Chapter 1

The Chemistry of transition elements

 Cont’d
• d-Block elements: The elements lying in the middle of periodic table
belonging to groups 3 to 12 are known as d – block elements

• Their general electronic configuration is (n – 1) d 1-10 n s 1-2 where (n – 1)

stands for penultimate (last but one) shell.

• Transition element: A transition element is defined as the one which has

incompletely filled d orbitals in its ground state or in any one of its
oxidation states.

• Zinc, cadmium, mercury are not regarded as transition metals due to

completely filled d – orbital

 Four transition series:

• 3d – transition series. The transition elements with atomic number 21(Sc)

to 30(Zn) and having incomplete 3d orbitals
 Cont’d
• 4d – transition series. It consists of elements with atomic number 39(Y) to
48 (Cd) and having incomplete 4d orbitals.

• 5d – transition series. It consists of elements with atomic number 57(La),

to 80(Hg) having incomplete 5d orbitals.

• 6d – transition series. It consists of elements with atomic number 89(Ac),

to 112 (Uub) having incomplete 6d orbitals.
Cont’d
Cont’d
 Cont’d
 Physical and chemical properties of transition elements

• There are several common characteristic properties of transition elements

 They often form coloured compounds

 They have a variety of different oxidation states.

 They are often good catalysts.

 They are silvery-blue at room temperature (except copper and gold).

 They are solids at room temperature (except mercury).

 They form complexes.

 Most of TM are paramagnetic

 Cont’d

 General Characteristics of transition elements

 Metallic character: All transition elements are metallic in nature, i.e. they
have strong metallic bonds. This is because of presence of unpaired
electrons.

 This gives rise to properties like high density, high enthalpies of

atomization, and high melting and boiling points.

 Atomic radii: The atomic radii decrease from Sc to Cr because the effective
nuclear charge increases.

 The atomic size of Fe, Co, Ni is almost the same because the attraction due
to increase in nuclear charge is cancelled by the repulsion because of
increase in shielding effect. Cu and Zn have bigger size because the
shielding effect increases and electron -electron repulsions increases.
 Cont’d
 Alloys formation: They form alloys due to similar ionic size. Metals can
replace each other in crystal lattice, e.g., brass, bronze, steel etc.

 variable oxidation states : They exhibit variable valiancy due to

involvement of (ns) and (n-1)d electrons in bonding. This is due to less
energy difference between these electrons.

• The 3d and 4s electrons are of similar energy so that both levels of

electrons are available for bonding.
Cont’d
 Cont’d
 Magnetic properties: Most of transition metals are paramagnetic in nature
due to presence of unpaired electrons. It increases from Sc to Cr because
number of unpaired electrons increases from Sc to Cr and then decreases.
 Catalytic properties: Most of transition metals are used as catalyst because
of (i) presence of incomplete or empty d – orbitals, (ii) large surface area, (iii)
varuable oxidation state, (iv) ability to form complexes, e.g., Fe, Ni, V2O3,
Pt, Mo, Co and used as catalyst.
 Formation of coloured compounds: They form coloured ions due to
presence of incompletely filled d – orbitals and unpaired electrons, they can
undergo d –d transition by absorbing colour from visible region and radiating
complementary colour.
 Formation of complexes: Transition metals form complexes due to (i)
presence of vacant d – orbitals of suitable energy (ii) smaller size (iii) higher
charge on cations.
 Cont’d
• Electron Configurations
Sc: [Ar]4s23d1
Ti: [Ar]4s23d2
V: [Ar]4s23d3
Fe:[Ar]4s23d6
Co:[Ar]4s23d7
Ni: [Ar]4s23d8
Cu: [Ar]4s13d10
Zn:[Ar]4s23d10
Cr: [Ar]4s13d5

Mn: [Ar]4s23d5
•
 Cont’d

 Comparison of physical and chemical properties between d- block and s

- block elements.

 d- block metals have smaller atomic radius than S - block elements. This
is because the screening effect of d- subshell electrons is poor.

 The increase in effective nuclear charge when the electron is added to the
same d- subshell makes the electrons contract. The atomic radius at first
decreases, then remains unchanged in the middle of the series. At the end,
the atomic radius increases again

 Because at the beginning, the increases in effective nuclear charge pulls in

the electron, resulting in a reduction of atomic size.
 Cont’d
 In the middle, since electrons are added to the inner 3d- subshell, the
increasing screening and repulsive effects of the electrons in the 3d subshell
cancel out the increase in effective nuclear charge. Hence there is a little
change in atomic radius.

 At the end, as more electrons are added to the same d- subshell, the screening
and repulsive effects reach a maximum. Hence the electron expands.

 The densities of d- block elements are higher than those of s- block

elements. Because d - block elements have close- packed structure and
with smaller atomic radius while s- block metals may not have close-packed
structure.

 The densities generally increase across the series. This is in agreement with
the change in atomic radius across the series.
 Cont’d
Trend: The 1st ionization enthalpies increase gradually across the series.

 Across the series, electrons are added to the inner 3d subshell. The inner d-
electrons can shield the outer 4s electrons less effectively, hence the
effective nuclear charge increases and 1st ionization enthalpies increase
gradually.

Trend: The 1st ionization enthalpies only increases slowly.

 It is because the increase in repulsion of 3d electrons cancels out the

increase in effective nuclear charge to a certain extent.

Trend: The successive ionization enthalpies exhibit a similar increase.

- The reason is the same as that for 1st ionization enthalphies

 Cont’d
• Some irregularities in the variation:
 The 1st ionization enthalpy of zinc is exceptional high because it has a full-
filled 3d subshell.
 The 2nd ionization enthalpy of chromium is higher than manganese. It is
because it has a half - filled 3d subshell which has extra stability.
 The 3rd ionization enthalpy of iron is smaller than manganese. It is
because the removal of the 3rd electron from iron gives a stable half - filled
3d subshell. Hence less energy is required.
 The electronegativity of d- block elements are higher than those of s- block
elements. It is because the d- block elements have smaller atomic radii and
hence the nucleus of the d- block elements can attract the electrons in a
bond more tightly.
 Moreover, the electronegativity of d- blocks increase gradually across the
series because the increase in effective nuclear charge.
 Cont’d
 The melting points of d- block elements are higher than those of s- block
elements. This is because the d- block elements have a close - packed
structure. Moreover d- block elements have smaller atomic radii and this
means the d- block metallic ions have a higher charge density and both the 3d
and 4s electrons of d- block elements delocalize to participate in the
formation of metallic bond.
 the reason is stronger metallic bond and presence of covalent bond formed
by unpaired d-electrons.
 In Zn, Cd, and Hg there is no unpaired electron present in d-orbital, hence
due to absence of covalent bond, their m.p. and b.p. are very low. (Volatile
metals Zn, Cd, Hg). In 3d series: Sc→Cr; m.p. b.p increases, All these mean
that the metallic bonds in d- block elements are stronger than those in s -
block elements.
 Cont’d

• Hardness of a metal is dependent on the strength of the metallic bonds. As

the metallic bond strength of d- block elements is stronger than that of s-
block elements, the d- block metals are harder than s- block elements.
 Cont’d
• Application of transition metals
Ion conduction
 The migration of atoms within a solid is strongly influenced by the defects
associated with non-stoichiometry.
 These defect sites provide pathways for atoms and ions to migrate through
the otherwise dense ensemble of atoms that form the crystals. Oxygen
sensors and solid state batteries are two applications that rely on oxide
vacancies.
Superconductivity
 Many superconductors are non-stoichiometric.
For example, yttrium barium copper oxide, arguably the most notable high-
temperature superconductor, is a non-stoichiometric solid with a formula
represented by YxBa2Cu3O7−x.
 Cont’d
• Transition metals and their compounds have many useful applications

 Fe is used to make steel and stainless steel

 Ti is used to make lightweight alloys

• Transition metal compounds are used as pigments

 TiO2 = white

 PbCrO4 = yellow

 Fe4[Fe(CN)6]3 (prussian blue)= blue

 Transition metal compounds are used in many industrial processes

Cont’d
Cont’d
Cont’d
Cont’d
 Cont’d
• Coloured ion formation
Many d-block complexes are coloured because photons of visible light give
rise to electronic transitions between the two sets of d orbitals.
Many transition metal ions are coloured due to d-d transitions. The energy
absorbed in excitation of an electron from a lower energy d orbital to a higher
energy d orbital corresponds to the frequency which generally lies in the visible
region.
The colour observed corresponds to the complementary colour of the light
absorbed.
The frequency of light absorbed is determined by the nature of ligand.

•
Cont’d
 Cont’d
Non-stoichiometric compounds
 Compounds with non-integer values of the atomic composition
 Non-stoichiometric compounds are chemical compounds with an elemental composition
that cannot be represented by usual integral numbers.
• Examples TiH1.7, ZrH1.9, VH 0.56, TiC, Fe3C, Fe0.94O etc.
 They are almost always inorganic compounds and almost invariably solids. In such materials
some small percentage of atoms are missing or too many atoms are packed into an otherwise
perfect lattice work.
 is represented by many metal oxides and sulfides.
 Non-stoichiometric compounds are usually caused by compounds with non integral
coefficients or varying ratios of atoms.
 Stoichiometric coefficients are used in chemical equations to know how much of an element is
needed to react with the other element(s).
 They are very useful in stoichiometric equations, for example finding how many moles of a
specific atom are produced in a chemical reaction.
 Cont’d
 However, in nonstoichiometric compounds these coefficients cannot be
determined due to:

 An atom is missing from the lattice structure of a solid, causing the other
atoms to change their oxidation states to maintain neutrality in the atom.

 Extra atoms are found in excess in the solid

 The missing atoms are replaced by atoms of a different element to

maintain the neutral charge.

 This phenomenon is most common in ionic compounds of transition metals,

specifically Oxides, Hydrides, Carbides, and Borides.

 It occurs most often in solids due to defects in the lattice of their crystalline
structures.
 Cont’d
 In these compounds there are specific ways to account for the missing or extra atoms.

 A variable is added to the coefficients to show that the compound is not entirely

stoichiometric.

1. If the metal/nonmetal ratio is greater than stoichiometric, then there is either excess metal or

missing nonmetal.

 If there is excess metal(interstitial atoms) it is represented as, for example Fe1+xO.

 If there is missing nonmetal, it is represented as, for example, MoO3-x

2. If the metal/nonmetal ratio is less than stoichiometric, then the situation is the opposite.

 Missing metal is represented by the compound Rh1-xO

 Extra nonmetal is represented by the compound WO2+x

3. If another element replaces the missing atoms, called impurity materials, it is best to

consider it as a simple solid solution.

 Cont’d

• The three most common causes of non-stoichiometric compounds

 The dots represent atoms in the lattice structure of a solid.
The vacancies are the missing atoms (defects) that can throw off the
proportions of the compound.
The interstitial atoms are the extra atoms that wedge themselves in the
framework of the solid and prevent the use of stoichiometric coefficients.
 The impurity are the substitutional atoms, or atoms of a different element
that fill the empty spaces caused by vacancies.
 Cont’d
• Example: stoichiometric iron(II) oxide, which is rare, has the formula FeO,
whereas the more common nonstoichiometric material has the formula
Fe0.95O.

• Iron sulfide Fe(1-x)S (x = 0 to 0.2).

 Cont’d
 The principal physical and chemical characteristics of these compounds are as
follows:
(i) They have high melting points, higher than those of pure metals.
(ii) They are very hard, some borides approach diamond in hardness.
(iii) They retain metallic conductivity.
(iv) They are chemically inert.

 Assignment one

• Studies with specific Reference to first series of transition metals (Sc, Ti, V, Cr,
Mn, Fe, Co, Ni, Cu and Zn)
 You are expected to prepare and present note on:
 Occurrence
 Extraction and uses
 Metal and its compounds
 Cont’d
• Catalytic properties of the metals in the synthesis of inorganic compounds and
organic compounds.
 Most of transition metals are used as catalyst because of
 presence of incomplete or empty d – orbitals
 large surface area
 variable oxidation state and ability to form complexes.
 e.g., Fe, Ni, V2O3, Pt, Mo, Co and used as catalyst
Haber process
 The Haber process is used to make ammonia, NH3, from the reaction of nitrogen
and hydrogen.
N2(g) + 3H2(g)→2NH3(g)
 The catalyst is iron metal – it is used to increase the rate of reaction and to
lower the temperature at which the reaction takes place.
 Cont’d
Contact process

 The contact process is used to convert sulfur dioxide, SO2, into sulfur trioxide, SO3,
in the manufacture of sulfuric acid, H2SO4.

2SO2(g) + O2(g) → 2SO3(g)

 The catalyst used is vanadium(V) oxide, V2O5, in which vanadium has the +5
oxidation state.

Hydrogenation of alkenes

 Hydrogen can be added across the C=C double bonds in unsaturated compounds
to make saturated compounds – the process is called hydrogenation.

 The catalyst is nickel metal – it is used to lower the temperature and pressure
needed to carry out the reaction
 Cont’d
Decomposition of hydrogen peroxide

 Hydrogen peroxide decomposes slowly at room temperature and pressure

into water and oxygen.

 A catalyst is added to increase the reaction rate.

2H2O2(aq) → 2H2O(l) + O2(g)

 A suitable catalyst is manganese(IV) oxide, MnO2, in which manganese has

the +4 oxidation state.

 The catalytic decomposition of hydrogen peroxide is often used in the

laboratory as a simple and convenient preparation of oxygen gas.
 CAPTER- 2

Chemistry of f-Block Elements

 Cont’d
 The elements in which the differentiating electron enters the anti
penultimate energy leveli.e. (n – 2)f, are called f – block elements.
 These are often called as inner transition elements or rare earth elements.
 The differentiating electron in transition elements may enter either 4f or 5f
orbitals based upon which they are differentiated into lanthanides and
actinides.
Lanthanides
 In lanthanides the differentiating electron enters 4f orbital. These are
cerium to lutetium. The name lanthanide is because they come
immediately after lanthanum.
Actinides
 In actinides the differentiating electron enters 5f orbitals. These are
thorium to lawrencium. These elements come immediately after actinium.
 Cont’d
• Characteristics of Lanthanides

Electronic configuration:

 General electronic configuration of f-block elements is (n–2)f1–14(n–1)d1–10ns2.

 Lanthanides [Xe]4f1–145d1–106s2

 Actinides [Rn]5f1–146d1–107s2

 All have electronic configuration with 6s2 is common but variable occupancy
of 4f and 5d-subshells due to the closeness in energy of 4f and 5d electrons.

 So it is considered that the 5d orbital remains vacant and the electrons enter
into the 4f orbital.

 Exception are:

 gadolinium, Gd (Z = 64) where the electron enters the 5d orbital due to the
presence of half filled d-orbital.
 Cont’d
 Ytterbium (z = 70) in which all the 4f orbital's are completely filled and the
differentiating electron of the next element that is lutetium (z = 71) enters the 5d
orbital.
 The complete electronic configuration of Lanthanides can be given as;
1s2 2s2 2p6 3s23p63d104s24p64d104f0-14 5s25p6 5d0-1 6s2.
Oxidation States
 Lanthanides show variable oxidation states.
 The most stable oxidation state of Lanthanides is +3.
 They also show +2 and +4 oxidation states due to the presence of either half filled
or completely filled or empty 4f sub shell.
 Lanthanides show only one stable oxidation state, which is not in the case of
actinides. The typical oxidation state of lanthanides is +3.
 Some elements show +2 and +4 also due to the presence of either half filled or
completely filled or empty 4f sub shell
 Cont’d
Examples:
 (a) a noble gas configuration (empty 4f) e.g. Ce4+ (f0)
 (b) a half filled f shell e.g. Eu2+ (f7)
 (c) a completely filled f shell e.g. YB22+ (f14)
Density
 They have high density ranging between 6.77 to 9.74 g cm-3. It increases with
increasing atomic number.
Melting and boiling point
 They have fairly high melting point but there is no definite trend in the melting
and boiling point of lanthanides.
Magnetic Properties
 The lanthanide ions other than f0 and f14 type are paramagnetic in nature due
to unpaired electrons in f-orbitals.
 The paramagnetism increases with increase in the number of unpaired
electrons.
 Cont’d
Color
 Many of lanthanide metals are silver white.
 The lanthanide ions with +3 oxidation state are colored both in solid state and in
aqueous solution.
 The color of a cation depends on the number of unpaired 4f electrons.
 When this orbital is empty, half-filled or full, such ions are found to be colourless.
 Thus La3+ ion (f0), Gd3+(f7) and Lu3+(f14) are colourless.
 In the case of other ions, it is seen that configurations with fn and f14-n have the same
colour, because they have the same number of unpaired electrons. The colours are
due to low-energy f - f electronic transitions.
• Like the transition elements (d block elements) the f-block lanthanides in their +3
oxidation state also produce colors in crystalline as well as in solution forms.
• The depth of the color increases with the increase in the number of unpaired
electrons in the f orbital
 Cont’d
• The compounds in which the lanthanides are in some other oxidation
state and iso electronic with their counterparts will not form colored
compounds.
 Cont’d
Size
 The size of the atomic and ionic radii is determined by both the nuclear charge
and by the number of electrons that are in the electronic shells.
 Within those shells, the degree of occupancy will also affect the size. In the
Lanthanides, there is a decrease in atomic size from La to Lu. This decrease is
known as the Lanthanide Contraction.
 The trend for the entire periodic table states that the atomic radius decreases as
you travel from left to right.
 Therefore, the Lanthanides share this trend with the rest of the elements.
• Lanthanide Contraction:
• The atomic size or ionic radii of tri positive lanthanide ions show a steady and
gradual decrease with the increase in atomic number from La to Lu.
• Although they show some irregularities, the ionic radii decrease steadily from
La to Lu.
 Cont’d
 This gradual decrease in the size with increasing atomic number is called lanthanide
contraction.
 The decrease in size is not regular throughout the lanthanides.
• Cause of lanthanide contraction
 The major cause for lanthanide contraction is due to the inappropriate shielding of the
4f electrons due to the improper shape of the f-orbitals.

 As the atomic number increases in the lanthanide series, for every proton in the
nucleus the extra electron goes to fill the 4f-orbitals.

 The 4f-electrons constitute inner shells and are rather ineffective in screening the
nuclear charge.

 Thus, there is a gradual increase in the effective nuclear charge experienced by the
outer electrons.

 So the attraction of the nucleus for the electrons in the outermost shell increases as
the atomic number increases and the electron cloud shrinks.
 Cont’d
Complex formation
 They don't have much tendency to form complexes because of low charge density. The
order of complex formation can be best represented as Ln4+ > Ln3+ > Ln2+.
Solubility
 Most of the salts of lanthanides are soluble in water as they show water of crystallization.
 This can be attributed to the availability of empty spaces in d and f orbitals.
 Most of the salts of lanthanides resemble the salts of group 2 elements like Ca, Ba in their
solubilities. Flourides, oxalates and carbonates are almost insoluble while chlorides and
nitrates are soluble.
 However, unlike the sulphates of Ca and Ba which are insoluble, the lanthanide sulphates
are soluble in water.
 With ammonium of Igroup I metals like Na and K lanthanides form double salts which can
be crystallized well. For example, Na2SO4 Ln2(SO4)3.8H2O.
 This property helps in the separation of lanthanides from one another due to the varying
solubility of these double salts.
 Cont’d
Metallic properties

 The hardness, melting and boiling points of the elements all increase from Ce
to Lu due to attraction between the atoms increase as the size decreases.

 This makes them good conductors of electricity and heat.

Reactivity

 All the lanthanides show the same electronic configuration and the +3
oxidation states, they show similarity in the reactivity which is greater than
the transition elements but reactivity decreases across row.

 This is due to shielding of the unpaired electrons of the inner 4f-orbital by the
outer 5s, 5p, and 5d orbital's.

 Due to the small change in the size of the ions, they show great similarity in
their chemical properties. The first few members are quite reactive
 Cont’d
 All lanthanides react rapidly upon exposure to air (all give trioxides except Ce which
forms CeO2). to form oxide.

 They also combine with the following non-metals –Nitrogen, Sulfur, halogens,
Hydrogen to form nitrides, silfides, halides and hydrides, respectively.

 Nitrides of composition LnN exist for all the lanthanoids and adopt the expected
rocksalt structure with alternating Ln3+ and N3-ions.

 Three different lanthanoid carbide stoichiometries are known: M3C, M2C3, and MC2.

 The M3C phases form for the heavier lanthanoids and contain isolated carbon atoms
and are hydrolysed by water to produce methane.

 The M2C3 phases form for the lighter lanthanoids La-Ho and contain the dicarbide
anion C22-, as is also found in CaC2.

 The MC2 phases show metallic properties and except for the elements that form stable
divalent cations, such as Yb, they can be expressed as Ln3+(C22−)
 Cont’d
 Sulfides of stoichiometry LnS may be obtained by direct reaction of the elements at
1000°C and adopt the rock-salt structure.

 Phases of composition Ln2S3 can also be obtained by reaction of the lanthanoid

trichloride with H2S.

 The hydrides are non-stoichiometric but have a composition of MH3.

 These hydrides liberate hydrogen from water. They also react with non-metals like
phosphorus, carbon and silicon and form their corresponding compounds.

 The lanthanides also liberate hydrogen from water as does their hydrides and a
vigorous evolution of same gas from dilute non-oxidizing acids.

 They act as a strong reducing agent because of the strong electro positive nature.

 Lanthanide compounds are generally predominantly ionic and usually contain

lanthanide metal in its +3 oxidation states.
 Cont’d
Actinides

 Actinides are termed as the second inner transition series. This series is
named after actinium, the first element of the series. Only the first four
elements occur in nature.

 The other elements are made by nuclear bombardment because most of

these are radioactive.
General characteristics of Actinides
Electronic Configuration: All the actinides have common 7s2 configuration and
variable occupancy of 5f and 6d sub shells.

 The general electronic configuration of actinium is [Rn] 5f0-146d0-27s2 where,

Rn is the electronic configuration of the element Radium.

 The irregularities in the electronic configuration are related to the stabilities

of half filled or full filled orbitals (f0, f7, f14 ).
 Cont’d
• Oxidation States: Unlike lanthanides, actinides show a variety of
oxidation states from +3 to +6 due to the very small energy gap
between 5f, 6d and 7s sub shells.
• The principal oxidation states are +3 and +4. The +3 oxidation state is
the most stable.
• The +4 oxidation state is the most stable in Th and Pu. +5 in Pa and Np
and +6 is seen in U. In actinides, the distributions of oxidation states
are uneven.
• Melting and boiling point: They have high melting and boiling points
like lanthanides but don’t show any regular trend with increasing
atomic number.
• Density: All actinides except thorium and amercium have high
density.
 Cont’d
• Electropositive character: These metals are highly electropositive in nature like
lanthanides.

• Ionization enthalpies: The actinides have lower ionization enthalpies than

lanthanides because 5f is more effectively shielded from nuclear charge than 4f.

• Magnetic behavior: All actinides are paramagnetic in nature which depends on

the presence of unpaired electrons.

• Radioactivity: All are radioactive in nature. First few members have relatively
long half lives but the remaining have half-lives from a few days to a few
minutes.

• Color of the ions: Actinides ions are generally colored due to f -f transitions. It
depends upon the number of electrons in 5f orbitals.

• Chemical behavior: They are highly reactive metals in fine state and a strong
reducing agent.
 Cont’d
 A few properties are given below:
 They react with boiling water to give oxide and hydride.
 They combine with most of the non-metals at moderate temperature.
 All these metals are attacked by HCl acid but the effect of nitric acid is very small.
Actinide Contraction
 The size of atoms or M+3 ions decrease regularly along the actinides series with
increase in atomic number from Th to Lr.
 The steady decrease in ionic radii with increase in atomic number is referred to as
actinide contraction just like lanthanide contraction.
 The reason of this contraction is the poor shielding effect of 5f electron by
another in the same shell which increases the effective nuclear charge and thus
contraction in size of the electron cloud.
 This is because 5f orbitals extend in space beyond 6s and 6p orbitals whereas, 4f
orbitals are buried deep inside the atom
 Cont’d
• Similarities Between Lanthanides and Actinides
 Both lanthanides and actinides involve the filling of f-orbitals.
 Both exhibit a common oxidation state of +3.
 Both are electropositive and very reactive.
 Both exhibit magnetic and spectral properties.
 Lanthanides exhibit lanthanide contraction and actinides exhibit actinide
contraction.
• Difference Between Lanthanides and Actinides
Lanthanides Actinides

They have the ability to show a maximum Actinides show variable oxidation states of +
oxidation state of + 4 3, + 4, + 5, + 6 and + 7.

They have smaller tendency to form They have a good tendency to form
complexes complexes with ligands such as thio-ethers.
All lanthanides are non-radioactive except They are radioactive in nature
promethium.
They do not form oxo-ions Actinides form oxo-ions such as UO+,
NpO2+.
 Uses of Lanthanides
• Uses of Lanthanides
• They are used in the production of alloys of steel to improve the strength and
workability of steel.

• A well known alloy is mischmetal which is used in making magnesium based alloy
(Mg mixed with 3% of mischmetal).

• This is a pyrophoric alloy which is used in making bullets, shells and lighter flints.

• Their oxides are used in the glass industry for polishing glass and making colored
glass for goggles and television screens.

• Mixed oxides of lanthanides are used in petroleum cracking.

• Due to their paramagnetic and ferromagnetic nature, they are used in magnetic
and electronic devices.

• Ceric sulphate is a well known oxidizing agent which is used in volumetric analysis.
 Cont’d
Uses of Actinides
 The most useful actinides are thorium, uranium and plutonium.

 Thorium is used in the atomic reactors and in the treatment of cancer. Their
salts are used in making incandescent gas mantles.

 Uranium is used as nuclear fuel.

 Their salts are used in the glass industry for imparting green color, ceramic
industry, textile industry and in medicines too.

 Plutonium is also used as nuclear fuel and for making atomic bombs.
 CHAPTER-3

Coordination Chemistry of Transition Metals

 Cont’d
 Transition metals differ from main group metals in several key properties.

 One of the more interesting aspects of transition metals is their ability to form
coordination compounds.

 Coordination compounds are formed between a metal atom or ion and a

molecule with one or more unshared electron pairs, called a ligand.

 Ligands may be classified according to the number of donor atoms they

contain.

 A mono dentate ligand donates a single electron pair to the metal or metal
ion. Common examples of mono dentate ligands include NH3, H2O, NO2-,
and CN-.

 A bidentate ligand, as the name suggests, donates two electron pairs to the
metal or metal ion. A good example is ethylenediamine, NH2CH2CH2NH2
 Cont’d
• Coordination compounds: are compounds composed of a metal atom or ion
and one or more ligands
– Metal ion
• Acts as a Lewis acid
– Ligand
• Acts as a Lewis base
 They are also called complexes or, if charged, complex ions.
• Ligands: are the atoms, ions, or molecules that surround the metal in a
complex ion.
• Coordination Number - the number of ligand atoms that are bonded
directly to the central metal ion.
• Coordination geometry: is the geometry or shape described by the attached
ligands. Coordination Compound Consist of a complex ion and necessary
counter ions
 Cont’d
 Complex ions: Species where transition metal ion is surrounded by a certain
number of ligands.
 Counter ion: Anions or cations that balance the charge on the complex ion
in a coordination complex.
E.g. [Co(NH3)5Cl]Cl2

Complex ion: [Co(NH3)5Cl]2+

Counter ions: 2 Cl-

• Where CN is
Coordination Number
Cont’d
 Cont’d
• Ligands
 Depending on the number of donor atoms present, ligands are classified as
monodentate, bidentate, or polydentate.
 Cont’d
• Nomenclature of coordination compounds
 Nomenclature rules
1. Name cation before anion. This is also the common order for simple salts.
E.g. Diammine silver(I) chloride, [Ag(NH3)2]Cl
potassium hexacyanoferrate(III), K3[Fe(CN)6]
2. In naming a complex ion, name ligands before the metal ion. but in formulas the
metal ion is written first.
E.g. Tetraammine copper(II) sulfate, [Cu(NH3)4]SO4
hexaammine cobalt(III) chloride, [Co(NH3)6]Cl3
3. Name ligands in alphabetical order
– If more than one of the same ligand is present, use a numerical prefix: di,
tri, tetra, penta, hexa, …
4. If the ligand name includes these prefixes or is complicated, it is set off in
parentheses and the second set of prefixes is used.
 Cont’d

 For Neutral ligands: use the name of the molecule (with some exceptions)
NH3 ammine- H2O aqua- CO carbonyl
CH3NH2 methylamine NH2CH2CH2NH2 ethylenediamine (en)
 Cont’d

Example

dichlorobis(ethylenediamine)cobalt(III) [Co(NH2CH2CH2NH2)2CI2]+

tris(bipyridine)iron(II), [Fe(NH4C5-C5H4N )3]2+

 Cont’d
Put oxidation state for metal in Roman numerals in ()

E.g. Tetraammine platinum(II), [Pt(NH3)4]2+

hexaamine cobalt(II)chloride, [Co(NH3)6]Cl2

How can we assign oxidation number?

Charge on complex = sum of charges For Neutral coordination compound,
on the metal and the ligands sum of charges on metal, ligands, and
counterbalancing ions = 0
 Cont’d
 When the complex is negatively charged, the names for the following metals
are derived from the sources of their symbols, rather than from their English
names:
 Cont’d
Name the following coordination compounds

a. [Co(H2O)6]Br2 c. [Pt(Ox)2]2-

b. [Co(NH3)5Cl]Cl2 d. [Cr(H2O)5Br]2+

Give the chemical formula of the following coordination compounds

a) Hexaaqua cobalt(III) bromide
(b) Sodium tetrachloro platinate(II)
 Cont’d
• Colour in coordination compounds

• Many d-block complexes are coloured because photons of visible light give
rise to electronic transitions between the two sets of d orbitals.

• Colors of some of the first-row transition metal ions in solution. From left to right.
Cont’d

Manganese is shown left

to right:
• Mn2+
• Mn3+
• Mn4+
• Mn6+
• Mn+7
 Cont’d

• Isomerism

 compounds that have the same composition but a different arrangement of

atoms

 The arrangements of the atoms differ, and this leads to different properties.

 Major Types

Structural Isomers

– isomers that have different bonds

1. Ionization isomers

Ionization isomers result from the interchange of an anionic ligand within the
first coordination sphere with an anion outside the coordination sphere.

E.g. [Cr(NH3)5SO4]Br& [Cr(NH3)5Br]SO4

 Cont’d
2. Linkage isomerism

Linkage isomers may arise when one or more of the ligands can coordinate to
the metal ion in more than one way, e.g. In [SCN] (both the N and S atoms
are potential donor sites.

E.g. [Co(NH3)5(SCN)]2+ vs. [Co(NH3)5(NCS)]2+

• Co-SCN vs. Co-NCS

3. Coordination isomerism

• Coordination isomers are possible only for salts in which both cation and
anion are complex ions; the isomers arise from interchange of ligands
between the two metal centres.

E.g. [Co(NH3)6][Cr(CN)6] & [Co(CN)6][Cr(NH3)6]

 Cont’d
4. hydration isomers

Hydration isomers result from the interchange of H2O and another ligand
between the first coordination sphere and the ligands outside it.
• e.g [Pt(H2O)4]2+[CuCl4]2- and [Cu(H2O)4]2+[PtCl4]2-
 Cont’d
Bonding in d-block metal complexes:

Valence Bond Theory

 This approach of coordination compounds was mainly developed by Linus Pauling.

 According to this approach, the formation of a complex is considered to be a reaction

between a Lewis base (ligand) and a Lewis acid (metal or metal ion) with the
formation of a coordinate covalent bond between the ligand and the metal.

 Valence Bond Theory predicts metal complex bonding arises from overlap of filled
ligand orbital's and vacant metal orbitals. Resulting bond is a coordinate covalent
bond.
 Cont’d
• Complex geometry can be linked to five main orbital hybridization
processes.

Tetrahedral Geometry: Gives [CoCl4]2– Three unpaired electrons, which makes it

paramagnetic and attracted by magnets.
 Cont’d
 Square Planar Geometry:Gives [Ni(CN) 4 ]2– All paired electrons, which makes it
diamagnetic and weakly repelled by magnets.

 Octahedral sp3d2 Geometry: Gives [CoF6 ] 3– Four unpaired electrons, which makes it
paramagnetic and is called a high- spin complex.
 Cont’d
 Octahedral d2 sp3 Geometry: Gives [Co(CN) 6 ] 3– paired electrons, which makes it
diamagnetic and is called a low-spin complex.

 The difference between sp3d2 and d2 sp3 hybrids lies in the principal quantum number
of the d orbital.
 In sp3 d2 hybrids, the s, p, and d orbitals have the same principal quantum number-High
Spin.
 In d2sp3 hybrids, the principal quantum number of the d orbitals is one less than s and p
orbitals-Low Spin.
 A complex’s magnetic properties determine which hybrid is being used
 Cont’d
• Limitations of Valence Bond Approach

 While the VB approach, to a larger extent offers explanation of structure and

magnetic behavior of coordination compounds, it has following
shortcomings:

i. It involves a number of assumptions.

ii. It does not give quantitative interpretation of magnetic data.

iii. It does not explain the color exhibited by coordination compounds.

iv. It does not give a quantitative interpretation of the thermodynamic or
kinetic stabilities of coordination compounds.
v. It does not make exact predictions regarding the tetrahedral and square
planar structures of 4-coordinate complexes.
vi. It does not distinguish between weak and strong ligand