The Asian School, Kingdom of Bahrain

Grade 12, Chemistry

d & f BLOCK ELEMENTS

d & f BLOCK ELEMENTS

1.2 Electronic configuration

1. INTRODUCTION
(1) In d-block elements with increase in atomic number, the d-
1.1 Definition orbitals of penultimate shell i.e. (n-1) d are gradually filled
by electrons. The general electronic configuration of d-
“The elements in which the last differentiating electron enters
block element is,
into the d-orbitals of the penultimate shell i.e.
(n-11) d1-10, ns0-2.
(n–1) d where n is the last shell are called d-block elements”.
(2) Depending upon the d-orbitals of which penultimate shell
A transition element may also be defined as the element
i.e. n = 4, 5, 6, 7 are filled, four rows (called series) os ten
which partially filled d-orbital in their ground state or most
elements each obtained. They correspond to 3d, 4d, 5d and
stable oxidation state.
6d subshells.
Cu (Z = 29) = 1s2 2s2 2p6 3s2 3p6 3d10 4s1
(3) Energy of ‘(n–1)d’ subshell is slightly greater than ‘ns’
Cu2+ = 1s2 2s2 2p6 3s2 3p6 3d9
subshell, hence orbital is filled first then (n – 1) d orbitals.
(Cupric ion)
(4) The general electronic configuration of d-block/d-series
The properties of these elements are intermediate between elements be shown as follows :
the properties of s-block and p-block elements.
1. First (3d) Transition Series (Sc–Zn)
These elements represent a change or transition in
properties from more electropositive elements (s-block) to
less electropositive elements (p-block). Therefore these
elements are called transition elements.
2. Second (4d) Transition Series (Y-Cd)
Position in the periodic table
The position of d-block element has been shown in periodic
table as follows :

3. Third (5d) Transition Series (La–Hg)

4. Fourth (6d) Transition Series

Exceptional configuration of Cr and Cu. The exceptions

observed in the first series are in case of electronic
(1) d-block elements lie in between ‘s’ and ‘p’ block elements, configurations of chromium (Z = 24) and copper (Z = 29). It
i.e. these elements are located in the middle of the periodic may be noted that unlike other elements, chromium and
table. copper have a single electron in the 4s-orbital. This is due
(2) d-block elements are present in, to the gain of additonal stability by the atom by either having
4th period (21Sc to 30Zn, 10 elements) o1st Transition series. half-filled configuration (i.e., containing 5 electrons in the
5th period (39Y to 48Cd, 10 elements) o2nd Transition series. d-sublevel) or completely filled configuration, (i.e.,
6th period (51La, 72Hf to 80Hg, 10 elements) o3rd Transition containing 10 electrons in the d-sublevel). The 3d-level in
series. case of chromium gets excatly half-filled with configuration
7th period (89Ac, 104Rf to 112Uub, 10 elements) o4th Transition 3d5 4s1 and that in case of copper, it gets completely filled
series. with configuration 3d10 4s1. This can be explained on the
basis of exchange energy
 d & f BLOCK ELEMENTS

Thus, the electronic configuration of chromium (Z = 24)

and copper (Z = 29) are 1s2 2s2 2p6 3s2 3p6 3d5 4s1 and 1s2 2s2 1.5 Metallic character
2p6 3s6 3p6 3d10 4s1 respectively.
Except for mercury which is a liquid, all the transition
elements have typical metallic structure. They exhibit all
1.3 Properties the characteristics of metals. ductile, have high melting and
boiling points, high thermal and electrical conductivity and
1. Atomic Raddii
high tensile strength.
(i) The atomic radii of the transition metals lie in-between those Transition elements have relatively low ionization energies
of s- and p-block elements. and have one or two electrons in their outermost energy level
(ns1 or ns2). As a result, metallic bonds are formed. Hence, they
(ii) Generally the atomic radii of d-block elements in a series behave as metals. Greater the number of unpaired d electrons,
decreas with increase in atomic number but the decrease in stronger is the bonding due to the overlapping of unpaired
atomic size is small after midway. electrons between different metal atoms.
Explanation 1.6 Melting Point
The atomic radius decreases with the increase in atomic
Transition metals have high melting points which is due to
number as the nuclear charge increases whereas the their strong metallic bond. The metallic bond. The metalic
shielding effect of d-electron is small. After midway, as the bonding depends upon the number of unpaired e–. The
electrons enter the last but one (penultimate) shell, the added melting point first increases (Sc-Cr), reaches a maximum value
d-electron shields (screens) the outermost electron. Hence, (Cr) and then decreases (Fe-Zn)
with the increase in the d-electrons, screening effect * Tungsten (W) has the highest melting point.
increases. This counterbalances the increased nuclear * Mercury (Hg) has the lowest melting point.
charge due to increase in atomic number. As a result, the * Mn has the lowest melting point in 3d series typicl
atomic radii remain practically same after chromium. For transition elements.
example in Fe, the two opposing tendencies almost
1.7 Ionisation energies or Ionisation enthalpies
counterbalance and there is no change in the size from Mn
to Fe. (i) The first ionisation enthalpies of d-block elements lie between
s-block and p-block elements. They are higher than those of s-
(iii) At the end of the period, there is a slight increase in the
block elements and are lesser than those of p-block elements.
atomic radii.
The ionisation enthalpy gradually increases with increase in
Explanation atomic number along a given transition series though some
irregularities are observed
Near the end of series, the increased electron-electron
Explanation
repulsions between added electrons in the same orbitals
(i) The increasing ionization enthalpies are due to increased
are greater than the attractive forces due to the increased
nuclear charge with increase in atomic number which reduces
nuclear charge. This results in the expansion of the electron
the size of the atom making the removal of outer electron
cloud and thus the atomic radius increases. difficult.
(iv) The atomic radii increase down the group. This means that (ii) In a given series, the difference in the ionisation enthalpies
the atomic radii of second series are larger than those of between any two successive d-block elements is very much
first transition series. But the atomic radii of the second less than the difference in case of successive s-block or p-
and third transition series are almost the same. block elements.
Explanation
The atomic radii of the elements of the second and third The addition of d electrons in last but one [(n — 1) or
transition metals are nearly same due to lanthanide penultimate] shell with increase in atomic number provides
contraction (or also called lanthanoid contraction) a screening effect and thus shields the outer s electrons
discussed later. from inward nuclear pull. Thus, the effects of increased
nuclear charge and addition of d electrons tend to oppose
1.4 Ionic radii each other.

(i) The trend followed by the ionic radii is the same as that (iii) The first ionization enthalpy of Zn, Cd and Hg are, however,
very high because of the fully filled (n-1) d 10 ns 2
followed by atomic radii.
configuration.
(ii) Ionic radii of transition metals are different in different (iv) Although second and third ionization enthalpies also, in
oxidation states.
general, increase along a period, but the magnitude of
(iii) The ionic radii of the transition metals are smaller than those increase for the successive elements is much higher.
of the representative elements belonging to the same period.
 d & f BLOCK ELEMENTS

(v) The high values of 3rd ionization enthalpies for Cu, Ni and In ‘3d’ series all element contain 2 electrons in ‘4s’ and hence
Zn explain why they show a maximum oxidation state of +2. they all give a common minimum oxidation state of +2.
(vi) The first ionisation enthalpies of 5d elements are higher as (Except ‘Cr’ and ‘Cu’ where minimum oxidation state is +1.]
compared to those of 3d and 4d elements. This is because The maximum oxidation state is given by Mn i.e. Mn+7 in
the weak shielding of nucleus by 4f electrons in 5d elements which two electrons are removed from 4s and five unpaired
results in greater effective nuclear charge acting on the electrons are removed from 3d orbitals.
outer valence electrons. (4) The highest oxidation state is shown by Ruthenium (Ru)
and Osmium (Os) i.e. +8.
1.8. Oxidation state
(5) Across the period oxidation state increases and it is maximum
“The net numerical charge assigned to an atom of an element at the centre and than decreases even if atomic number
in its combined state is known as its Oxidation state or increases. The element which shows highest oxidation state
Oxidation number”. occur in the middle or near the middle of the series and than
decreases.
(1) With the exception of few elements, most of the d-block
elements show more than one oxidation state i.e. they show (6) Transition metals also show zero oxidation states in metal
variable oxidation states. The elements show variable carbonyl complex. (Nickel tetracarbonyl).
oxidation state because of following reasons: Example : Ni in Ni (CO)4 has zero oxidation state.
(i) ‘(n-1) d’ and ‘ns’ orbitals in the atoms of d-block elements (7) The bonding in the compounds of lower oxidation state
have almost same energies and therefore electron can be (+2, +3) is mostly ionic and the bonding in the compounds
removed from ‘(n-1)d’ orbitals as easily as ‘s’ orbitals of higher oxidation state is mostly covalent.
electrons.
(8) The relative stabilities of some oxidation states can be
(ii) After removing ‘s’ electrons, the remainder is called Kernel explained on the basis of rule extra stability, according to
of the metal cations. In d-block elements, the kernel is which d0, d5 and d10 are stable configurations.
unstable and therefore it loses one or more electrons from
For example, the stability order of some ions is as follows:
(n – 1)d electrons. This results in formation of cations with
different oxidation states. Ti4+ (3d0, 4s0) > Ti3 (3d1, 4s0)
(2) All transition elements show variable oxidation state except Mn2+ (3d5, 4s0) > Mn3+ (3d4, 4s0)
last element in each series. Fe3+, (3d5, 4s0) > Fe2+ (3d6, 4s0)
(3) Minimum oxidation state = Total number of electrons in 4s (9) Cu+2 is more stable than Cu+1 even when Cu+1 is 3d10 while
lost. Maximum oxidation state = (Total number of electrons Cu+2 is 3d due to high heat of hydration.
in 4s + number of unpaired electrons in 3d lost).
Variable oxidation states shown by 3d-series of d-block elements.

Oxidation States

ELECTRONIC Sc Ti V Cr Mn Fe Co Ni Cu Zn

CONFIGURATION d1s2 d 2s 2 d 3s 2 d4s 2 d5s 2 d 6s2 d 7s 2 d8s 2 d9s 2 d 10 s 2

d5s 1 d 10 s 1

+1 +1

+2 +2 +2 +2 +2 +2 +2 +2 +2 +2

+3 +3 +3 +3 +3 +3 +3 +3 +3

+4 +4 +4 +4 +4 +4 +4

+5 +5 +5 +5 +5

+6 +6 +6

+7
 d & f BLOCK ELEMENTS

(iv) The values of Eo for Mn, Ni and Zn are more negative than
1.9 Standard electrode potentials (E o) and chemical expected from the generall trend. This is due to greater
reactivity stability of half-filled d-subshell (d5) in Mn2+, and completely
Thermodynamic stability of the compounds of transition filled d-subshell (d10) in Zn2+. The exceptional behaviour of
elements can be evaluated in terms of the magnitude of Ni towards Eo value from the regular trend is due to its high
ionisation enthalpies of the metals — smaller the ionisation negative enthalpy of hydration.
enthalpy of the metal, stabler is its compound. Trends in the M3+/M2+ Standard Electrode Potentials
In solution, the stability of the compounds depends upon (i) A very low value for Eo (Sc3+/Sc2+) reflects the stability of
electrode potentials rather than ionization enthalpies. Sc3+ ion which has a noble gas configuration.
Electrode potential values depend upon factors such as
enthalpy of sublimation (or atomisation) of the metal, the (ii) The highest value for Zn is on account of very high stability
ionisation enthalpy and the hydration enthalpy, i.e., of Zn2+ ion with d10 configuration. It is difficult to remove
an electron from it to change it into +3 state.
' sub H
M s  o M g , ('subH is enthalpy of sublimation/
(iii) The comparatively high value of Eo (Mn3+/Mn2+) shows
atomisation) that Mn2+ is very stable which is on account of stable d5
' iH configuration of Mn2+.
M s  o M  g  e , ('i H is ionisation enthalpy)
(iv) The comparatively low value of Eo (Fe3+/Fe2+) is on account
' hyd H
M  g  aq o M  aq , (' hyd H is enthalpy of of extra stability of Fe3+ (d5), i.e., low third ionization enthalpy
of Fe.
hydration)
(v) The comparatively low value for V is on account of the
The total energy, ' T H, for the process involving
sublimation, ionisation and hydration simultaneously, i.e., stability of V2+ ion due to its half-filled t 32g configuration
o M  aq  e  , will be the sum
for the process, M s  (discussed in unit 9).
of the three types of enthalpies, i.e., Chemical Reactivity and Eo Values. The transition metals
vary very widely in their chemical reactivity. Some of them
'TH ' sub H  ' i H  ' hyd H.
are highly electropositive and dissolve in mineral acids
Thus, 'T H, is the total enthalpy change when solid meal, whereas a few of them are ‘noble’, i.e., they do not react with
M is brought in the aqueous medium in the form of simple acids. Some results of chemical reactivity of transition
monovalent ion, M+ (aq). metals as related to their Eo values are given below :
(i) The metals of the first transition series (except copper) are
relatively more reactive than the othr series. Thus, they are
oxidized by H+ ions though the actual rate is slow, e.g., Ti
and V are passive to dilute non-oxidizing acids at room
temperature.
(ii) As already explained, less negative Eo values for M2+/M
along the series indicate a decreasing tendency to form
Trends in the M2+/M Standard Electrode Potentials divalent cations.
(i) There is no regular trend in the Eo (M2+/M) values. This is (iii) More negative Eo values than expected for Mn, Ni and Zn
because their ionization enthalpies (I1 + IE2) and sublimation show greater stability for Mn2+, Ni2+ and Zn2+.
enthalpies do not show any regular trend.
(iv) Eo values for the redox couple M3+/M2+ indicate that Mn3+
(ii) The general trend towards less negative Eo values along and Co3+ ions ar the strongest oxidizing agents in aqueous
the series is due to the general increase in the sum of first solution whereas Ti2+, V2+ and Cr2+ are strongest reducing
and second ionization enthalpies. agents and can liberate hydrogen from a dilute acid, e.g., 2
(iii) Copper shows a unique behaviour in the series as it is the Cr2+ (aq) + 2 H+ (aq)  o 2 Cr3+ (aq) + H2 (g)
only metal having positive value for Eo. This explains why
is does not liberate H2 gas from acids. It reacts only with 1.10 Catalytic Property
the oxidizing acids (HNO3 and H2SO4) which are reduced.
The reason for positive Eo value for copper is that the sum Most transition elements and their compounds have good
of enthalpies of sublimation and ionization is not balanced catalytic properties because
by hydration enthalpy. (a) They possess variable oxidation state.
 d & f BLOCK ELEMENTS

(b) They provide a large surface area for the reactant to be

absorbed. 2. COMPLEX FORMATION

Catalysts Uses Transition metal ions form a large number of complex

compounds. Complex compounds are those which have
TiCl4 + Al (C2H5) Ziegler-Natta catalyst, used in a metal ion linked to a number of negative ions (anions) or
neutral molecules having lone pairs of electrons. These
polymerisation of ethylene ions or molecules are called ligands. They donate lone
V2O5 Contact process SO2 o SO pairs of electrons to the central transition metal ion forming
coordinate bonds
Fe Haber Bosch process
A few examples are given below :
PdCl2 Wacker’s process for CH CHO [Fe(CN)6]3–, [Fe(CN)6]4–, [Cu(NH3)4]2+, [Zn(NH 3)4]2+,
[Ni(CN)4]2– and [Ptcl4]2–
manufacturing
Such complex compounds are not formed by s - and p -
Pd Hydrogenation of alkene, alkyne
block elements.
etc
Explanation. The transition elements form complexes
Pt/PtO Adam’s catalyst for selective because of the following reasons :
reduction (i) Comparatively smaller size of their metal ions.
Pt Catalytic convertor, for (ii) Their high ionic charges.
cleaning (Because of (i) and (ii), they have large charge/size ratio)
car exhaust fumes (iii) Availability of vacant d-orbitals so that these orbitals can
Pt/Rh Ostwald’s process : accept lone pairs of electrons donated by the ligands.

NH o NO 2.1 Interstitital Compounds

Cu Oxidation of alcohols The transition metals form a large number of interstitial

compounds in which small atoms such as hydrogen,
1.11 Magnetic Behaviour carbon, boron and nitrogen occupy the empty spaces
(interstitial sites) in their lattices (Fig.).
When a substance is placed in a magnetic field of strength They are represented by formulae like TiC, TiH2, Mn4N,
H, the intensity of the magnetic field in the substance may Fe 3 H, Fe 3 C etc. However, actually they are non-
be greater than or less than H. If the field in the substance stoichiometric materials, e.g., TiH1.7, VH0.56 etc. and the
is greater than H, the substance is a paramagnetic material bonds present in them are neither typically ionic nor
and attracts line of force. If the field in the substance is less covalent. Some of their important characteristics are as
than H, the substance is diamagnetic. Diamagnetic materials follows:
tend to repel lines of force. The magnetic moment of a (i) They are very hard and rigid, e.g., steel which is an
substance depends on the strength of magnetic field interstitial compound of Fe and Cis quite hard. Similarly,
generated due to electronic spin, there is a change in electric some borides are as hard as diamond.
flux which leads to induction of magnetic field. The electron (ii) They have high melting points which are higher than those
is also under orbital angular momentum or orbital spin. It of the pure metals.
leads to generation of magnetic moment. (iii) They show conductivity like that of the pure metal.
In first transition elements series the orbital angular magnetic (iv) They acquire chemical inertness.
moment is insignificant the orbital contribution is quenched
by the electric fields of the surrounding atoms so magnetic 2.2 Alloy formation
moment is equal to the spin magnetic moment only.
Alloys are homogeneous solid solutions of two or more
P eff n (n  2) BM metals obtained by melting the components and then
cooling the melt. These are formed by metals whose atomic
n o no. of unpaired electron. radii differ by not more than 15% so that the atoms of one
metal can easily take up the positions in the crystal lattice
Maximum transition elements and compounds are
of the other (Fig.)
paramagnetic due to presence of unpaired electrons.
Now, as transition metals have similar atomic radii and
 d & f BLOCK ELEMENTS

other characteristics, hence they form alloys very readily. oxides are amphoteric.
Alloys are generally harder, have higher melting points
For example, the behaviour of the oxides of manganese
and more resistant to corrosion than the individiual metals.
may be represented as follows :
The most commonly used are the ferrous alloys the metals
chromium, vanadium, molybdenum, tungsten and 2 8 /3 3 4 7

manganese are used in the formation of alloy steels and MnO Mn 3O 4 Mn 2 O 3 MnO 2 Mn 2 O 7
Basic Amphoteric Amphoteric Amphoteric Acidic
stainless steels. Some alloys of transition metals with non-
transition metals are also very common. e.g., brass Thus, Mn2O7 dissolves in water to give the acid HMnO4.
(Cu + Zn) and bronze (Cu + Sn)
3.2 KMnO4 Potassium permanganate

It is prepared from the ore called chromite or ferrochrome

or chrome iron, FeO.Cr2O3. The various steps involved
are as follows :
(i) Preparation of sodium chromate. The ore is finely
powdered, mixed with sodium carbonate and quick lime
and then roasted, i.e., heated to redness in a reverberatory
furnace with free exposure to air when sodium chromate
(yellow in colour) is formed and carbon dioxide is evolved.
Quick lime keeps the mass porous and thus facilitates
oxidation.

4FeO.Cr2O3 + 8Na2CO3+ 7O2 

o 8Na2CrO4 + 2Fe2O3 + 8CO2
Chromite ore Sod. chromate Ferric oxide

After the reaction, the roasted mass is extracted with water

when sodium chromate is completely dissolved while ferric
oxide is left behind. Ferric oxide is separated out by
filtration.
3. COMPOUNDS OF TRANSITION ELEMENTS
(ii) Conversion of sodium chromate into sodium dichromate.
The filtrate containing sodium chromate solution is treated
3.1 Oxides with concentrated sulphuric acid when sodium chromate
(i) The metals of the first transition series form oxides with is converted into sodium dichromate.
oxygen at high temperature. 2Na 2 CrO 4  H 2SO 4 
o Na 2 Cr2 O7  Na 2SO 4  H 2 O
Sod.chromate Conc. Sod. dichromate
(ii) The oxides are formed in the oxidation, states +1 to +7 (as
Sodium sulphate being less soluble crystallizes out as
given in Table 8.10, page 8/14).
decahydrate, Na2SO4. 10H2O and is removed. The clear
(iii) The highest oxidation state in the oxides of any transition solution is then evaporated in iron pans to a specific
metal is equal to its group number, e.g., 7 in Mn2O7. Beyond gravity of 1.7 when a further crop of sodium sulphate is
group 7, no higher oxides of iron abov Fe2O are known. formed. It is removed and the solution is cooled when
Some metals in higher oxidation state stabilize by forming orange crystals of sodium dichromate, Na2Cr2O7. 2H2O
oxocations, e.g., VV as VO2 , VIV as VO2+ and TiIV as TiO2+. separate on standing.
(iii) Conversion sodium dichromate into potassium
(iv) All the metals except scandium form the oxides with the
dichromate. Hot concentrated solution of sodium
formula MO which are ionic in nature. As the oxidation
dichromate is treated with calculated amount of potassium
number of the metal increases, ionic character decreases,
chloride when potassium dichromate, being much less
e.g., Mn2O7 is a covalent green oil. Even CrO3 and V2O5
soluble than sodium salt, crystallizes out on cooling as
have low melting points.
orange crystals.
2 8/ 3 3 4 7
MnO Mn 3O 4 Mn 2O 3 MnO 2 Mn 2O 7 Na Cr O  2KCl 
o K 2 Cr2 O7  2NaCl
2 2 7
Sodium dichromate Potassium dichromate
(v) In general, the oxides in the lower oxidation states of the
metals are basic and in their higher oxidation states, they
are acidic whereas in the intermediate oxidation state, the
 d & f BLOCK ELEMENTS

6. Oxidising properties. It is a powerful oxidising agent. In

3.3 Properties the presence of dilute sulphuric acid, one molecule of
potassium dichromate furnishes 3 atoms of available
1. Colour and Melting point. It forms orange crystals which
oxygen as indicated by the equation :
melt at 669 K.
2. Solubility. It is moderately soluble in cold water but freely K 2 Cr2 O 7  4H 2SO 4 
o K 2SO 4  Cr2 SO 4 3
+
soluble in hot water.
4H2O + 3O
3. Action of heat. When heated to a white heat, it
decomposes with the evolution of oxygen. or Cr2 O72  14H   6e 
o 2Cr 3  7H 2 O

4K 2 Cr2 O7 
o 4K 2 CrO4  2Cr2 O3  3O 2 Mol. wt. 294
? Eq. wt. of K 2 Cr2 O 7 49
6 6
4. Action of alkalies. When an alkali is added to an orange
red solution of dichromate, a yellow solution results due (i) It liberates I2 from KI
to the formation of chromate.
K 2 Cr2 O 7  7H 2SO 4  6KI 
o 4K 2SO 4  Cr2 SO 4 3
K 2 Cr2 O7  KOH 
o 2K 2 CrO4  H 2 O
Pot. dichromate Pot.chromate 3I2  7H 2 O

(ii) It oxidises ferrous salts to ferric salts

or Cr2O72  2 OH  
o 2 CrO42   H 2 O
K 2 Cr2 O7  7H 2SO4  6FeSO4 
o K 2SO 4  Cr2 SO4 3
On acidifying, the colour again changes to orange red
due to the reformation of dichromate.
3Fe2 SO 4 3
 2H 2 O
2 K 2CrO4  H 2SO4 
o K 2 Cr2 O7  K 2SO4  H 2 O (iii) It oxidises H2S to sulphur

or 2 CrO 24  2 H  
o Cr2 O72  H 2O K 2 Cr2 O 7  4H 2SO 4  3H 2S 
o K 2SO 4  Cr2 SO 4 3

This interconversion is explained by the fact that in + 7H2O + 3S

dichromate solution, the Cr2 O72 ions are invariably in (iv) It oxidises sulphites to sulphates and thiosulphates to
sulphates and sulphur
equilibrium with CrO24  ions at pH = 4, i.e.,
K 2 Cr2 O 7  4H 2SO4  3Na 2SO3 
o K 2SO 4  Cr2 SO 4 3

2 pH 4 2 
Cr O2 7  H 2 O YZZZZ 2CrO  2H
ZZZZX 4 + 4H2O + 3Na2SO4
Orange red Yellow
dichromate chromate (v) It oxidises nitrites to nitrates

On adding an alkali (i.e., increasing the pH of the solution), K 2 Cr2 O7  4 H 2 SO4  3NaNO2 
o K 2SO 4  Cr2 SO4 3
the H+ ions are used up and according to the law of
chemical equilibrium, the reaction proceeds in the forward + 3 NaNO3 + 4 H2O
direction producing yellow chromate solution. On the (vi) It oxidises halogen acids to halogen
other hand, when an when an acid is added (i.e., pH of the
solution is decreased), the concentration of H+ ions is K 2Cr2 O7  14 HCl 
o 2KCl  2CrCl3  7H2 O  3Cl2
increased and the reaction proceeds in the backward (vii) It oxidises SO2 to sulphuric acid
direction producing an orange red dichromate solution.
K 2 Cr2 O 7  H 2 SO 4  3SO 2 
o K 2 SO 4  Cr2 SO 4  3H 2 O
5. Action of concentrated sulphuric acid 3

(a) In cold, red crystals of chromic anhydride (chromium (viii) It oxidises stannous salts to stannic salts
trioxide) are formed.
Cr2O72  14 H   3Sn 2  
o 2 Cr 3  3 Sn 4   3 Sn 4  7 H 2 O

K 2 Cr2 O7  2H 2SO 4 
o 2CrO3  2KHSO4  H 2O (ix) It oxidises ethyl alcohol to acetaldehyde and acetic acid.

(b) On heating the mixture, oxygen is evolved. K 2 Cr2 O7  4H 2SO 4 

o K 2SO 4  Cr2 SO 4  4H 2 O  3O
3

2K 2 Cr2 O7  8H 2SO 4 
o 2K 2SO 4  2Cr2 SO 4 3 CH 2CH 2OH O 
o CH3CHO  H 2 O
Ethyl alcohol
+ 8H2O + 3O2
 d & f BLOCK ELEMENTS

Structures of chromate and dichromate ions.

CH3 CHO O 
o CH3 COOH
Acetaldehyde Acetic acid

Test for a drunken driver. The above reaction helps to

test whether a driver has consumed alcohol or not. he is or
asked to breathe into the acidified K2Cr2O7 solution taken
in a test tube. If the orange colour of the solution changes
into green colour (due to Cr2(SO4)3 formed in the reaction),
the driver is drunk, otherwise not.
7. Chromyl chloride test (Reaction with a chloride and conc.
sulphuric acid). When heated with concentrated
or
hydrochloric acid or with a chloride and strong sulphuric
acid, reddish brown vapours of chromyl chloride are
obtained.

K 2 Cr2 O7  4KCl  6H 2SO4 

o 2CrO2 Cl2  6KHSO 4  3H 2 O 3.4 Potassium Permanganate (KMnO4)
Chromyl chloride
Re d vapour
Preparation
8. Reaction with hydrogen peroxide. Acidified K2Cr2O7 On a large scale, it is prepared from the mineral, pyrolusite,
solution reacts with H2O2 to give a deep blue solution MnO2. The preparation involves the following two stesp:
due to the formation of peroxo compound, CrO (O2)2.
(i) Conversion of MnO2 into potassium manganate. The finely
2  powdered pyrolusite mineral is fused with potassium
Cr2 O  2 H  4 H 2 O2 
7 o 2 CrO5  5 H 2 O
hydroxide or potassium carbonate in the presence of air
The blue colour fades away gradually due to the or oxidising agent such as potassium nitrate or potassium
decomposition of CrO5 into Cr3+ ions and oxygen. chlorate when green coloured potassium manganate is
formed.

The structure of CrO5 is in which Cr is in +6 2MnO2 + 4KOH + O2 

o 2K2MnO4 + 2H2 O
Potassium manganate
oxidation state.
2MnO2 + 2K2CO3 + O2 
o 2K2MnO4 + 2 CO2
Uses.
(i) In volumetric analysis, it is used as a primary standard for MnO2 + 2KOH + KNO3 
o K2MnO4 + KNO2 + H2O
the estimation of Fe2+ (ferrous ions) and I– (iodides) in
3MnO2 +6KOH+KClO3 
o 3K2MnO4 +KCl+2H2O
redox titrations.
Potassium manganate thus formed undergoes
Note
disproportionation in the neutral or acidic solution as
Na2Cr2O7 is not used in volumetric analysis because it is follows, if allowed to stand for some time :
deliquescent. VI VII IV
3 MnO 24   4 H  
o2 MnO4  MnO 2  2 H 2 O
(ii) In industry, it is used Manganate ion Permanganate ion

(ii) Oxidation of potassium manganate to potassium

(a) In chrome tanning in leather industry.
permanganate.
(b) In the preparation of chrome alum K2SO4.Cr2(SO4)3.
(a) Chemical oxidation. The fused mass is extracted with
24H2O and other industrially important compounds
water and the solution after filtration is converted into
such as Cr2O3, CrO3, CrO2Cl2, K2CrO4, CrCl3 etc. potassium permanganate by bubbling carbon dioxide,
(c) In calico printing and dyeing. chlorine or ozonised oxygen through the green solution.
(d) In photography and in hardening gelatine film. 3K 2 MnO 4  2CO2 
o 2KMnO 4  MnO 2 p 2K 2 CO3
(iii) In organic chemistry, it is used as an oxidising agent. 2K 2 MnO4  Cl2 
o 2KMnO 4  2KCl
2K 2 MnO4  H 2 O  O3 
o 2KMnO4  2KOH  O 2
The carbon dioxide process is uneconomical as one third
of the original manganate is reconverted to manganese
Lakshya Educare
 d & f BLOCK ELEMENTS

dioxide. However, this process has the advantage that (ii) It oxidises sodium thiosulphate to sodium sulphate.
the potassium carbonate formed as a by-product can be
8KMnO4  3Na 2S2 O3  H 2 O 
o 3K 2SO 4  8MnO 2 
used for the oxidative fusion of manganese dioxide. In
the chlorine process, potassium chloride obtained as a 3Na 2SO 4  2KOH
by-product is lost.
(iii) It oxidises hydrogen sulphide to sulphur.
PROPERTIES
2KMnO4  4H 2S 
o 2MnS  S  K 2SO4  4H 2 O
1. Colour. Potassium permanganate exists as deep purple
black prisms with a greenish lustre which become dull in (b) In alkaline solution. In strongly alkaline solution, MnO24 
air due to superficial reduction. (manganate) ion is produced.
2. Solubility. It is moderately soluble in water at room
2KMnO4  2KOH 
o 2K 2 MnO 4  H 2 O  O or
temperature and it is more soluble in hot water.
MnO14  e 
o MnO24 
3. Action of heat. When heated to 513 K, it readily
decomposes giving oxygen. Mol. wt. 158
? Eq. wt. of KMnO 4 158
2KMnO4 
o K 2 MnO4  MnO 2  O2 1 1
Pot. manganate
Potassium manganate is also further reduced to MnO2
At red heat, potassium manganate formed decomposes
into potassium manganite (K2MnO3) and oxygen. when a reducing agent is present.
2K 2 MnO4 
o 2K 2 MnO3  O2
K 2 MnO4  H 2 O 
o MnO2  2KOH  O
4. Action of heat in current of hydrogen. When heated in a
current of H2, solid KMnO4 gives KOH, MnO and water or MnO 24  2H 2 O  2 e  
o MnO2  4OH 
vapours.
'
So the complete reaction is :
2KMnO4  5H2  o 2KOH  2MnO  4H 2 O
2KMnO4  H2 O 
o 2MnO2  2 KOH  3O
5. Oxidising property. Potassium permanganate is powerful
oxidising agent. The actual course of reaction depends or MnO 4  2H 2 O  3 e 
o MnO2  4OH 
on the use of the permanganate in (a) neutral (b) alkaline
which is the same as that for neutral medium. Hence,
or (c) acidic solution.
equivalent weight of KMnO4 in weakly alkaline medium is
(a) In neutral solution. Potassium permanganate acts as a same as that in the neutral medium, viz., 52.67
moderate oxidising agent in neutral aqueous solution
Some oxidizing properties of KMnO4 in the alkaline medium.
because of the reaction :
These are given below :
2KMnO4  H 2 O 
o 2KOH  2MnO2  3O (i) It oxidises potassium iodide to potassium iodate.
  
or MnO  2H 2 O  3 e 
4 o MnO2  4OH 2KMnO 4  H 2 O  KI 
o 2MnO 2  2KOH  KIO3
Pot. iodate

Thus, MnO 4 ion gains 3 electrons. Also, according to or 

I  6OH  
o IO  3H 2 O  6 e 
3
the above equation, in neutral medium, from two moles of
In this case, iodine is not liberated unlike the case of acidic
permanganate, three oxygen atoms are available. In fact,
medium.
during the course of reaction, the alkali generated renders
the medium alkaline even when we start with neutral Similar reaction takes place with KBr.
solutions. Hence, Eq. wt. of KMnO4 in neutral or weakly (ii) It oxidises olefinic compounds to glycols, i.e., when an
alkaline medium olefinic compound is shaken with alkaline KMnO4, pink
Mol. wt. 158 colour of KMnO4 is discharged.
52.67
3 3
Some oxidizing properties of KMnO4 in the neutral medium.
These are given below :
(i) It oxidises hot manganous sulphate to manganese dioxide.
Alkaline KMnO4 used for this test is known as Baeyer’s
2KMnO4  3MnSO4  2H2 O 
o K 2SO4  2H2SO 4  5MnO2
reagent. It is used for oxidation of a number of organic
Presence of ZnSO4 or ZnO catalyses the oxidation. compounds.
 d & f BLOCK ELEMENTS

(c) In acidic medium. Potassium permanganate in the (viii) It oxidises HX (where X = Cl, Br, l) to X2
presence of dil. sulphuric acid, i.e., in acidic medium, acts
as a strong oxidising agent because of the reaction 2KMnO4  3H 2SO4  10 HX 
o K 2SO4  2MnSO 4 

2KMnO4  3H 2SO 4 
o K 2SO 4  2MnSO 4  3H 2 O  5O 8H 2 O  5X 2

(ix) It oxidises ethyl alcohol to acetaldehyde

or MnO4  8H   e 
o Mn 2   4H 2 O.
2KMnO4  3H 2SO 4  5CH3 CH 2 OH 
o K 2SO 4  2MnSO4 
Since in the above reaction, MnO4 ion gains 5 electrons
of five atoms of oxygen are available from two molecules 5CH 3 CHO  8H 2 O.
of KMnO4. Hence. Uses.

Mol. wt. 158 (i) It is often used in volumetric analysis for the estimation
Eq. wt. of KMnO 4 31.6 of ferrous salts, oxalates, iodides and hydrogen peroxide.
However, it is not a primary standard because it is difficult
Some oxidizing properties of KMnO4 in the acidic medium. to obtain it in the pure state and free from traces of MnO2.
These are given below : It is, therefore, always first standardised with a standard
(i) It oxidises H2S to S. solution of oxalic acid.

2KMnO4  3H2SO 4  5H 2 S 
o K 2SO4  2MnSO 4  2H 2 O  5O
Remember that volumetric titrations inolving KMnO4 are
carried out only in presence of dilute H2SO4 but not in the
(ii) It oxidises sulphur dioxide to sulphuric acid. presene of HCl or HNO3. This is because oxygen produced
from KMnO4 + dill. H2SO4 is used only for oxidizing the
2KMnO4  5 SO2  2H 2 O 
o K 2SO 4  2MnSO4  2H 2SO 4
reducing agent. Moreover, H2SO4 does not give any
  oxygen of its own to oxidiize the reducign agent. In case
(iii) It oxidises nitrites NO 2 to nitrates NO3 , arsenites
HCl is used, the oxygen produced from KMnO4 + HCl is
AsO33  to arsentates AsO 34 and sulphites and partly used up to oxidize Hcl to chlorine and in case HNO3
is used, it itself acts as oxidizing agent and partly oxidizes
thiosulphates to sulphates.
the reducing agent.
2KMnO 4  3H 2SO4  5KNO2 
o K 2SO4  2MnSO4  (ii) It is used as a strong oxidising agent in the laboratory as
well as in industry. It is a favourite and effective oxidising
3H 2 O  5KNO3 agent used in organic synthesis Alkaline potassium
(iv) It oxidises oxalates or oxalic acid to CO2 permanganate is used for testing unsaturation in organic
chemistry and is known as Baeyer’s reagent.
2KMnO 4  3H 2SO4  5C2 H 2 O4 
o K 2SO4  2MnSO4 
(iii) Potassium permanganate is also widely used as a
disinfectant and germicide. A very dilute solution of
8H 2 O  10 CO 2
permanganate is used for washing wounds and gargling
(v) It oxidises ferrous sulphate to ferric sulphate (i.e., ferrous for mouth sore. It is also used for purifying water of
salt to ferric salt). stinking wells.

2KMnO4  8H 2SO4  10FeSO4 

o K 2SO4  2MnSO 4  (iv) Because of its strong oxidizing power, it is also used for
bleaching of wool, cottong, silk and other textile fibres
5Fe2 SO4 3
 8H 2 O and also for decolourisation of oils.

(vi) It oxidises H2O2 to H2O and O2. This is because acidified

KMnO4 is a stronger oxidising agent than H2O2.

2KMnO 4  3H 2SO4  5H 2 O2 
o K 2SO4  2MnSO4 

8H 2 O  5O 2

(vii) It oxidises potassium iodide to iodine

2KMnO 4  3H 2SO 4  10KI 

o K 2 SO 4  2MnSO 4 

8H 2 O  5I 2
 d & f BLOCK ELEMENTS

THE LANTHANIDE SERIES

1. INTRODUCTION

These elements are classified by the filling up of the

antipenultimate 4f energy levels.

2. PHYSICAL PROPERTIES

Electronic Configuration and oxidation states

Element Electronic Electronic Oxidation States
Configuration Configuration of M3+

Lanthanum La [Xe] 5d1 6s2 [Xe] +3

Cerium Ce [Xe] 4f1 5d1 6s2 [Xe] 4f 1 +3 (+ 4)

Praseodymium Pr [Xe] 4f 3 6s2 [Xe] 4f 2 +3 (+ 4)

Neodymium Nd [Xe] 4f 4 6s2 [Xe] 4f 3 (+2) +3

Promethium Pm [Xe] 4f 6s2 [Xe] 4f 4 (+2) +3

Samarium Sm [Xe] 4f 6 6s2 [Xe] 4f 5 (+2) +3

Europium Eu [Xe] 4f 7 6s2 [Xe] 4f 6 (+ 2) +3

Gadolinium Gd [Xe] 4f 7 5d1 6s2 [Xe] 4f 7 +3

Terbium Tb [Xe] 4f 9 6s2 [Xe] 4f 8 +3 (+ 4)

Dysprosium Dy [Xe] 4f 10 6s2 [Xe] 4f 9 +3 (+ 4)

Holmium Ho [Xe] 4f 11 6s2 [Xe] 4f 10 +3

Erbium Er [Xe] 4f 12 6s2 [Xe] 4f 11 +3

Thulium Tm [Xe] 4f 13 6s2 [Xe] 4f 12 (+ 2) +3

Ytterbium Yb [Xe] 4f 14 6s2 [Xe] 4f 13 (+ 2) +3

Lutetium Lu [Xe] 4f14 5d1 6s2 [Xe] 4f 14 +3

2.1 Oxidation state Oxidation numbers (+II) and (+IV) do occur, particularly
when they lead to :
The sum of the first three ionization energies for each element
1. a noble gas configuration e.g. Ce4+ (f 0)
are low. Thus the oxidation state (+III) is ionic and Ln3+
dominates the chemistry of these elements. The Ln2+ and 2. a half filled f shell, e.g. Eu2+ and Tb4+ (f7)
Ln4+ ions that do occur are always less stable than Ln3+. 3. a completely filled f level, e.g. Yb2+ (f14).
d & f BLOCK ELEMENTS

As we move along the lanthanide series, the nuclear charge

NOTE increases by one unit at each successive element. The new
electron is added into the same subshell (viz., 4f). As a result,
The 4f electrons in the antipenultimate shell are very the attraction on the electrons by the nucleus increases and
effectively shielded from their chemical environment this tends to decrease the size. Further, as the new electron
outside the atom by the 5s and 5p electrons. Consequently is added into the f-subshell, there is imperfect shielding of
the 4f electrons do not take part in bonding. They are one electron by another in this subshell due to the shapes
neither removed to produce ions nor do they take any of these f-orbitals. This imperfect shielding is unable to
significant part in crystal field stabilization or complexes. counterbalance the effect of the increased nuclear charge.
Crystal field stabilization is very important with the d- Hence, the net result is a contraction in the size though the
block elements. The octahedral splitting of f orbitals 'o is decrease is very small. It is interesting to note that in
only about 1kJ mol–1. Whether the f orbitals are filled or lanthanides, the decrease in the atomic radius for 14 elements
empty has little effect on the normal chemical properties. [Ce (58) to Lu (71)] is only 11pm (from 183 to 172 pm).
However, it does affect their spectra and their magnetic Similarly, decrease in ionic radii from Ce3+ to Lu3+ is only
properties. 17 pm (103 to 86 pm)
The contraction is similar to that observed in any transition
series. The cause is also similar, just as in the transition
2.2 Atomic radius
series where the contraction is due to imperfect shielding of
In lanthanide series, with increasing atomic number, there is one d electron by another. But the shielding of one 4f electron
a progressive decrease in the atomic as well as ionic radii of by another is less than one d electron by another with
increase in nuclear charge along the series.
trivalent ions from La3+ to Lu3+. This regular decrease in the
atomic and ionic radii with increasing atomic number is
known as lanthanide contraction.

Atomic and Ionic radii (pm) of lanthanum and lanthanoids.

Element La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

Atomic Radii (Ln) 187 183 182 181 181 180 199 180 178 177 176 175 174 173 172

Ionic Radii (Ln3+) 106 103 101 99 98 96 95 94 92 91 90 89 88 87 86

2.3 Magnetic behaviour calculated by considering spin as well as orbital contribution,

i.e,
Paramagnetism is shown by the positive ions of lanthanides
except La3+ (lanthanum ion, f0) and Lu3+ (lutetium ion, f14). P eff 4 S (S  1)  L ( L  1) B.M.
This property of the lanthanides is due to presence of where S is spin quantum number and L is orbital quantum
unpaired electrons in the incomplete 4f subshell. number.
lanthanides differ from transition elements in the fact that
their magnetic moments do not obey ‘spin only’ formula, NOTE

viz., P eff n ( n  2) B.M. where n is the number of Separation of the Lanthanide Elements
unpaired electrons. This because in case of transition Since the change in ionic radius is very small, the chemical
elements, the orbital contribution is quenched by the electric properties are similar. This makes the separation of the
field of the environment but in case of lanthanides, 4f orbitals element in pure state difficult. Separation is done by Ion
lie to deep to be quenched. Hence, their magnetic moment is Exchange methods which is based on the ionic size.
 d & f BLOCK ELEMENTS

2.4 Colour
93 Neptunium Np 5f 4 6d1 7s2 +3, +4, +5,+ 6, +7
The Lanthanides are silvery white metals. However, most of
the trivalent metal ions are coloured, both in the solid state 94 Plutonium Pu 5f 6 7s2 +3, +4, +5, +6, +7
and in aqueous solution. This is due to the partly filled-f-
95 Americium Am 5f 7 7s2 +2, +3, +4, +5, +6
orbitals which permit f-f transition.
96 Curium Cm 5f 7 6d1 7s2 +3, +4
NOTE
97 Berkelium Bk 5f 9 7s2 +3, +4
Lanthanides ions with x f electrons have a similar colour
98 Californium Cf 5f 10 7s2 +2, +3
to those with (14–x) f electrons e.g., La3+ and Lu3+ are
colourless, Sm3+ and Dy3+ are yellow and Eu3+ and Tb3+ 99 Einsteinium Es 5f 11 7s2 +2, +3
are pink.
100 Fermium Fm 5f 12 7s2 +2, +3

101 Mendelevium Md 5f 13 7s2 +2, +3

2.5 Hydroxides
102 Nobelium No 5f 14 7s2 +2 ,+3
The hydroxides Ln(OH)3 are precipitated as gelationous
precipitates by the addition of NH4OH to aqueous solutions. 103 Lawrencium Lr 5f14 6d1 7s2 +3
These hydroxides are ionic and basic. They are less basic 104 Rutherfordium Rf 4f14 6d2 7s2
than Ca(OH)2 but more basic than Al(OH) 3 which is
amphoteric. The metals, oxides and hydroxides all dissolve
in dilute acids, forming salts. Ln(OH)3 are sufficiently basic 1. OXIDATION STATE
to absorb CO2 from the air and form carbonates. The basicity
decreases as the ionic radius decreases from Ce to Lu. Thus Unlike Lanthanides, Actinides show a large number of
Ce(OH)3 is the most basic, and Lu(OH3), which is the least oxidation states. This is because of very small energy gap
basic, is intermediate between Scandium and Yttrium in basic between 5f, 6d and 7s subshells. Hence, all their electrons
strength. The decrease in basic properties is illustrated by can take part in bond formation. The dominant oxidation
the hydroxides of the later elements dissolving in hot state of these element is +3 (similar to Lanthanides). Besides
concentrated NaOH, forming complexes. +3 state, Actinides also exhibit an oxidation state of +4. Some
Actinides show still higher oxidation states. The maximum
Yb(OH)3 + 3NaOH o 3Na+ + [Yb(OH)6]3– oxidation state first increases upto the middle of the series
and then decreases, e.g., it increases from + 4 from Th to +5,
Lu(OH)3 + 3NaOH o 3Na+ + [Lu(OH)6]3– +6, and +7 for Pa, U and Np but decreases in the succeeding
elements.
ACTINIDES SERIES The Actinides resemble Lanthanides in having more
compounds in +3 state than in the +4 state. However, the
The elements and their Oxidation States compounds in the +3 and +4 state tend to undergo
hydrolysis.
Atomic Element Symbol Outer Oxidation Further, it may be noted that in case ofActinides, the distribution of
electronic states* oxidation states is so uneven that it is of no use to discuss their
chemistry in terms of their oxidation states.
structure
2. ATOMIC RADIUS
1 2
89 Actinium Ac 6d 7s +3
The Actinides show Actinide contraction (very much like
90 Thorium Th 6d2 7s2 +3, +4 Lanthanide contraction) due to poor shielding effect of the
5f-electrons. As a result, the radii of the atoms or ions of
91 Protactinium Pa 5f 2 6d1 7s2 +3, +4, +5 these metals decrease regularly across the series. The
contraction is greater from element to element in this series
92 Uranium U 5f 3 6d1 7s2 +3, +4, +5, +6 due to poorer shielding by 5f electrons. This is because 5f
orbitals extend in space beyond 6s and 6p orbitals whereas
4f orbitals are buried deep inside the atom.
 d & f BLOCK ELEMENTS

Differences :
3. MAGNETIC BEHAVIOUR
The show differences in some of their characteristics as
Like Lanthanides, the Actinides elements are strongly follows :
paramagnetic. The variation in magnetic susceptibility of
Lanthanides Actinides
Actinides with the increasing number of unpaired electrons
is similar to that of Lanthanides but the values are higher (i) Besides + 3 oxidation state (i) Besides +3 oxidation state,
for the Actinides than the Lanthanides.
they show + 2 and +4 oxi- they show higher oxidation
4. COLOUR dation states only in few states of +4, +5, +6, + 7 also.
cases.
These metals are silvery white. However, Actinide cations
are generally coloured. The colour of the cation depends (ii) Most of their ions are (ii) Most of their ions are
upon the number of 5f-electrons. The cations containing colourless coloured
no 5f-electron or having seven 5f-electrons (i.e., exactly (iii) They have less tendency (iii) They have greater tendency
half-filled f-subshell) are colourless. The cations containing towards complex formation towards complex formation.
2 to 6 electrons in the 5f-subshell are coloured both in the
crystalline state as well as in aqueous solution. The colour (iv) Lanthanides compounds are (iv) Actinides compounds are
less basic. more basic
arises due to f–f transition e.g. Ac3+ (5f 0) = colourless, U3+
(5f 3) = Red, Np3+ (5f 4) = Blue, Pu3+ (5f 5) = Voilet, Am3+ (v) Do not form oxocation (v) From oxocations e.g.
6 3+ 7 3+ 0
(5f ) = Pink, Cm (5f ) = Colourless, Th (5f ) = Colourless UO22 , PuO22 and UO+
as so on.
(vi) Except promethium, they (vi) They are radioactive.
COMPARISON OF LANTHANIDES AND are non-radioactive
ACTINIDES
(vii) Their magnetic properties (vii) Their magnetic properties
Similarities : can be explained easily. cannot be explained easily,
as they are more complex.
As both Lanthanides and actinides involve filling of f-
orbitals, they show similarities in many respects as follows :
(i) Both show mainly an oxidation state of +3.
(ii) Both are electropositive and very reactive.
(iii) Both exhibit magnetic and spectral properties.
(iv) Actinides exhibit Actinide contraction like Lanthanide
contraction shown by Lanthanides.