and
it is now called pi- meson.
The pion occurs in positive, negative and neutral forms and has a mass
about 270 times the electron. It has properties like spin and parity which
125
qualify to be the field particle. The theory of nucleon forces based on Pi-
meson may be stated as follows. Every nucleon is surrounded by a meson
field through which it interacts with other nucleons, just as a charged body
interacts with other charged bodies through an electro magnetic field. The
pion then serves the same function in the meson field as the photon does in
the electro magnetic field.
Interaction between the two nucleons occurs by the transfer of a pion

from one particle to the other. In order to account for the existence of the
meson field, it is postulated that neutrons and protons are continuously
emitting and absorbing, positive, negative and neutral pions. These mesons
remain free for such an extremely short time that they are undetectable and
these mesons are called 'Virtual Mesons'. The meson has a mass of about
270Me. The uncertainly in energy corresponding to this is about 2.22 x
10 - 1 4 erg. Hence the time interval in which a virtual meson can exist without
being detected is about 5 x 10 - 2 4 sec.
∆E x ∆t = h/2Õ ; ∆t = h
2Õ x ∆E
= 6.63 x 10- 2 7
2 x 3.14 x 2.22 x 10- 4
~ 5 x 10- 2 4 s e c
The distance a meson can travel and get remain undetected is 5 x 10- 2 4
x 3 x 101 0 cm/s = 1.5 x 10- 1 3 cm (3 x 101 0 cm is the maximum speed of meson)
This distance is close to the range of nucleon forces; hence the concept of
virtual emission of mesons appears justified.
The force between a proton and a neutron could result alternatively

from the transfer of a positive pion from the proton to the neutron and the
transfer of a negative pion from neutron to proton.
126
P++ n o Po Õ+ no no + P+
Init ial state Pion T ransf er Fi nal Stat e
P++ n o P+ Õ- no no + P +
Init ial state Fi nal Stat e
i.e., the positive proton is converted into a (neutral) neutron and vice versa,
leaving the combination unchanged. In such a change from one nucleon to the
other, the spin angular momentum is conserved. Experimentally it is known
that the spin of Pi- meson is zero. (Neutron and proton each have a spin of ½
). The interaction of a Pi- meson field is called strong interaction. Coupling
constant calculations shows that for the pion- nucleon field, the value of the
coupling constant is about 15. It is about 2000 times greater than the
coupling constant of an electromagnetic field.
Repulsion has been accounted for by the transfer of two or three pions
between nucleons.
i) Discuss the concepts of

1) N/P ratio and
2) Binding energy
ii) Discuss in detail the different types of nuclear- nucleon forces.
10.3 Let us Sum Up

Packing fraction and finding energy calculations are explained. N/p
ratio and like different types of nucleon forces are discussed. Meson theory is
also discussed.
127
i) Packing fraction and binding energy curves.

ii) N/P ratio and the stabilities of nuclei
iii) Nucleon – Nucleon forces- strong interaction pions and heavier mesons.
10.5 Refe rence s
1) Atomic physics – J.B.Rajan. S.Chand & Co, New Delhi.

2) Source book on atomic energy – Glass tone
East- West press, New Delhi.
128
LESSON – 1 1
CONTENTS

11.1 INTRODUCTION
11.2 NUCLEAR STRUCTURE
11.2.1 LIQUID DROP MODEL
11.2.2 SHELL MODEL
11.2.3 COLLECTIVE AND UNIFIED MODEL
11.3 LET US SUM UP
11.5 REFERENCES
To study and understand the behaviour of nucleus on the basis of

different types of models proposed for the nucleus.
11.1 INTRODUCTION
The forces between the nucleons could not be explained quantitatively

and hence several models have been proposed for the nuclear structure. The
liquid drop is discussed first and then the shell model, representing a
diametrically opposed point of view, can be discussed. The collective and
unified models. Combine certain features of the other two models.
11.2.1 LIQUID DROP MODEL
Since the binding energies and volumes of nuclei are approximately

proportional to the number of constituent nucleons, (indicating saturation
character) the nucleus has been compared to a drop of liquid. N.Bohr
proposed the liquid drop model of the nucleus to explain nuclear reactions on
the basis of compound nucleus theory. According to this model, each nucleon
129
in a nucleus interacts with adjacent nucleons, in the same manner as

molecules in a liquid. Hence any excess energy of a given nucleon would be
very rapidly shared among the other nucleons. The energy levels of the
nucleons are thus regarded as quantum states of the nucleus (or liquid drop)
as a whole, rather than of a single nucleon. The application of the liquid drop
model in nuclear fission has already been considered. Other achievements of
the model related to nuclear binding energies and the properties of isobars
will now be considered.
calculation of Nuclear Binding Energies.
Since nuclear forces are of a short range character each nucleon will be
held strongly by those in the immediate vicinity. But each will be unaffected
by the others. As a result, to a first approximation, there will be an attractive
(or volume) energy, proportional to the number of nucleons in the nucleus; in
other words the energy term will vary approximately as the mass number, A.
This energy can be represented as a1 A, where a1 , is a constant. This value of
energy of attraction is correct when the number of protons is equal to the
number of neutrons. But most nuclei contain an excess neutron. These extra
neutrons are inevitably in higher quantum states, than the other nucleons and
they contribute a smaller amount (Per nucleon) to the total bind i ng e n e r g y.
Statistical calculations indicate, the energy corresponding to this 'asymmetry
effect' or composition effect, can be represented as : -a 2 ( A -2Z) 2/A , where (A-
2Z) is the neutron excess and 'a2 ' is a constant. Long range electrostatic
forces due to repulsion of protons, decrease the binding energy by a quantity
proportional to = - a 3 ( Z 2 /A 1/3
), where 'a3 ' is a proportionality constant.
The nucleon at the surface of the nucleus will be less tightly bound
than those in the interior. The binding energy is reduced by an amount,
proportional to the surface area of the nucleus. This 'surface effect' is given
by the term = - a 4 A 2 / 3 ( A 2 / 3 is the area). The influence of even or odd- odd
nuclei can be represented a term = ± a 5 / A + sign corresponds to even – e v e n
nuclei and – sign to odd- odd typ e.
130
by adding all the above mentioned terms, the binding energy B.E can
be written as:
B.E. = a1 A – a2 ( A - 2Z) 2 – a 3 Z2 – a 4 A2 / 3 ± a5 / A - -- - (1)

A A1 / 3
the five constants must be known for calculating B.E. a3 can be obtained from
electrostatic theory. The other four constants are empirical and can be
obtained from experimental data. Differentiating with respect to Z and
e qua t in g t o zero, 'a 2 ' can be calculated. a5 is zero for an odd-even or an even-
odd nuclei, the two remaining constants, and a4 can be calculated from the
known binding energies of any two nuclides of this type. The spin- effect
constant a5 is obtained empirically from binding energies of even- even
nuclei.
Inserting these constant in equation (1) we have:

B.E.(MeV) =15.75A – 23.7 (A- 2Z) 2 – 0.710 Z2 - 17.8A 2 / 3 ± 130
A A1 / 3 A …..(2)
The relative effects of the various factors on binding energy can be

seen by performing calculations for nuclides of low, medium and high mass
numbers.
40
Ca, B.E. per nucleon is about 8.52MeV.
20
The estimated binding energies for

40 120 238
Ca Sn a n d U are
20 50 92
342, 1019and 1805MeV, compared with values 342, 1026 and 1800 MeV,
respectively derived from atomic masses.
131
Calculate the binding energy/nucleon for

120 238
sn and U using the
50 92
above equation and tabulate the values corresponding to the different effects.
The Values agree well with the observed binding energies upto three
significant figures.
For elements of high atomic number, the decrease in binding

energy/nucleon is mainly due to the marked increase in the electrostatic
repulsion of the protons. This is responsible for the a -particle emission, by
elements of high atomic numbers and also for the liberation of energy
accompanying nuclear fission.
By plotting the binding energy against atomic number, of nuclides of

odd mass numbers, a parabolic curve can be obtained. All isobaric nuclides
whose binding energies are less than that of the stable nuclides, will lie on
the two arms of the parabolic curve. They will be unstable and decay in an
appropriate manner. The nuclides of lower atomic numbers (on the left arm of
parabola) would exhibit negative b - decay.
For e.g.,
73 b- 73 b- 73
Zn Ga Ge (Stable )
30 31 32
Isobars on the right arm of the parabolic curve have more protons and decay
either by the emission of positron or by electron capture.
73 b+ 73 Ec 73
Se As Ge (Stable)
34 33 32
For isobars of even mass number, the results are different due to the
inclusion of the odd-even (spin effect). For all nuclides with even numbers of
protons and neutrons, the bindings energy is increased, and for those with
132
odd numbers of protons and neutrons, it is decreased. This indicates that no

st a bl e o dd-odd nuclide should exist. For isobars of odd mass numbers, the
instability is greater and hence the half life should be shorter.
In a chain of b - disintegration, the half- life increases regularly as
stability is approached. For e.g., in the chain (b - decay)
133 133
Sb Cs
51 55
(stable) – the half life increases from 2.3min to 5.3days as Cs is approached.

For even mass numbers also a similar effect in noticed
140 16s 140 1.1min 140
= xe Cs Ba
54 55 56
11.2.2 NUCLEAR SHELL – MODEL
This model is sometimes referred to as 'independent particle model'. It

is based on the fact that there are specific numbers of protons and neutrons,
generally known as magic numbers or shell numbers, for which the nuclei
exhibit exceptional stability. This is like atoms containing certain numbers of
closed shells of electrons. T.H.Bartlett indicated the possibility that nucleons
might occupy quantum groups or shells just as electrons in an atom.
It was pointed out that the concept of nuclear shells could explain the
magnetic moments of nuclei. Magic numbers of nucleons are 2,8,20,50,82 and
126. T hese apparently represent closed shells in the nucleus. Elements having
the largest numbers of stable isotopes are those containing 20 and 50 protons
or 20, 50 and 82 neutrons. Sn- 50 has ten isotopes and also three isotopes of
odd mass numbers (115,117 and 119). The more abundant nuclides in the
universe are those with magic numbers of neutrons or protons
16 20
O Ca etc,
8 40
133
Nuclides containing magic numbers of neutrons, have small cross sections for
neutron capture (they are stable). When the neutron numbers are 50,82 or
126, the cross sections for neutron capture are much lower for 1MeV
neutrons.
Similarly for thermal neutrons, extremely low cross sections for (n,¡ )
reaction are observed, when the nuclei contain 20, 50, 82,or 126 neutrons.
Excited nuclides 17 87 13 7
O kr xe lose neutrons
8 36 54
readily to get the magic number of neutrons. The alpha particle energy is
exceptionally large, when the decay product (daughter nuclide), belongs to
the magic number category, during the radioactive decay of the heaviest
nuclides.
The end products of the four radioactive series,

206 207 208 209
Pb Pb Pb and Bi, contain magic numbers.
82 82 82 83
The following also can be correlated with the special stability of magic
numbers.
1) High binding energy of the last neutron in such nuclides.
2) The departure of the total binding energy determined from the atomic
mass from that calculated using equation (2)
3) a - particle emission among isotope of certain elements of medium
mass number.
4) The non existence of stable isotopes of elements – 43 and elements –
61.
5) The variation of quadruple moments with the numbers of neutrons and
protons.
Hence the behaviour of atomic nuclei, can be correlated with excess or

deficiency of nucleons, with respect to closed shells of magic numbers just as
134
the chemical and spectral properties of atoms are dependent on excess or

deficiency of electrons.
In the shell model each nucleon is essentially independent of the other.

The other nucleons provide the potential energy field which determines the
quantum states and hence the numbers in closed shells. In the shell model the
c o u p l i n g ( l - s) concept is employed to account for the total number of
nucleons (magic numbers) in different shells. Each 'l' levels is split into two
sublevels characterized by the j term.
j=l+½ and j=l- ½ (except l=0). Each of these sublevels can

accommodate (2j+1) neutrons and (2j+1) protons. For eg., when l =1, j=3 / 2
and ½ (2j+1) = (2 x 3 / 2 +1) = 4 nucleons with j = (3 / 2 ) and (2j+1) = (2 x ½
+1) = (2 x ½ + 1) = 2 nucleon with j = ½, written as (3 /2 ) 4 and (½) 2 ; a rr ange d
in this manner each shell can have a magic number of nucleons such as
2,20,50,82, and 126 l=0 will have '2' nucleons l=1 will have 8 nucleons etc
The spin of a nucleus with odd mass number, in the ground state should
123
depend only on the odd nucleon. The nuclide Sb has one proton beyond
51
the closed shell of 50 and its spin is 7/2, as expected l=4 and j=l- ½ = 4-½ =
7/2.
The shell model gives a qualitative interpretation of the observed
nuclear magnetic moments, by relating this property to the j value of the odd
proton, certain groups of two or three isotopes of odd atomic number and odd
mass number have identical spins and closely similar magnetic moments e.g.
107 109
Ag and Ag; In – 113 and In – 11 5 ;
The quadrupole moment is a measure of the deviation of the charge

distribution, in a nucleus from the spherical form. Nuclei with closed shells
of nucleons should have a sphericlaly symmetric charge distribution, and
therefore zero quadrupole moment. Experiments indicate that this is true.
135
For nuclei beyond closed shells, the quadrupole moment is negative.

The quadrupole moment of an odd proton is not very different from t h a t
caused by an odd neutron. The shell model predicts that a proton would
produce a greater distortion in the spherical charge distribution and give a
larger quadrupole moment. This is a failure of the shell model.
11.2.3 Collective and unified model

This model differs in a fundamental respect from the independent
particle model by postulating, a mutual interaction between nucleons. As a
result of the collective or co- operative action among the particles, the
nucleus behaves like a drop of liquid and may suffer permanent deformation.
The deformation is not stationary. This travels around the nucleus producing
motions which are equivalent to oscillations and rotations of the nucleus as a
whole. the collective model requires a distortion of the nuclear core, and an
associated quadrupole moment, when the odd particle is a neutron. When the
numbers of nucleons are in between the values for closed shells, the
collective model predicts larger quadrupole moments than expected from the
independent particle mode l.
On the basis of collective models, the nuclear- rotational energy levels

have been postulated. The levels have integral values of rotational quantum
number. Consider the nuclei with mass number from 150 to 190 (and over
220). They lie between closed nucleon shells, such nuclei, with large
deformation, have their nuclear rotational energy levels very close.
For nuclei with numbers of nucleons, near to closed shells, the spacing
of rotational energy levels are large. In such nuclei, the vibratio na l e ne rgy
levels should also be considered. Vibrational and rotational energy levels are
superimposed, like ordinary molecules.
Rotational energy values for Pu- 238 have been determined and are very
close to the theoretical ratios of the energies.
136
The unified model of the nucleus is an attempt to combine the desirable

features of both the concepts. According to this model the individual
nucleons move in a potential field that can be deformed, especially in the
regions between closed shells. Because of this distortion, the order of filling
of the nucleon quantum states is often different from that required by the
independent particle model. Other states have also been introduced to
explain the various energy levels. These are known as "Nilsson State s" .
Thus this model has been able to explain the behaviour of nuclei, such as
magic numbers, spins, quadrupole moments, low energy excited states etc.

1. Discuss the liquid drop model and indicate how binding energies can
be ca lc ulated on the basis of this model.
2. a) Write an account of the magic numbers.
b) Discuss the shell model on the basis of closed shells of magic
numbers.
3. Write a note on collective model.
11.3 Let us Sum Up

T h e d i f f e r e nt types of nuclear models are discussed in details. Their
successor and failures in explaining the behaviour of nucleus are also
indicated. Calculation of finding energy and the various effects involved is
illustrated.
11.4 Points for discussion

1) Different types of nuclear models and their successes and failures in
explaining the behaviour of nucleus
2) Calculations of binding energies and the various effects involved.
11.5 Refe rence s

1) Source book on atomic energy. G l a s s t o n e – East West press – N e w
Delhi.
137
LESSON-12
CONTENTS
12.1 INTRODUCTION
12.2 NUCLEAR PARTICLES
12.2.1 NEUTRON
12.2.2 ELEMENTARY PARTICLES
12.3 LET US SUM UP
12.5 REFERENCES
The aims and objectives of this lesson are is to learn, the discovery of
neutron and understand a few other elementary particles.
3.1 INTRODUCTION
This lesson describes the discovery and properties of neutron. A few

elementary particles such as mesons etc are also described. The primary
radiation arising from the bombardment of 'Be' by µ - particles was thought
t o b e ¡ - rays. But Chadwick proved that the particle obtained in the above
reaction was uncharged, with a mass approximately that of the proton.
9 4 12 1
Be + He C+ n+Q
4 2 6 0
3.2.1 NEUTRONS
Chadwick obtained the mass of the neutron using the reaction:

11 4 14 1
B + He N + n
5 2 7 0
138
Since the atomic masses of the nuclides B- 1 1 , H e -4 and N- 1 4 , a r e

known the mass of the neutron can be calculated using the Q value of the
r e a c t i o n . T h e a - pa r t i c l e ( H e-4) obtained from polonium had on energy of
5.25MeV. The mass equivalent of this will be 0.00565amu 'Q' of the reaction
in mass unit = - 0.00154. For B- 11, H e- 4 and N- 14, Chadwick used the v a l ue s
of 11.00825 amu, 4.00106 and 14.0042 amu respectively. From the Q value
and the other atomic masses, Chadwick obtained a value of 1.0067amu. For
the neutron mass. From the reaction.
2 1 1
D +¡ H + n;
1 1 0
more accurate value of the mass of the neutron was obtained as 1.00867am.
In the C- 12 scale the values is 1.008665amu.
Radioactivity of the Neutron:
I n t h e b - decay, a neutron is converted into a proton and an electron

together with an antineutrino. If the mass of the antineutrino is zero then,
1 1 o
n H + e
0 1 -1
would involve an energy release of 0.782MeV.
1.008665 amu (for 1 n) and 1.007825 amu for proton ie., (1.008665-
0
1.007825)= 0.000840amu.
This corresponds to the energy of 0.782MeV. Since the energy is

released in this reaction, it would occur spontaneously. The half- life for this
b - decay can be shown to be about 20min. Experimental values of half life
has been found to be 700sec. This is in agreement with the calculated
value(~20min). Hence it can be proposed that the free neutron is radioactive
and disintegrates with the emission of an electron, leaving proton as a
residual particle.
139
140
Diffraction Neutrons
Neutrons like other particles (proton, a - particle etc) should exhibit

diffraction. In other words neutron should have wave properties like
electrons, in accordance with Debroglie's relation l = h/mv.
Experimentally neutrons were found to be diffracted by crystals like

sodium chloride, like X- rays. The energy 'E' of the neutron is kinet i c e n er g y
equal to ½ MV2 ; l = h
2mE
l = 6.627 x 10- 2 7
2 x 1.67 x 10- 2 4 x 1.6 x 10- 1 2 E
1.67 x 10- 2 4 =m (mass of neutron)

l = 2.87 x 10- 9 cm, where 'E' is in electron volts
E
For neutrons to be diffracted l would have to be 2 x 10- 8 cm and hence

neutrons having 0.02ev would exhibit diffraction phenomenon with crystals.
Calculate the wavelength of neutron having an energy of 0.06ev.

Compare this with that of an electron, having the same energy.
141
X- ray diffraction depends only on the number of orbital electrons of the

atom. Hence it is not feasible to detect positions of hydrogen and other light
atoms, by X- rays. In the diffraction of neutrons, however , it is in the
scattering by the nucleus, which determines the extent of diffraction. In this
respects, the effect of hydrogen, is quite considerable. Hence neutron
diff raction makes possible the location in crystals of hydrogen and other light
atoms. Alloys of cu and Ni are studied easily by neutron diffraction.
A fair yield of neutron can be obtained by (a ,n) reaction with

Beryllium.
2
D ( ¡ ,n) 1 H and 9 B e ( ¡ ,n) 8 Be have been largely used to produce
neutrons. These are photo neutron reactions. Slow neutrons can be detected
by their reactions with B- 10;
10 1 7 4
B + n Li + He + 2.5MeV
5 0 3 2
This energy is carried off by Lithium and alpha particle. These produce
considerable ionization in their tracks. By using a chamber of suitable and
using enriched B-10, every neutron entering the chamber can be counted by a
counter.
3.2.2 ELEMENTARY PARTICLES

i) Antineutron
The antineutron, like the positron and antiproton, however would not
be a constituent of ordinary matter. After the availability of a fair source of
antiprotons, antineutron was discovered. When a proton and and antiproton,
meet mutually annihilation takes place. If the two particles come fairly close
to each other, although not close enough for annihilation to occur, it is
possible for electric charge to be transferred from positive proton to the
negative antiproton or vice versa. Because of this both parti c l e s w o u l d
become electrically neutral.
Proton + antiproton neutron + antineutron
142
Antiprotons produced by means of Bevartron, were allowed to enter a

vessel of liquid hydrogen. About three out of every thousand antiprotons
interacted with hydrogen to form antineutron. The neutron annihilated the
antineutron produced, and energy was released. A flash of light in a detector
accompanied the release of energy. Although neutron is electrically neutral,
it has the properties of a small magnet, associated with a spinning negative
charge. It is possible that the neutron has some structure in which, an
electrically charged centre is surrounded by a region of opposite charge. It
can be assumed then, while spinning in the same direction, the neutron and
antineutron will produce oppositely directed, magnetic fields. It has been
established that an antineutron can exist so that there is an attractive force
between antiproton and antineutron.
ii) Muons and Mesons:
The existence of both positive and negative particles having masses

heavier than electrons and lighter than protons, in cosmic rays was
established. These particles were produced in the laboratory and were found
to have a mass about 206.8times that of an electron.
These particles are now known as "muons ' C m - particles) Both positive
and negative muons are singly charged particles. They carry a charge positive
and negative equal in magnitude to that of an electron.
A negative muon interacts with a proton in an atom produci n g a

neutron plus energy. If this does not occur within 2 x 10- 6 seconds, negative
muon breaks down spontaneously into an electron, together with a neutrino
and antineutrino, and energy. Mean life time of a negative muon is about 2.3
x 1 0 - 6 seconds. Positive muon does not generally interact with matter. It has
the same mean life time as negative muon. It decays to positron and energy.
m+ ( o r m- ) e + (or e- ) + neutrino + antineutroni + energy
143
Pi-Mesons (or pions)
Pions having masses intermediate between the electron and proton were
found in cosmic rays. These particlescalled pi(or Õ ) Mesons have also been
produced in the laboratory. They occur in three forms Õ + , Õ - and the third
is electrically neutral, Õ o . Õ + and Õ- mesons have masses 273.2times
heavier than e l e c t r o n . Õ o is lighter (264.3times that of electron) Õ (- )
interacts with proton more readily than m- to form a neutron.
Õ- + p n+¡ or n+Õ o
They decay giving muons thus:
Õ+ m+ neutrino + energy
Õ- m- antineutrino + energy
Õ + and Õ - mesons have a mean life time of 2.6 x 10- 8 sec (less than 100 times
that of a muon) Õ o mesons have a very short life and hence are not observed
in cosmic rays. In the laboratory Õ o was produced by bombarding Beryllium,
carbon or other element with protons of high energy. Neutral pion has a
lifetime of 10- 1 6 seconds. Õ o decays very rapidly; all its mass is converted
into energy. In Õ o , the particle and antiparticle are indentical.
K-Mesons or KAONS
Another particle having mass between electron and prton. It is the

Kmeson or kaon. K- meson exists as positive and negative and in two neutral
forms. The charged K- mesons have the same mass, namely 966.6electron
masses. They have the same life time: 1.2 x 10- 8 sec. Each type of charged
kaon can decay in six different ways, the products being pions, muons,
- +
sometimes with e or e and a neutrino (or antineutrino) negative kaons can
inter act readily with protons in atoms.
144
12.3 Let us Sum Up

i) Neutron; its discovery and different types of neutron reactions are
d iscussed Neutron diffraction method is explained.
ii) Elementary particles like a) antineutron; b) muons and mesons; c)
pions; d) kaons are discussed.
1) Write notes on:
a) Neutron its discovery, reactions and diffraction methods.
b) Different types of elementary particles.
12.5 Refe rence s

1) Source book on atomic energy. Glass tone – East West press – New Delhi.
145
UNIT – V
LESSON – 1 3
CONTENTS
13.1 INTRODUCTION
13.2 ALPHA, BETA, GAMMADECAY, NUCLEAR ISOMERISM
13.2.1 ALPHA, BETA- AND GAMMA DECAY – TH EORIES
13.2.2 NUCLEAR ISOMERISM
13.3 LET US SUM UP
13.5 REFERENCES
The aims of this lesson are to study and understand the theories
concerned with the decay of µ , b a n d ¡ particles. After going through this
lesson you would be able to learn the existence of nuclear isomers.
13.1 INTRODUCTION
Radio elements either in the pure state or as compounds emit radiations

quite spontaneously and without any preliminary treatment. In this lesson, the
p r op e rti e s of µ , b a n d ¡ rays would be reviewed and theories of concerned
with the decay of these particles would be studied. In the magnetic field ¡ -
rays are not affected at all, the b - particles are considerably deflected and
the direction of, deflection indicates that they are negatively charged. The
µ -rays are also deflected in a magnetic field and the direction of deflectio n
indicates they are positively charged. Certain radio elements emit µ - particles
which are identified with Helium nuclei. Since outside the nucleus except
nothing electrons exist, the µ - particles must be supposed to proceed out of
146
the nucleus it self. b - particles identified with electrons should also arise
from the nucleus. The emission of b -particles is irreversible and the b - decay
gives rise to a new atom, which is different from the parent atom. Henceb -
particle cannot be extra nuclear electron ¡ - rays have been identified with
electromagnetic radiation ' ¡ '- rays emitted are of extremely short wave length.
Any radiation of shorter wavelength, as at least some of the ¡ - rays are, must
therefore come from nucleus.
Another type of radioactive decay i.e., by isomeric transition, has been

brought to light by a study of artificial radionuclides, although it is actually
an aspect of the familiar gamma – ray emission. F.Soddy predicted the
existence, of isobaric isotopes having different radioactive properties.
Substances of this type have become known as nuclear isomers. The
phenomenon is known as nuclear isomerism.
THEORY OF ALPHA DECAY
In experiments on the scattering of µ - particles, it was found that even

the fastest of such particles from radioactive sources, having an energy of
10MeV, are generally repelled by atomic nucleus. It is an undoubted fact that
radioactive nuclei emit alpha particles, hence such particles must be able to
exist, at least for a short time within such nuclei. The interaction between a
radioactive nucleus and an alpha particle (inside or outside the nucleus) can
be understood by a potential energy diagram i.e., a plot of potential energy v s
distance from centre of nucleus. The diagram shows increasing electrostatic
repulsion of an alpha particle as it approaches the nucleus. The sharp fall in
potential energy indicates the region within the nucleus. This implies
attraction of the alpha particle by the nucleons in the nucleus. The potential
barrier represents a repulsive force. It can be shown that the force of
repulsion between a proton and a nucleus is less than for an alpha particle,
whereas there is essentially no repulsion between a nucleus and a neutron
calculations indicate than an alpha particle must have an energy of 25MeV to
147
get into the nucleus from outside. Therefore an alpha particle must have the
same out of energy to escape from the nucleus.
In other wards a potential barrier prevents the escape of the µ - particle

from the nucleus. But µ - particle are produced from radioactive sources with
energy as low as 4 MeV, and for no natural element does the µ - particle
energy exceed 10.6MeVwave mechanics shows that there should be a
definite, if small, probability that such a particle from the interior will be
found outside the nucleus. In other words, there is a definite probability that
the alpha particle will escape from the nucleus even when its energy is less
than that of the top of the hypothetical barrier.
It follows, therefore, that greater the energy of the alpha particle in a

radioactive atom, the more likely is it to be found outside the nucleus. This is
the fundamental basis of the fact that radio elements which disintegrate
rapidly emit alpha particles, of high energy and long range, whereas the long
lived elements produce particles of relatively low energy and short range. An
approximate value of the frequency with which alpha particles reach the
exterior surface of the nucleus can be obtained by dividing the radius of the
nucleus by the estimated speed of the alpha particle. If this frequency
expressed as the number per second is multiplied by the probability of
escape, the result would give the frequency with which alpha particles
actually escape. The value of l (decay constant) will in general be larger the
greater the energy of the µ -particle. Using simplifying assumptions, the wave
mechanical treatment leads to a relationship between the decay constant,l
and the energy of the alpha particle. This equation is similar to the Geiger
Nuttal l rule .
3
Log l = / 2 A log Eo+B1 . 'A' is the slope when log l is plotted against
E o . B 1 is a constant for each radioactive series. The wave mechanical theory
of µ -decay shows that for naturally occurring radio elements, the energy of
the alpha particle must be at least 3.8MeV, if the decay constant is to be
148
greater than 10- 2 0 s e c - 1 . Thorium with a half life of 1.39 x 101 0 years emits
alpha particles with the lowest energy, 4 MeV.
Assuming the radius of the nucleus is about 10- 1 2 cm and the speed of
the alpha particle moving in the nucleus as 108 cm/sec, then an alpha particle
would find itself at the exterior of the nucleus. 108 /10 - 1 2 = 102 0 time/sec.
If the decay constant say for Th-C' is 107 s e c - 1 , then the alpha particle
escape probability would be:
10 2 0 x escape probability = l
10 2 0 x escape probability = 107
then escape probability = 107 /10 2 0 = 10- 1 3
This means even with a very s h o r t - lived radio element Th- C', an alpha
particle with an energy of 9 MeV, makes on the average, 101 3 attempts to
escape from the nucleus. For Th the escape probability is 1/103 8
THEORY OF b -DECAY
When the energy of b -particles is plotted against the number of

b -particles emitted a maximum is observed (Emax). From the energy
distribution it can be shown that the average energy of the b - particles from a
given source is considerably less than the maximum energy. Energy
considerations during the emission of b -particles indicated that the electrons
which are emitted as b - rays by radioactive nuclei must result from the
spontaneous conversion of a neutron into a proton and electron. Pauli
suggested that this process was accompanied by the emission of another
particle, called a neutrino, this was assumed to be electrically neutral and to
have very small rest mass, compared to that of the electron.
1 1 0 0
n Proton + electron + neutrino
0 1 -1 0
149
I n t h e b - decay process the proton remains in the nucleus, but t h e

electron and neutrino are ejected. In order to account for the continuous
distribution of energy among b - particles Pauli suggested that the total
available energy, equal to Emax, was divided between the electron (b particle)
and the neutrino. Thus the difference between Emax and the actual value for
any b -particle would be carried off by neutrino. If a spin quantum number of
½ is assigned to neutrino, spin can be conserved in the conversion of a
neutron into a proton and electron (b - particles ).
b - decay is an example of the phenomenon known as weak interaction in

contrast to the stronger electromagnetic interaction and the even stronger
interaction between nucleons. For emission of b - particles no barrier exists
and relatively long half lives are accounted for by the weakness of the
interaction between the neutron and proton with the electron – neutrino field.
POSITIVE b -DECAY:
Nuclei having too many protons, for stability emit positive b -particles,
called positrons.
1 1 0 0
P n + e + neutrino
1 0 +1 0
The energies of positive b - particles have a continuous distribution of

energy. The emitted neutrino shares energy with positron and also conserves
spin.
GAMMA RAY EMISSION
Gamma rays are electromagnetic in nature like other radiations, one

might say these rays emitted by radioactive nuclei are merely the excess of
energy radiated away in the form of quanta by the excited nucleus returning
to a more stable state- Experiments indicate that this is actually the ca s e . T he
¡ - ray emission is usually accompanied by µ o r b - disintegration, of a
radioactive nucleus. Owing to the emission of µ o r b particle from the
150
nucleus, the nucleus becomes excited and hence transition can take place
from this excited state to another of lower energy with the consequent
emission of the excess of energy as a '¡ - ray. If there are several lower states
transitions may take place to these states giving rise to '¡ ' – ray spectra.
'¡ '- ray spectrum has been experimentally observed. Certain atoms are known
to disintegrate without emitting '¡ - ray e.g, RaE emits b -particles without
¡ - ray emission. After the b - particle is ejected the resulting product nucleus
is left in an excited state, which therefore returns to the normal state by the
e m i s s i o n o f ¡ - rays. As regards the ¡ -rays associated with µ disin te gr a ti on ,
there are reason to believe that the ¡ - rays may be emitted either before or
after the departure of µ - partic les.
INTERNAL CONVERSION OF GAMMA RAYS.
Information concerning gamma ray energies has been obtained from the
phenomenon now known as 'internal conversion'. In emerging from a nucleus
the ¡ - ray (photon) may produce a kind of photo electric effect with one of
the orbital (or extra nuclear) electrons of the same atom. As a result, the
energy of the photon is transferred to the electron. The ¡ -ray is then said to
be 'internally converted'. The electron which interacts with the ¡ -r a y p h ot o n
is ejected from the atom with kinetic energy 'E- P' where 'E' is the ¡ - ray
energy and 'P' is the binding energy of the electron in the atom of the element
e m i tti ng t he ¡ - radiation. This is presumed to be the daughter element in the
given disintegration. If the ejected electron came from the K- level of the
atom then, 'P' can be replaced by Ek. Ek is the energy of the K- line of the
cha rac te ristic X- rays of the daughter element. Hence kinetic energy o f t h e
ejected electron is E- Ek. If the electron comes from the L-Level, then kinetic
energy of the ejected electron is E- EL.
As a result of internal conversion a number of groups of electrons

having discrete energies are emitted. Because of their definite energies, the
internal conversion electrons are said to give a line spectrum, which is super
imposed upon the continuous spectrum of beta particles. As a general rule
151
only a small proportion of the ¡ - ray photons have their e ne rg ie s i nte rn a ll y

converted. The fraction of the energy so converted, called the internal
conversion coefficient depends on the energy of the gamma rays.
The energies of the internal conversion electrons have been determined

by the magnetic spectrograph. If to these are added the energy values for the
appropriate K,L etc., lines of the characteristics X- rays spectrum of the
daughter element, the sum should give the energies of the ¡ -ray prior to
conversion. For example in the conversion of Ra- B Ra- C, the
energy of the electron emitted is added to the characteristic X-r a y e n e r gi e s
(say K.L etc) of the daughter element (Ra – C), the ¡ - ray energies are
obtained. These values are in excellent agreement with the accepted values
for the energies of gamma rays. For eg: Energy of ejected electron = 0.0368
MeV; 'L' line of Ra-C has the energy = 0.0161 MeV. The total 0.0368 +
0.0161 = 0.0529 MeV is the ¡ - r ay e nergy.
The binding energies of the electrons, obtained by subtracting their

measured kinetic energies from the known gamma ray energies, and the
observed frequencies of the characteristics X- rays are definitely those of the
daughter and not of the parent. These facts provide clear proof that the
¡ - rays are emitted from the excited daughter nucleus, which remains after the
parent has ejected either an alpha or b - particles.
ORBITAL ELECTRON CAPTURE
In some instances, where N/P ratio is low, position activity is

expected. Another type of decay has been found to occur with artificial
nuclides. Instead of a proton being converted into a neutron with the
emission of a position, the nucleus capture one of the extra nuclear (orbital)
electrons, which immediately combines with a proton to form a neutron, thus
with a neutrino being formed at the same time.
1 0 1 0
P+ e n+ neutrino.
1 -1 0 0
152
This process increases N/P ratio. This gives rise to a product with the same
mass number and the atomic number decreases by one unit.
55 0 55
Fe + e Mn
26 -1 25
This process is known as decay by orbital electron capture. The

electron is usually captured from the K- level, for such an electron is more
likely to be found near the nucleus. This process is also known as K- electron
capture or K- capture. Examples of L- level capture are known but they are not
common. Due to K- capture, characteristic X- rays of the product nucleus are
emitted. For eg.,
49 0 49
V + e Ti, this process gives rise to
23 -1 22
K-series of X- rays belonging to 'Ti'. This shows that vanadium decays by

K-electron capture. If as a result of orbital electron capture, the product
nucleus is left in the ground state, the change will not be accompanied by
¡ - rays. The decay of 49V, by K-capture is not accompanied by gamma- rays.
Such a K- capture is known as pure K-capture. In most instances, however the
product nucleus is found in a high- energy excited state and the excess energy
is given off in the form of gamma radiation. This ¡ - radiation is internally
converted; the energy of the gamma ray photon is transferred to an orbital,
which is consequently ejected. Thus characteristics X- rays lines of the
product nucleus are produced. It is possible to show that for positron
emission a minimum of 1.02MeV energy is required. If the energy is less than
this value, then K-capture would occur. When the energy is less than
1 . 0 2 M e V K - capture is favoured. Positron emission is unknown among the
heaviest elements. In these cases several cases of K-capture have been
recorded.
153
13.2.2 NUCLEAR ISOMERISM
Study of radioactive decay of artificial nuclides, indicates a transition

known as Isomeric transition. Nuclides having the same mass number and
same atomic number, but having different radioactive properties are known as
nuclear isomers. This phenomenon has been called nuclear isomerism.
O.Hahn found U- Z to be isotopic with and also to have the same mass number
a s U - X2 . But both differ in the rates of decay. Later several isomers had been
reported; for e.g., Br2 . When a target containing bromine was bombarded
with slow neutrons, the product was found to exhibit three different half life
periods of radioactive decay, Viz, 17.6 min, 4.5hr and 35.3hr. The reaction is
o f ( n, ¡ ) type. The explanation for this behavior is as follow:
80
Br exhibits nuclear isomerism; each isomer has a different half- life.
The difference between the nuclear isomers of 8 0 Br, and in fact of all other
cases of nuclear isomerism is attributed to difference in the nuclear energy
states. One isomer represents the nucleus in the ground state, whereas the
other is the same nucleus in an excited state of higher energy. Frequently the
transition from a higher to a lower energy state (associated with ¡ - rays)
requires a very short time, less than about 10- 1 3 sec. The excited state then
has an extremely short life. If the transition is "forbidden", the high-energy
state (excited state), referred to as 'meta stable state', will have an
appreciable h alf- life. This half- life varies from small fraction of a second to
several days. Such a metastable state represents one isomeric form of the
particular nuclear species, whereas the ground state, ie., the state of the
lowest energy, represents the other. For eg, in the case of 8 0 Br, the meta
stable form is represented as 8 0 Br m . Nuclear isomers can be obtained by
various ways.
82 83
(Kr(d,P) Kr m and 80
Se (µ , n ) 8 3 K r m
Three types of nuclear isomers may be distinguished. Isomers of

independent decay each; isomer decays independently of the other with its
154
own particular half- life. In such cases transition from metastable to ground
state is highly forbidden
52
e xamples: Mn (b + , 5.7days, b + , 21 min)
71
Zn (b - , 4.1hr, b - 2.4 min)
115
Cd(b - , 43 days, b - , 2.3 days)
The second class of isomers are called genetically related isomers. The
parent meta stable state decays to the ground state with a definite half- l if e , a
¡ - ray photon is expelled. This decay process is known as isomeric transition
(IT). In most cases the gamma rays are internally converted characteristic
X-rays are emitted. The ground state decays to form the product with another
half- life. Examples are:
44
Sc (IT, 2.44 days, b + 3.91hr)
80
Br (IT, 4.5 hr; b - 17.61min).
Half life of IT is longer than that of the b decay (+ or - ).
The third category of nuclear isomerism is that in which, the active

species are isomers of stable nuclei. The decay process now involves an
isomeric transition from the meta stable excited state to the ground state of
the stable nuclide, accompanied by the emission of ¡ - ray emission. More
than 30 stable species are known. Examples, 8 3 K r , S r - 8 7 , A g - 1 0 7 , S n - 117,
Ba-137, are known to form metastable states of appreciable half- life . Iso mers
of short life are also known.
1) Discuss the theories of µ a n d b - dec ay

2) The speed of the µ - particle moving in a nucleus is 105 cm/sec. if the
radius is assumed to be 10- 1 2 cm and decay constant 104 s e c - 1 , calculate the
escape probability of the µ -particle.
1) Discuss the theory of ¡ - ray decay.
2) Discuss the different types of nuclear isomers
155
3) Discuss the orbital electron capture. How are characteristics ¡ - rays

produced in an orbital capture?
13.3 Let us Sum Up

a and b decay and the theories of a , b a n d g- decay are discussed in
detail Different types of nuclear isomers and their production are
explained. Internal conversion of g- ray is explained.

i) The production of different types of nuclear isomers
ii) Internal conversion of ¡ - ray
iii) The µ a n d b decay theories.
13.5 Refe rence s

i) Atomic Physics by J.B.Rajan S.Chand & CO, New Delhi – 1972
ii) Source book on atomic energy – Glass tone – E a s t – West press- De lhi.
156
LESSON – 1 4
CONTENTS
14.1 INTRODUCTION
14.2 Q- VALUE IN NUCLEAR REACTIONS, COULOMBICBARRIER,
NUCLEAR CROSS SECTIONS
14.2.1 NUCLEAR REACTIONS – Q VALUES
14.2.2 COULOMBIC BARRIER AND NUCLEAR CROSS SECTIONS
14.3 LET US SUM UP

14.5 REFERENCES
Th e aims and objectives of this lesson are to understand the calculation

of 'Q' values of different types of nuclear reactions and also to understand the
concepts of coulombic barrier and cross sections.
14.1 INTRODUCTION:
The bombardment of nitrogen by µ - particle was the first artificial

transmutation reaction studied. The nuclear reaction may be represented as
14 4 17 1
N + He O + H. The reaction energy corresponding to
7 2 8 1
such reaction is termed as the 'Q' value. The best value of reaction energy
obtained for the above reaction was about – 1.26MeV. From the masses and
kinetic energies of the reactant nuclei and product nuclei, one can calculate
the reaction energies. High energies are required to surmount the coulombic
barrier. To reach the nucleus of an atom an µ - particle should have energies
of the order of 20 to 30MeV, according to classical electrostatic theory.
157
Nuclear cross sections represent the effective area of cross section of a

single nucleus of a given species for a particular reaction.
14.2.1 NUCLEAR REACTIONS – Q VALUE.
A nuclear reaction equation, satisfying the universal principal of

conservation of energy can be written in a general way:
Mo + (M1 + E1 ) = (M2 + E2 ) + (M3 + E3 )
M 0 , is the rest mass of the nucleus bombarded, M1 and E1 , the mass and
kinetic energy, respectively of the projectile, M2 and E2 and M3 and E3
similar quantities of the two products of transmutations, viz, the outgoing
particle and the product nucleus. It is to be noted that the two sides of the
above equation can be expressed in terms of either energy or mass.
In the nuclear reaction equation, the reaction energy is known as Q

value.
Q = (M0 +M 1 ) – ( M 2 + M3 ) = E3 + E2 – E 1 Hence 'Q' can be calculated

using the masses of the particles involved or by means of the kinetic energies
of the particles. Q may be positive or negative, depending on the nature of
the process. Thus, if Q is positive, that is if the process is accompanied by
liberation of energy, there must be a decrease of mass – the total mass of the
products will then be less than that of the interacting nuclei by an amount
equivalent to this energy. A negative value of 'Q' means that the ene r g y i s
absorbed and there is a gain of mass on the nuclear reaction.
7
When Li is reacted with 'H, the energy liberated 'Q' value was found
to be 17.2 MeV; hence the mass equivalent of this energy is 17.2 = m(amu) x
931 m=0.0185 amu ; since Q is positive, it can be calculated that sum of the
masses of the products will be less than the interacting nuclei by 0.0185 amu
7
Li + 1H 4
He + 4 He
158
7
Masses of interacting particles = Li = 7.0160
1
H = 1.0078
8.0238 amu
2 4 He = 2 x 4.0026 = 8.0052
loss of mass = 8.0052 – 8. 0238
= 0.0186 amu and this is close to the equivalent of energy
released. 0.0186 x 931 = 17.3 MeV
This also establishes Einstein's mass energy relationship. T h e a t o m i c

masses of certain nuclides, either too unstable or too rare to be measured by
mass spectrometer methods, have been determined from nuclear reaction
17
energies. O is obtained as result of the interaction of the µ - p ar tic l e wi th
nitrogen nucleus.
14
N + 4 He 1
H + 17
O + Q. From the known energy of the
µ -particle and the measured range of proton, the nuclear reaction energy Q is
found to be –1.16MeV. The mass equivalent of this energy = - 1.16/931 =
-0.00124 amu. Since 'Q' is negative in this reaction, the total mass of the
products will be greater than those of the interacting particles. The atomic
14
masses of N and 4 He are: 14.00307 and 4.00260, respectively. Total mass of
reactants = 18.00567. Total mass of products 1 H = 1.00782, Q= - 0.00124.
Hence mass of 1 7 O would be = 18.00567 – 1.00658

= 16.9991 amu
COULOMBIC BARRIER:
Nuclear reactions of various nuclei with charged particles involve the

electrostatic or coulombic barrier. It can be shown that at any distance 'd',
the energy of the electrostatic (or coulomb) repulsion of an µ - p a r t i c l e ,
having two unit positive charges, by an atomic nucleus with 'Z' such charges
(Z=atomic number) is 2Ze2 /µ , where 'e' is the unit electronic charge. It is
clear that the energy with which an alpha particle is repelled from a nucleus
159
increases with the atomic number. Hence nucleus having high atomic n u m b e r
would repel strongly an energetic alpha particle. Therefore alpha particles of
energies in the range 20 to 30 MeV, would only be able to surmount the
potential barrier required to react with nuclei of high atomic numbers. The
application of wave mechanics, to the problem of nuclear penetration showed
that particles could both leave and enter the atomic nucleus even though their
energies are considerably less than the top of the hypothetical barrier.
G.Gamow showed that not only was the energy barrier lower, but the
probability of penetrating it and reaching an atomic nucleus also increased,
as the charge and mass of the incident particle decreased. Thus for a given
value of the particle energy, a proton with unit charge and unit mass, is much
more likely to enter the nucleus than an alpha particle, carrying two charges
and having a mass of four units.
NUCLEAR REACTION CROSS SECTIONS
The efficiency of a nuclear reaction can be defined in terms of the

number of particles emitted (or of nuclei undergoing transmutation). The
interaction probability is expressed in terms of a quantity known as 'nuclear
cross section'. when the probability of the process if high, the nuclear cross
section will be large; on the other hand when the probability is low, the c r o s s
section will be small.
If 'I' is the number of incident particles striking in a given time a

certain area of target material, containing 'No' target nuclei per sq cm and 'A'
is the number of these nuclei that undergo interaction in the specified ti me,
then the nuclear cross section 's ' expressed as sq cm per nucleus, is defined
by:
A
s = cm 2 /nucleus
No x I
s Na is the fraction of the surface, which is capable of taking part in

the nuclear reaction (Na = atoms/sq cm)
160
This also represents the fraction of the incident particles 'I' falling on
the target surface. The number actually reacting is = s Na I and this is equal
to 'A', the number of target nuclei undergoing transmutation.
A= s x Na x I i.e., A
-- -- - = s
NaI
Hence 's ' gives the effective cross section of a single nucleus for a
given nuclear reaction. The larger the fraction of the incident particles
reacting, the greater is the probability that the process will occur under the
given conditions. The value (s ) of the nuclear cross section depends on i) the
nature of the target element, ii) on the particular reaction under consideration
and iii) the energy of the incident particle. The total cross sections for all
processes in which the incident particles are removed, can be determined by a
simple procedure. Let Io be the number of incident particles, in a narrow (or
collimated beam), falling in a given time on the target material, which is on
the form of a sheet of thickness 'x'cm, and 'I' is the corresponding number of
these particles, emerging from the other side of the sheet in the narrow beam,
the difference Io- I has been removed in various nuclear reactions then
I
= e -N x s
- 'N' is the number of target nuclei/cc and 's ' is the total cross
Io
section. Hence it is possible to determine 's ' from measurements of the
intensity of the beam of incident particles before and after passage through
the target material.
Experimental values for nuclear cross sections are usually in the

neighbourhood of 10- 2 5 to 10- 2 3 sq cm per nucleus. 's ' may be as high as 10- 1 8
cm 2 /nucleus. The average diameter of the nucleus may be taken as 10- 1 2 cm
and the actual area of cross section is approximately 10- 2 4 cm 2 . ' s ' i s
expressed in the unit of barn equal to 10- 2 4 cm 2 /nucleus. Nuclear cross
sections are frequently in the range of 0.1 to 10 barns.
161
A c u r ve showing the variation of 's ' with the energy of the incident
particle is called the excitation function, of that reaction. In the case of Cu-
63 with protons in the energy range upto 35MeV, the excitation function
cu rves show, that at the lowest energies (p,n) reaction predominates; at about
15MeV the (p,pn) and (p,2n) reactions start to replace the (p,n) process. The
cross section for a given nuclear process increases with the energy of the
incident charged particle, provided there is no competitive reaction.
Competing reactions cause the cross section to decrease at high energies.

1. Discuss the principle of Q- value
2 2 3 1
2. In the (d,n) reaction: D + D He + n + Q
1 1 2 0
Q has been to and to be 3.16MeV. Using this value indicate how you
would obtain the mass of the neutron.

1. Write a note on coulombic barrier
2. Discuss nuclear cross section.
14.3 Let us Sum Up

Q- values is defined – calculation of Q- value is illustrated. Nuclear
cross section and Coulombic barrier are discussed in detail. The use of Q-
value in calculating the mass of 1 7 O is illustrated.

i) Q- Value and its uses
ii) Evaluation of nuclear cross section
iii) Coulombic barrier
14.5 Refe rence s

1) Atomic physics – J.B.Raj an – S.Chand & Co New Delhi (1972)
2) Source book on a atomic energy – Glasstone East- West press.
162
LESSON – 1 5
15.1. INTRODUCTION
15.2 NUCLEAR REACTIONS
15.2.1. Different types of nuclear reactions

15.2.2 Spallat ion
15.3 LET US SUM UP
15.5 REFERENCES
The aims and objectives of this lesson are to learn, the different types
of nuclear reactions and to know how they are brought about.
15.1. INTRODUCTION
The first successful nuclear transformation using artificially

accelerated protons was achieved by Rutherford. The nuclear reactions thus
achieved can be written as,
7 1 4 4 1
Li + H He + He, Where H is the incident
3 1 2 2 1
proton and the two helium nuclei are the alpha particles formed. The process
occurred to a detectable extent with protons of 125,000 eV ie., 0- 125 MeV, a
value considerably less than the height of the potential barrier between a
lithium nucleus and a proton, namely about, 0.45 MeV. Artificial nuclear
reactions have been classified in six general categories. The various types of
processes are (i) transmutation (ii) stripping and pick up (iii) fission (iv)
spallation (v) fragmentation and (vi) scattering.
163
N u c l e a r r e a c t ion is represented by a simple method for e.g.1 4 N

(a ,p) 1 7 O, is the reaction in which 1 4 N, is the target nucleus; the 'a ' pa rt i c l e
is called the incident particle or projectile; a proton is ejected (P) and an
17O, nucleus known as the recoil nucleus, remains. The general group of
nuclear reactions studied by Rutherford can be referred to as (a ,p) type.
i) Transmutation reactions :
These reactions involve particles of energy 50 MeV. In the first step
the target nucleus completely absorbs the projectile to form what is called, a
'compound nucleus'. Before forming the compound nucleus, the projectile
must overcome the barrier due to electrostatic repulsion forces. It hasbeen
found that the deuteron is capable of initiating several nuclear
transformations, through the formation of the compound nucleus, at relatively
low energies. In the compound nuclear redistribution of additional energy
takes place rapidly.
The avera ge life of a compound nucleus, i.e. the average time elapsing
between the capture of the projectile and the emission of a particle is
estimated to be 10- 1 4 sec or less. The nature of the particles expelled from
the compound nucleus, depends on i) its excess or excitation energy ii) the
heights of the various coulomb barriers, iii) stability of the remaining (re-
coil) nucleus. Since no barrier exists for neutrons, these particles will in
general be able to escape from the compound nucleus, much more readily
than either, protons, deuterons or alpha particles. This is especially true
when the target nucleus has high atomic number. For target elements of
small atomic number, neutrons are more strongly bound in the compound
nucleus than protons. The energy barrier is not also too high and the ejection
of a proton or a -particle may occur. The compound nucleus can given rise
to different reactions, depending on the available energy.
63 2 65
cu + H Zn (Compound nucleus)
29 1 30
164
65 65
Zn Zn + ¡
30 30
64 1
Zn + n
30 0
64 1
cu + H etc.
29 1
a) Transmutation by protons :
In these reactions the projectile has less than about 50 MeV energy.
For a number of lighter elements (P, ¡ ) process is observed for eg 27 Al
(P, ¡ ) 28 Si, other examples are 7 L i ( P , ¡ ) 8 Be, 14
N (P, ¡ ) 15
O, 19
F (P, ¡ )
20 50 51
Ne, cr (P , ¡ ) Mn.
If the incident proton has an energy in excess of 20 MeV, the

compound nucleus has sufficient excitation energy to permit the expulsion of
63
two or more nucleons. Examples are : Cu (p, pn) 6 2 Cu, 63
C u ( P , 2 n) 62
Zn,
88
Sr (P, 3n)86 Y.
If proton energies are more than50 MeV, more than three nucleons may
be emitted. (P, a ) reaction is expected only with targets of low atomic
number, for eg.
14 1 11 4
N+ H C + Hc; rare case of a (P, d) reaction
7 1 6 2
9 1 8 2
with Be + H Be + H; (p, d) are more common with heavier
4 1 4 1
elements and protons of fairly high energy, but they appear to be pick- up
reactions not involving compound nucleus formation.
165
b) Transmutation by deuterons:
The deuteron is a particularly effective projectile for causing nuclear

transmutations, because a relatively small amount of energy, about 2 Mev, is
sufficient to cause its rupture into a neutron and proton. This small binding
energy of the nucleons of a deuteron facilitates nuclear changes. In the (d, p)
reaction, the efficiency of the process increases with increasing energy of the
incident particle. Oppenheimer – Philips mechanism, explains the ease of the
(d, p) reaction. According to this the deuteron behaves as a relatively loose
combination of a neutron and a proton, since the binding energy is relatively
small. When the deuteron approaches a nucleus, the electrostatic forces of
the positive charges tends to force the proton away, but the neutroni s n o t
affected. If the energy of the incident deuteron exceeds about 2 MeV, the
proton portion breaks off and be repelled, but the neutron will enter the
target nucleus. If enough energy is available neutron may also be expelled.
Then the reaction (d, pn) occurs. (d, p) reactions are observed with all
elements. Examples :
7 2 8 1
Li + D Li + H
3 1 3 1
114 2 115 1
Cd + D Cd + H
48 1 48 1
209 2 210 1
Bi + D Bi + H
83 1 83 1
2 2 3 1
D + D T + H (3 T – is tritium); deuterons of moderate
1 1 1 1
energies give neutrons i.e., (d,n) type.
2 3 3 1
D+ T He + n
1 1 2 0
166
2 3 4 1
D+ T He + n This reaction is a convenient
1 1 2 0
method for producing neutrons with 14MeV energy. Other examples are:
6 2 7 1
Li + D Be + n
3 1 4 0
209 2 210 1
Bi + D Po + n. At high energies over 50 MeV, the
53 1 54 0
(d,n) reaction like the (d,p) reaction, becomes a stripping process, that does
not involve compound nucleus formation to any extent (d,a ) are observed
only with deuterons of moderately high energy and elements of fairly low
atomic weight.
40 2 38 4
Ca D K + He; others are 6 Li ( d, a ) 4 H e ,
20 1 19 2
20
N e ( ( d , a ) 18 F, 26
M g ( ( d , a ) 2 4 , Na, ((d,2n), (d,3n), (d,2p) and ((d,pa ) a r e
also known when high energy deuterons (about 20 MeV or more) are used.
c) Transmutation by 3 T:
When tritons obtained by the action of 10MeV deutrons on Be, are

used as projectiles, (t,p) reactions occur.
29 3 61 1
e.g., Co + T Co + H; (t,p) reaction probably occurs by
27 1 27 1
oppenheimer – Philips mechanism. The proton present in the triton is repelled

by the target – nucleus, leaving the two neutrons to combine with the target
nucleus to form a compound nucleus. In 6 Li (t ,d) 7 Li and 6 3 c u ( t , d ) 6 4 c u a l s o
the oppenheimer – Philips mechanism operates.
167
d. Transmutation by alpha particles:
(a , p) process was the first artificial transmutation studied. This occurs

in common with elements of low atomic number. With highly accelerated a -
particles this reaction occurs even with elements of higher atomic numbers
(above potassium) (a , n) rea ctio n:
9 4 12 1
e.g., Be + He C + n. By using energetic alpha particles,( a , n )
4 2 6 0
reactions have been observed with the heaviest elements, including uranium
and artificial elements of higher atomic numbers with increase in energy of
the a -particles, (a ,n p), (a ,3n), (a ,4n ), (a ,3np) have been detected.
e. Transmutation by radiation:
By using gamma radiation, deuterium nucleus could be disintegrated

into a neutron and a proton:
2 1 1
D +¡ H+ n. Gamma ray from Th- C, has sufficient
1 1 0
2
energy to breakup the D nucleus.
1
9 8 1
Be + ¡ Be + n. Reaction of this type brought about by high
4 4 0
e ne rg y ra d ia t i on, have been described as photo disintegrations or as photo

nuclear reactions. When the 17- MeV, radiations produced by the
bombardment of lithium by protons were employed, number of nuclei
exhibited photo nuclear reactions of the (¡ ,n) type. A neutron can be
removed from any nucleus by ¡ - rays of about 10MeV, energy. If the ¡ - ray
energy is not sufficient, to remove a neutron, the nucleus may enter into one
168
of its excited states; the excess energy is then emitted as radiation. Such a
process is described as (¡ - ¡ 1 ), where the energy of ¡ 1 is equal to or less than
that of the incident photon.
f) Nuclear reaction with heavy ions:
Accelerated carbon ions and 'Al' target is an example of a nuclear

reaction with heavy ions. 2 7 A l ( 1 2 C, a n)3 4 cl and 1 9 7 Au( 1 2 C , 4 n ) 2 0 5 At. The
particle energy is relatively high (about 10 MeV) per nucleon, certain
reactions in which heavy ions take part are called transfer reactions'.
14 14 13 15
N+ N N + N (Neutron is transferred)
7 7 7 7
14 10 13 11
N+ B N + B (Neutron is transferred)
7 5 7 5
14 14 13 15
N + N C + O (Proton is transferred)
7 7 6 8
15.2.2 Fission, Spallation and Fragmentation Reactions
Fission can also be initiated by charged particles of high energy

(compare with neutron). Fission with energetic charged particles can occur
with many nuclides of lower mass number. Alpha particles of about400MeV,
energy can cause fission of Bi, Pb, Tl, Pt and Ta and 200MeV deuterons are
effective for Bi, Pb and Tl. The lightest element that is known to undergo
f i s s i o n b y a - pa r t i c l e s i s Ta (Z- 73). In the fission of Ta-181 by high energy
protons, the masses of the product nuclei vary from about 60- 1 2 0 . T h e
distribution of the products depends to some extent on the energy of the
projectile particles. Another type of reaction, different from fission, but also
leading to many different product nuclei, was discovered in 1947 by
169
G.T.Seaborg. When bombarded by high energy charged particles e.g.,

400MeV protons or 200-MeV deuterons, many target nuclei do not break up
into two parts of similar mass, as in fission. Instead such nuclei emit various
numbers of nucleons commonly 10 to 20 and to a lesser extent up to 30 or
more, singly or in clusters , leaving a series of products, with mass numbers
lower than that of the target nucleus.
The name "Spallation" is used to describe this type of reaction.

Spallation is known to occur with many different nuclei from the lightest e.g,
Mg to the heaviest using charged particles with energies of several million
electron volts. With heavier elements, fission and spallation often occur at
the same, time as indicated by the masses of the product nuclei. In spallation
most of the products have masses that differ from that of the product by up to
10 to 20 units, smaller amounts of lighter products. The mass with
distribution of the products is the only way of distinguishing between fission
and spallation.
75
For example when arsenic ( As) is bombared by high energy a -
4 33 38
particles ( He), one of the mirror products is cl, the net decrease in
2 17
the number of protons is 18 and that in the number of nucleons is 41; this
75 38
particular mode of spallation is expressed as As (a , 18Z41a) cl. Some
33 17
75 38
writers use the equivalent representation As (a , 9 a 23n) cl,
33 17
but this is misleading as it implies the emission of 9a particle, which may or

may not occur. The mechanism suggested for high energy fission and
spallation, by R.Serber is generally accepted . The high energy projectile
enters the target nucleus and strikes a single nucleon; the latter known as the
knock- on particle, may be ejected or it may strike another nucleon, which
may in turn be ejected or it may share its energy with other particles in the
nucleus. The incident particle may still have enough energy to strike or
170
possibly eject another nucleon, or again the energy may be shared and so on.
This stage of the process is cascade in which several knock- on nucleons may
be expelled from the target nucleus. When the cascade is over within 10- 2 2
sec or so, the remaining nucleus is left in a highly excited state. It is similar
to a compound nucleus, but with a much larger amount of excess energy. A
distribution of energy then occurs, over a period of about 10- 1 4 s e c , a n d
several individual nucleons (or small groups of nucleons) are emitted. The
result would then be a spallation reaction. Alternatively and simultaneously,
after expelling a few nucleons the excited nucleus may split into two parts in
various ways, thus undergoing fission.
In reactions of some nuclei, particularly of medium or high mass

number, with high energy particles, the products include finite quantities of
nuclei with mass numbers from 18 to 32, e.g., 1 8 F, 24
Na, 28
Mg a n d 32
P . T he s e
are apparently too light to be fission either or spallation products. Reactions
leading to the formation of such species are called nuclear fragmentation.
After the cascade stage mentioned above but before there has been time for
the energy to be distributed in the excited residual nucleus, a relatively large
amount of energy may be concentrated in a limited region of the nucleus. As
a result, there is a rapid break up of the nucleus, leading to the f or mat i on of
nuclei consisting of 20 or 30 nucleons.
1. Discuss the different types of nuclear reactions

2. Explain the oppenheimer – Philips mechanism
1. Compare the fission and spallation reactions

2. Write a note on fragmentation
171
15.3 Let us Sum Up

Nuclear reactions brought about by different types of particles are
explained open Himer-Philips mechanism is discussed. Spallation reaction
and its mechanism are explained.
1) Compound nucleus formation in nuclear reactions

2) Philips- oppenheimer mechanism
3) Mechanism of spallation reaction.
15.5 Refe rence s

1) Atomi c Physics – J.B.Rajan S.Chand & Co
2) Source book on atomic energy – By Glasstone East West press.
172
UNIT VI
LESSON – 1 6
CONTENTS

16.1 INTRODUCTION
16.2 NUCLEAR FISSION AND FUSION
16.2.1 FISSION – THEORIES
16.2.2 FISSILE AND FERTILE NUCLIDES
16.2.3 FUSION – STELLAR ENERGY
16.3 LET US SUM UP
16.5 REFERENCES
The aims and objectives of this lesson are

i) To learn and calculate the energy released in nuclear fission and
fusion reactions.
ii) To study the theories of fission
16.1 INTRODUCTION
In the fission process a nucleus, after interacting with a projectile

particle, breaks up into two nuclei of roughly similar mass plus a few
nucleons. The nucleons obtained in the fission process are invariably
neutrons. The most important of fission is that caused by neutrons. But
fission can also be initiated by charged particles of high energy. The neutron
fission is restricted to a few heavy nuclei, whereas fission with energetic
charged particles can occur with many nuclides of lower mass number. Thus
alpha particles of about 400MeV can cause fission of bismuth, lead, thallium
and platinum.
173
The fission process is accompanies by the liberation of large amounts

of energy. The important point to remember is that fission, which is initiated
by neutrons, is also accompanied by the emission of neutrons. These emitted
neutrons cause a chain reaction to occur and more energies and neutrons and
produced. Uranium can be split by neutrons of all energies, i.e, by slow,
intermediate and fast neutrons. Fission of more abundant U- 238 requires fast
neutrons with energy exceeding 1MeV,
233 239
U Pu are fissionable by neutrons of all
92 94
energies. Fission cross sections are generally high for slow neutrons. Fission of Th
requires fast neutrons of energies of about 1 MeV. Protactinium also requires
fast neutrons. The combination of two or more of the lightest nuclei by a
process of fusion, like fission, result in the liberation of energy.
Many reaction between nuclei of low mass number can be brought

about by accelerating one or other of the nuclei in a suitable manner. These
are fusion reactions, accompanied by the release of energy. The energy of the
sun is due to the fusion reaction.
The power production corresponding to the fission of 1 g of Uranium

or Plutonium per day would be 1 mage Watt. To obtain the same amount of
power by combustion would require more than 3 tons of coal per day or 600
gallons of fuel oil per day.
16.2 NUCLEAR FISSION AND FUSION

16.2.1 FISSION THEORIES
Before studying the theories of nuclear fission one should know the
amounts of energy liberated in a nuclear fission reaction. In the fission
reaction we have to calculate the mass loss, in a nuclear fission reaction. But
we kn ow the energy corresponding to the mass loss of l a m u = 931 MeV.
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lamu= 1
6.0225 x 10- 2 4
= 1.6604 x 10- 2 4
E = m x c2
= 1.6604 x (2.998 x 10 1 0 ) 2 x 1 0 - 2 4
E = 1.6604 x 10- 2 4 x (2.998 x 10 1 0 ) 2 g cm /sec2 x cm
= 1.6604 x 10- 2 4 x (2.998 x 10 1 0 ) 2 e r g s
(note g cm2 / sec2 = ergs)
= 1.4924 ergs
= 1.602 x 10- 1 2 ergs = 1ev
hence E = 1.4924 x 10- 3 e v
1.602 x 10- 1 2
E = 931.4 MeV / amn
A l th ou g h U - 235 splits in many different ways, the nuclei obtained in

the greatest yield in fission by slow neutrons have mass numbers of about 95
and 139. The initial products are radioactive and undergo several stages of
negative b - decay ultimately, after the emission of a total of seven beta
particles (electrons), the stable nuclides Mo- 95 and La – 139 are formed.
The fission process in this particular case can be represented as:
235 1 95 139 O 1
U+ n Mo + La + 7b + 2 n
92 O 42 57 - 1 0
Some neutrons are always liberated in the fission process. The atomic mass of U-
235 is 235 – 0439amn and the mass of neutron is 1.0087amu.
The total mass on the left hand side of the equation is 236.0526amu.
The masses of Mo- 95 and La- 139 are 94.9058 and 138.9061 amu, respectively
175
and the mass of the electron is 0.00055amu; the total mass on t he right side
is 235.8332 amu. The mass loss is equal to 236.0526 – 235. 8332
= 0.219amu
Energy equivalent of this mass is

= 0.219 x 931.4MeV
~ 204 MeV
The actual process of fission is probably accounted for by the large

value of repulsive force in heavy nuclei, and so it is responsible both for
fission and for the release of energy accompanying the nuclear reaction.
The energy released in the fission process appears in several different

forms. The major part occurs as kinetic energy of fission fragments and a
substantial amount as radioactive decay energy of the fission products. In
addition, neutron and gamma rays liberated at the instant of fission carry
appreciable amount of energy. Thermal neutron fission of U- 235 is far from
symmetrical. If the compound nucleus splits into two equal of fragments, the
mass of each is 117or 118, only 0.01% of the nuclei under going fission by
thermal neutrons break up in this manner. There are 90 possibl e m a s s
numbers in the range of from 72 to 161, it is understandable that this may
represent the total number of different nuclides formed as direct fission
fragments. The amount of symmetrical fission by thermal neutrons is about
0.02% for U- 233 and 0.04% for Pu- 239.
Experimental studies indicated that for each atom of uranium

undergoing fission between three and four neutrons were emitted on the
average. The average number of neutrons released per fission increases with
the energy of the neutrons inducing fission. Thus in the fission of U- 2 3 5 b y
14MeV neutrons, an average of 4.5 neutrons are produced per fission. The
average number of neutrons increases in general with the number and the
atomic number of the fissioning nucleus. The great majority (over 9 9 % ) o f
the neutrons produced in fission are released within about 10- 1 4 sec. These are
referred to as prompt neutrons. A small proportion of fission neutrons are
176
delayed neutrons, which are emitted sometime after the fission process has
taken place. In the fission of U- 235 by neutrons upto atleast 1MeV energy,
0.65% of the neutrons emitted is delayed. The emission of delayed neutrons
is an important factor in the control of nuclear fission reactors. For thermal
neutron fission of plutonium – 239, about 0.21% of the neutrons are delayed,
and for U- 233, about 0.26% are delayed.
THEORY OF NUCLEAR FISSION

A useful approach to understanding the mechanism of fission is by means of
the liquid – drop model of the nucleus. It is postulated that, just as the
surface tension forces tend to maintain a liquid drop in a stable from which
resists distortion, so the nuclear forces serve to keep the nucleus in s stable
state. Only if considerable distortion occurs due to the addition of energy a
drop of liquid can be broken into two smaller drops. Similarly for a nucleus
to undergo fission, there must be considerable distortion, which will be
possible only if additional energy is available. This is the basis of the
interpretation of fission indicated by Meitner and Frisch.
The general idea of the proposed mechanism for fission may be

understood by considering a drop of liquid which is made to break up into
two smaller droplets, by the application of a suitable force. The system
passes through a series of stages. The drop is at first spherical, it is then
elongated into an ellipsoid. If insufficient energy is available to overcome
the surface tension, the drop will return to its original spherical shape. But, if
the deforming force is sufficiently large, the liquid acquires a s h ap e si mi la r
to a dumbbell. Once it has reached this stage, it is unlikely to return to the
spherical form, but it will rather split into two droplets.
The situation in nuclear fission is regarded as analogous to that just

considered for a liquid drop. A large nucleus combines with a neutron to
form a compound nucleus; the energy gained by the nucleus is equal to the
binding energy of the additional neutron plus any kinetic energy the neutron
may have possessed. The excitation energy may then be emitted a s g a m m a
177
radiation or the compound nucleus could, if sufficient energy were available

split in to one or more nucleons.
If the nucleus has obtained enough energy to permit it to form the dumbbell
shape, (like the liquid drop), the restoration to the initial shape (spherical)
becomes very improbable. The reason is that the electrostatic repulsion
between the positive charges on the two ends of the dumbbell, can now over
come the relatively small portion of the nuclear binding force, operative in
t h e c o n s t r icted region of the dumbbell. Consequently the dumbbell shaped
nucleus, undergoes fission to two separate nuclei. The series of changes just
described can occur only if it is accompanied by a net decrease of mass, that
is, by an emission of energy. The state, consisting of two separate nuclei is
then more stable.
CRITICAL ENERGY FOR FISSION
The critical energy (or activation energy) required for fission to occur is the
energy that must be supplied to the original nucleus in order to deform the
nucleus to the dumbbell state.
The repulsive energy is proportional to Z2 /A / 3 , whereas the surface energy

depends on A2 / 3 . Therefore the ratio of these two energies namely, Z2 /A, for a
given nucleus is a measure of the ease with which, it will undergo fission.
The large the value of Z2 /A, the smaller the amount of energy that must be
supplied from outside sources to cause fission to occur.
It was shown that if the electrostatic repulsion energy was more than twice
the surface energy, a nucleus should undergo instantaneous fission. The
condition for instantaneous fission was shown to be.
178
0.710 Z2 >2 x 17.8 x A2 / 3

A1 / 3
Z2
or > 50
A
The closer Z2 /A for a particular nucleus is to 50, then shorter should be

the half life for spontaneous fission. IfZ2 /A is approximately less thann 40
fission cannot occur at a significant rate unless energy is supplied to the
nucleus; this is the 'Critical energy' of fission. For plutonium – 239, Z2 / A s
37.0, for Uranium – 233 it is 36.4 and for Uranium – 235 it is 36.0, these are
fairly high, but they are sufficiently less than the limiting values to require
appreciable energies for fission. The critical energy for U- 2 3 5 a f t e r
absorbing a neutron has been estimated to about 5.5 MeV. Similar values
have been estimated for the other two fissile species. For lighter elements
such as bismuth, lead and tantalum Z2 /A is about 30 or less and critical
energy for fission is large. It can be understood, why fission does not occur
with these substances.
Fission process has also been explained by potential energy diagram. In

this diagram, the energy of the fragments is plotted as a function of their
distance apart. The exact shape of the curve depends on the target nucleus. At
the extreme left of the diagram, the fission fragments are supposed to be
brought together (i.e,) the point at the left of diagram represents the energy
of the target nucleus and an incident neutron. At the extreme right the fission
fragments are at a considerably distance apart and their interaction is zero.
This diagram is similar to the activation energy diagram. The top of the
barrier corresponds to the state of critical deformation of the nucleus. If
fission is to occur then the target nucleus plus neutron (i.e,) the compound
nucleus, must acquire sufficient energy to reach the top of the barrier. By
using neutrons of 1 MeV energy, the energy of the system is increased so that
it now lies above the barrier and fission takes place.
The critical energy depends on the quantity Z2 /A for the given nuclide.
T h e l a rge the value of Z2 /A, more closely will the energy of the compound
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nucleus, approach that of the critical deformation energy. Calculations

indicate the U- 235 could be fissioned by slow neutrons. Whereas fast
neutrons are required for fission reaction when U - 238 is used U- 233 and Pu-
239 would also undergo fission by means of thermal neutrons. Their critical
deformation energies are about 5.1MeV and 4.8MeV for U- 233 and Pu- 239
respectively. In the case of Th- 2 32 , P a - 231 and Np-237, critical deformation
energies are about 6.0 to 6.6 MeV. In these three cases neutrons of about 1.1
MeV energy must be absorbed to produce critical deformation leading to
fission. Thus U-2 3 5 , U -233 and Pu-239, which contain even numbers of
protons and odd number of neutrons, are called fissile nuclides. Np.237, with
an odd number of protons and an even number of neutrons, and Th- 2 3 2 a n d
U- 238 which are of the even- even type are fissionable species requiring fast
neutrons to induce fission.
NUCLEAR POWER PRODUCTION
A large amount of energy is released in a fission reaction which is a chain

reaction induced by neutron. Hence power can be produced by means of a
nuclear reactor. It can be shown that 1gm atom of U-235 (235grams) by
means of a fission reaction, would produce 1.93 x 101 3 w a t t - sec energy. It
follows that the complete fission of 1 gram releases 8.2 x 101 7 ergs. It is
equivalent to 8.2 x 1010 watt- sec or 8.2 x 107 kilo watt- sec. This is equivalent
to 2.3 x 104 (Kw- h) or 2.3 x 104 / 2 4 = 0.96 x 103 kilo watt days.
T h e ( h e at ) power production corresponding to the fission of 1gm of uanium

or plutonium/day would thus be 0.96 x 103 kilo watts, roughly 1000 kilo
watts or 1 mega watt. The same amount of power can be obtained only by the
combustion of about 3 tons of coal or about 600 gallons of fuel oil per day.
The total number of nuclei 'A' undergoing fission per second in the reactor is
given by the expression.
A=nvNs V
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Where 'n' is the average neutron density, ie the number per cc, U is the
average speed, so that, 'nv' is the average neutron flux; 'N' is the number of
fissile nuclei (U- 235) per cc, s square cm is the cross section for fission, a n d
'V' cc is the volume of the reactor. 3.1 x 101 0 fission per cc produce 1 watt of
power, hence the power 'P' of a nuclear reactor in watts is obtained upon
dividing the fission rate 'A', by 3.1 x 101 0 (ie)
nu Ns V
P= Watts
…. (1)
3.1 x 101 0
The product 'NV' is equal to the total number of fissile nuclei in the
reactor and this is related to the mass 'm' grams by
235 x N x V
m= where 235 is
the atomic
6.02 x 102 3
weight of U- 235. The fission cross section s of U-235, for thermal neutrons is 577
barns (ie) 577 x 10- 2 4 c m 2 and upon inserting these values in equation (1), we
have ,
P= 4.8 x 10- 1 1 mn υ
This equation shows that the power output of a given reactor,

containing a definite amount of fissile material, is proportional to the neutron
flux- nv. Therefore reactor power is generally determined by measuring the
appropriate neutron flux, by means of a suitably calibrated instrument. In the
reactor the chain reaction has to be controlled. Controls are necessary to
prevent the chain reaction from becoming too violent. Once the desired
energy level is reached, control rods of Cd, boron steel or other material with
a l a r g e capture cross section for slow neutrons are used. These rods are
inserted in the reactor to such a depth as will permit them to absorb all
excess neutrons. In other words, when the reactor has reached a
predetermined power level, the control rods serve to keep the effective
multiplication factor to unity. If it is required to increase the power, the
181
controls are partially removed, the multiplication factor then exceeds unity
and then neutron flux increases.
When this attains the desired value the controls are inserted to the
extent necessary to keep the flux (or power level) constant.
When the shutting down the reactor, the control rods are inserted to a
considerable depth, the rods then capture so many neutrons than the effective
multiplication factor becomes less than unity. Then neutron flus thus
decreases and the nuclear chain reaction then is no longer maintained. A
reactor consists of an active core in which the fission chain is maintained and
in which most of the energy of fission is released, as heat. The core contains
the fissile material in a suitable form i.e the reactor fuel, and also a
moderator if it is required to slow down the neutrons. The relative amounts of
and nature of the fuel and moderator determine the energy of the neutrons
causing most of the fission. The core is surrounded by a reflector of a
material which is largely dependent on this neutron energy. The combination
of core and reflector, to gether with other components present, e.g, coolant
and structure must be capable of maintaining a fission chain.
The operation of the reactor at appreciable power levels depends on the

ability to remove the heat produced by fission as fast as it is liberated. This
involves the use of a coolant, which must circulate through the reactor core
in such a manner as to maintain a temperature distribution that is as uniform
as possible. If the energy generated in the reactor is to be converted into
electrical power, then the heat must be transferred to a working fluid to
produce steam or hot gas. The resulting vapour or gas can be used to generate
power in a conventional manner, for example by means of a turbine.
Reactors are classified as "thermal", "Fast" or intermediate "according to the

neutron energy region in which the majority of the nuclear fissions occur. In
thermal reactors most fissions are due to the absorption of slow neutrons. In
order to slow down the fast neutrons released in fission a sufficient amount
of moderator must be included, in the core of the reactor.
182
Thermal reactors have the great advantage of flexibility in size. The size can
be attained by Varying the nature and properties of the fuel and the
moderator size. For example a reactor with natural uranium as fuel and
graphite as moderator, is roughly 20 feet across at least with a fuel material
highly enriched in U-235 and ordinary water as moderator, a thermal reactor
may have linear dimensions of not more than one or two feet. An important
draw back to thermal reactors is the loss of neutrons due to parasit ic c aptur e
by constructional and other materials as well as by fission products.
In a fast reactor, the majority of fissions occur by interaction of fissile

material with neutrons of high energy. The use of a moderator or of any
material of low mass number, which might slow down the neutrons, must
consequently be avoided as for as possible. Parasitic capture of neutrons is a
relatively minor problem in a fast reactor. On the other hand there is some
limitation in the choice of fuel materials. A fast reactor requires an enriched
fuel containing about 20 to 25% of fissile material, e.g, U-2 35, U- 233 or PU-
239. A disadvantage of a fast reactor is the larger mass of fissile material
necessary to attain criticality. Because there is no moderator, the critica l si z e
may be quite small e.g, a foot or less across, and then the heat removal is
difficult when the operating power is high. The outstanding as pect of certain
fast reactors is their ability to breed fissile material, Plutonium– 239, in
p a r t i c u l a r . I t is mainly for his reason that such reactors are alternating
interest.
An intermediate reactor is one in which fissions are caused mainly by

neutrons slowed down into a broad energy range between fast and thermal
energies. Some moderation is necessary, but not as much as in a thermal
reactor. In a sense an intermediate reactor is compromise between thermal
and fast reactors. Parasitic capture of neutrons can be less than in a thermal
reactor. An intermediate reactor also offers the possibility of breedingP υ-
239.
U- 233 is fissionable by slow neutrons and it is obtained from Th- 232

by means of neutrons available in a reactor.
183
232 233 b 233

233
Th+n Th Pa
U
90 90 23.5m 91 27.4d 92
16.2.2 FISSILE AND FERTILE NUCLIDES
U- 235 will undergo fission by neutrons of any energy, from almost

zero upward, but U-238, requires neutrons of al least 1 MeV to induce
fission. U-233 and Pυ – 239 are like U-235 in the respect that neutrons of any
energy can induce fission, such species are known as fissile nuclides. On the
other hand, U- 2 3 8 , T h - 232 and certain other species, which have a fission
threshhold at about 1 MeV are said to be fissionable nuclides. In general
fissile nuclides have either an even number of protons and an odd number of
neutrons or odd numbers of both. Of the fissionable nuclides, only the even-
even species U- 238 and Th-232 are of practical interest, because they can be
converted into fissile nuclides by reaction with neutrons. Both U- 238 and Th-
232 will undergo fission by fast neutrons with energy greater than 1 MeV,
but it is not possible to sustain a chain reaction in these isotopes. Since both
U- 238 and Th- 232 can be converted into fissile species, however, they are
referred to as 'fertile materails'.
One of the remarkable aspects of nuclear reactors is that they can be

designed so as to produce their own fuel, by conversion of fertile to fissile
material. Such reactors are called regenerative reactors or convertors.
Plutonium production reactors fall in this category. In these reactors U- 235
serves to maintain the fission chain, but some of the neutrons are captured by
the fertile U- 238 with the ultimate formation of plutonium- 2 3 9 . A
regenerative reactor can produce useful energy while converting fertile
material into new fissile material, to replace that consumed. Consider a
reactor with U- 233 as the fissile material. For every one of these nuclei
undergoing fission, more than on would be produced by the capture of
neutrons in Th.232. Such reactors are called breeders and the regeneration
process is known as breeding. By the use of breeding, the stock pile of fissile
184
material could be steadily increased. Thus not only would all the fertile
material be converted into fissile material, but the amount of the latter
available, and hence the rate of power production could be steadily increased.
This would not go on indefinitely, because a time would be reached in the ultimate
future when all the fertile material was consumed.
16.2.3 FUSION STELLER ENERGY
The energy obtained by the fusion of light nuclei would be more practical
than the energy that would be obtained by the fission of heavy nuclei. The
liberation of energy in fission is due-essentially to the binding energy per
nucleon being less in the heavy elements, than it is in those of intermediate
mass number formed in fission. In the case of fusion, the combination of two
more of the lightest nuclei should result in the liberation of energy.
Many reactions between nuclei of low mass number can be brought about by
accelerating one or other of the nuclei, in a suitable manner. These are often
fusion processes accompanied by release of energy. To have practical value,
fusion reactions must occur in such a manner as to make them self sustaining,
that is more energy must be released than is consumed in initiating the
reaction.
S o m e i n d i c a t i on of how this might be achieved can be obtained by

considering the source of the enormous amounts of energy produced
continuously in the stars. A.S. Eddington suggested that the energy of the sun
resulted from the mutual annihilation of positive and negati v e c h a r g e s .
Eddington proposed that stellar energy was liberated in the formation of
helium from hydrogen.
Energy might be liberated in th stars as a result of nuclear fusion reactions

occurring at the very high stellar temperatures, from 15 to 30 millio ns,
degrees Kelvin. Such processes are called thermonuclear reactions and these
185
reactions can occur at rates sufficient to account for the release of large
amounts of stellar energy.
In order for two nuclei to interacts, they must have enough kinetic ene r g y t o
over come the electrostatic repulsion barrier which tends to keep them apart.
Simple calculations indicate that for the nuclei of the lowest atomic number
e.g., the isotopes of hydrogen the energy required to make the nuclear
reactions occur at a detectable rate is about 0.1 MeV. But the temperature
would have to be as high as 1000 million degrees Kelvin, if the average
energy of the particles is to be 0.1MeV. Such temperatures are considerably
higher than those existing in stars. At any given temperature, there is a
Maxwellian distribution of energies among the molecules of a gas. At
temperatures of millions of degrees a gas does not consists of molecules, but
rather of a completely ionized system called a 'Plasma'. A plasma contains
e qua l qua nt it ies of positively charged nuclei (ions) and negative electrons.
The concept of distribution of energies should be applied. Therefore there
will always be a certain proportion of nuclei, which have energies greatly
exceeding the average. Thus at a temperature of 20million degrees, for
example, where the average kinetic energy is only 0.002 MeV, there are an
appreciable number of nuclei with energies of 0.1MeV or more. These have
sufficient energy to permit them to take part in thermonuclear fusion
re act ions, resulting in the release of energy.
Most of the thermonuclear reactions are due to nuclei with energies in excess
of the average H.H. Bethe suggested the following to explain nuclear
reactions at high temperatures. Two sets of nuclear reactions have been found
to account for the energies of what are called "Main Sequence" stars. The
first is known as the 'Carbon Cycle', in which the carbon acts as a sort of
catalyst in facilitating the combinations of four protons to form a Helium
nucleus. The second is known as the proton – proton chain, since the first
step involves the combination of two protons. Other nuclear reactions
accompanied by the release of energy undoubtedly occur in older (holter)
stars.
186
In the carbon cycle (Bethe's) a proton interacts with a C - 12 nucleus, with a

release of fusion energy.
12 1 13 13
C + H N ene r gy. N
is radioactive and has a
6 1 7 7
half life of 10.1min; hence it decays as:
13 13 O
N C + e (Positron)
7 6 +1
1
13
The Stable C nucleus reacts with another H, releasing more energy.
1
13 1 14
+ H N + energy.
6 1 7
1
14
N combines with another H to yield energy
1
14 1 15
N + H O + energy.
7 1 8
15
O is a position emitter with a half life of 2.05min
8
15 15 O
O N + e and finally the 1 5 N int eracts
8 7 +1
with the fourth proton
15 1 12 4
N + H C + He. When we add all the
7 1 6 2
above equations, we have
1 4 O
4 H He + 2 e + energy
1 2 +1
187
The net result in thus the conversion of four hydrogen atoms into a
helium atom, plus energy amounting to a total of about 26.7MeV.
In the Proton – Proton chain, two protons fuse to produce a deuterium

nucleus and a positron:
1 1 2 O
H + H D + e + energy
1 1 1 +1
2 1 3
D + H He + energy
1 1 2
3 3 4 1
He + He He + 2 H + energy
2 2 2 1
The energy released is the same as in carbon- cycle, namely 26.7 MeV
for each helium nucleus. at low temperatures (Stellar), the proton- proton
chain predominates, but as the temperature is raised, the carbon cycl e r a pi dl y
becomes of increasing significance. Thus in hotter stars (larger), all the
energy comes from the carbon cycle but in the smaller (cooler) stars, the
proton- proton chain is the main source of energy.
Self Check Exercise-1
1. Discuss the theory of nuclear fission

2.a) Show that 1 amu = 931 MeV
b) Calculate the energy released in the fission reaction.
235 1 95 139 0
1
U+ n Mo + La + 7
b + 2 n
92 0 42 57 -1
o
188
Se l f Check E xercise – 2
1. Discuss the different types of nuclear reactors

2. Write a note on fissile and fertile nuclides
3.a) Discuss the fusion reaction by using Bethe's carbon cycle and proton –
proton chain.
b) Explain how power production is feasible using fusion reactions?
16.3 Let us Sum Up

Fission theory is discussed in detail. Fusion reactions in stars are
explained. Bethe’s carbon cycle is illustrated. Nuclear power
production is discussed. The feasibility of power production using
fusion reaction is indicated.
i) Theories of fission
ii) Fusion reactions in stars
iii) The feasibility of power production from fusion reactions.
16.5 Ref erences
1) Source book on atomic energy – Glass tone – East, West, New Delhi.
2) Theory and problems of physical chemistry- Schaum's Outline Series –
McGraw – Hill New Delhi.
189
LESSON – 1 7
CONTENTS

17.1 INTRODUCTION
17.2 SYNTHETIC ELEMENTS
17.2.1 THE TRANSURANIUM ELEMENTS
17.3 LET US SUM UP
17.5 REFERENCES
The aim of this lesson is to study the synthesis of elements by artificial

means. After going, through this lesson you would be able to learn the
methods by which several transuranium elements have been obtained.
17.1 INTRODUCTION
In view of the existence of the lanthanide series, there has been much
speculation concerning the possibility of the occurrence of an analogous
'actinide series', beginning with the element actinium, atomic number 89. The
four elements of this possible series, whose properties were genera l l y kn o w n
at the time, namely actinium, thorium, protactinium and uranium are placed
in groups IIIA, IVA, VA and VIA. Prior to 1945, most chemists would have
doubted the existence of an actinide series. A study of the chemical
properties of the new "artificial" elements, Np(93), Pu(94), Am(95), Cm(96),
Bk(97), Cf(98), Es(99), Fm(100), and Md (101), has shown clearly that these
elements have properties, which would make them members of a series
similar to the lanthanide series. The nearly studies of the transuranium
elements led to the development of the remarkable techniques of quantitative
ultramicro chemistry, this made possible experiments with fractions of a
190
cubic centimeter of solutions containing a few millionths of a grain of

dissolved substance.
17.2 SYNTHE TIC ELEM ENTS

Neptuni um (93)
A thin layer of uranium oxide was exposed to slow neutrons. A non

recoiling beta emitting product (t ½ = 23min) was obtained. This was shown
to be U- 239. This U-239 decayed emitting b r a y s to give, Np (93) (t ½ =2.3
days)
238 1 239
U + n U +¡
92 0 92
239 239 O
U Np + e (b - decay)
92 93 -1
This new synthetic element does not precipitate with H2 S in acid solution; it is not
reduced to the metallic state by Zn. In a reducing SO2 solution, Np would be
precipited with Ce (III) as fluoride ie, NpF3 or NpF4. The neptunium activity
could be separated with sodium uranyl (VI) acetate. Np resembles U; both
exist in III, IV, V and VI oxidation states. NpO2 and NpF4 are more stable.
Another isotope of Np, Np- 238 (t ½ =2.1 days) was obtained by

Seaborg:
238 2 238 1
U+ D Np +2 n; Np – 2 3 8
is b active.
92 1 93 0
Eight Np isotopes with mass numbers ranging from 231 through 241 have
been obtained by the bombardment of either one or other of the isotopes of
Uranium by deutrons or alpha particles. Tracer techniques are used to
191
identity the synthetic elements like the transuranium, elements. In this

technique an inactive carrier is used to follow the behaviour of a radio active
element present in tracer amounts. Provided the material has a reasonably
strong activity, it is possible to, trace quantitites as small as 10- 1 0 gm or less.
For example if an appreciable quantity of 'Th' is added as carrier to a
solution containing a tracer amount of Np, in the reduced state in aqueous
hydrofluoric acid, it will be found that the Thorium fluoride (ThF4)
precipitated contains essentially those of the neptunium activity. From this it
followed that Np forms an insoluble fluoride namely NpF4. Using ultramicro
chemical techniques extremely small amounts (from 1mg to 0.02mg)of
synthetic elements are analysed. Quantitatively Np has oxidation states III,
IV and VI in solutions.
Pu : Plutonium – 238 named after Pluto is an alpha emitter and is formed from Np-
238:
238 238 O
Np Pu + e
93 94 -1
Tracer techniques showed that plutonium like neptunium is precipitated as

fluoride or iodate with a rare earth element or thorium as a carrier.
Pu- 239 is an important fissile material. It is formed from Np- 239.
239 239 O
Np Pu + e ; Pu- 239 is an alpha emitter with a half
93 94 -1
lifeof 24, 360years. Several isotopes of Pu have been obtained by nuclear reactions.
232 Pu : 235 U (µ , 7n)

234 Pu : 233 U (µ , 3n)
237 Pu : 235 U (µ , 2n)
241 Pu : 238 U (µ , n)
192
Pu has four oxidation states, III, IV,V and VI. Like Np Pu resembles
Uranium in many of its chemical properties. The IV state of Pu is more stable
than VI state. The stable oxide of Pu in PuO2 .
PuO 2 PuO 3 . P u F 4 , Pu (IO 3 ) 4 and Pu(0H)4 are insoluble like those of

1500o C
thorium.
Plutonium metal (used as a reactor fuel) is made by heating the PuF4 with calcium
in a closed vessel:
Pu F 4 + 2 Ca Pu + 2Ca
F2 .
Am: Americium: Third transuranic element obtained as follows: U- 2 3 8 i s

bombarded with 40-M e V 'µ ' particle to get Pu- 241.
238 4 241 1
U+ He Pu + n
92 2 94 0
241 241 O
Pu Am + e ; 241 Am is also obtained by
94 95 -1
(µ ,2n) reaction with Pu- 239. Am has the stable III state. Am is
separated from the rare earth carriers by Ion- exchange methods. Am x 3
(x=Cl, Br,I) are known.
Ba(Vapour)
AmF3 Am- silvery white metal – m . p t
o
1000 C
134o'c
cm: curium obtained by bombarding Pu- 239 using cyclotron with µ - part icle.
193
239 4 242 1 242

Pu + He Cm + n; cm has
t ½ = 162.5days
94 2 96 0 96
It was also obtained from metastable Am- 242
242 242 0
Am Cm + e+¡ . From this reaction cm was obtained
95 96 -1
as cm 2 O 3 . 13 isotopes of Cm (from 238 to 250) are known.
Bk and Cf: Berkelium (is analogus to terbium)
241 4 243 1
Am + He Bk +2 n
Bkwas seperated
95 2 97 0
from Am by ion exchange methods. Bk exists predominantly in the (III) state. eight
isotopes (mass numbers 243 through 250) are known t ½ of Bk is 4.5hrs.
Californium (Cf) is obtained by the action of 35MeV alpha particle on cm- 242 . T h e
reaction is (µ ,n)
242 4 245 1
Cm + He Cf +2 n; Cf- 245
has t½ 44 min
96 2 98 0
Cf exists only in the (III) oxidation state. Es(Einsteinium) and fermium (Fm): Es-
247 is obtained by the reaction:238U (14N, 5n) 247 Es. It has 11 isotopes
from 245 to 256. Es-254 (t ½ =270days) is obtained in weighable amounts.
Fm- 248 is obtained using.
240 Pu (12C,4n) reaction

240 12 248 1
Pu + C Fm +4 n
94 6 100 0
238 16 249 1
U+ O Fm +5 n
92 6 100 0
194
238 16 250 1
U+ O Fm +4 n
92 8 100 0
Mendelevium (Md): atomic no 101. A very small amount of Es253 is

bombared with 48MeV alpha particles. The product nuclei were collected by
recoil on a gold foil, so that they were free from Es. The gold foil was
dissolved and the new element isolated by the ion- e xc han ge method.
Md-256has a t ½ of 1.5hrs
253 4 255 1
Es + He Md +2 n
99 2 101 0
No: Nobelium (102): produced by the bombardment of cm- 246 with C- 12 ions using
the heavy ionaccelerator
246 12 254 1
Cm + C No +4 n
96 6 102 0
Obtained also by:

238
U ( 2 2 Nc,6n) 254
No ; 2 4 3 Am ( 1 5 N, 4n ) 254
No
102 102
No- 252 produced from Cm has t ½ of 2.5sec.
LW: Lawrencium (103): The method used to obtain the new element was to
bombard a mixture of californium, with mass numbers 249, 250, 251 and 252,
with a beam of B- 10 and B- 11 ions from the heavy ion accelarator . Lw was
found to be an alpha particle emitter. By counting the alpha particles, its t ½
was found to be about 8 sec.
Element 104 (Kurchatovium):
242 22 260 1
Pu + Ne 104 + 4 n – b y
bombarding Pu- 242
94 10 104 0
195
us i n g N e - 22 ions, t ½ was given as 0.3sec. The chloride of the new element was
reported to be more volatile than the chlorides of other transuranium
elements.
Self Check Exercise – I
1) Discuss the synthesis of transuranium elements

2) Compare the properties of transuranium elements with those of rare
earths.
17.3 Let us Sum Up

The synthesis of transuranium elements is explained in detail. Several
nulear reactions are illustrated. The synthesis of Pu-239 (an important
fissile material) is indicated. The exidation states of tr ansuranium
elements are also explained.
i) Discussion of several nuclear reactions

ii) Discoveries of transuranium elements and their seperation.
17.5 Ref erences
2) Theory and problems of physical chemistry- Schaum's Outline Series –
196
LESSON – 1 8
CONTENTS

18.1 INTRODUCTI0ON
18.2 HOT ATOM CHEMISTRY AND RADIO ISOTOPES
18.2.1 HOT ATOM CHEMISTRY
18.2.2 APPLICATIONS OF RADIO ISOTOPES
18.3 LET US SUM UP
18.5 REFERENCES
After going through this lesson you would be able to understand the simple
principle of hot atom chemistry and you would be able to learn about and use
in future, the radio isotopes.
18.1 INTRODUCTION
Several isotopes both radioactive and inactive have been employed to

investigate various chemical processes. The isotopic method represents a
powe rful tool for the solution of numerous problems in biology, physiology,
chemistry, physics and other sciences. Some of these problems, particularly
those having an important bearing on life processes, could not have been
solved without the use of isotopes.
It is only in recent years that isotopes have become available in such variety
and in such quantity as to make their use as wide spread as it is at present
time.
197
The more important applications of isotopes depend on the fact that the
chemical properties of isotopes of a given element are essentially identical. A
radioisotope can be detected by its radioactivity, and an inactive isaotope of
particular mass can be identified by means of the spectrometer. Therefore,
the characteristics property of the isotope namely, its activity or mass can act
as a 'tag' or 'label'. The element which has been tagged or labeled is
consequently called a tracer element.
In general an element can be labeled by changing its natural isotopic

composition. For example ordinary 'C' contains 1.1% of C- 13, but if the
proportion of this isotope in a particular compound is increased, the carbon
has become labeled.
Suppose that acetic acid, in which only the CH3 carbon is labeled, is supplied
to an organism then among the metabolic products, appears CO2 gas. Upon
testing the gas it is found to be inactive, This shows that the carbon in the
'CO 2 ' originated from the – COOH group and not from the CH3 - group.
This example is a simple illustration of the type a problem for which an

unequivalent solution could not possibly obtained without the use of an
isotopic tracer.
18.2.1 HOT ATOM CHEMISTRY
The name "hot atom chemistry" is given to the study of chemical reactions
resulting from the transfer to valence bonds of energy produced in nuclear
processes of various kinds.
Isomeric transition is sometimes accompanied by the breaking of a chemical

bond.
This many make possible a separation of the isomeric nuclei. An interesting

example is provided by the isomers of tellurium, for (eg) Te-131. If to a
Tellurate solutions (Te (VI), containing this species, is added some ordinary
198
inactive tellurite (Te(IV), then upon separating the latter chemically, it is

found to contain the 25- minutes isomer. This is explained as follows: the
gamma ray emitted by the upper (1.2days) isomeric state undergoes internal
conversion, resulting in the ejection of an electron from a K or L level of t h e
product atom, that is from the lower (25min) isomeric state. As a result of
what is known as the "Auger effect', the high energy of this inner (KorL)
electron is transferred to one or more of the outer electrons (Valence
electrons), which are consequently removed from the atom. This detachment
of valence electrons from the 25- min isomer results in the breaking of some
of the bonds between the tellurium and oxygen atoms, consequently the
isomeric transition is accompanied by a change from the VI to the I V
oxidation state i.e., from tellurate to tellurite.
L.Szilard and T.Chalmers employed, this type of hot atom chemistru, to

separate the product of an (n,¡ ) reaction from the targot material. The
emission of a ¡ -ray photon following the capture of a neutron causes the
residual nucleus to recoil; the recoil energy is sufficient to break the
chemical bond attaching this particular atom to the remainder of the
molecule. The product atom, although isotopic with the target atom, will thus
be in a different chemical form, and a seperation from the oroginal material
becomes possible. for example, if an aqueous solution of NaclO3 is subjected
to the action of slow neutrons, the reaction 3 7 cl(n,¡ ) 3 8 cl takes place, but
many of the cl- 38 atoms formed are detached from the chlorate and pass into
solution as cl(- ) ions. By adding a small amount of in active chloride to the
solution and precipitating with silver nitrate, the resulting Agcl is found to
carry the whole of the cl- 38 act ivit y.
18.2.2 APPLICATIONS OF RADIO ISOTOPES
In much of the work in which an isotope is used as a tracer it is necessary to

introduce the tracer element into a certain compound to be studied. In
biochemical investigations the object of the study is to determine the fate of
the different portions of a given compound. The preparation of labeled
199
compounds has become an important aspect of tracer studies. For example

consider the synthesis of C- 1 4 l a b e l e d acetic acid (CH3 – group is to be
labeled) BaCO3 containing C- 14 is employed. The sequence of reactions can
be represented as:
H P
NaCN
BaC * O 3 C* O 2 C* H3 OH C* H3 I
C * H3 CN
(H+) Catalyst I2
H2 O
* *
CH 3 CN CH 3 COOH
To L abel – COOH, carbon, consider the reaction:
CH 3 Mg Br + * CO 2 CH 3 * COOH
TRACER APPLICATIONS:
The use of isotopic tracers in biological studies is to obtain information that

w i l l m a k e possible a better understanding of many complex processes which
take place in living organisms.
Linseed Oil, which contains fats derived from doubly and triply unsaturated
acids, was partially "hydrogenated" by means of deuterium as as to give a
mixture of both saturated and unsaturated fats, in which two or four of the
hydrogen atoms attached to the carbon were replaced by deuterium. The
resulting deutero fats were fed to animals. The analysis showed that the
major part of the deuterium was found to have been deposited in the fatty
portion of the body. Further studies indicated that the saturated fats are
desaturated by the removal of deuterium and at the same time the unsaturated
fats are saturated by the addition of hydrogen (or deuterium) from water.
Deuterium studies indicate tat only singly unsaturated fats could take part in
the equilibrium. Such deuterium studies in animals indicate that the highly
unsaturated fats are indispensible in the sense that they must be supplied in
the diet, the body being unable to synthesis them. By lebeling various dietary
200
amino acids with both isotopic nitrogen and deuterium it has been shown
that the formation of creatine in the body requires contributions from three
amino acids, namely glycine, arginine and methionine. The creatine is
produced in this manner and is converted into creatine at a fairly steady rate,
Creatine is the an hydride of the amino acid creatine, an important
constituent of animal tissue. An approximately constant amount of creatine is
excreted daily in the urine. Tracer studies using radio active iron as tracer
indicate that iron is stored in the body in the form of an iron- protein
combination known as ferritin. When the store of ferritin has attained its
normal value it does not increase further, no matter how much iron may be
supplied orally. If the iron reserves decrease, then the amount of ferrition
decreases, the body is able to absorb iron.
Radio iron studies that indicate iron remains in the hemoglobin as long
as the red blood- corpuscles are intact. But when the corpuscles are destroyed,
the iron is not lost, it is almost wholly retained in the body and is rapidly
incorporated into the hemoglobin of new red corpuscles. It is this
phenomenon which accounts for the small absorption of iron from the food
under normal conditions.
Radioactive isotopes have become a valuable tool in the diagnosis and

understanding of many diseases. A simple instance is provided by the use of
radio sodium to study cases of restricted circulation of blood. A small
quantity of sodium chloride solution, in which the sodium has been labeled
w i t h N a - 24, is injected into a vein of the patient's fore arm, a gamma ray
counter is then placed in contact with one of the feet. If the blood circulation
is normal, the presence of radioactivity is very soon detected in the foot, it
increases rapidly and reaches a maximum value within less than an hour. If
there is a circulatory impairment of some kind, however, the radioactivity
will increase slowly, showing that blood has difficulty in reaching the foot.
By moving the counter to different parts of the body the position of the
restriction can be located, and the necessary treatment applied.
201
It has been found by introducing iron-59 into the blood of a normal human
being that the iron is deposited in and then removed from the marrow, the
spleen and the liver in a manner that is specific for the particular organ. In
cases of anemia (deficiency of red blood cells) and polycythemia (excess red
cells), the normal behaviour is changed in a manner typical for each disease.
In the case of anemia the activity of iron- 59 increases with time. But in the
case of a normal human being the activity increases and then decreases with
time. In refractory anemia associated with hypoplastic (under developed
marrow), for example, the iron is found preferably in the liver rather than in
the marrow where the re d blood cells are formed.
The tracer experiments have also demonstrated that red cell formation is
controlled by a hormone called erythropoietin, which circulates in the blood
stream. At normal conditions are associated with an excess or deficiency of
this hormone.
V i t a m i n B - 12 (comples organic compound containing cobalt) has been

prepared with the cobalt as a radioactive isotope, either co- 57, - 5 8 o r –6 0 a n d
its rate of absorption and loss from the body has been studied with the whole
body counter. From the results it is possible to distinguish three types of
behavior, normal, second, inability to absorb B- 12 from the intestine and
third pernicious anemia, in which there is a deficiency of the vitamin i n
blood. Whol e- body radiation measurements with labeled B- 12 are being used
in the study of pernicious anemia. The position of tumours have been
identified using radio isotopes. I- 131 has been used to study the functioning
of thyroid gland. Brain tumor is detected using tracers like the positron
emi tt er G a- 58 and the isomer of technetium- 99 in the form of pertechnetate
ion. After injection of the radioactive tracer the location of the brain tumor
can be found by means of a suitable scintillation camera or a multiple
detector scanner.
Co- 60 obtained from the reaction 59Co(n'¡ )6 0 Co, is usedin cancer therapy.
202
Brain tumors are destroyed using an internal source of alpha particles (and
lithium ions).µ - particles are obtained from B- 10 by means of (n, µ )
reaction.
Radio active isotopes have been extensively employed in agricultural

research. The use of P-32, is indicated below. Phosphoric acid containing a
k n o w n p roportion of P- 32, is converted into a phosphate such as calcium
superphosphate, tricalcium phosphate or hydroxyapatite suitable for use as a
fertilizer. A definite quantity of the labeled phosphorous is then applied to
the soil, in which plants are grown. At certain intervals a number of these
plants are harvested and the total phosphorous derived from both soil and
fertilizer, is determined by chemical analysis of their ash. The radioactivity
of the plant ash, combined with the measured specific activity of the
fertilizer, gives the amount of phosphorous which the plant takes up from the
fertilizer.
It has been shown by such studies that (in poor soil conditions) corn requires
most of its phosphorous fertilizer at the beginning and less toward the end of
the growth with potatoes on a similar soil, from 50 to 60% of the
phosphorous uptake came from the fertilizer during the whole period of the
growth.
Radioactive tracers have been employed in several industrial processes.

Wetting, detergency and floation of minerals, adsorption and lubrication are
examples of surface phenomena upon which work has been done with
radioactive tracers. Age hardening, annealing, quenching and cold rolling of
alloys have been subjected to radio tracer studies to understand the effects of
such treatments.
Acti vation Analysis is a powerful tool in many aspects of science and

industry. The basic principle of activation analysis is that one (or more) of
the stable isotopes of a given element is activated "i.e, converted into a
radioactive nuclide, by a suitable nuclear treatment e.g, bombardment with
203
neutrons, with accelerated particles or by high energy X-rays. The product

can then be identified by its radiation, i.e, beta particles, or gamma rays and
by its half life. By using a comparison sample containing a known amount of
the particular element and treating it in exactly the same way as the unknown
specimen, the analysis can be made quantitatively. The most common
application of the techniques is probably in testing highly purifie d subst ances
for traces of impurities. Construction materials and moderators for nuclear
reactors, for example, must be exceptionally free from elements that capture
neutrons to a significant extent. Activation analysis provides a sensitive
means for detecting such impurities. Small amount of oxygen present in the
steel is detected by measuring gamma ray from N-16 produced by the
16
reaction O(n,p) 1 6 N
Tracer Analysis
Tracer analysis involves the addition of a known amount of an isotopic

material (a known amount refers to a known rate of particle emission as
determined by a suitable counter) suppose it is required to analyse a solution
for the element 'A', present in very small amount. Let the element B be one
which forms an insoluble compound AB; a solution of 'B' is prepared with
one of its radio isotopes in known proportion i.e, known specific activity.
The solution 'B' is then added to 'A', to precipitate all of the 'A' as the
insoluble 'AB'. The precipitated AB is separated and counted. From the
observed count rate the total quantity of 'B' in the precipitate can be
calculated, this is equivalent to the amount of 'A' in the precipitate.
Solubilities of a sparingly soluble salts can be determined by tracer method.

A sample of Pb (NO3 ) 2 is prepared containing a known ratio of the alpha
emitting isotope Ra- D. The nitrate is dissolved in water and a solution of
sulphate is added. The solid PbSO4 containing Ra- D as tracer is then used to
prepare a saturated solution in water. This solution is evaporated a n d i t s µ -
activity measured. The total amount of lead in the solution and hence the
204
solubility of lead sulphate can be calculated from the known proportion of

Ra- D.
The dilution principle has been applied to determine the volume of water in
the body. For this purpose either the stable isotope D2 or tritium can be used
as a tracer. A definite volume of water containing one of these isotopes is
injected into the body and after allowing about an hour for uniform mixing to
take place, a sample serum is withdraw and its isotope content is measured.
From the change in concentration, the volume of water in the body can be
calculated. If the isotope concentration is found to be decreased by a factor
of 1000, for example the volume of water in the body is 1000 times that
originally injected.
Age of uranium can be estimated as follows:

Nt = NO e - l t ; N O = U - 238 originally present in the mineral and Nt is the amount left
after the lapse of time 't'. This represents the age of the m ineral. Since
essentially all the U-238 has been converted into Pt- 206, the quantity of Pl-
206 present is equal to:
(N O - Nt) Therefore = (2 3 8 U = 2 3 8 U + 2 0 6 Pl) e l t knowing the amount of U- 238

and Pl - 206 present and knowing l of U-238, 't' the age of the mineral can be
estimated.
By means of radio carbon dating the age of a dead wood or animal can be
estimated.
Several radio nuclides have been employed as heat sources for power
generation in satellites. Pu-238 is the heat source in the 25- walt thermo
electro generator used in some satellites.

205
1) Explain the term 'hot atom chemistry' and discuss its applications.
2) Discuss the uses of radio isotopes in the fields of

i) Biology
ii) Medicine
iii) Agriculture.
3) Discuss tracer analysis
1) A sample of 14 CO2 was to be mixed with ordinary CO2 for a biological

tracer experiment. In order that 10 cm3 of the diluted gas at STP should have
10 4 dpm, how many/mci of radioactive C-14 are needed to prepare 60L of the
diluted gas? (Ans: ~27 mci).
2) In order to determine the volume of the blood in an animal, a 1.00ML of an

aqeous solution containing tritium is injected into the animal's blood serum.
The sample injected has an activity of 1.8 x 106 CPS (Counts/sec). After
sufficient time, 2.00ML of blood are withdrawn from animal and the activity
of the sample of blood is found to be 1.2 x 10 4 CPS. Calculate volume of
animal's blood (Ans: ~ 300ML).
3) A sample of uraninite, was found to contain 0.214g Pl- 206, for every gram of
uranium. If all the lead came from the disintegration of U-238, estimate the
9
age of the mineral (T50 U-238 = 4.5 x 10 yrs)
18.3 Let us Sum Up

Hot atom chemistry is defined. The uses of radio isotopes in the fields of
biology, medicine and agriculture are discussed in detail. Tracer studies are
illustrated.

1) Hot atom chemistry – definition and other examples.
206
2) Several uses of radio isotopes
18.5 Ref erences

2) The o ry a nd problems of physical chemistry- Schaum's Outline Series –
207
UNIT – V I I
LESSON – 1 9
CONTENTS

19.1 INTRODUCTION
19.2 EXPERIMENTAL METHODS FOR DETECTION OF NUCLEAR
RADIATIONS
19.2.1 CLOUD CHAMBER
19.2.2 BUBBLE CHAMBER
19.3 LET US SUM UP
19.5 REFERENCES
The lesson describes the various experimental techniques such as cloud

chamber, bubble chamber for the detection of nuclear radiations, After going
through this lesson you would learn how such instruments like Wilson's cloud
chamber made possible the discovery of particles like positron, muon,
various mesons and other particles.
19.1 INTRODUCTION
Instruments like cloud chamber are useful for the study of artificial
transmutation. A single cloud chamber photograph can demonstrate with
compelling evidence how many fragments are formed in a single
transmutation, process and the directions in which they fly away and how far
they are able to travel through the gas in the chamber.
208
19.2.1 CLOUD CHAMBER
In 1911, Wilson showed that the path of a single ionizing particle

could be made visible. The apparatus is known as cloud chamber. Air
contained in an enclosed space can be saturated with the vapour of water or
any other liquid the amount of the vapour necessary to produce saturation
decreasing as the temperature is lowered. Imagine a vessel containing air
saturated with water vapour enclosed by a piston. The piston is maintained in
position by the pressure of air below it. If the pressure under the piston is
suddenly released, so that it falls, it will result in the immediate expansion of
the air or gas in the vessel. The sudden adiabatic expansion causes the air to
be cooled and it now contains more vapour at this lower temperature. If
particles of dust are present in air, they will act as condensation nuclei, and
the excess of water vapour will separate out as fine droplets of liquid in the
form of a cloud or mist.
The air is saturated with water vaopur and the piston is allowed to
drop to such an extent as will expand the volume of the air by a factor of
1.25 to 1.37 this being the range in which cloud formation can occur. If an
ionizing particle enters the chamber, either immediately before, during or
immediately after the expansion, the ions left in the path will act as
condensat ion nuclei, a close array of fine droplets, ie. a kind of linear cloud,
called a cloud track will thus be formed. By using strong illumination from
the side, the track appears as a white line on the dark back ground. This can
be photographed by means of two cameras at right angles, so that a record
can be attained from which the path of the single ionizing particle in three
dimensions can be studied. Cloud chamber photographs have shown that
alpha particles travel in straight lines.
In the earlier cloud chambers a layer of water or oil was used on the
floor of the chamber as a seal for the piston and this meant that the piston
could be used only in the horizontal position. Wilson constructed a cloud
chamber in which the piston was replaced by a thin rubber diaphragm fixed at
its edge. The diaphragm was maintained in a state of tension by means of
209
compressed air in the back or lower part of the chamber, and when this was
released the gas in the chamber underwent sudden expansion. A cloud
chamber of this type can be used in any desired position. To saturate air in
the Wilson's chamber water was initially used. But ethyl alcohol or propyl
alcohol or a mixture of alcohol and water can be employed to saturate the air
in the chamber. The use of alcohol gives better condensation on positive ions,
than does water alone and in addition, the extent of expansion necessary for
droplet formation is diminished from 1.25 to 1.10 at ordinary pressure. Cloud
chambers containing argon are also employed. The pressures range from
b e l o w a tmospheric to about 200 atm. The higher pressures are desirable for
the study of high energy (or long range) particles which might otherwise pass
right through the chamber without taking part in an event of interest.
For the study of radioactive radiations and for many similar purposes,
relatively simple cloud chambers, with air at ordinary pressure, are quite
adequate. Because of the low penetrating power of alpha particles, the source
of the radiation, must be inside the chamber. But a substance emittin g ' b '
particles can be placed outside and the rays allowed to enter through a
'window'. Gamma rays and x- rays, yield cloud tracks because they liberate
electrons which produce ionization in their paths. These tracks are however
very faint. By making visible the track of an ionizing particle, the range of
the particle and its energy can be calculated.
Eo = 2.12- R 2 / 3 - -- - - - -(1)
Eo = initial energy of the alpha particle in MeV and R is its range in

cms of air .
By counting the drops in the cloud track the specific ionization can be
determined and the nature of the particle identified, it is thus possible to
distinguish between an alpha particle, a proton, a meson and an electron. The
µ particle has the highest specific ionization and gives a short dense track,
210
while an electron, unless it is moving with very high speed, leaves a track
which is diffuse. By determining the radius of curvature of the cloud track in
a magnetic field of known strength, the momentum of the particle can be
estimated. The direction of curvature indicates the sign of the electric charge
of the ionizing particle. The discovery of the position was made in this
manner.
The basic disadvantage of the condensation cloud chamber is that, be

cause of the low density of the gas, the significant phenomenans are not very
frequent.
19.2.2 Bubble Chamber
In 1952 D.A.Glaser at the University of Michigan conceived the idea of

using super heated liquid to display the track of ionizing particles, just as a
cloud chamber uses a super heated vapour. The instrument based on this
concept is called a bubble chamber, be cause the tracks consist of a series of
closely spaced bubbles, analogues to the small droplets of liquid in the cloud
chamber.
Glaser found that when such a super heated liquid was exposed to
nuclear radiation, the resulting ions acted as nuclei for the production of
small bubbles. The bubbles are spaced at something like a hundredth of an
inch apart depending on the specific ionization of the imitating particle, so
that they appear as a fairly continuous track which indicates the path of the
particle. As in the cloud chamber, the tracks can be photographed against a
dark background.
The medium in the first bubble chambers was diethyl either, but liquid
hydrogen, D 2 , He, propane and other liquids have been used successfully. For
studying the interaction of particles with protons, the liquid in the chamber is
hydrogen. Along with liquid H2 , C 3 H 8 is also used, in the chamber.
211
For neutron interactions liquid deuterium is employed in the chamber.

For studying 'g' rays, liquid containing heavy atoms is favoured. Freon type
compounds such as trifluoro bromomethane and liquid xenon have been
employed in the chamber.
The operation of a bubble chamber is similar in many respects to that

of an expansion cloud chamber. The liquid is compressed and the temperature
is raised to well above the normal boiling point at atmosphere pressure. For
(eg) propane has a normal boiling point of - 42 o C. It is compressed to about
21 atmospheres and heated to a temperature of 58o C . T h e pressure is then
decreased suddenly and the liquid becomes super heated. In this condition it
is sensitive to the passage of ionizing particle. Even if no such particles enter
the chamber, boiling with bubble formation would invariably occur within a
short time. Regardless of whether a particle track is formed or not, the liquid
must be recompressed before it is again ready for operation.
The earliest bubble chambers had linear dimensions of only one inch or
two and were made with smooth glass or lined internally with glass. Larger
bubble chambers (upto 14 feet in length) have been designed for tracking
particles of higher and higher energies. Bubble chambers are almost
invariably placed in a magnetic field, of known strength. The momentum of
t h e c ha r ge d particles can then be determined from the radius of curvature of
the bubble track. For particles of high momentum, the curvature is small, and
difficult to measure unless a strong magnetic field is used.
In many studies with high energy particles, it is necessary to analyze a

large number of bubble chamber events and then to plot the data in a suitable
manner to obtain the probability distribution of various events. This
statistical analysis can also be performed by a computer. The results are then
displayed in some convenient graphic manner for use of interpretation.
212
Nuclear Emulsion
In 1909 Miigge (Germany) and S.Kinoshita (Japan) observed that the
blackened regions of a developed photographic plate, resulting from exposure
to alpha particles, appeared to be made up of individual grains. It was later
realized that the positions of the grains were related to the path of the alpha
particles. It was found that ionizing particles, in general record their tracks
in a photographic emulsion, as a series of closely spaced black specks of
silver.
Because of the relatively high density (and stopping power) of the

photographic emulsion, the tracks produced by charged particles are very
short compared with those found in a cloud chamber. These tracks do not
differ greatly from bubble tracks. Due to the development of special nuclear
track emulsions this method is largely employed in tracking charged
particles. They were widely used in cosmic ray studies and led to the
discovery of Pi- a nd K - mesons.
T h e co m p o sition of emulsion had been changed so as to make itmore

suitable for the study of various ionizing particles, such as alpha partiles,
protons, mesons and even electrons. By adding Boron or lithium to the
emulsion neutrons can also be detected. The modern emulsion contain silver
bromide to the extent of 80% or more of the dry weight, this being about ten
times the quantity present in plates or films used for normal photographic
purposes. The silver halide grains are extremely small. The smaller the grain,
the more sensitive is the emulsion to ionizing radiations originally the
emulsions were deposited (roughly one eighth of a centimeter thick) on glass
plates. Now, stripped emulsions are available without backing.
The tracks produced in a photographic emulsions are very short, (eg) a

few thousandth's of an inch for alpha particles from radioactive sources, but
they can be magnified and photographed.
The photograph emulsion resembles the Wilson cloud chamber in the

respect that it can record individual events involving atomic nuclei and other
213
charged particles. Information concerning the particles involved can be

obtained from measurements on the photographic tracks. Tracks caused by
heavy, strongly ionizing particles have numerous thin wavy tracks projecti ng
from their sides. These are called delta rays and are produced by electrons
ejected from the nuclei in the path of the particle. From the number of delta
rays per unit track length, the magnitude of the charge in the particle can be
estimated.
B y t h e use of very strong magnetic fields, the deflection of long (but

not short) tracks in photographic emulsions has been observed. This gives the
sign of the charge, but the large amount of scattering makes the deflected
tracks useless for calculation of momentum. This is a disadvantage of nuclear
emulsion.
1) How is a cloud formed in the cloud chamber?

2) What are the other compounds that can be used in the cloud chamber?
Indicate the advantage.
1) How does a bubble chamber work? Discuss the advantages when

compared to the cloud chamber.
2) Write a note on nuclear emulsion method, in tracking nuclear particles.
19.3 Let us Sum Up

The designs of cloud chamber and applications are explained in detail.
The advantages of bubble chamber and nuclear emulsion techniques are
indicated.
214
i) The designs of the cloud chamber and applications

ii) The advantages of the bubble chamber and nuclear emulsion
techniques.
19.5 Re fer en ce s
1) Source book on Atomic Energy by Glass tone – East West press India.
215
LESSON – 2 0
CONTENTS

20.1 INTRODUCTION
20.2 THE DIFFERENT TYPES OF COUNTERS
20.2.1 Proportional Counters
20.2.2 Scintillation counters
20.3 LET US SUM UP
20.5 REFERENCES
After going through this lesson, you would be able to understand

i) some of the most useful procedures for the detection and
measurement of radiations like Alpha & Beta particles.
ii) the way in which the measurements of radiations are carried out.
20.1. INTRODUCTION
Becquerel found that gases become electrical conductors that is they

are ionised, as the result of exposure to radiations from radioactive
substances. The amount of radioactivity could be measured, by measuring
the extent of ionisation by a radioactive source.
A rapidly moving charged particle like alpha or beta particle has the
ability to eject – orbital electrons from the atoms or molecules of a gas
through which it passes, thus converting them into positive ions. The ejected
electrons attach themselves to other atoms or molecules, to form negative
ions. Thus the passage of a charged particle, through a gas results in the
formation of Ion-pairs consisting mainly of positive ions and free electrons.
A term 'Specific ionisation' is used to express the intensity of ionisation
216
produced by a charged particle in its path. It is the number of ion- pairs

formed per cm of path. For particles of same mass and energy, the specific
ionisation increases with the magnitude of the charge, and for particles of the
same energy and charge it increases with the mass.
The total number of ion- pairs produced by a charged particle is

determined largely by the energy.
20.2.1 PROPORTIONAL COUNTERS :
One has to understand the behaviour of ion- pairs in electric fields.

Quantitative measurements of radiations are based on counting of individual
particles, as well as on the determination of total radiation received in a
given interval of time. For these purposes instruments have been developed
in which the positive and negative ions formed by the ionising radiations are
driven towards the collecting electrodes, by means of an applied potential
under various conditions.
Consider for example an apparatus consisting of a vessel, containing

gas or air, in which two electrodes, connected to a battery are fixed. The
circuit also contains a current measuring instrument. Normally the air in the
vessel does not conduct electricity and hence no current is observed. If any
ionising radiation such as alpha or beta particle enters the vessel and when a
small electric potential is applied to the electrodes, the ion- p ai r s p r od u c e d
and the applied potential would produce a pulse of current. The magnitude of
the charge collected and therefore the size of the current pulse will depend on
two factors viz.
i) the number of ion-pairs produced between the electrodes and
ii) the applied voltage.

217
When logarithm of pulse size is plotted against applied voltage a

number of regions could be obtained. A few these regions have been
employed to measure the radiations.
The proportional counter is based on the fact that, for a given applied
voltage across the electrodes, the size of the current pulse is proportional to
the number of Ion- pairs produced between the electrodes. This condition is
best obtained by using a cylindrical chamber, which acts as the negative
electrode, with a central wire, is the positive electrode.
When the voltage is high enough, the electric field near the central
wire becomes so large that the electrons, produced by the primary ionization
of the gas, by an alpha or beta particle, would move toward it with very high
speed. When the speed becomes very high the electrons would cause the
ionization of the other atoms or molecules in the gas, this produces more
electrons which cause further ionization. This multiplication effect is often
known as 'Townsend avalanche or Townsend Cascade.
The total number o f i o n - pairs produced by a single primary ion- p a i r i s

called the gas amplification factor. The size of the current produced by a
single particle is thus increased to a very great extent, so that considerably
less external amplification is required. Pulse counting is employed in a
proportional counter.
In the proportional counter the magnitude of the potential ranges from

500 to 800 volts. Various gases have been employed for filling proportional
counter tubes. A mixture is used consisting of a simple gas such as hydrogen
or Argon, which favours high amplification and a gas like carbon dioxide,
methane or pentane, to provide stability of operation For (eg) a typical gas
mixture consists of methane and 10 to 20% by volume of argon.
The total pressure is always less than 1 atm. Because of the

proportional character of the amplification, an alpha particle will give a
larger pulse than a Beta particle or a gamma ray photom. Hence proportional
218
counting instruments are particularly useful for counting alpha parti c l e s i n

the presence of beta particles and gamma rays.
Geiger – Muller Counter
This counter is widely used in radioactive counting. It is known as G-

M counter. Because the detecting portion is commonly in the form of a tube,
the names Geiger - Muller tube or G-M tube are commonly used.
The essential difference between the proportional and the GM counter

is that, in the proportional counter an electron from an ion-pair, produces an
avalanche at one point only, whereas in the G.M. Counter, the avalanche
spreads along the whole length of the central wire. In the Geiger counter, the
amplification is so great that the size of the pulse is almost independent of
the number of Ion- pairs. When the applied potential in the instrument reaches
a value known as 'Geiger threshold potential', the number of pulses per
minutes ( due to the production of ion- pairs by the entering alpha or beta
particles), becomes essentially constant. The range of potential over which
this occurs is known as 'Geiger – plateau'. Beyond this plateau, continuous
discharge occurs and counting is not possible. Most G.M counters are filled
with gas at pressure below atmospheric pressure, when the plateau may
extend over a range of two or three hundred volts in the region from about
800 to 1500 volts. The trouble with GM counter is that, the separate pulses
produced by different particles entering the Geiger tube are not resolved. To
improve the resolving power of the G.M counter a mixture of gases like argon
and methane is used for filling the Geiger tube. This quenches the discharge
(self quenching) and resolution is improved.
When properly quenched (internally or externally) a G.M counter will

have a resolving time of about 200 micro second, in other words, particles
arriving at intervals of not less than 2 x 10- 4 seconds will give separate
pulses. If the particles were produced at a uniform rate, a maximum of 5000
pulses could be counted per second. Actually the practical counting rate is
less- than this maximum.
219
The GM tube is almost invariably used to determine the rate at which

radiation is being received at a particular point. For this purpose the output
of the GM tube, generally without amplification is applied to a counting rate
meter.
Because of their versatility GM tubes have been made in great variety

of sizes and shapes from 1 cm to 1 m in length and from 0.3 cm to 10 cm in
diameter. The walls can be of metal, e.g., copper, or a metal cylinder may be
supported inside a glass tube. In another form of GM tube the interior
surface of the glass tube is coated with a thin layer of an electrical conductor
like silver or graphite. The central wire of the GM tube (which acts like
anode) is usually made of tungsten, with a thickness of 0.02 to 0.05 mm the
pressure in the GM tube is usually less than atmospheric pressure.
G- M counters are mainly used for counting beta and gamma rays,
partly became it is difficult to make tubes with windows thin enough to be
penetrable by alpha particles. When the penetrating power of the beta
radiation is small, the tube may have a very thin glass or mica window
through which the particles can pass.
In health protection operation, it is required to know that radioactive

material is present and to know a rough indication of the quantity of
radiation. For this purpose the GM counter with a rate meter is very
convenient. GM tubes are rarely designed to detect alpha particles, because
of their short range in air and small penetrating power.
For the detection and rough measurement of the intensity of a l p h a

particles, some form of proportional counter is generally used.
20.2.2. SCINTILLATION COUNTER :

This is one of the oldest methods of counting particles. It is based on
small flashes of light (or scintillations), which are produced when certain
materials are exposed to nuclear radiations. The production of these
220
scintillations, involves the initial formation of high energy (or excited)

electronic state of the molecules (or atoms). The excess energy which has
been obtained from the nuclear radiation, is then emitted within a very short
time as a flash of light. Each particle produces a flash of light.
The first attempt to count alpha particles by observing the

scintillations they generated in a diamond was made by E- Regen e r i n
Germany in 1908. Ruther Ford and Geiger, at the same time compared the
number of pulses, produced by Ra- c source, in an ionization counter and the
number of scintillations produced by the same source, on a ZnS screen and
they found that the numbers were the same. Thus if each alpha particle gives
one pulse in the counter, it also gives one flash in the scintillation counter.
In this manner, Ruther Ford and Geiger established the reliability of

the scintillation method of counting, alpha particles. Certain organic and
inorganic phosphors which produce scintillations when exposed to nuclear
radiations, are transparent to the light they emit. Therefore large quantities
of the scintillator can be used in the counter. This ensures high probability
of interaction with the radiation and high detection efficiency. Thus using a
photo multiplier tube in a scintillation counter along with the phosphor, helps
in the counting of particles from a radio active source. A large clear crystal
o f n a p h t h a l e n e as phosphor was employed with a phototube in the
scintillation counter.
The crystal of the phosphor, surrounded by thin aluminium foil, is

attached to the top, close to the cathode of the phototube. The purpose of the
foil is to reflect the light flashes on to the cathode. A particle of nuclear
radiation (or gamma ray photon) entering the phosphor causes a flash of
light, which falls on the photo cathode. As a result electrons are emitted and
these are subsequently multiplied to produce a relatively large electric pulse
at the output of the tube. Of the solid organic scintillators, anthracene and
transstilbene appear to be the best. Liquid scintillators (solution containing
xylene as the solvent and a few percent of diphenyl oxazole as the solute
have also been employed in scintillation counters. One of the best inorganic
221
scintillators expecially for gamma rays, is crystalline sodium iodide with

0.1%. Thallium as activator. Zns, activated by Ag is an excellent
scientillator and is made in thin layers. Its chief application lies in the study
of alpha particles. Inert gases have also been used as scintillators.
When rapid response is required NaI scintillator cannot be

satisfactorily used. (the light pulse produced has long decay time)
Scintillation counters have found many uses due to the following

reasons :
i) they are simple ii) Flexible and versatile
iii) high sensitivity to all forms of nuclear radiations.
iv) rapid response v) very short resolving time
vi) can be used to measure photon energies
vii) superior to GM counters for gamma ray detection.
Self Check Exercise –1
1. How are ion- pairs produced in an ionization chamber?

2. Discuss the design and uses of proportional counters.
3. Write a note on G.M. counter and also indicate its advantages
Self Check Exercise –2
1. Discuss the design and uses of scintillation counters

2. How many types of phosphors are used in the scintillation counters?
20.3 Let us Sum Up

The designs and advantages of different types of counters are explained
in a detailed manner. The G.M. Counter is explained and its advantage is
indicated. Examples of different types of phosphors used in Slintillation
counter are given.
222
i) The designs and advantages of different types of counters

ii) A comparative study of different types of phosphors employed in
scintillation counters.
20.5 Refe rence s

i) Inorganic chemistry J.D. Lee
ii) Source book on atomic energy – gl a sst o n – East west press
- Indi a
223
LE SSON – 21
CONTENTS
21.1 INTRODUCTION
21.2 PARTICLE ACCELERATORS
21.2.1 CYCLOTRONS
21.2.2 BETATRON- BEVATRON
21.3 LET US SUM UP
21.5 REFERENCES
The aim of this lesson is to make an in depth study of different types of

particle accelerators.
After going through this lesson one would be able to understand
i) The design and the uses of accelerators for accelerating the various
types of particles
ii) The energies attained by different particles, when particles are
accelerated by various types of accelerators.
21.1 INTRODUCTION
A particle accelerator is a device for increasing the kinetic energy of

electrically charged particles. Upto about one tenth of the velocity of light,
the kinetic energy can be calculated by means of ½ Mo V2 , where mo is the
rest mass of the particle and V its velocity.
Since 'm' is constant, increase of kinetic energy implies increase of

v e l o c i t y . I t is for this reason that the machine employed for increasing
kinetic energy, is called an 'accelerator'. As the velocity of the particle
approaches the velocity of light, its mass also increases. Under these
224
circumstances, an accelerator can increase the kinetic energy with very little
increase in velocity.
M a n y n u c l ear reactions have been studied by high energy particles.

Accelerators have been used in the creation of new particles. The muon and
mesons have been discovered using high energy particles. Several additional
particles not previously known have been found using high energy particles.
Calculations indicate that protons with energy of 5.6billion electron volts
would be required to create antiprotons and antineutrons. The anti protons
and antineutron are not known to occur in nature. For the discovery of
antiprotons and antineutrons. Beaverton accelerator was designed at the
University of California.
Accelerators have also been designed to study the nuclear structure, the
nuclear forces and strong and weak inter actions.
Protons of 400 to 1000 MeV energy are used to produce intense beam
of pions. Natural decay of pions may inturn yield muons and neutrons of high
energy.
The growth of high energy particle physics is due to the particle

accelerators.
21.2.1 CYCLOTRO NS
Lawrence modified the 'Wideroe' Cylindrical (linear accelerators)

accelerator by using a magnetic field to make the charged particles follow a
spiral path, of increasing radius. The length of the path would then increase
automatically with the speed of the particles. The 'cyclotron' was desi gne d on
the basis of this principle.
The first accelerator to yield protons of energy in excess of 1 MeV –

was the cyclotron constructed by Lawrence and Livingston in 1932. It had a
magnet with pole faces 11 inches in diameter. The energy to which a particle
225
can be accelerated in a cyclotron increases with the radius of the magnet and
with the strngth of the magnetic field.
The cyclotron consists of two flat semicircular boxes known as 'dees'

because of their shape. These does are surrounded by a closed v e s s e l ,
containing a gas at low pressure, placed between the poles of a magnet. A
radio- frequency alternating potential, of about 10 to 20 mega cycles per
second, is applied between the dees, which act as electrodes. An electrically
heated filament in the vessel, produces a stream of electrons, which cause
ionization of the gas such as deuterium or helium contained in the vessel. The
filament thus can be regarded as the source of positive ions (protons),
deuterons or alpha particles. Suppose that at any particular instant the
alternating potential is in the direction which makes the first 'dee' positive
and the second 'dee' negative. A positive ion from the source would be
attracted to the second D which is negative), but as a uniform magnetic field
a c t s i n a direction at right angles, the particle will move in a circular path.
The radius 'r' of the particle is given by r = mv/Be ……… (1) where
'm' is the mass of the ion, 'e' is its charge 'v' its velocity and 'B' is the
strength of the magnetic field.
While it is in the interior of the dee, the speed of the ion remains
constant. But after describing semicircular path through the second dee, the
particle reaches the gap between the dees, where it becomes subject to the
action of the applied potential difference. When the first dee, becomes
negative, (because of the alternating potential) the positive ion will be
accelerated toward the first dee. Since its energy is consequently greater than
it was originally the ion will move faster, i.e, 'v' will increase. Therefore the
circular path in the first dee will have larger radius, under the influence of
the magnetic field, as per equation (1). The significant property of the
cyclotron is that the time taken by the particle to traverse the semicircular
path is independent of the velocity of the particle or of the radius of the path.
In other words, the increase in length of the path, due to the larger radius, is
exactly compensated by the increase in velocity of the ion. The time taken to
226
traverse the path 'T' is given by T= p r/V ----------- (2); r = radius of the path.
from (1) T = p m/Be ---- ---- --- (3).
Thus 'T' is independent of both V and r. This means that if the

frequency of oscillation is adjusted to the nature of the ion and to the
strength of the magnetic field, the charged particle will always keep in phase
with the changes of electric potential between the dees. Thus each time the
particle crosses the gap from first dee (D1 ) to second dee, ( D 2 ) it will receive
an additional impulse toward D2 ; on the other hand when it crosses from D2
t o D 1 it will be accelerated toward D1 , for the direction of potential will then
be reversed. The result of these repeated impulses is that the energy of the
ion is steadily increased, and at the same time it describes a flat spiral of
increasing radius. Eventually the ion reaches the periphery of the dee and it
can be brought out of the dee chamber by means of a deflecting plate, which
is charged to a high negative potential. The attractive force acting on the
positive ion draws the latter out of its spiral path, and it can be used to
bombard any desired material. Although the above description refers to a
single particle, the source supplies ions continuously, thus a stream of high
energy particles will emerge from the cyclotron.
The maximum velocity at the periphery is given by : BeR/m (R is the

radius of the dee).
Therefore the kinetic energy 'E' of the ion, coming out of the cyclotron
is: E= ½ M (BeR/m)2 E = B2 R 2 /2 x e2 /m. It can be seen from this equation
that the maximum energy acquired by a particle is determined by B2 R2 .
Therefore in order to obtain ions of high energy, it is necessary to increase
the strength and size of the magnet. By using a 60 inch cyclotron alpha
particles of 40MeV were obtained.
SYNCHROCYCLOTRON
At higher energies, the rest mass of the particle increases (due to

increase in velocity). For example a deutron having an energy of 20 MeV
227
(obtained from 60 inch cyclotron) has a velocity about 0.145 times the
velocity of light. Its effective mass is 1.01 times the rest mass, as given by.
m = mo/ 1- V2 /C 2 ; V is the velocity of the particle, mo is its rest mass and 'C'
the velocity of highest.
At higher energies, the mass of the particle increases to such an extent

that its effect becomes appreciable. As the mass of the ion increases, the time
of transit 'T' also increases (T & m at constant B). Because of this the
particle will no longer be in phase with the alternating potential, and
consequently it will gain no additional energy.
For the 'T' to be unaffected by the increase in mass, the magnetic field
is left unchanged but the frequency of the oscillating potential is decreased
so that fm = constant, f = frequency m – mass of the particle. MCmillan
(1945) pointed that if the oscillation frequency is adjusted continuously to
coincide with the decreasing frequency of revolution of the particl,the
revolution of the charged particle is automatically synchronized with the
changing frequency of the alternating of potential. The action is similar to
that in a synchronous motor and hence the name 'Synchrotron' was proposed
by Mc Millan.
The cyclotron was modified to permit variation of oscillation frequency

to compensate for the increase in mass of the accelerated ions. Hence the
machine is referred to as a 'Synchrocyclotron' or a frequency modulated
cyclotron. It uses a single dee instead of two dees, the oscillating potential
being applied between it and a ground connection. Every time a charged
particle enters or leaves the dee, it acquires additional energy, so that it
follows a spiral path (just as if two does were employed) R.F frequency is
decreased to compensate for the gain in mass of the particle as its speed
increases. By using improved frequency modulators, protons of 720MeV
energy were produced.
228
ELECTRON CYCLOTRON:
The conventional cyclotron is not used to accelerate electrons because

of the large relativistic increase in mass even at fairly low energy. This is
because mo for electron is very small compared with that of a proton or
deuteron.
For a specified particle energy, a lower magnetic field strength is

required in a cyclotron of a given size for the acceleration of electrons than
for protons because of smaller mass. Electron cyclotrons have been designed
wit hout iron- core magnets, the necessary magnetic fields being provided by
the passage of electric currents through suitably shaped coils.
21.2.2 BETATRON:
For the acceleration of electrons to high energies, above approximately

1MeV, the cyclotron principle is not applicable. Electrostatic accelerators of
the type 'van de Graff' generator are useful upto 10 to 20 MeV. For energies
of the order of 100 MeV, other devices have to be employed. For this
purposes, D.W.Kerst developed 'Betatron', since it was designed to accelerate
electrons (which are identical with beta particles). The first useful induction
accelerator, the betatron, accelerated an electron to an energy of 2.3 MeV.
The action of the betatron is based on the familiar principle of

transformer. In the transformer an alternating current applied to a primary
coil induces a similar current, usually with a higher or lower voltage, in the
secondary windings.
In the betatron the secondary is an annular (ring shaped) evacuated

glass (or ceramics) tube. It is often called a 'dough nut'. This is placed
between the poles of a specially shaped electromagnet, energized by pulsed
current passing through the coils. The purpose of this magnet is to produce a
strong field in the central space or "hole" of the dough nut, and therefore it is
constructed with a good amount of iron in the core. Heated filaments produce
229
electrons and these are given initial acceleration by application of an electric

field having a potential difference of 20,000 to 70,000 volts. Even with low
energies, thus obtained, the electrons travel at very high speeds, from nearly
1/5th to ½ the velocity of light.
As the field strength starts to increase, the partly accelerated electrons

are injected into the doughnut. The energy of the moving electrons is
increased due to an induced EMF, within the doughnut, caused by the
growing magnetic field.
Since the electrons are moving in a magnetic field, the electrons are
forced into a curved path. The increasing magbetic field keeps them moving
in a circle of constant radius. The equation r = mv/Be shows that as the field
strength moves in proportion to the momentum of the electrons, 'r', remains
constant. Thus, the electrons are kept moving around the doughnut in a fairly
stable, circular path. in each trun the electron acquires energy. When the
magnetic field reaches the maximum point of the since wave cycle, a pulse
current is sent through an auxiliary coil, which suddenly changes the
magnetic field. The high energy electrons are displaced from their stable path
and can be used to produce x- rays or can be used for other purposes.
Betatron can produce electrons with very high energies. Since the
operation of the betatron is unaffected by the increase in mass of the
electrons, due to increase in energy, it would appear that extremely high
energies might he possible by means of betatron. But the accelerated
electrons lose energy by radiation and hence there is a limit to the energy
that can be acquired by electrons in the betatron. Energy losses have been
minimized by means of large doughnut radius (120cms)
PROTON SYNCHROTRON
Attempts were made to produce particles of very high energies in the

range of thousands of MeV ie billion electron volt (109 ). Radiation losses, i n
the case of electrons prevented from acquiring electrons of BeV range. But
230
with protons loss due to radiation is small. Hence protons can be accelerated
to very high energies using cyclic accelerator.
By means of 'Proton Synchrotron' 2 to 3 BeV protons were produced.

The proton synchrotron consists of four quadrants joined by straight pieces.
In the Berkeley beavatron, the radius of each quadrant is about 55' and the
connecting pieces are ~20' long. Alternating current is used for energing
purposes. The magnet consists of a large number of plates surrounding only
the quadrants of the doughnut. Protons accelerated to about 6 to 10 MeV,
initially by vande Graff generator, is injected into the synchrotron. After
having their energy increased, as a result of many revolutions, the protons
are removed by a deflector. Injection and removal take place outside the
magnetic field.
To keep the protons in the synchrotron moving in a circular path of

constant radius, the strength of the magnetic field is increased in proportion
to the momentum. Similarly for proper synchrotron action, the frequency of
the radio frequency alternations is increased in such a manner that the
condition of phase stability is maintained.
In proton synchrotron deviations from circular path, of particles occur,

as a result of fluctuations. The deviations are observed both in horizontal and
vertical direction. The magnet is designed in such a way that both the
deviations are decreased.
Zero gradient synchrotron is designed to accelerate particles to higher

energies by using a stronger magnetic field than in the conventional
synchrotron.
1. Calculate the mass of an electron, when its velocity becomes equal to

1/5th the velocity of light.
231
2. Discuss the cyclotron in detail.
Self Check Ecercise – 2
1. Discuss the principle of synchrocyclotron
2. Write briefly on
i) Betatron
ii) Bevatron
21.3 Let us Sum UP

i) Cyclotron and its design are discussed in detail. Synchroogclotron is
explained. Betatron and Bevatron are discussed in detail. Zero gradient
synchrotron is explained.

i) Cyclotron and its design
ii) How does the mass increase affect the operation of cyclotron and the
modifications introduced in Synchrocylotron?
iii) The different types of proton synchrotrons to be discussed.
21.5 Refe rence s

1) Source book on atomic energy by Glass tone – East West press India.
232
U NIT VIII
T HE RMAL ANALYSIS
LESSON – 2 2
CONTENTS

22.1 INTRODUCTION
22.2 THERMAL ANALYSIS
22.2.1 TG – D T A
22.2.2 APPLICATIONS
22.3 LET US SUM UP
22.5 REFERENCES
The aims and objectives of this lesson are to understand the

methodologies of different thermal analyses techniques such as thermo
gravimetric analysis and differential thermal analysis . After going through
this lesson you would be able to use these methods to
· Obtain information concerning the detailed structure and composition
of different phases of a given sample.
· Understand how heats of reactions are obtained and used to determine
the purity of materials.
22.1 INTRIDUCTION
22.2.1 TG – DT A – RELATED TECHNIQUES
Thermal analysis includes a group of techniques in which specific

physical properties of a material are measured as a function of temperature
(Table 1.1). The production of new high – technology materials and the
resulting requirement for a more precise characterization of these substances
have increased the demand for thermal analysis techniques. Current areas of
233
application include environmental measurements, composition analysis,

product reliability, stability, chemical reactions and dynamic properties.
Thermal analysis has been used to determine the physical and chemical
properties of polymers, electronic circuit boards, geological materials, and
coals. An integrated, modern thermal analysis instrument (Figure 1.1) can
measure transition temperatures, weigh losses, energies of transitions,
dimensional changes, and viscoelastic properties.
Thermal analysis is useful in both quantitative and qualitative

analyses. Samples may be identified and characterized by qualitative
investigations of their thermal behaviour. Information concerning the
detailed structure and composition of different phases of a given sample is
obtained from the analysis of thermal data. Quantitative results are obtained
from changes in weight and enthalpy as the sample is heated. The
temperatures of phase changes and reactions as well as heats of reaction are
used to determine the purity of materials.
Table 1.1
SUMMARY OF THERMAL ANALYSIS THECHNIQUES
Techniques Q uantity Measured Typical application
Differential scanning Heats and Temperatures Reaction kinetic, purity
calorimetric (DSC) of transitions and analysis polymer cures
reactions
Differential thermal Temperat ur es of Phase diagrams, thermal
analysis (DTA) transitions and reactions stability
Thermo gravimetric Weight change Thermal stabil ity
analysis (TGA) compositional analysis
Thermo mec hanical Dimension and viscosity Softening temperatures,
analysis (TMA) changes expansion coefficients
Dynami c mechanical Modulus, damping and Impact resistance,
analysis (DMA) viscoelastic behavior mechanical stability
Evolved gas analysis Amount of gaseous Analysis of volatile
(EGA) products of thermally organic components of
234
induced reaction shale
FIG –
22.1
235
The use of microprocessors has both enhanced and simplified the

techniques of thermal analysis. The sample is heated at a programmed rate in
the controlled environment of the furnace. Changes in selected properties of a
sample are monitored by specific transducers; which generate voltage signals.
The signal is then amplified, digitized and stored on a magnetic disk along
with the corresponding direct temperature responses from the sample. The
data may also be displayed or plotted in real time. The microcomputer is used
to process the data with a library of applications software designed for
thermal analysis techniques. The multitasking capabilities of some computer
systems allow a single microcomputer to operate several thermal analyzers
simultaneously and independently.
A major advantage of microcomputer systems in thermal analysis is

that the operator seldom, if ever, needs to repeat an analysis because of an
improper choice of ordinate scale sensitivity. The software does this
rescaling after all the data have been collected. In some systems both axes
are automatically rescaled after the last data point has been received. When
the amount of time necessary to obtain thermal data is considered, the
advantage is obvious. For example, a differential scanning c al o r i m et r i c r un
10 o C/min from room temperature to 1100 o C takes 100 min, and thus the
rerun of the sample would take longer than 2hr including the time required
for cooling and sample reloading.
DIFFERTIAL SCANNING CALORIMETRY AND DIFFERENTIAL

ANALYSIS
Differential scanning calorimetry (DSC) has become the most used

thermal analysis techniques. In this technique, the sample and reference
materials are subjected to a precisely programmed temperature change. When
a thermal transition (a chemical or physical change that results in the
emission or absorption of heat) occurs in the sample, thermal energy is added
to either the sample, or the reference containers in order to maintain both the
sample and reference at the same temperature (Figure 1.2(a)). Because t h e
236
energy transferred is exactly equivalent in magnitude to the energy absorbed

or evolved in the transition, the balancing energy yields a direct calorimetric
measurement of the transition energy. Since DSC can measure directly both
the temperature and the enthalpy of a transition or the heat of a reaction, it is
often substituted for differential thermal analysis as a means of determining
these quantities except in certain high- temperature applications.
In differential thermal analysis (DTA), the difference in temperature

between the sample and a thermally inert reference material is measured as a
function of temperature (usually the sample temperature) (Figure 1.2(b). Any
transition that the sample undergoes results in liberation or absorption of
energy by the sample with a corresponding deviation of its temperature from
that of the reference. A plot of the differential temperature, ∆T, versus the
programmed temperature, T, indicates the transition temperature (s) and
whether the transition is exothermic or endothermic. DTA and
thermogravimetric analyses (measurement of the change in weight as a
function of temperature) are often run simultaneously on a single sample.
FIG –2 2 . 2 (a ) &
(b)
In DTA, the furnace contains a block with identical and symmetrically
located chambers. The sample is placed in one chamber and a reference
material such as a -Al 2 O 3 , is placed in the other chamber. A thermocouple is
237
inserted into the centre of the material in each chamber. The furnace and
sample blocks are than heated by a microprocessor – controlled heating
element. The difference in temperature between sample and re fe r en ce ( S ,R )
thermocouples, connected in series opposition, is continuously measured.
After amplification (about 1000 times) by a high – again, low – noise dc
amplifier for microvolt – level signals, the difference signal is recorded as
t h e y - axis. The temperature of the furnace is measured by an independent
thermocouple and recorded as the x- axis. Because the thermocouple is placed
in direct contact with the sample, DTA provides the highest thermometric
accuracy of all thermal methods. DTA can be used in the temperature range
from - 190 to 1600o C. Sample sizes are similar to those used in DSC.
Although the area of a DTA peak is proportional to the heat of

reaction and the mass of the sample, it is inversely proportional to the
sample's thermal diffusivity, which is a function of grain size and
compactness. This inverse relationship prevents. DTA peak areas from being
used to provide direct calorimetric measurements. It is necessary to calibrate
a DTA instrument for each type of sample and to carefully control
experimental parameters to obtain useful thermodynamic data.
THERMOGRAVIMETRY
Thermogravimetry (TG) or thermogravimetric analysis (TGA) provides

a quantitative measurement of any weight changes associated with thermally
i nduced tr ansitions. For example, TG can record directly the loss in weight as
a function of temperature or time (when under isothermal conditions) for
transitions that involve dehydration or decomposition. Thermogravimetric
curves are characteristics of a given compound or material due to the unique
sequence of physical transitions and chemical reactions that occur over
definite temperature ranges. The rates of these thermally induced processes
are often a function of the molecular structure. Changes in weight result f r o m
physical and chemical bonds forming and breaking at elevated temperatures.
These processes may evolve votatile products or from reaction products that
result in a change in weight of the sample. TG data are useful in
238
characterizing materials as well as in investigating the thermodynamics and

kinetics of the reactions and transitions that result from the application of
heat to these materials. The useful temperature ranges for TG is from
ambient to 1200o C in either inert or reactive atmospheres.
In TG the weight of the sample is continuously recorded as the

temperature is increased. Samples are placed in a crucible or shallow dish
that is positioned in a furnace on a quartz beam attached to an automatic
recording balance. Figure 1.3 shows a TG instrument that contains a taut-
band suspension electromechanical transducer. The horizontal quartz beam is
maintained in the null position by the current flowing through the transducer
coil of an electromagnetic balance. A pair of photosensitive diodes acts as a
position sensor to determine the movement of the beam. Any change in the
weight of the sample causes a deflection of the beam, which is sensed by one
of the photodiodes. The beam is then restored to the original null position by
a feedback current sent from the photodiodes to the coil of the balance. The
current is proportional to the change in weight of the sample.
.
o
Linear heating rates from 5 to 10 C/min are typical. Sample sizes range
from 1 to 300mg. Computer software allows the computation of ∆w/ ∆t,
which is important in kinetic interpretations of reactions and processes. TG
has been used in the kinetic analysis of polymer stability, Compositional
239
analyses of multi component materials, atmosphere analyses and corrosion

studies, moisture and volatiles determinations, and accelerated tests of aging.
EVOLVED GAS DETECTION AND ANALYSIS
The analysis of the purge gas exit stream from differential thermal
analysis, differential scanning calorimetry, and thermogr avimetric analyzers
is useful in establishing mechanism and stoichiometric relationship of
thermal decompositions. In evolved gas analysis (EGA) the absolute
identities of the gaseous components are determined, whereas in evolved gas
d et e ct io n ( EGD ) the presence of only a single. preselected component of the
evolved gas is sensed. An appropriate analyzer may be coupled to a
thermogravimetric system for performing either EGA of EGD. The resulting
hyphenated methods are powerful analytical tools. Two analyzers that have
been successfully coupled to TG systems are mass spectrometers (MS) and
flame ionization detectors (FID). The TG- MS or TG- MS-MS combination is
used for evolved gas analysis, whereas the TG- FID combination provides
evolved gas detection. These hyphenated methods are used in studies of the
votatile organic pyrolysis products of oil shales.
The simultaneous TG- DTA- MS analysis of copper sulfate- pentahydrate

is shown in figure. 1.4. The quadrupole mass spectrometer detects the
temperature- d ependent intensity changes of water during dehydration to
300 o C. The evolution of sulpur dioxide during the two- s t e p s u l f a t e
o
decomposition to copper (II) oxide between 600 and 900 C is also clearly
seen. Electron – impact ionization in the MS is responsible for the production
of sulfur monoxide (SO) radical ions.
240
FIG –
22.5
22.2.2 APPLICATIONS
METHODOLOGY OF THERMOGRAVIMETRY,
DIFFERENTIAL SCANNING CALORIMETRY
AND DIFFERENTIAL THERMAL ANALYSIS
Thermogravimetry (TG)
The weight- change TG curve for calcium oxalate monohydrate is shown

in Fig- 1.5. Water is evolved beginning slightly above 100o C. At about 250o C
the curve breaks at the stoichiometry corresponding to that of the anhydrous
s a l t . F u r t her heating gives definite weight plateaus for the carbonate (from
500 to 600o C) and finally the oxide (hotter than about 870o C ) . E x a c t
locations of the weight plateaus are dependent on the heating rate (a slower
heating rate shifts values to lower temperatures) and the ambient atmosphere
around the sample particles. The curve is quantitative in that calculations can
be made to determine the stoichiometry of the compound at any given
temperature.
Thermal analysis is affected by the experiments\a l c o n d i t i o n s.

Deviations caused by instrumental factors include furnace atmosphere, size
and shape of the furnace and sample holder, sample holder material and its
241
resistance to corrosive attack, wire and bead size of the thermocouple

junction, heating rate, speed and response of the recording equipment, and
location of the thermocouples in the sample and reference chambers. Another
set of factors that influence the results depends on the sample
characteristics;' these include layer thickness, particle size, packing density,
amount of sample, thermal conductivity of the sample material, heat capacity,
the ease with which gaseous effluents can escape, and the atmosphere
surroundings the sample.
Thermogravimetry, a valuable tool in its own right, is perhaps most

useful when it complements differential thermal analysis studies. Virtually
all wei ght-change processes absorb or release energy and are thus measurable
by DTA or DSC, but not all energy- c hange processes are accompanied by
changes in weight. This difference in the two techniques enables a clear
distinction to be made between physical and chemical changes when the
samples are subjected to both DSC (or DTA) and TG tests.
FIG –
EXAMPLE - 1 22.5
Thermogravimetry can also be used to determine the composition of

complex materials such as carbon black- filled rubber. Figure 1.6 shows the
242
result of rapidly heating a rubber sample in an inert atmosphere of nitrogen

from room temperature to 950o C and then quickly changing the atmosphere to
air. Heating the sample in an inert environment results in the
FIG –
22.6
pyrolitic decomposition of the rubber and gives the first major weight loss
observed in the scan. The addition of air at 950o C causes the carbon black to
undergo combustion to produce the second loss in weight, leaving in the
balance pan only inert filler. All the major components of the rubber sample
were determined quantitatively from a single TG scan.
DIFFERENTIAL SCANNING CALORIMETRY (DSC)

AND DIFFERENTIAL THERMAL (DTA)
In general, each substance gives a DSC or DTA curve in which the

number, shape and position of the various endothermic and exothermic
features serves as a means of qualitative identification of the substance.
When an endothermic change occurs, the sample temperature lags behind the
reference temperature because of the heat in the sample. The initiation point
for a phase change or chemical reaction is the point at which the curve first
243
deviates from the baseline. When the transition is complete, thermal diffusion
brings the sample back to equilibrium quickly. The peak (or minimum)
temperature indicates the temperature at which the reaction is completed.
When the break is not sharp, a reproducible point is obtained by drawing one
line tangent to the baseline and another tangent to the initial slope of the
curve.
Various behaviors deduced for a DTA curves are shown in Figure 1.7.
The heat capacity at any point is proportional to its displacement from the
blank
FIG –
22.7
baseline. A broad endotherm indicates a slow change in heat capacity. A
"Second – order or glass" transition observed as a baseline shift (T1 ) , de n ot es
a decrease in order within the system. This is the temperature at which a
polymer changes from a brittle, glasslike material to a tough, resilient
material. The lower the glass transition temperature, the lower the
temperature at which the polymer is useful in applications, such as adhesives
o r i m p a c t -resistant structures. In a thermoset, a high glass transit ion
temperature indicates incomplete cure of the resin; In a thermoplastic, a high
galss transition temperature indicates the use of the wrong plasticizer or
incomplete reaction in the formation of the polymer itself. Endotherms
generally represent physical rather than chemical changes. Sharp endotherms
(T 3 ) are indicative of crystalline rearrangements, or solid- state transitions for
relatively pure materials. Broader endotherms (T2 ) cover behaviour ranging
244
from dehydration and temperature dependent phase behaviors to the melting

of polymers. Exothermic behaviour (without decomposition) is associated
with the decrease in enthalpy of a phase or chemical system. Narrow
exotherms usually indicate crystallization (ordering) of a metastable system,
whether it be supercooled organic, inorganic, amorphous polymer, or liquid,
or annealing of stored energy resulting from mechanical stress. Broad
exotherms denote chemical reactions, polymerization, or curing of
thermosetting resins. Exotherms with decompositions can be either narrow or
broad depending on the kinetics of the behavior. Explosives and propellants
are sharpest, and the "Unzipping" of polyvinyl chloride is rapid, whereas
oxidative combustion and decomposition are generally broad.
On cooling one would expect the reverse of features observed on the

heating cycle (Figure 1.7). Since T4 does not recur on cooling, the reaction is
obviously nonreversible (perhaps a pyrolytic decomposition). Instead of
taking the system up to T4 , the cooling cycle be started before that
temperature. As it cools, the substance is seen to lose its transition peak at
T3. Judging from the area under the T2 peak, the transition energy of T3 h a s
been added to T2 . This indicates a metastable condition at T 3 , with the
retained energy being released in one large step at a lower temperature.
Further along the cooling curve, the glass transition at T1 falls properly into
place to complete the cycle.
Determining the significance of thermoanalysis curves is not always a

straightforward task. A reference library of curves of specific interest to a
particular laboratory is vital. Computerized systems offer the capability of
storage and quick retrieval of data. Thermoanalysis data on commercial
products or thermal transition points for pure substances reported in the
literature are of little value for the comparison with a dynamically scanned
thermal profile. Complementary techniques are valuable. The correlation of
thermally evolved gaseous products with differential scanning calorimetry or
differential thermal analysis transitions using evolved gas analysis or evolved
gas detection often assists in elucidating the decomposition mechanism.
245
Running thermal decompositions in inert, oxidative, or special atmospheres

can often provide valuable clues from changes in the curves.
Example – 2
The TG and DTA curves of manganese phosphinate monohydrate are

shown in Fugure.1.8. The weight – loss data (TG curve) from a 200- mg
sample run under vacuum and with the analysis of effluent gases showed the
loss of 1 mole of water at 150o C, 1 mole of phosphine at
FIG –2 2 . 8 ( a ) &
(b)
246
360 o C, and the slow loss of another mole of water starting around 800o C.
After comparison with the DTA curve, two major peaks remain unidentified:
the large exotherm at 590o C and the endotherm at 118o C, plus several smaller
thermal features. Thermogravimetric data obtained from runs performed
under vacuum and in a nitrogen atmosphere failed to show any loss
associated with these peaks. Each sample was measured for its real density.
The resulting data are shown on the DTA curve, Undoubtedly the sharp DTA
exotherm at 590o C represents a phase change. The relatively small endotherm
starting above 900o C must represent a recrystallization exotherm following
the elimination of water. Which is superimposed on the latter endotherm. The
peak at 1180o C is due to melting. With this information the thermal
decompositions reaction and phase changes are:
Mn(PH 2 O 2 ) 2 H 2 O (s ) Mn(PH 2 O 2 ) 2 (s) + H2 O(g)

Mn(PH2 O 2 ) 2 (s ) Mn HPO 4 (s) + PH3 ( g )
µ - MnH P O 4 (s ) b - MnHPO 4 (s)
2 MnHPO4 ( s ) Mn 2 P 2 O 7 (s) + H2 O(g) (and recrystallization)
Mn 2 P 2 O 7 (s) Mn 2 P 2 O 7 (l )
Thermal studies with polymers can predict a product's performance in

use – that is, its stiffness, toughness, or stability. Melting point, Phase-
transition, Pyrolysis, and curing temperatures are accurately measured. Once
a polymer has been broadly classified by other, methods, curves are often
used to establish, by comparison with known reference materials, the degree
of polymerization, the thermal history of the sample, crystal perfection and
orientation, the effect of different coreactants and catalysts, the percentage
of crystalline polymer, and the extent of chain branching. For example,
curves for a low- molecular- weight, nonlinear, branched – chain polymer
show a continuous series of rather broad and low- melting- p oi nt en do ther ms,
whereas a high- molecular- weight, stereo regular, linear polymer reveals a
single narrow and higher- melting- point endotherm. If a polymer has been
incompletely cured, the heating cycle may reveal an exotherm at a
247
temperature close to the one used for the polymerization reaction. An

exotherm just below the melting temperature indicates "cold crystallization,"
which results if a sample is quenched quickly after being melted. On
reheating, crystallites form rapidly and exothermically just prior to remelting
of the polymer. Annealing temperatures are similarly revealed as exotherms.
If the molecular weight or density of a polymer has been established by

appropriate (often lengthly) methods, subsequent determination of its melt
temperature (a 15- min process) can be related to molecular weight or density.
Product quality is maintained subsequently by simply examining curves of
polymer materials to obtain molecular weights or densities from an
appropriate calibrated graph.
Instead of using the traditional method of preparing a derivative from

the organic sample and a reagent, the sample is heated with a specific reagent
at a programmed heating rate in a selected atmosphere. The DTA or DSC
curve shows the derivative – forming reaction, the physical transitions of the
sample or reagent (whichever is in excess), and the physical transitions of the
intermediates and final products. When one reactant is volatile and in excess,
a rerun usually shows only the derivative characteristics.
The area of exotherms or endotherms is used to calculate the heat of

the reaction or the heat of a phase transition. Suitable calibration is necessary
with DTA equipment, but the values are given directly with DSC instruments.
Example – 3
Polyethylene is a semi crystalline thermoplastic that when heated

undergoes a process of melting. This melting destroys the crystal structure of
the polymer and is an endothermic process. Although plastics usually melt
over a temperature range, the melting point is defined as the temperature at
which the melting is complete. The melting point of a plastic is an important
property because it is minimum temperature for processing the plastic and the
maximum temperature for applications where structural integrity is required.
248
A second important property for the characterization of semi crystalline

thermoplasticsc is the percent crystallinity. Many physical properties that
gives the plastic its useful attributes are dependent on the percent
crystallinity.
Both the melting point and the percent crystallinity are obtained from a
single differential scanning calorimetry scan (Figure 1.9). The melting point
is taken as 133o C, where the melting is approximately complete. Since
di f f e r e nt i al scanning calorimetric is directly quantitative, the peak area is
equal to the heat fusion. Hf , in units of calories per gram. The percent
crystallinity is determined by assuming that the heat of fusion is proportional
to the percent of crystallinity of the sample. Thus if the heat of fusion of
100% Polyethylene has been determined to be 68.4 cal/g and the measured
heat for the sample is 54.5 cal/g the percent crystallinity is 79.7%, as shown
in figure 1.9.
FIG –
22.9
249

1. What are the different thermal analysis techniques? give their
applications in a few words.
2. What is the importance of microcomputer system in thermal analysis.
3. Explain the process of DTA.
4. Give any one disadvantage of DTA .
1. Describe thermogravimetry.
2. Discuss the thermogravimetric method with an example.
3. 20 Mg sample of crystalline calcium oxalate of molar mass 146, in a
thermal study loses about 2.46mg H2 O above 150o C. Formulate the
sample.
Activity:
Run a TGA and DTA for a known sample from the instrument available
in the Chemistry Department of Bharathiyar University.
Model Answer
4. Although the area of a DTA peak is proportional to the heat of a

reaction and the mass of the sample, it is inversely proportional to the sample
thermal diffusivity which is a function of grain size and compactness. The
inverse relation prevents, DTA peak areas from being used for direct
calorimetri c me asurements. It is necessary to calibrate a DTA instrument for
each type of sample and to carefully control experimental parameters to
obtain useful thermodynamic data.
22.3 Let us Sum Up

i) Theories of TGA and DTA are discussed in detail ii) Experimental
methods are illustrated iii) The applications of TGA and DTA techniques are
illustrated using typical TG and DTA curves for a few compounds.
250
22.4 Points for Discussions:

i) The different thermal methods and their application may be discussed.
ii) Obtain TGA and DTA curves from a standard source and try to
interpret the results.
22.5 Refe rence s
1) ATKINS PHYSICAL CHEMISTRY – 7th Edn. OUP – INDIAN - 2 0 0 2

2) Instrumental methods of analysis – Willard, Merrtts Dean – 7th Edn
CBs New Delhi.
251
LESSON – 2 3
CONTENTS
23.1 INTRODUCTION
23.2 AUGER ELECTRON SPECTROSCOPY (AES)
23.2.1. Principle and experimental method
23.2.2. Applications
23.3 LET US SUM UP
23.5 REFERENCES
The aim of the lesson is to study and understand the auger emission
phenomenon and to understand the importance of Auger emission
spectroscopy in studying surfaces of solids. After studying this lesson you
would be able to learn :
The principle of Auger ef fect

Auger effect effectively takes the fingerprint of the material.
23.1 INTRODUCTION
When an atom is excited by the removal of an electron from an inner

energy level, it may return to its normal state by transferring an electron
from some outerlevel to the vacant inner level. The energy of this transition
either appears as X rays or is used to eject a second electron from the outer
shell Fig. 2.1. This latter method is called the Auger emission process;
observation of the energy of such an ejected electron leads to a method of
252
analysis known as Auger emission spectroscopy (AES). If X rays are

emitted, their wavelengths are characteristic of that element and their
intensities are proportional to the number of excited atoms. Thus, X- ray
emission methods can be used for both qualitative and quantitative
measurements.
Atoms are excited in several ways : by direct bombardment of the

material with electrons (direct emission analysis, electron probe
microanalysis, and Auger emission spectroscopy), by bombardment with
protons or other particles (particle induced x-ray emission, PIXE), or by
irradiation of the material with X rays of shorter wavelength. In the latter
case, the exciting X radiation causes an inner electron to be ejected with
subsequent emission of the characteristic X rays of the sample (fluorescence
analysis). It is also possible to measure the energy of the electrons ejected
from the sample, and this leads to a method of analysis known as electron
spectroscopy for chemical analysis (ESCA)
Another method of X- ray analysis uses the differing absorption of X

rays by different materials (absorption analysis). Major discontinuities in the
absorption of X rays by an element occur when the energy of the X rays
becomes sufficient to knock an electron out of an inner level of an atom.
Still another method of using X rays in analytical work is the

diffraction of X rays from the planes of a crystal (diffraction analysis). This
method depends on the wave character of the X rays and the regu l a r s p a c i n g
of planes in a crystal. Although diffraction methods are used for quantitative
analysis, they are most widely used for qualitative identification of
crystalline phases.
Since electrons quickly lose their energy by colliding with molecules,

methods that involve electron bombardment or detection of emitted electrons
must be carried out in a vacuum. Furthermore, since electrons cannot
penetrate deeply into solid materials or escape from any significant depth
when generated in a solid, such methods characterize the surface layers of
253
solids and are useful for analyzing surfaces. Auger electron spectroscopy
(AES) and electron spectroscopy for chemical analysis (ESCA), are carried
out in a vacuum and usually characterize not more than the outer 2 nm of the
surface under investigation.
In 1913 Moseley first showed the extremely simple relationship

between atomic number, Z, and the reciprocal of the wavelength, 1/l for
each spectral line that belongs to a particular series of emission lines for
each element in the periodic table. This relationship is expressed as
c
--- = a(Z - s ) 2 …. ( 1)
l
23.2 AUGER EMISSION SPECTROSCOPY (AES)

23.2.1 AES measures electrons emitted from a surface, induced by
electron bombardment (Fig. 2.1b). The first step is ionization of an inner
atomic level by a primary electron. Once the atom is ionized, it must relax
b y e mitting either a photon (an X ray) or an electron (the nonradiative Auger
process). In most instances nature chooses the Auger process. For example,
a KLL Auger transition means that the K- level electron undergoes the initial
254
ionization, An L- l e vel e le c tron moves in to fill the K- level vacancy and, at

the same time, gives up the energy of that transition (L to K) to another
L- level electron, which then becomes the ejected Auger electron. Other
Auger electrons originate from LMM and MNN transitions. At this point the
atom is doubly ionized. The energy of the ejected electron is a function only
of the atomic energy levels involved in the Auger transition and is thus
characteristic of the atom from which it came. A threshold energy, related to
t h e t ransition energy, exists and a primary energy five to six times greater
than the Auger energy maximizes the sensitivity to that particular transition.
All elements except hydrogen and helium produce Auger peaks. Most
elements have more than one intense Auger peak so that a recording of the
spectrum of energies of Auger electrons released from any surface, compared
with the known spectra of pure elements, enables a chemical analysis to be
made.
Since an excited atom can lose energy by the X- ray emi ssion pr oc e ss or
by Auger electron emission, the relative sensitivities of these two techniques
are complementary when considering the relative abundance of X rays and
Auger electrons after ionization of a particular level. In the light elements
(Z < 30), the Auger process dominates, which makes AES relatively more
sensitive. For heavier elements, the electron microprobe becomes more
sensitive for transitions following ionization of inner shells. The sensitivity
of AES is maintained, however, by utilizing Auger transition between outer
shells – for example, MNN – where the Auger process dominates.
Although the penetration of the primary electron beam may be as deep

as 1 mm for high- energy electrons, the Auger electrons emitted are, on the
average, of much lower energies. Electrons of such low energy must
originate very close to the surface if they are to escape without being lost by
inelastic scattering before reaching the surface. Typically, Auger electrons
come from the first few atomic layers; the sampling depth is about 2 nm.
255
The sensitivity of the Auger technique is determined by the probability

of the Auger transitions involved, the incident beam current and energy, and
the collection efficiency of the energy analyzer. With a high – s e n s i t i v i t y
cylindrical mirror analyzer (CMA), the detection limit for the elements varies
between 0.1 and 1 atomic percent (or 10- 3 of a monolayer). Because the
electron beam can be focused to a small diameter (50 mm), it is possible to
do spatial resolution or surface mapping of a sample. When operated in this
manner, AES is usually referred to as the Auger microprobe. AES is
traditionally run with high- intensity electron guns and low- resolution
analyzers, resulting in fast analysis. Unfortunately, this limits one to
primarily elemental information with little information on chemical bonding,
such as one clearly obtains in the chmical shifts of electron scattering for
chemical analysis (ESCA), or in the molecular fragments found in secondary
ion mass spectrometry (SIMS). For example, hydrocarbon compounds appear
in AES only as a C peak, since H is not observed.
Fig. 2.2 shows the Auger spectra of Ag, Cd, In and Sb, the (MNN
transitions). The spectra are very similar; the only major difference is the
shifts in energy from one element to the next. These shifts are of the order
of 25eV and, since the peak positions can be measured to an accuracy of + 1
eV, there is no ambiguity in the identification of adjacent elements in the
p e r i o d i c chart. Auger spectra of all the elements lie between 50 and 1000
eV. The KLL transitions correspond quite nicely with tabulated X- ray
energies. There are, however, some minor differences due to the energy
Auger electrons must lose in escaping from the sample. The Auger lines are
relatively broad due to the double uncertainty of the exact origins and
destinations within a sublevel of both the electrons that fall into inner levels
and those being expelled from outer level. Lines due to LMM transitions
tend to correlate with X- ray energies, but some lines begin to appear that the
selection rules for photon emission forbid. As the atomic number increases,
the Auger spectra become more complex and may overlap.
256
FIG –
23.2
The strength of AES is its ability to give both a qualitative and

quantitative nondestructive analysis of the elements in the immediate surface
atomic layers from a very small area of a solid. When combined with a
c on t ro l l e d r em oval of surface layers by ion sputtering, AES provides the
means to solve some very important problems, such as corrosion on metallic
surfaces. To provide ion sputtering for surface cleaning and / or depth
profiling, the sample chamber is backfilled with argon and an electron impact
source is used.
AES Instrumentation
The Auger spectrometer consists of an ultra- high vacuum chamber
console, a sample carrousel and manipulator unit, and a combination electron
257
gun / energy analyzer unit. Auxiliary equipment often includes a grazing

incidence electron gun and a sputter ion gun for cleaning surfaces and
profiling studies. Auger spectrometer are available as large- b e a m ( ~25- mm)
depth- profiling instruments or as Auger microprobes with beam diameters of
5mm. If an instrument is to be used as a high- sensi t ivit y depth profiler and
also as a high lateral resolution microprobe, two electron guns may be
required to realize the optimum use of each operating mode.
The energy distribution of electrons emitted from the target, NE is

evaluated by scanning the negative voltage applied to the outer cylinder of
the cylindrical mirror analyzer (CMA) (Fig. 2.3) Thus as the voltage applied
to the outer cylinder is scanned, the secondary electron distribution is
measured by the current output of the analyzer. Because the Auger pea k s a r e
superimposed on a rather large continuous background of secondary
electrons, it has become popular to differentiate electronically the NE
function.
FIG –
23.3
258
23.2.2 Quantitative Analysis with AES — APPLICATIONS
Quantitative analysis is possible in principle. The relative intensities

of peaks depend on the following variables: inner- level ionization cross
sections, Auger transition rates, and inelastic scattering of the emitted Auger
electrons. With careful calibration, quantitative analysis of a homogeneous
sample should be achieved with an accuracy of about 10%. Thus, although
quantitative Auger spectroscopy is- not very exact, it is still of significant
value in surface analysis.
The difficulties in the quantification of Auger data are illustrated in

depth- profiling analysis. In this operation the change in peak shape of the
differentiated spectra distorts the conventional peak- height estimates of
concentration. Changes in peak shape occur because of changes in the
oxidation state of the emitting atom. This is particularly severe in cases
where bonding orbitals are involved in the Auger transitions. Peak- 'shape
changes also may be induced by matrix effects, since the energy loss
mechanisms and their effect on peak shape may be different in different
matrices. To provide accurate quantitative information within the normal
quantitative limits of AES, it is necessary to use the total Auger current. This
i s e x p r e ssed by the area under the curve for the peak of interest, with
background subtracted. By using undifferentiated data and integrating over
the total number of Auger electrons in the peak, one still has a choice of the
limits of integration. Now chemical shifts may be observed and a depth
profile can be realized with no artifacts.
Scanning Auger Microprobe (SAM)

The scanning Auger microprobe has a finely focused, scanning electron
beam as the probe for AES analysis of a surface. For a surface area, the SAM
provides an electron micrograph, an Auger image of selected elements on a
cathode ray tube display for observation or photographing, and a depth-
composition profile. First, the cathode ray tube image is used to determine
specific points or an area of interest on the sample surface. From the
259
micrograph obtained, points of interest or an area up to 200 mm can be

chosen for compositional analysis.
The image mode is useful because the positions of various elements in

the sample are delineated in a few minutes. An xy recording of a line scan
across a selected region of the image for a given element gives a relative
quantitative measure of its concentration.
The t hi n- fi lm ana lyzer mode of the SAM simultaneously sputter- etches

a relatively large surface area (several millimeters in diameter) and
multiplexes the Auger signals from a smaller area about 15 mm in diameter.
U p t o - six selected Auger peaks can be recorded as the surface is etched.
Depth resolution is about 10% of the total etched thickness. Elements are
detected when present in quantities down to 0.1%of a monolayer.
At best, the spatial resolving power of SAM'is 500 nm with tungsten

thermionic emitters as the electron source. The use of LaB6 , emitters extends
the resolying power to 100-200 nm because of their high electron optical
brightness. Field emitters, which provide even higher brightness, are
expected to allow one to analyze smaller areas in less time when they come
into use.
Many surface composition problems involve compositional in-

homogeneity, both in depth and across a material surface. Scanning Auger
microscopy offers high resolution in the form of scanning electron
microscope- type images, combined with elemental mapping capabilities. For
example, graphite present in spherical nodules indicates that a specimen of
cast iron is ductile cast iron. Examination of the carbon Auger images shows
carbon to be present not only in the graphite nodules but also, at lower
concentration, in regions between nodules. Carbo'n is not evident in the
circular regions around nodules. The iron Auger image shows iron to be
present everywhere in the specimen surface except in the graphite regions.
260

1) Explain how Auger emission occurs?
2) Compare the Auger emissions with other X-ray meth ods
3) Explain the terms KLL and MNN transitions.
Model answers
3) KLL Auger transition means that the K level electron unde rgoe s ini ti al
ionisation, an L- level electron moves into fill the K- level vacancy and at the
same time gives up the energy of that transition (L to K) to another L- level
electron, which then becomes the ejected Auger electron. In MNN transitions
the atom is doubly ionised.

1) Indicate the limitation in AES method.
2) Discuss the applications of the AES techniques.
23.3 Let us Sum Up

i) Auger emission is explained; ii) Auger emission is compared with
o t h e r X -ray methods. Applications of AES are illustrated. The limitation of
AES method is also indicated.

i) Comparison of various X- ray techniques
ii) The importance of AES in the analysis of surfaces by SAM
23.5 Refe rence s

CBs New Delhi.
261
L E SS ON - 2 4
CONTENTS
24.1 INTRODUCTION
24.2 PHOTO ELECTRON SPECTROSCOPY
24.2.1THE TECHNIQUE
24.2.2 ULTRAVIOLET PHOTO ELECTRON SPECTROCOPY AND
X- RAY PHOTO ELECTRON SPECTROSCOPY
24.3 LET US SUM UP
24.5 REFERENCES
To understand the spectral methods such as ultraviolet photoelectron

spectroscopy and X- ray photo electron spectroscopy.
The objective is to
i) Learn the importance of these techniques in studying the surface

characteristics of solids.
ii) How UPS can be used to study the details of valence shell electrons.
24.1 INTRODUCTION
PHOTO ELECTRON SPECTOSCOPY
The technique of Photoelectron spectroscopy (PES) measures the

ionization energies of molecules when electrons are ejected from
different orbitals, and uses the information to infer the orbital
energies. The technique is used to study solids and the important
information that it gives about species at or on surfaces.
262
24.2.1 THE TECHNIQUE
Because energy is conserved when a photon ionizes a sample, the

energy of the incident photon hv must be equal to the sum of the
i o n i z a t i o n e n e r g y , I, of the sample and the kinetic energy of the
photoelectron, the ejected electron (Fig.3.1)
FIG – 2 4 . 1
263
1
hn = me v2 + 1
…. (1)
2
This equation (which is like the one used for the photoelectric effect,
can be refined in two ways. First, Photoelectrons may originate from
one of a number of different orbitals, and each one has a different
ionization energy. Hence a series of different kinetic energies of the
photoelectrons will be obtained, each one satisfying
1
hn = me v2 + 1i
…. (2)
2
w h e r e 1 i is the ionization energy for ejection of an electron from an

orbital i . Therefore, by measuring the kinetic energies of the
photoelectrons, and knowing n these ionization energies can be
determined. Photoelectron spectra are interpreted in terms of an
approximation called Koopmans theorem. Which states that the
ionization energy 1i is equal to the orbital energy of the ejected
electron (formally 1i = - Ei). That is, we can identify the ionization
energy with the energy of the orbital from which it is ejected. The
theorem is only an approximation because it ignores the fact that the
remaining electrons adjust their distributions when ionization occurs.
The ejection of an electron may leave an ion in a vibrationally

excited state. Then not all the excess energy of the photon appears as
kinetic energy of the photo electron, and we should write.
1
hn = me v2 + 1i + E+ vib
2
w h e r e E + v i b is the energy used to exite the ion into vibration. Each

vibratioal quantum that is excited leads to a different kinetic energy of
the photoelectron, and gives rise to the vibrational structure in the
photo electron spectrum.
264
The ionization energies of molecules are several electrovolts

even for valence electrons, so it is essential to work in at least the
ultraviolet region of the spectrum and with wavelengths of less than
about 200nm. Much work has been done with radiation generated by a
discharge through helium: the He(I) line (1s1 2p 1 1s2 ) lies at 58.43nm,
corresponding to a photon energy of 21.22 eV. Its use gives rise to the
technique of ultraviolet photoelectron spectroscopy (UPS). When core
electrons are being studied, photons of even higher energy are needed
to expel them: X-rays are used, and the technique is denoted XPS. A
mode rn version of PES makes use of synchrotron radiation, which may
be continuously turned between UV and X- ray energies. The additional
information that stems from the variation of the photoejection
probability with wavelength is a valuable guide to the identity of th e
molecule and the orbital from which photo ionization occurs.
Example – 1
Photoelectrons ejected from N2 with He (I) radiation had kinetic

energies of 5.632eV (1eV = 8065.5cm – 1 ). Helium (I) radiation of
wavelength 58.43nm has wavenumber 1.711 x 105 c m – 1 and therefore
correspondents to an energy of 21.22eV.
Then from eqn 21.2 eV = 5.63 eV+Ii So Ii = 15.59 eV. This ionization
energy is the energy needed to remove an electron from the HOMO of
th e N 2 molecule, the 3s g bonding orbital.

Under the same circumstances, photoelectrons are also detected
at
4.53eV. To what ionization energy does that correspond? Suggest on
origin.
The kinetic energies of the photoelectrons are measured using

an electrostatic deflector that produces different deflections in the
265
paths of the photoelectrons as they pass between charged plates

(Fig.3.2). As the field strength is increased, electrons of different
speeds, and therefore kinetic energies, reach the detector. The electron
flux can be recorded and plotted against kinetic energy to obtain the
photoelectron spectrum.
FIG – 2 4 . 2
24.2.2 Ultraviolet Photoelectron Spectroscopy
A typical photoelectron spectrum (of HBr) is shown in (ig.3.3).

If we disregard the fine structure, we see that the HBr lines fall into
two main groups. The least tightly bound electrons (with the lowest
ionization energies and hence highest kinetic energies when ejected)
are those in the nonbonding lone pairs of Br (with I = 11.8 eV). the
266
next ionization energy lies at 15.2 eV, and corresponds to the removal
of an electron from the H- Br s bo nd.
FIG – 2 4 . 3
The HBr spectrum shows that ejection of as electron is

accompanied by a long vibrational progression. The Franck- condon
principle would account for this progression if ejection were
accompanied by an appreciable change of equilibrium bond length
between HBr and (HBr)+ because the ion is formed in a bond-
compressed state, which is consistent with the important bonding effect
of the s electrons. The lack of much vibrational structure in the two
267
ba nds la bel ed 2 P is consistent with the nonbonding role of the Br4pp

lone pair of electrons, for the equilibrium bond length is little changed
when one is removed.
Example
The highest kinetic energy electron in the spectrum of H2 O u s i n g

21.22 eV. He radiation are at about 9 eV and show a large vibrational
spacing of 0.41 eV (or 3310 cm – 1 ), which is similar to the vibrational
wavenumber of the symmetric stretching mode of the neutral H2 O
molecule (3652 cm – 1 ). Therefore, we can suspect that the electron is
ejected from an orbital that has little influence on the bonding in the
molecule. T hat is, photoejection is from a largely nonbonding orbital).
X-Ray Photoelectron Spectroscopy
In XPS, the energy of the incident photon is so great that

electrons are ejected from inner cores of atoms. As a first
approximation, core ionization energies are insensitive to the bonds
between atoms because they are too tightly bound to be greatly affected
by the changes that accompany bond formation, so core ionization
energies are characteristics of the individual atom rather than the
overall molecule. Consequently, XPS gives lines characteristics of the
elements present in a compound or alloy. For instance, the K- shell
ionization energies (eV) of the second-row elements are
Li Be B C N O F
50 110 190 280 400 530
690
Detection of one of these values (and values corresponding to ejection

from other inner shells) indicates the presence of the corresponding
element. This appliation is responsible for the alternative name
268
electron spectroscopy for chamical analysis (ESCA). The technique is

mainly limited to the study of surface layers because, even though X-
rays may penetrate into the bulk sample, the ejected electrons cannot
escape except from within a few nanometers of the surface. Despite (or
because of) this limitation, the technique is very useful) for studying
the surface state of
heterogeneous
c a t a l y s t s , t h e
differences between
surface and bulk
structures and the
FIG – 2 4 . 4
processes that can cause damage to high – temperature superconductors

and semiconductors wafers.
269
Whereas it is largely true that core ionization energies are

unaffected by bond formation, it is not entirely true, and small but
detectable shifts can be detected and interpreted in terms of t h e
environments of the atoms. For example, the azide ion, N3 , gives the
spectrum shown in Fig.3.4. Although the spectrum lies in the region of
400 eV (and hence is typical of N1s
it has a doublet electrons),
+
structure with splitting 6 eV. This splitting can be understood b y no t i n g
that the structure of the ion is N = N= N, with more negative charges
on the outer two 'N' atoms than on the inner, the formal charges are (-
1, + 1 , - 1). The presence of the negative charges on the terminal atoms
lower the core ionisation energies, whereas the positive charge on the
central atom rises it. This inequivalence of the atoms results in two
lines in the spectrum with intensities in the ratio 2: 1 observations like
this can be used to obtain valuable information about the presence of
chemically inequivalent atoms, of the same element.
The other applications are give below : The XPS (X- r a y p h o t o

electron spectroscopy) is able to finger print the materials present .
The UPS which examines electron ejected from valence shells, is more
suited to establishing the bonding characteristics and the details of
valence shell electronic structures of the substances on the surfaces.
Its usefulness is its ability to reveal which orbitals of the adsorbate are
involved in the bond to the substrate. For example the photo emission
spectroscopy studies indicate the differences in p electron energies of
benzene in the free state and in the adsorbed state, on palladium. This
difference is due to the fact that benzene molecules tie parallel to the
surface and are attached to it by their p - orbital.

1. State Koopman's theorem. How is it useful?
2. Discuss the applications of PES & UPS – spectroscopies
Model answer – self check exercise-1
hn = KE + Ii
hn = 21.22 ev and KE = 4.53ev
270
Hence I = 21.22 – 4.53

16.7ev – this corresponds to the origin of the electron from 1p u .
24.3 Let us Sum Up

i) Kopopman’s theorem is explained.
ii) Applications of PES and UPS spectroscopies are discussed.
iii) PES spectrum of HBr is illustrated.

1) Analysis of Ionisation energies from photo electron spectroscopy
provides evidence for the molecular orbital structures of molecules.
2) One can specify which is the Homo of the molecule from the ionisation
energy value.
3) Analysis of the photo electron spectrum of a molecule like HBr shows,
that the lowest energy bands correspond to Bromine lone pair – and the
highest energy band corresponds to removal of 's ' bond electron.
24.5 Refe rence s

CBs New Delhi.
271

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1.0 AIMS AND OBJECTIVES

S o m e n o n - metals have the tendency to resemble carbon in certain

have the tendency of form chains, to a limited extent. There is no

2 S i 2 H 6 + 7O2 4 SiO2 + 6 H2 O. This reaction is kinetically

1.2.1 HETERO CATENATION:

The phenomenon of hetero catenation or chains built up of alternating

condensed poly phosphates such as sodium triphosphates, are largely used as

Silicon forms a very large number of compounds containing

i) Or tho Silicate s: A wide variety of minerals contain discrete (SiO4 ) 4 -

I n Z n 2 SiO 4 (Willemite) and Be2 S i O 4 (Phenacite) Zn and Be have a

Pyrosilicates are rare, for e.g., Thortveitite (Sc2 ( S i 2 O 7 ) S i - O-S i b o n d

The co ordination number of the metal changes from 6 to 7 and then to

If two oxygen atoms per tetrahedron are shared, ring structures of

The mineral chrysatile Mg3 ( O H ) 4 ( S i 2 O 5 ) is white asbestos and is a

W hen S iO 4 units share three corners the structure formed is an infinite

(i) Clay minerals (Kaolinite)

consider the formation of a two layer structure. If a Si2 O 5 layer is placed

Three Dimensional Silicates

Sharing all four corners of a Si O4 tetrahedron results in a three

Granite is made up of feldspars. We have orthoclase feldspars:

The ultramarines are now produced synthetically is obtained by heating

1.2.2 ISOPOLY AND HETEROPOLYANIONS

Transition metals in their higher oxidation states are similar to

The structure of CrO3 consists of infinite linear chains of Cr O4 tetrahedra.

repulsion, in the larger octahedra. As a result, the structures tend to be small

The isopoly an ions may be considered to be portions of a closest

It has been found that there is a cavity in the center of a metatungstate

C o in [(Si W1 1 O 3 9 ) Co (H2 O)] 6 - is 6 coordinate, the heteropoly anion

Fig.1.2(a) and (b) Bonding and structure of tetraborane, B4H10. (From

The appropriate combinations of three orbital wave functions, j B1 , j B2 ( S P 3

Y b= bonding Mo, Y a = antibonding MO and Y n = nonbonding. Each bridging

B4 H 1 0 + 2 Me3 N Me 3 N B 3 H 7 + Me3 N BH3 .

Fig 1.2 Symmetric (a) and Unsymmetric (b) Cleavage of Tetraborane

[B 1 2 H1 2 ] 2 - is a highly symmetric borohydride. It is obtained from B3 H8 - ion .

5[B 3 H8 ] - [B 1 2 H1 2 ] 2 - + 3[BH4 ]- + 8H2

T h e [ B 1 2 H 1 2 ] 2 - is a regular icosahedron of atoms, each of the twenty

The systems C2 B1 0 H1 2 is isoelectronic with [B1 2 H 1 2 ) 2 - and can be

The acetylene may be unsubstituted or substituted, in which case, the

Hence this anion [C2 B9 H1 1 ] 2 - has a resemblence to

2[C 2 B 9 H 1 1 ] 2 - + Fecl 2 [(C 2 B 9 H1 1 ) 2 F e ] 2 - + 2cl-

This has structure similar to ferrocene.

Self Check Exercise m- 1

2) Describe with examples, the isopoly anions.

Self Check Exercise – 2

1) Discuss the structures of molybdates and tungstates

1.3 Let us Sum Up

1.4 Points for Discussions

i) Silicates ad their structures

Concise Inorganic chemistry – V edition – J . D . L e e – B l a c k w e l l .

2.0 AIMS AND OBJECTIVES

Compounds containing metal- metal bonds are as old as chemistry

M e t a l c l u s ter compounds can be conveniently classified into two

i) Have formal oxidation states –1 to +1, while those in

The transition metals (late transition metals) typically form class

The best studied compound is (Re2 x 8)2 - ion; obtained by reducing

It has two unusual features. Re- Re bond distance is 224pm compared

The isoelectronic (Mo2 C l 8 ) 2 - is known. Both Re (III) and Mo(III) form