CHEMISTRY LECTURE NOTES

COURSE : VIKAAS (JA )

(LECTURE No. 1 TO 6)

TOPIC : PERIODIC TABLE

& PERIODICITY

Number of lectures are allotted strictly

according to lecture plan so try to finish in
prescribed lectures.

RESONANCE PERIODIC PROPERTIES - 1

 LECTURE # 1
Introduce Modern Periodic Table to the students for Few Minutes :

RESONANCE PERIODIC PROPERTIES - 2

DIAGONAL RELATIONSHIP :
Some elements of certain groups of 2nd period resemble much in properties with the elements of third period
of next group i.e. elements of second and third period are diagonally related in properties. This phenomenon
is known as diagonal relationship.
2nd period Li Be B C

3rd period Na Mg Al Si
Diagonal relationship arises because of
(i) similar size of atom and ions
(Li = 1.23 Å & Mg = 1.36 Å ; Li+ = 0.76 Å & Mg2+ = 0.72 Å)
(ii) similar polarising powers (charge to radius ratio)
(iii) similarity in electronegativity values
(Li = 1.0 & Mg = 1.2 ; Be = 1.5 & Al = 1.5)

THE PERIODICITY OF ATOMIC PROPERTIES :

(I) EFFECTIVE NUCLEAR CHARGE :
Between the outer most valence electrons and the nucleus of an atom, there exists finite number of shells
containing electrons. Due to the presence of these intervening electrons, the valence electrons are unable to
experience the attractive pull of the actual number of protons in the nucleus. These intervening electrons act
as shield between the valence electrons and protons in the nucleus. Thus, the presence of intervening
(shielding) electrons reduces the electrostatic attraction between the protons in the nucleus and the valenece
electrons because intervening electrons repel the valence electrons. The concept of effective nuclear charge
allows us to account for the effects of shielding on periodic properties.
The effective nuclear charge (Zeff) is the charge felt by the valence electron. Zeff is given by Zeff = Z – .
Where Z is the actual nuclear charge (atomic number of the element) and  is the shielding (screening) constant.
There are some simple rules for determining the degree to which electrons in the various types of orbitals
shield other electrons from the nucleus & hence for determining the Zeff experienced by other electrons.
Write the full electronic configuration.
If the electron in question resides in an s or p orbital,
1. All electrons in principal shells higher than the electron in question contribute zero to .
2. Each electron (other than in the question) in the same principal shell contributes 0.35 to .
3. Electrons in the (n – 1) shell each contribute 0.85 to .
4. Electrons in deeper shells each contribute 1.00 to .

If the electron in question resides in a d or f orbital,

1. All electrons in principal shells higher than electron in question contribute zero to .
2. Each electron (other than in the question) in the same principal shell contributes 0.35 to .
3. All inner-shell electrons [i.e., (n – 1) and lower] uniformly contribute 1.00 to .

Sum the shielding constants from steps 1–4 for s or p orbital or from steps 1–3 for d or f orbital and subtract
them from the actual nuclear charge (Z) of the atom in question to obtain the Zeff felt by the electron in question.
(Source : Basic Inorganic Chemistry (Third Edition) By Cotton Wilkinson and Gaus)
The relative extent to which the various orbital penetrate the electron clouds of of other orbitals is s > p > d > f.
Thus for any given principal quantum number n, an electron will experience the greatest effective nuclear
charge when in s-orbital than p-orbital and so on.
____________________________________________________________________________________________________
What is the effective nuclear charge at the periphery of nitrogen atom when a extra electron is added during the
formation of an anlon. Compare the vlaue of Zeff when the atom is ionized.
____________________________________________________________________________________________________

RESONANCE PERIODIC PROPERTIES - 3

Sol. Ground state electron configuration of N(Z = 7) = 1s2 2s2 2p3
Electron configuration of N– = (1s2) (2s2 2p4)
Shielding constant for the last 2p electron,
 = [(5 × 0.35) + (2 × 0.85)] = 3.45
 Zeff = Z –
Zeff for last p electron on N– = 7 – 3.45 = 3.55
Electron configuration of N+ = (1s2) (2s2 2p2)
Shielding constant for the last 2p electron,
 = [(3 × 0.35) + (2 × 0.85)] = 2.75
Zeff for last electron on N+ = 7 – 2.75 = 4.25

2. ATOMIC RADIUS :
(A) Covalent radius :
It is one-half of the distance between the centres of two nuclei (of like
atoms) bonded by a single covalent bond. Covalent radius is generally
used for non-metals.

Single Bond Covalent Radius, SBCR (bond length) -

dA  A
(a) For homodiatomic molecules dA–A = rA + rA or 2rA so, rA =
2
 (b) For heterodiatomic molecules in which electronegativity remains approximately same.
dA – B = rA + rB

Do not tell this formula in class. Only for reference of faculty.

 For heteronuclear diatomic molecule, A–B, where difference between the electronegativity values of atom A
and atom B is relatively larger,
dA – B = rA + rB – 9.0 
Electronegativity values are given in pauling units and radius in picometers.
 = XA – XB where XA and XB are electronegativity values of high electronegative element A and less
electronegative element B. This formula is given by Stevenson & Schomaker.

LECTURE # 2

(B) Van der Waals radius (Collision radius) :

It is one-half of the internuclear distance between two adjacent
atoms in two nearest neighbouring molecules of the substance in
solid state.
 Van der Waal’s radius does not apply to metals. Its magnitude
depends upon the packing of the atoms when the element is in
the solid state.

Comparision of covalent radius and van der Waal’s radius

(i) The van der Waal’s force of attractions are weak, therefore, their internuclear distances in case of atoms held
by van der Waal’s forces are much larger than those of between covalently bonded atoms. Therefore van der
Waal’s radii are always larger than covalent radii.
(ii) A covalent bond is formed by the overlaping of two half-filled atomic orbitals, a part of the orbital becomes
common. Therefore, covalent radii are always smaller than the van der Waals radii. For example,

Elements H O F S Br
Covalent radius (Å) 0.37 0.66 0.64 1.04 1.11
van der Waal's radius (Å) 1.20 1.40 1.35 1.85 1.95

RESONANCE PERIODIC PROPERTIES - 4

(C) Metallic radius (Crystal radius) :
It is one-half of the distance between the nuclei of two adjacent metal atoms in the
metallic crystal lattice.
 Metallic radius of an element is always greater than its covalent radius. It
is due to the fact that metallic bond (electrical attraction between positive charge of
an atom and mobile electrons) is weaker than covalent bond and hence the
internuclear distance between the two adjacent atoms in a metallic crystal is
longer than the internuclear distance between the covalently bonded atom.
For example : Metallic radius Covalent radius
K 231 pm 203 pm
Na 186 pm 154 pm
 rcovalent < rcrystal < rvander Walls

Variation in a period: On moving left to right due to increased nuclear charge the size decreases.
Variation in a group: On moving top to bottom due extra addition of a shell the size increases.
---------------------------------------------------------------------------------------------------------------------------------------------------------------------
Note : This portion is not properly discussed so do explain all these a bit slow
Some Irregularities
(a) The atomic radius of inert gas (zero group) is given largest in a period because it is represented as van der
Waals’s radius which is generally larger than the covalent radius. The van der Waal’s radius of inert gases
also increases from top to bottom in a group.

Talk about general trend. Do not stress on exception. Need not memorize.
(b) In the transition series (e.g. in first transition series), the covalent radii of the elements decrease from left
to right across a row until near the end when the size increases slightly. On moving from left to right, extra
protons are placed in the nucleus and the extra electron are added. The orbital electrons shield the nuclear
charge incompletely. Thus the nuclear charge attracts all the electrons more strongly, hence a contraction
in size occurs. The radii of the elements from Cr to Cu, are very close to one another because the extra
electron being added increasses the repulsion between the electrons and counter balances the increased
nuclear charge on the outer electrons (4s). As a result of this, the size of the atom does not change much
in moving from Cr to Cu and for zinc this repulsion even dominates the nuclear charge so size slightly
increases.
Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
Atomic radius (Å) 1.44 1.32 1.22 1.18 1.17 1.17 1.16 1.15 1.17 1.25

(c) rAl  rGa

because of d orbital contraction.
(d) 4d 5d (Zr – Hf)
( lanthanide contraction)
The lanthanide contraction counter balances almost exactly the normal size increase on descending a group
of transition elements. Thus covalent and ionic radii of Nb (5th peroid) and Ta (6th period) are almost same
due to poor shielding of f-orbitals electrons.
Note: Define lanthanide and transition metal contraction.
IONIC RADIUS :

 The sizes of ions increases as we go down a group (considering the ions of same charge). For
example :
Li+ < Na+ < K+ < Rb+
Be2+ < Mg2+ < Ca2+ < Sr2+
F– < Cl– < Br – < –
 Cation is smaller than parent atom but anion is bigger than parent atom.

 The species containing the same number of electrons but differ in the magnitude of their nuclear
charges are called as isoelectronic species. For example, N3– , O2–, F–, Ne, Na+ , Mg2+ and Al3+ are all
isoelectronic species with same number of electrons (i.e 10) but different nuclear charges of +7, +8, +9,
+10, +11, +12 and +13 respectively.

RESONANCE PERIODIC PROPERTIES - 5

 Within a series of isoelectronic species as the nuclear charge increases, the force of attraction by the
nucleus on the electrons also increases. As a result, the ionic radii of isoelectronic species decrease with
increases in the magnitude of nuclear charges. For example,
Al3+ Mg2+ Na+ F– O2– N3–

Ionic radii increase

As effective nuclear charge decrease.

 Zero group elements should not be considered while comparing the size or ionic radii as their atomic
radii are expressed as van der Wall’s radii.

LECTURE # 3
Ionisation Energy ( Ionisation potential)
Min amount of energy required to remove an electron from an isolaled gaseous atom / species.

(I.E.)1 M(g)  M+(g) + e– H = +ve

(I.E.)2 M+(g)  M2+ (g) + e–

(I.E.)3 > (I.E)2 > (I.E.)1 – Difficult to remove an electron from a positively charged ion than from a neutral
atom.

Factors affecting I.E.

(a) Size Size   I.E. 

(b) Zeff Zeff   I.E.  but   (i.e. Zeff  ) E 

(c) Electronic configuration – For a stable electronic configuration i.e. half filled or fully filled configurations
(stable because of symmetry) I.E. will be larger
(d) The relative extent to which the various orbital penetrate the electron clouds of of other orbitals is s > p > d
> f. Thus for any given principal quantum number n, an electron will experience the greatest effective nuclear
charge when in s-orbital than p-orbital and so on. Hence the order of I.E. is as follows : s > p > d > f

Teach following portion a bit slowly

Periodicity
L–R I.E.  (Zeff  )

T–B I.E.  (Size  )

rregularities
(a) In  period ( also in  period )

Be > B, N > O, Ne >> F

(b) .E.Ga> .E.Al
size same extra nuclear charge 
(c) 5d > 3d > 4d
(lanthanide contraction)
Note : I.E. can be correlated with the reactivity e.g., (a) Noble gases are inert towards chemical reactivity.
(b) low I.E. of alkalimetals correlate with their high reactivity.
---------------------------------------------------------------------------------------------------------------------------------------------------------------------

RESONANCE PERIODIC PROPERTIES - 6

Puts some examples of ionization energy here

Electron Affinity (E.A)

The energy released when an electron is added to an isolated gaseous atom to produce a monovalent anion
is known as e.a. and enthalpy change of this process is known as electron gain enthalphy
Heg   ve
M(g) + e–  M–(g) energy released
E.A.   ve

Heg   ve
energy absorbed
E.A.   ve
(E.A.)2 is always +ve – because of electrostatic repulsion between anion and electron (having same charge).
M–(g) + e –  M2–(g) Heg2 = + ve

Factors affecting E.A.

(a) Size Size   E.A. 

(b) Zeff Zeff   E.A.     E.A. 

(c) E.C. Stable E.C. will have smaller or –ve E.A

Periodicity
L  R Zeff   E.A. 

T B Size   E.A.  (Except 3rd period elements)

Irregularities
(a) nd period

(b) E.A. 3P > 2P

E.A (low) B C N O F
(added electron goes to the samller n = 2 and suffer significant repulsion from the other electrons present in
this level.)

E.A.(high) Al Si P S Cl
(added electron goes to the bigger n = 3 i.e. occupies larger region of space and the electron-electron
repulsion is much less.)

(c) Noble gases have large positive electron gain enthalpies because the electron has to enter the next higher
principal quantum level leading to a very unstable electronic configuration.
e.g.H in kJ / mol of groups 16th and 17th
S Se Te Po O
–200 –195 –190 –174 –141

Cl F Br I At
–349 –328 –325 –295 –270

LECTURE # 4
Electonegativity.
A qualitative measure of the ability of an atom in a chemical compound to attract shared electrons to itself
iscalled electronegativity not a measurable quantity. A number of numerical scales of electronegativity have
been proposed.
Differences in E.A. & E.N.

RESONANCE PERIODIC PROPERTIES - 7

(a) E.A. is defined in isolated gaseous state while E.N. is defined in bonded state
(b) E.A. is a absobule term, it has proper units while E.N. is a relative concept has no units

Different Scales of Measurement of Electonegativity.

(a) Pauling’s scale : Linus Pauling developed a method for calculating relative electronegativities of most
elements. According to Pauling

(a)  = XA – XB = O.208 E.A B  E A  A  EB B (All bond energies are in kcal / mol)

EA-B = Bond enthalpy/ Bond energy of A – B bond.

EA - A = Bond energy of A – A bond
EB –B = Bond energy of B – B bond

(b)  = XA – XB = O.1017 E.A B  E A  A  EB B

(All bond energies are in kJ / mol.)

(b) Mulliken’s scale : Electronegativity  (chi) can be regarded as the average of the ionisation energy (IE) and
the electron affinity (EA) of an atom (both expressed in electron volts).
IE  EA
M =
2

Only For Faculty refrence. Not to be told in class.

Paulings’s electronegativity P isrelated to Mulliken’s electronegativity M as given below.

P = 1.35 (M)1/2 – 1.37

Mulliken’s values were about 2.8 times larger than the Pauling’s values.

Factors affecting Electronegativity.

(a) Size Size   EN 

(b) Zeff Zeff   EN     EN 

(c) Charge on cationic species
A3+ > A2+ > A+1 (for the same element)
Greater the charge on cation, greater E.N value
(d) Charge on anionic species
A3– < A2– < A–
(e) State of hybridization
Greater the %s character  greater the attraction on the shared pair  Greater will be E.N
sp > sp2 > sp3

Electronegativity of some elements according to Pauling scale

Elements H Li Be B C N O F Na P S Cl Br I

Electronegativy 2.1 1.0 1.5 2.0 2.5 3.0 3.5 4.0 0.9 2.1 2.5 3.0 2.8 2.5

Periodicity
L – R  Zeff  E.N  T – P  Size  E.N 

---------------------------------------------------------------------------------------------------------------------------------------------------------------------
Note : BE SLOW AND EXPLAIN PROPERLY

RESONANCE PERIODIC PROPERTIES - 8

Applications
Prediction of nature of bond
(a) XA = XB  pure covalent bond (b) XA  XB  partly ionic + covalent

Only for faculty refrence (Debatable theory) Not to be done in class

Acc. to pauling, if
XA – XB = 1.7 50% ionic
 < 1.7 more covalent less ionic  > 1.7 more ionic less covalent
Henny smith formula % ionic character = 16 + 3.5 2   = | XA – XB|
Bond to be 50% ionic  = 2.1

Q. Calculate % ionic character of bond formed between the most electropositive element Cs (x = .7) and most
electronegative element F (x = 4.0). According to Hanny Smith formula % ionic character
= 16(3.3) + 3.5 (3.3)2 = 52.8 + 38 .115 = 91.915 %

LECTURE # 5
(a) Inert pair effect : The outer shell ‘s’ electrons (ns2) penetrate to (n – 1) d electrons and thus become closer
to nucleus and are more effectively pulled towards the nucleus. This results in less availability of ns2 electron
pair for bonding of ns2 electron pair becomes inert. The inert pair effect begins after n  4 and increases with
increases value of n.
(i) Dominance of lower oxidation state on moving down the group in boron, carbon & nitrogen family may also
be explained by the inert pair effect.
(ii) The inert pair effect is not the explanation of why monovalency , bivalency and trivalency in group 13, 14
& 15. It merely describe what happens, i.e. two electrons do not participate in bonding. The reason that they
do not take part in bonding in energy.
Order of stability of oxidation state according to Inert pair effect :

Tl   Tl 3
Pb 2
 Pb  4 Ga   In   Tl  Sn 2  Pb 2 Sb 3  Bi3
3 3 3 4 4
Bi 3  Bi 5 Ga  In  Tl Sn  Pb Sb 5  Bi 5

(b) Note: Discussion of all sheets

LECTURE # 6
(Shift to chemical bonding)
Types of Oxides and acidic / basic nature of oxyacids and hydra acid :
(a) Acidic oxides
(a) Solution in water will be acidic in nature (b) will react with base but not with an acid
Ex. H2 O
SO2  H2 O
 H2SO3 Sulphurous acid  SO3  H2SO4 sulphsic acid
H2 O
CO2  H2CO3 Carbonic acid
generally non-metallic oxider are acidic oxides
(b) Basic oxides
(a) Solution in water will be basic in nature (b) will react with an acid but not with a base
Ex. H2 O
Na2O  H2 O
 2NaOH CaO  Ca(OH)2
Generally, metallic oxides are basic oxides

(c) Amphoteric oxides

Can react with an acid as well as with a base.
Ex Generally, metalloids or elements close to metalloids can form ampholeric oxides.

RESONANCE PERIODIC PROPERTIES - 9

 BeO  BeO + 2HCl  BeCl2 + H2O, BeO + 2NaOHNaAlO2 (Sodiuni meta aluminate)
ZnO  ZnO + HCl  ZnCl2 , ZnO + NaOH Na2ZnO2 (sodium zincate)

SnO  (stannous oxide)

SnO + HCl SuCl2, SnO + NaOH  Na2SnO2 (sodium stanite)
SnO2  (stannic oxide)
SnO2 + 4HCl  SnCl4 SnO2 + NaOH  Na2SnO3 (sodium stanate)
(d) Neutral oxides : will not react with acids or bases
CO, N2O, NO, OF2
(e) Amphiprotic oxide : which can accept and release H + ions
Ex.  H2O

Periodicity in nature of oxides

(a) L  R, metallic character  and non-metallic character  . So, basic character of oxides  and acidic
character 

Na 2O SiO 2 SO 3 Cl2 O 7
MgO Al 2 O 3 P2 O 5
strongly weakly strongly strongly
basic Amph acidic
basic acidic acidic acidic

(b) T  B, metallic character  so, basic character of oxide will 

LiOH LI2O , NaOH Na2O, KOH K2O
RbOH Rb2O, CsOH Cs2O
Basic character increases down the group
(c) If the same element is forming oxides in diff OXn states, then greater the Oxdn no greater will be acidic nature

2 3 4 6 7
MnO < Mn 2 O 3 < MnO 2 < MnO 3 < Mn 2 O 7
more basic neutral acidic more
basic acidic

oxides are anlydrides of oxyacid or hydroxides

4 4 6
H O H O +5  H2 O
H2SO 3 2 SO 2 , H2SO 4 2 SO3, H2CO3   CO2

5
+5
H3PO 4  P2O5 (P4O10) , H3PO3  P2O3 (P4O6)

HNO3  N2O5 , HNO2  N2O3 , HClO4  Cl2O7, HClO3  Cl2O5

HClO2  Cl2O3, HClO  Cl2O , NaOH  Na2O , Ca(OH)2  CaO
4 5 3
H2 O
Mixed anhydrides. ClO 
2  HClO3 + HClO2
For oxy acids
(a) On moving L  R non metallic character  acidic strength 
H3BO3 < H2CO3 < HNO3 H2SiO3 < H3PO4 < H2SO4 < HClO4
(b) On moving T  B, non – metallic character  acidic strength 
HNO3 > H3PO4 > H3AsO4 HClO4 > HBrO4 > HO4
(c) If same element is forming oxycids in different oxidation states then, Greater the oxidation no. of the element
greater will be the acidic strength
HNO3 > HNO2 > H2N2O2 HClO4 > HClO3 > HClO2 > HClO

RESONANCE PERIODIC PROPERTIES - 10