d-Block Elements

The elements having incompletely filled d-orbitals in ground state or in their most
common oxidation state are called d-block elements.
Also called transition metals because they have properties intermediate between those
of metals and nonmetals and there is a transition from metallic character to non-metallic
character through d block elements.
They all are metallic in nature.
General electronic configuration: (n ─ 1) d1 ─ 10 ns0─ 2 ( valence electron enters d orbital of
penultimate shell)
Classification:
(i) 1st transition series (3d series): consists of 10 elements of 4th period
21Sc to 30Zn.
(ii) 2nd transition series (4d series): consists of 10 elements of 5th period
39Y to 48Cd.
(iii) 3rd transition series (5d series): consists of 10 elements of 6th period
57La , 72Hf to 80Hg.
(iv) 4th transition series (6d series): incomplete series.
89Ac , 104Rf-----------
3d series:
Element: 21Sc 22Ti 23V 24Cr 25Mn 26Fe 27Co 28Ni 29Cu 30Zn.

E.C. 3d14s2 3d24s2 3d34s2 3d54s1 3d54s2 3d64s2 3d74s2 3d84s2 3d104s1 3d104s2

4d series:
Element: Y
39 Zr
40 Nb
41 42 Mo 43 Tc 44 Ru 45 Rh 46 Pd Ag
47 Cd.
48

E.C. 4d15s2 4d25s2 4d45s1 4d55s1 4d65s1 4d75s1 4d85s1 4d105s0 4d105s1 4d105s2

5d series:
Element: La
57 Hf
72 Ta
73 74W Re
75 Os
76 Ir
77 Pt
78 Au
79 Hg.
80

E.C. 5d16s2 5d26s2 5d36s2 5d46s2 5d56s2 5d66s2 5d76s2 5d96s1 5d106s1 5d106s2

6d series :
1 2
89Ac : 6d 7s
2 2 ------------------------
104Rf: 6d 7s
(Exceptions because: 1. Half filled and completely filled sets of orbitals are relatively
more stable. 2. There is a small energy difference b/w (n-1) d and ns orbitals.)

Q: Write down the electronic configuration of (i) Cr3+ (ii) Cu+ (iii) Co2+ (iv) Mn2+
[ 1st remove electrons from 4s, then 3d]]
Q: Why are Zn,Cd and Hg generally not considered as transition elements?
1
Ans: because they donot have partly filled d subshell in their ground state or their
common oxidation state ie Zn2+ ,Cd2+ , Hg2+.(d10 configuration).They do not show
properties of transition metals to any appreciable extent. However they are
considered as end members of the transition series to maintain a rational
classification of elements.

Q: On what ground can you say that Sc is a transition element but Zn is not?
Ans: 21Sc : 3d14s2 , has partly filled d orbitals in its ground state but 30Zn: 3d104s2 ;
does not have partly filled d subshell in its ground state as well as in most common
oxidation state ie Zn+2

Q: Silver atom has completely filled d orbitals in its ground state. How can you say
that it is a transition metal?
Ans: 47Ag: 4d105s1.In +2 oxidation state ,the configuration is d9 ie d subshell is
incompletely filled. Hence it is a transition metal.

Q: The d1 configuration is very unstable in ions. Why?

Ans: Because such ion easily loses one electron to acquire stable d0 configuration.

Q: In what way is the electronic configuration of transition elements different from

that of non-transition elements?
Ans: (i) General electronic configuration for transition metals is: (n ─ 1) d1 ─ 10 ns0─ 2
Whereas for non-transition elements it is ns1─ 2 (s-block) or ns 2 np1─ 6
(p-block)
(ii) In non-transition elements ,only the outermost shell is incomplete while in
transition elements ,the penultimate shell is also incomplete.

Q: There are greater horizontal similarities in the properties of the transition

elements in contrast to the main group elements. Why?
Ans: Because in transition elements ,electrons enter in to (n-1)d subshell and not in the
outer ns subshell.So d block elements have similar valence shell electronic
configuration and differ from one another only in number of electrons in d orbitals
of the penultimate shell.Hence they show resemblance in their physical and
chemical properties.

Q:Discuss the metallic nature of transition elements.

Ans: Except Mercury(liquid) ,all the transition elements have typical metallic structure
(hcp,ccp or bcc) .They are hard,lustrous,malleable,ductile,have high melting and
boiling points,high thermal and electrical conductivity and high tensile strength.
This is because: (i) they have relatively low ionisation energy.
(ii) they have 1 or 2 electrons in their outermost (ns) shell and can loose these
electrons readily and therefore are metallic.
Furthur the strength of metallic bond depends upon
number of unpaired electrons. More the number of unpaired electrons, stronger
is the metallic bond. As we move from left to right in a transition series,number of
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 unpaired d electrons increases up to middle ,so strength of metallic bond and
hence hardness increases up to middle and then number of unpaired electrons will
decrease, so strength of metallic bond decreases and hence hardness decreases.

Q: Cr, Mo and W are very hard while Zn, Cd and Hg are soft metals. Why?
Ans: Cr, Mo and W have maximum number of unpaired d electrons(d5) .More the
number of unpaired d electrons, stronger is the metallic bonding. That is why these
metals have strongest metallic bonds and are very hard. But Zn,Cd and Hg have no
unpaired electrons (d10),so they are soft metals. Hg is even liquid at room
temperature.

Q: The transition metals have very high melting and boiling points(higher than s
Block metals) and their melting and boiling points increase as we move from left to
right in a transition series,reaches a maximum value and then decrease, as the
atomic number increases. Mn,Tc and Re have abnormally low melting points.
Discuss.
Ans: This is because of strong metallic bonding, as not only valence ns electrons but also
(n-1) d electrons participate in metallic bonding.Greater the number of unpaired d
electrons,stronger is the metallic bonding.In a particular series, the metallic strength
increases up to the middle up to d5configuration , then as the number of unpaired
electrons decreases accordingly the melting point and boiling point decreases.
In 3d series,Cr has highest melting point.
Mn,Tc and Re have exactly half filled stable
electronic configuration (n-1)d ns2.Electrons are tightly held by the nucleus so that
5

the delocalization of electrons is less and metallic bonding is much weaker than the
preceding element.
Zn,Cd and Hg have no unpaired electrons.
Metallic bonding is the weakest .So they are soft metals with very low melting
points. Hg is liquid at ordinary temperature
Tungsten (W) – Metal with highest melting point.

Q: The enthalpies of atomization of transition metals are high.Why?

Ans: It is enthalpy change involved in breaking the metallic lattice of the crystalline
metals into atoms. Higher values of enthalpies of atomisation are due to strong
metallic bonds.As both ns and (n-1)d electrons participate in metallic bonding.
Greater the number of unpaired d electrons,stronger is the metallic bonding.In a
particular series, the metallic strength increases up to the middle up to d5
configuration. Accordingly enthalpies of atomization increase and then decrease
after midway

Q: In 1st transition series the enthalpy of atomization of Zn is the lowest ie 126

kJ/mol. Why?
Ans: It is enthalpy change involved in breaking the metallic lattice of the crystalline
metals into atoms.In Zn , There are no unpaired d electrons (d10) and so metallic
bonds are very weak.
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Q: Metal-Metal bonding is more frequent for 4d and 5d series transition metals (2nd
&3rd series) than that for 3d series (1st series).Why?
Ans: In 4d and 5d series elements ,metallic bonds are stronger This is because electrons
are loosely held to participate easily in metallic bond formation than in 3d series.
This is further evident from the fact that 2nd &3rd transition series elements have
greater enthalpies of atomization than corresponding elements of 1st series.

Q: The Atomic/ionic radii of d block elements in a series decrease with increase in

atomic number but the decrease is small after midway.At the end of the series,there is
a slight increase in radii.Discuss.
Ans: eg in 1st transition series,atomic radii decrease from Sc to Cr and become almost
constant from Cr toCu, Zn has comparatively high atomic radius.
In the beginning as atomic number increases, nuclear charge increases so
atomic radius decreases.
As new electrons enter in to (n-1) d subshell, these electrons
shield the outermost s electrons from nuclear pull. More the number of d – electrons,
more will be shielding effect and this effect also cancels the effect of increased
nuclear charge, so atomic size remains almost constant after midway.
Towards the end of the series ,interelectronic repulsions increase due to
pairing of electrons in d orbitals.This results in expansion of the electron cloud and
thus the atomic radius increases.
The atomic radii of 2nd series are larger than those of 1st transition
series because number of shells increases. However atomic radii of 2nd and 3rd
series elements are nearly the same. This is due to lanthanoid contraction.

Q: How does Density vary along a transition series?

OR
Q: There is in general an increase in density of elements from Titanium (Z=22) to
Copper(Z= 29) .discuss.
Ans: As we move from left to right along a series, atomic mass increases. However
atomic volume decreases due to increase in nuclear charge. Hence density
increases.
However it is observed that the density in a given series reaches a
maximum value at group VIII and then decreases.This is due to their small radii and
closely packed structure .After groupVIII ,interelectronic repulsions sufficiently
increase and therefore atomic volume increases and consequently density
decreases.
Iridium and Osmium have maximum density among d block elements.

Q: The ionisation enthalpy gradually increases with increase in atomic number along a
given transition series though some irregularities are observed. Discuss.
Ans: As the atomic number increases, the nuclear charge increases, so atomic size
decreases and removal of valence electron becomes difficult. Therefore ionisation
enthalpies increase.
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 The irregular trend in the 1st ionisation enthalpy of 3d metals is due to
the fact that the removal of electrons alters the relative energies of 4s and 3d
orbitals. Thus there is reorganization energy accompanying the ionisation. This
results in to the releases of exchange energy which increases as the number of d
electrons increases and also from transference of s electrons into d orbitals.
Cr :low 1st ionisation energy because Cr+ has stable d5 configuration.
Zn :very high 1st ionisation enthalpy due to stable completely filled
(n-1)d10ns2 configuration .

Q: In a given series,the difference in the ionisation enthalpies b/w any two successive
d- block elements is much less than difference in case of successive s-block or p-
block elements.Why?
Ans: In transition elements as we move from left to right, the incoming electrons enter
into (n-1) d subshell. These d electrons screen the outer s electrons from nuclear
pull .As the number of(n-1) d electrons increases ,the outer ns electrons are
shielded more and more. Thus the effect of increasing nuclear charge is opposed by
the increases in magnitude of screening effect. As a result the ionisation enthalpies
show a little variation only.

Q: Explain the irregular trends in 2nd and 3rd ionisation enthalpies of 3d series
elements.
Ans: In general both 2nd and 3rd ionisation enthalpies increases along a period but
magnitude of increases for the successive elements is much higher
Cr and Cu : very high 2nd ionisation enthalpies,due to half filled d5and fully filled
d10stable configurations of Cr+ and Cu+ ions respectively,removal of 2nd electron is
difficult.
Zn: low 2nd ionisation enthalpy,removal of 2nd electron gives stable d10 configuration.
Mn: very high 3rd ionisation enthalpy,3rd electron has to be removed from stable d5
Configuration.
Fe: very low 3rd ionisation enthalpy, removal of 3rd electron gives stable d5
configuration.
Cu,Ni,Zn:very high ionisation enthalpies,so show maximum oxidation state of +2.

Q: How would you account for the irregular variation of ionisation enthalpies(1st
and 2nd) in the 1st series of the transition elements?

Q: How can you predict the thermodynamic stability of a particular oxidation state
on the basis of ionisation enthalpy values?
Ans: Smaller the ionisation enthalpy of a metal, stable is the compound.
eg Ni(II) compounds are thermodynamically more stable than Pt(II) compounds
because sum of the the 1st two ionisation enthalpies in Nickel (ΔiH1 + ΔiH2 =
2.49 x103 kJ/mol) is less than that for Platinum( ΔiH1 + ΔiH2 =2.66x103 kJ/mol).
On the other hand Pt(IV) compounds are thermodynamically
more stable than Ni(IV) compounds because sum of 1st four ionisation enthalpies is
less for Pt (9.36x103 kJ/mol) than for Ni(11.29x103 kJ/mol).
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Q: K2PtCl6 is a well known compound while the corresponding K2NiCl6 is not
known. Why?

Q: Explain how the Eo values decide the stability of compounds in aqueous solution.
Ans: Stability of a compound in solution depends upon electrode potentials rather
than ionisation enthalpies.The lower the E0red value (more negative value) ,the
greater is the stability of that oxidation state.
Further Electrode potential values depend upon factors such
as enthalpy of sublimation(+ve), the ionisation enthalpy (+ve) and the enthalpy of
hydration (-ve) .ie.
ΔHsub
M(s) → M(g)
ΔiH
M(g) → M+(g) + e─
ΔHhyd
M (g) + H2O → M+(aq)
+

The total enthalpy change,when solid metal changes to monovalent ion in aqueous
medium ; ΔTH = ΔsubH + ΔiH + ΔhydH
The electrode potential is a measure of ΔTH. The smaller the value of total energy
change for a particular oxidation state in aqueous solution,greater will be the stability of
that oxidation state.

Q: Explain the trends in the M2+/M standard electrode potentials for 3d series
elements.
Ans: (Refer to the graph given in book)
Ti V Cr Mn Fe Co Ni Cu Zn
EO (M2+ (aq)/M) - 1.63 - 1.20 -0.91 -1.18 -0.44 -0.28 -0.25 0.34 -0.76
( In V)
EO (M2+/M) for any metal is related to the sum of the enthalpy changes taking place
in the following steps:
ΔsubH
M(s) → M(g)
ΔiH
M(g) → M2+(g) + 2e─
ΔhydH
M (g) + H2O → M2+(aq)
2+

(i)There is no regular trend in the EO (M2+/M) values.Because their ionisation

enthalpies (IE1+IE2) and sublimation enthalpies do not show any regular trend.
(ii) Except Cu, all of them are good reducing agents(-ve EO values) but their reducing
character is less as compared to the s-block metals.This is due to high enthalpy of
sublimation ,enthalpies of ionisation and poor enthalpy of hydration of their
ions.So transition metals are comparatively less reactive.
(iii) Along the series, EO (M2+/M ) values increases ie become less negative,showing a
decreasing tendency to form M2+ ions across the series.This is due to general
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 increase in sum of 1st and 2nd ionisation enthalpies.
(iv)Cu is the only metal having positive value of EO.It is because sum of
sublimation enthalpy and 1st &2nd ionisation enthalpies for Cu is very high and is
not balanced by very low enthalpy of hydration.
(v) Due to positive EO , Cu does not liberate H2 gas from acids.It reacts with the
oxidising acids only ie conc.nitric acid & sulphuric acid.
(vi) The values of EO for Mn,Ni and Zn are more negative than expected from general
trend. This is due to highly stable d subshell(d5) in Mn2+and fully filled d subshell
(d10) in Zn2+ .The exceptional behaviour of Ni is due to its high negative
enthalpy of hydration.

Q: Compare the stability of +2 oxidation state for the elements of the 1st transition
series.
Ans: 1. Sc is highly stable in +3 oxidation state only.
2.In general stability of +2 oxidation state decreases along the series as the sum of
sublimation enthalpy and ionization enthalpies increases. however there
is no regular trend.
3.Mn2+ and Zn2+ are highly stable due to half filled and completely filled stable
configuration .
4. Ni2+ is exceptionally stable due to its relatively higher hydration enthalpy.
5.Cu has only little tendency to change into Cu2+ due to its very high sum of
sublimation enthalpy and 1st and 2nd ionization enthalpy values.

Q: The EO (M2+/M) value for Cu is positive (0.34V).What is possibly reason for this?

Q: Why are Mn2+ compounds more stable than Fe2+ towards oxidation to their + 3
state?

Q: Why is the EOvalue for Mn3+/Mn2+ couple much more positive than that for
Cr3+/Cr2+ or Fe3+/Fe2+?Explain.
Ans: Mn2+is very stable due to its stable d5 configuration.

Q: Why is Cr2+ strongly reducing and Mn(III) oxidising when both have
d4 configuration?
Ans: because Cr3+ has d3configuration which has half filled t2g level and thus extra
stability. Also EO (Cr3+/Cr2+) value is negative.So Cr2+easily changes to Cr3+ and acts
as a reducing agent. However Mn changes from Mn3+ to Mn2+ which has extra
stability due to d5configuration.

Q: Cr2+ is a strong reducing agents in aqueous solution and can liberate hydrogen
from dilute acid. Complete the following equation:
Cr2+ (aq) + H+ (aq) →
Ans: 2 Cr2+ (aq) + 2 H+ (aq) → 2 Cr3+ (aq) + H2 (g)

7
Q: Given M2+/M and M3+/M2+ EOvalues for some metals:
Cr2+/Cr ─ 0.9V Cr3+/Cr2+ ─ 0.4V
2+/
Mn Mn ─ 1.2V Mn3+/Mn2+ +1.5V
Fe2+/Fe ─ 0.4V Fe3+/Fe2+ + 0.8V
Use this data to comment upon:
(i)the stability of Fe3+ in acid solution as compared to that of Cr3+ or Mn3+and
(ii)the ease with which iron can be oxidized as compared to a similar process for
either Cr or Mn metal
Ans: (i) lower the value of EOred ,more is the stability of oxidation state. so Fe3+ is
more stable than Mn3+ but less stable than Cr3+.
(ii) for Cr and Mn, +2 oxidation is more stable than that for Fe .So iron is less easily
oxidized in comparison.

Q: Co (II) is stable in aqueous solution but in presence of a strong ligand /

complexing reagent, it is easily oxidized to Co3+ ion .Why?
Ans: Co3+ ( 3d6, 4s0 ) In presence of strong ligand,pairing occurs.Thus there are no
unpaired electrons and it is highly stable .However in Co2+ ( 3d7 ),there is one
unpaired electron even after pairing in presence of strong ligand.Hence Co2+ is
oxidized to more stable Co3+ .

Q: Calculate the number of unpaired electrons in the following gaseous ions: Mn3+ ,
Cr3+ ,V3+ ,Ti3+ .Which one is the most stable in aqueous solution?
Ans: Cr3+ due to half filled stable t2g configuration

Q: Which is a strongest reducing agent Cr2+ or Fe2+ and why?

Ans: EO (Cr3+/Cr2+ ) value very low, Cr3+stable; EO (Fe3+/Fe2+ ) value high, Fe2+ difficult
to oxidize.

Q: Out of Cr3+ and Mn3+,which is stronger oxidising agent and why? Also state
which is more paramagnetic and why?
Ans: Mn3+ gets easily reduced to Mn2+ with stable half filled d5 configuration .
Cr3+ has 3 unpaired electrons whereas Mn3+ has 4 unpaired electrons. So Mn3+is
more paramagnetic.

Q: Transition metals show variable oxidation states.Why?

Ans: This is because there is only a little energy difference between ns and (n-1) d
orbitals ,therefore both ns and (n-1) d electrons participate in bonding and hence a
variety of oxidation states are obtained. In general lower oxidation state
is exhibited when only ns electrons participate in bonding and higher oxidation
states are shown when ns as well as (n-1) d electrons participate in bonding.

Q: To what extent do the electronic configurations decide the stability of oxidation

states in the 1st series of transition elements? Illustrate with example.
Ans: In general ,the minimum oxidation state shown by any transition metal is equal to
the number of ns electrons.For the 1st five members of each transition series, the
8
highest oxidation state shown is generally equal to the sum of ns and (n-1) d
electrons. For the remaining five elements, the maximum oxidation state is not
related to their electronic configuration.
The oxidation states which leads to noble gas configuration, half filled or fully filled
d orbitals, are more stable.eg. In the 1st transition series electronic configuration of
Mn is [Ar]3d54s2 .It shows oxidation states of +2 to +7,but Mn(II) with d5
Configuration) is most stable.

 The most common oxidation state in 1st row transition metals is +2 (obtained by
lose of s electrons) except Sc.
 Sc (Z=21) exhibits only +3 Oxidation State because after losing 3 electrons, it
acquires stable noble gas configuration.
 Compounds of transition metals in +2and +3 oxidation states are generally
ionic in nature and those in higher oxidation states are covalent in nature.eg all
bonds are covalent in MnO4─,CrO42─. Thus M2+ or M3+ ions in 4d and 5d series
are generally less stable than those of 3d series.
 The elements which show the greatest number of oxidation states occur in or
near the middle of the series .This is due to maximum number of unpaired d
electrons. Here both ns and (n-1) d electrons participate in bonding.eg.Mn 3d54s2
shows all oxidation states from +2 to+7.
 The highest oxidation state shown by any transistion metal is +8 by Osmium and
Ruthenium.
. In 1st transition series,Cu shows +1 oxidation state most frequently because
Cu, 3d104s1 can easily lose one electron to give stable 3d10configuration.
 Successive oxidation states for any transition element differ by unity.eg VII ,VIII
,VIV ,VV.This is unlike non transition elements where oxidation state normally
differs by two units .eg PbII,PbIV ; SnII ,SnIVetc.
 In case of transition elements,the higher oxidation states are more stable for
heavier elements.eg in gp 6 ,Mo(VI) and W(VI) are found to be more stable than
Cr(VI).(Cr(VI) in acidic medium is a strong oxidising agent but MoO3 and WO3
are not). This is unlike non transition elements,where lower oxidation states are
more stable for heavier members due to inert pair effect.
 Transition metals also show low oxidation states in some compounds.eg zero in
Ni(CO)4 and Fe(CO)5.Here ligand CO not only forms sigma bond with the metal
atom but also has π acceptor character.
 The compound of transition metals with F& O exhibit the highest oxidation
states as F and O are small in size, the most electronegative elements and very
strong oxidizing agents. So they can oxidize the metal to its highest oxidation
state.eg Osmium shows an oxidation state of +6 in OsF6 and vanadium shows +5
in V2O5.
 For halides,the highest oxidation states are +4 for Ti(TiX4),+5 for V(VF5), +6 for
Cr(CrF6),+7 for Mn(MnO3F)Beyond Mn ,no metal shows higher oxidation states
of more than +3.(only FeX3,CoF3)
 In the lower oxidation states,fluorides are unstable.eg TiF2,VF2,CuF do not exist.
 All Cu(II) halides are known except CuI2 which is highly unstable
9
 2Cu2+ + 4I─ → Cu2I2 + I2
I being a good reducing agent is easily oxidized by Cu2+
─

 The relative stability of oxidation states can be known from the standard electrode
potential values.eg.Cu(I) compounds are unstable in aqueous solution and
undergo disproportionation as follow:
2 Cu+(aq) → Cu2+(aq) + Cu(s)
The greater stability of Cu2+ is due to its highly negative hydration enthalpy than
that of Cu+ which compensates for the high 2nd ionisation enthalpy of Cu. Also
from reduction potential values:
Cu+(aq) + e─ → Cu(s), EO = 0.52V
Cu2+(aq) + 2e─ → Cu(s), EO = 0.34V
Thus Cu is reduced more easily and hence is less stable than Cu2+.
+

 Oxometal anions have highest oxidation state eg Cr in Cr2O72─ and CrO42─ has an
oxidation state of +6 whereas Mn in MnO4─ has an oxidation state of +7.This is
due to oxygen which is highly electronegative and an oxidising element.
 For oxides,the highest oxidation state is same as that of group number up to gp
7(Sc2O3 to Mn2O7).Beyond Mn ,the maximum oxidation state is +3 (Fe2O3).
 O stabalises the highest oxidation states even more than F.eg highest fluoride
of Mn is MnF4 whereas highest oxide is Mn2O7.It is due to tendency of O to
form multiple bonds with the metal atoms.
As the oxidation state of a metal increases,ionic character decreases eg Mn2O7 is a
covalent green oil. MnO Mn3O4 Mn2O3 MnO2 Mn2O7
→ionic character decreases.
 The oxides in the lower oxidation state of the metal are basic and in higher
oxidation state are amphoteric/acidic.This is because in lower oxidation
state,some of the valence electrons of the metal are not involved in bonding.So it
can donate electrons and behave as base.In the higher oxidation state,valence
electrons are involved in bonding and are not available for donation.So it can
accept electrons and hence transition metal oxides behave as acid.eg.
(i) MnO Mn3O4 Mn2O3 MnO2 Mn2O7
Basic amphoteric amphoteric amphoteric acidic
Mn2O7 dissolves in water to give acid HMnO4.
(ii) V2O3 V2O4 V2O5
Basic less Basic amphoteric
V2O5 reacts with both alkalies as well as acids to form VO42─ & VO4+ resp.
(iii) CrO Cr2O3 CrO3
Basic amphoteric acidic
CrO3 Dissolves in water to give acids H2CrO4 and H2Cr2O7

*Most common oxidation states of 3d series elements:

Sc Ti V Cr Mn Fe Co Ni Cu Zn
+3 +4 +5 +3&+6 +2&+7 +2&+3 +2&+3 +2 +2 +2
Q: Explain briefly how +2 state becomes more and more stable in the 1st half of the
1st row transition elements with increasing atomic number.
Ans: Except Sc ,all 1st row transition elements show an oxidation state of +2 due to loss
10
 of two 4s electrons.In the 1st half,as we move from Ti2+to Mn2+,more and more of d
orbitals are half filled ,imparting high stability to +2 state.In the 2nd half, Fe2+ to
Zn2+ ,electrons in the 3d orbitals pair up and the number of half filled orbitals
decreases.Hence, the stability of +2 state decreases.

Q: Name the transition element which does not exhibit variable oxidation states.

Q: Which of the 3d series metals exhibit the largest number of oxidation states and
why?

Q: Which metal in 1st series exhibit +1 oxidation state most frequently and why?

Q: Why is the highest oxidation state of a metal exhibited in its oxide or fluoride
only?

Q: Explain why Cu+ ion is not stable in aqueous solutions?

Q: Mn shows the highest oxidation state of +7 with Oxygen but with Fluorine ,it
Shows the highest oxidation state of +4.Why?

Q: How is the variability in oxidation states of transition metals different from that
of non transition metals? Illustrate with examples.

Q: Name the oxo-anions of 1st series of transition metals in which the metal exhibits
the oxidation state equal to its group number.Why the highest oxidation state is
exhibited in oxo-anions of a metal?

Q: Why the lowest oxide of a transition metal is basic,the highest is acidic?

Q: What may be the stable oxidation state of the transition element with the
following d electron configurations in the ground state : 3d3 ,3d5 ,3d8 ,3d4?
Ans: 3d3 :V(+5) , 3d5 : Mn(+2) , 3d8 : Ni (+2), 3d4 : Cr( +3).

Q: How would you account for the increasing oxidising power in the series:
VO2+ < Cr2O72─ < MnO4─
Ans: because stability of lower oxidation increases in order: V4+ < Cr 3+ < Mn 2+

Q: Mn(III) undergo dispropotionation reaction easily.Why?

Ans: changes to more stable oxidation state.ie.
Mn3+ → Mn2+ + Mn7+

Q: Discuss the magnetic properties of transition metals.

Ans:The substances which are weakly attracted by magnetic field are called
paramagnetic. Paramagnetism is a property due to the presence of unpaired
electrons. Most of the transition metal ions and their compounds are
11
 paramagnetic ,as they contain unpaired electrons in (n-1) d orbitals.As the
number of unpaired electrons increases from 1 to5 towards the middle of any
transition series, the magnetic moment and hence paramagnetic character also
increases. The transition metals which have all the electrons paired, are diamagnetic
ie they are weekly repelled by the magnetic field.
The magnetic moment of an electron is given by
μ= √ n(n+2) B.M. where n is number of unpaired electrons and B.M. stands for Bohr
Magneton.

Q: Calculate the magnetic moment of a divalent ion in aqueous solution if its atomic
number is 25.
Ans: n=5 , μ = 5.92 BM

Q: Calculate the spin only magnetic moment of M2+(aq) ion (Z= 27).
Ans: n=3 , μ = 3.87 BM

Q: What can be inferred from the magnetic moment values of the following complex
species? Example magnetic moment
K3[Fe(CN) 6] 2.2
2+
[Fe(H2O)6] 5.3
K2[MnCl 4] 5.9
Ans: n =1, μ = 1.73 BM
n =2, μ = 2.83 BM
n =3, μ = 3.87 BM
n =4, μ = 4.89 BM
n =5, μ = 5.92 BM
K4[Fe(CN) 6] has one unpaired electron.pairing of d electrons occurs.CN- is a
strong ligand. d2sp3 hybridisation, inner orbital octahedral complex.
[Fe(H2O)6]2+ has 4 unpaired electron. No pairing occurs. H2O is a weak ligand.
sp3 d2 hybridisation, outer orbital octahedral complex.
K2[MnCl 4] has 5 unpaired electron. No pairing occurs. Cl is a weak ligand.
sp3 hybridisation, tetrahedral complex.

Q: The transition metals generally form coloured compounds.Account for this.

Ans: Most of the transition metal compounds are coloured both in the solid state
and in aqueous solution because of d-d transition of unpaired electrons.
In a transition metal ion,all the d orbitals have same energy ie they are
degenerate.When ligands approach these ions,the five d orbitals loose their
degeneracy and split in to two sets of orbitals ie. t2g and eg.This is called Crystal
Field Splitting.
[Splitting diagram from book]
Now one or more electrons from lower set of d
orbitals after absorbing definite amount of energy get excited into higher set of d
orbitals, where it becomes unstable and falls back to ground state by emitting
radiations in the visible region and giving definite colour.
12
 eg Cu2+ salts look blue due to absorption of the red wavelength.
In [Ti (H2O)6] 3+,Ti has d1 configuration and the electron is present in t2g orbital in
ground state.On absorption of yellow wavelength,the electron is excited to the eg
orbital.and the blue and red light will be transmitted.Thus the solution of
[Ti(H2O)6] 3+ will appear purple.
Sc3+ and Ti4+ have completely empty d orbitals and are colourless.
Cu+,Ag+,Au+,Zn2+,Cd2+ and Hg2+ have completely filled d orbitals and there are
no vacant d orbitals for promotion of electrons ,hence they are colourless
* colour absorbed complementary colour transmitted
Violet greenish-yellow
Blue yellow
Blue-green red
Yellowish- green violet
Yellow dark blue
Orange blue
Red bluish-green
Q: CuSO4.5H2O is blue but CuSO4 is colourless?
Ans: In CuSO4.5H2O , five water molecules act as ligands and result in crystal field
splitting and hence d-d transition occurs.But in CuSO4 there is no ligand ,so splitting
of d orbitals and hence d-d transitions are not possible.Therefore later is colourless.

Q: Predict which of the following will be coloured in aq. Solution? Ti3+,V3+ ,Cu+ ,Sc3+
,Mn2+ ,Fe3+,Co2+ .Give reasons.
Ans: Ti3+ , Mn2+ ,Fe3+ ,Co2+ due to presence of unpaired d electrons.

Q: Why Cd2+ salts are white?

Q: Transition metals form a large number of complex compounds.Explain.

Ans: Transition elements form large number of complexes like: [Fe(CN)6]3-,[Fe(CN)6]4- ,
[Cu(NH3)4]2+ etc . due to (i) comparatively smaller size of metal ions
(ii) large effective nuclear charge.
(iii) availability of vacant d orbitals to accept lone pair of electrons donated by
ligands.

Q: Transition elements and their many compounds act as good catalysts.Explain.

Ans: Many of the transition metals and their compounds are used as catalysts. Eg
(i)V2O5 in manufacture of H2SO4 in contact process.
(ii) finally divided Nickel in hydrogenation of oils.
(iii) Fe and Mo in synthesis of NH3 in Haber’s process.
(iv)MnO2 in decomposition of H2O2.
(v) Pt in preparation of nitric acid by Ostwald process.
This is because of
(i)They have vacant orbitals and easily form intermediate with suitable reactants.
The intermediates give alternative reaction paths of lower activation energy.
(ii) They show variable oxidation state and they have tendency to change their
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 oxidation state during reaction,it sometimes helps them to act as catalyst.
eg Vanadium changes its oxidation state from+5 to+4 and then again to +5 as
shown below;
SO2 + V2O5(catalyst) → SO3 + V2O4
2V2O4 + O2 → 2V2O5 (catalyst)
Overall reaction : V2O5
SO2 + O2 → SO3
(iii) Transition metals have large surface area and adsorb reactants on their surface.
Thus reactants come closer,and react faster.Hence the rate of reaction
increases.

Q: What are interstitial compounds? Why are such compounds well known for
transition metals?
Ans: Interstitial compounds are the compounds formed when small elements like
H,C,N,B etc.are trapped in interstitial sites in crystal lattices of certain metals.eg.
TiC, TiH1.7, Mn4N,Fe3H, VH0.56etc.These are non-stoichiometric in nature and are
neither ionic nor covalent.Some of their important characteristics are as follow:
(i)They are very hard,certain borides are comparable to diamond in hardness.
(ii) They have high melting points,higher than those of pure metals.
(iii) These are good conductors of electricity.
(iv)They are chemically inert.

Q: Why do transition metals form Alloys?

Ans:The tendency of transition metals to form large number of alloys is due to their
almost similar atomic sizes.Hence in the crystal lattice,atoms of one metal can be
easily replaced with atoms of another transition metal.This results in the formation
of solid solutions or alloys.eg. Brass(Copper-Zinc) , Bronze(Copper-Tin), Stainless
steel(Iron,Chromium& Nickel), Tungsten steel( Iron & Tungsten),Chrome steel(Iron
and Chromium).Some properties of alloys are: They are hard,have higher melting
point than the metals itself,and are more resistant to corrosion.

Q: Explain preparation of potassium dichromate (K2Cr2O7) from chromite ore.

Ans: Ore: Chromite ore(FeCr2O4)
Step I Conversion of chromite ore into sodium chromate: Chromite ore is fused
with sodium carbonate in excess of air, yellow coloured sodium chromate is
obtained.
4FeCr2O4 + 8Na2CO3 + 7 O2 → 8Na2CrO4 + 2Fe2O3 + 8CO2
The fused mass obtained above is extracted with water.Sodium chromate goes
in to solution leaving behind the insoluble Fe2O3 .
Step II Conversion of sodium chromate into sodium dichromate:
2Na2CrO4 + H2SO4(conc.) → Na2Cr2O7 + Na2SO4 + H2O
Sodium sulphate being less soluble crystallizes out as Na2SO4 10 H2O and is
removed.Orange solution of Na2Cr2O7 is obtained.
Step III Conversion of sodium dichromate into potassium dichromate:
14
 Na2Cr2O7 + 2 KCl → K2Cr2O7 + 2 NaCl
Potassium dichromate being much less soluble than sodium salt,crystallizes
out on cooling as orange crystals.

Q: What happens when potassium dichromate is heated strongly?

Ans: When heated strongly,it decomposes with the evolution of oxygen
heat
4K2Cr2O7 → 4 K2CrO4 + 2Cr2O3 + 3O2
potassium chromate
Q: Explain the action of alkali on potassium dichromate.
Ans: When alkali is added to an orange solution of dichromate ions,a yellow solution is
obtained due to formation of chromate ions.
K2Cr2O7 + 2 KOH → 2 K2CrO4 + H2O
On acidifying the above solution,it again changes to orange red due to formation of
dichromate ions.

Q: What is the effect of increasing pH on a solution of potassium dichromate?

OR
Q: An aq. Solution of potassium dichromate is yellow but changes its colour on
decreasing the pH of the solution.Explain.
Ans: In aqueous solution ,dichromate and chromate ions exist in equilibrium and are
interconvertible by changing the pH of the solution.
pH=4
Cr2O72─ + H2O = 2CrO42─ + 2H+
(Orange /red) (yellow)
On adding an alkali( ie. Increasing the pH of solution),the H+ ions are used up and
according to LeChatlier Principle, the reaction proceeds in the forward direction
producing yellow chromate solution.On the other hand when an acid is added
(ie.pH of the solution is decreased) the conc. of H+ ions increases and the reaction
proceeds in the backward direction producing an orange red dichromate solution.

Q: Draw the structures of chromate and dichromate ions.

Q: Describe the oxidising action of K2Cr2O7 and write the ionic equations for its
reaction with (i) iodide (ii) iron(II) solution (iii) H2S .
Ans: It is a powerful oxidising agent.In presence of dil H2SO4 ,1 molecule of K2Cr2O7
furnishes 3 atoms of nascent oxygen.
K2Cr2O7 + 4 H2SO4 (dil) → K2SO4 + Cr2( SO4)3 (green) + 4H2O + 3O
Or Cr2O72─ + 14H+ + 6e─ → 2Cr3+ + 7H2O
(Eq. wt.of K2Cr2O7 = Mol.wt./ 6 = 294 / 6 = 49)

eg. (i) It oxidizes I─ to I2

K2Cr2O7 + 4 H2SO4 (dil) → K2SO4 + Cr2( SO4)3 + 4H2O + 3O
6KI + 3 H2SO4+ 3O → 3K2SO4 + 3 I2 + 3H2O
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Overall reaction: K2Cr2O7 + 6KI + 7H2SO4 → 4K2SO4 + Cr2( SO4)3 + 3 I2 + 7H2O
Or Cr2O72─ + 14H+ + 6I─ → 2Cr3+ + 7H2O + 3 I2
(ii) It oxidizes H2S to S
K2Cr2O7 + 4 H2SO4 (dil) → K2SO4 + Cr2( SO4)3 + 4H2O + 3O
H2S + O → H2O + S ] x3
Overall reaction: K2Cr2O7 + 3H2S + 4H2SO4 → K2SO4 + Cr2( SO4)3 + 3 S + 7H2O
Or Cr2O72─ + 8H+ + 3H2S → 2Cr3+ + 7H2O + 3 S
(iii) It oxidizes ferrous salts to ferric salts
K2Cr2O7 + 4 H2SO4 (dil) → K2SO4 + Cr2( SO4)3 + 4H2O + 3O
2FeSO4 + H2SO4+ O → Fe2( SO4)3 + H2O ] x3
Overall reaction: K2Cr2O7 + 7H2SO4 + 6FeSO4→ K2SO4 + Cr2( SO4)3+ 3Fe2( SO4)3 +
2H2O
2─ + 2+ 3+ 3+
Or Cr2O7 + 14H + 6Fe → 2Cr + 6Fe + 7H2O

 Test for a drunken driver: He is asked to breathe in to acidified solution of

K2Cr2O7 taken in a test tube.If its orange color changes to light green ,the driver is
drunk . Alcohol is oxidized to acetic acid and K2Cr2O7 is reduced to Cr2( SO4)3.
 In Cr2O72─ & CrO42─ ions,Cr has d0 configuration.Hence orange and yellow
colour of these ions are not due to d-d transition but due to charge transfer ie.
Momentry transfer of charge from O atom to metal atom changing O─ to O2─ ion
and reducing the oxidation state of Cr from+6 to +5.

Q: Explain the preparation of potassium permanganate(KMnO4) from

Pyrolusite ore.
Ans:Ore: Pyrolusite,MnO2.(blackish brown)
(i) Conversion of pyrolusite into potassium manganate: The finally powdered
pyrolusite is fused with potassium hydroxide or potassium carbonate in
presence of air or oxidising agent like potassium nitrate,when green potassium
manganate is formed.
2 MnO2 + 4KOH + O2 → 2 K2MnO4 + 2H2O
or 2 MnO2 + 2 K2CO3 + O2 → 2 K2MnO4 +2CO2
or MnO2 + 2KOH + KNO3 → K2MnO4 + KNO2+ H2O
(ii) Conversion of potassium manganate into potassium permanganate: It is
done either by chemical oxidation or by electrochemical oxidation.However
electrochemical oxidation is preferred on industrial scale.
a) Chemical oxidation:
3 K2MnO4 +2CO2 → 2KMnO4 + MnO2 ↓ + 2 K2CO3
Or 2 K2MnO4 + Cl2 → 2KMnO4 + 2KCl
b) Electrolytic oxidation:
K2MnO4 = 2K+ + MnO42─
H2O = H+ + OH─
At anode : MnO4 → MnO4─ + e─
2─

At cathode : 2H+ + 2e─ → H2

The purple coloured solution is filtered and evaporated under controlled
conditions to obtain dark purple crystals of potassium permanganate.
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Q: What happens when potassium permanganate is heated?
Ans: 513K,Δ
2KMnO4 → K2MnO4 + MnO2 + O2

Q: What happens when an acidic solution of K2MnO4 is allowed to stand for some
time.What is this type of reaction called?
Ans: Disproportionation occurs as follow:
VI VII IV
3MnO42─ + 4H+ → 2MnO4─ + MnO2 + 2H2O

Q: Draw the structures of paramagnetic manganate and diamagnetic permanganate

ions .

Q: Explain the oxidising properties of potassium permanganate in acidic medium.

Ans: potassium permanganate in presence of dil H2SO4 acts as a strong oxidising agent
because of the reaction:
2 KMnO4 + 3 H2SO4 (dil) → K2SO4 + 2MnSO4 + 3H2O + 5O
Or MnO4─ + 8H+ + 5e─ → Mn2+ + 4H2O
(Eq. wt.of KMnO4 = Mol.wt./ 5 = 158 / 5 = 31.6)
eg (i) It oxidizes I─ to I2
2 KMnO4 + 3 H2SO4 (dil) → K2SO4 + 2MnSO4 + 3H2O + 5O
2KI + H2SO4+ 5O → K2SO4 + 5 I2 + 5H2O
Overall reaction: 2 KMnO4 + 10KI + 3H2SO4 → K2SO4 + 2MnSO4 + 5I2 + 8H2O
Or 2MnO4─ + 16H+ + 10 I─ → 2Mn2+ + 8H2O + 5 I2

(ii) It oxidizes H2S to S

2 KMnO4 + 3 H2SO4 (dil) → K2SO4 + 2MnSO4 + 3H2O + 5O
H2S + O → H2O + S ] x5
Overall reaction: 2 KMnO4 + 5H2S + 3H2SO4 → K2SO4 + 2MnSO4 + 5S + 3H2O
Or 2MnO4─ + 16H+ + 5S2─ → 2 Mn2+ + 8H2O + 5 S

(iii) It oxidizes ferrous salts to ferric salts

2 KMnO4 + 3 H2SO4 (dil) → K2SO4 + 2MnSO4 + 3H2O + 5O
2FeSO4 + H2SO4+ O → Fe2( SO4)3 + H2O ] x5
Overall reaction: 2 KMnO4 + 8H2SO4 + 10FeSO4→ K2SO4 +2MnSO4 + 5Fe2( SO4)3 +
8H2O
─ + 2+ 2+ 3+
Or MnO4 + 8H + 5Fe → Mn + 5Fe + 4H2O

(iv)It oxidizes oxalic acid to CO2

2 KMnO4 + 3 H2SO4 (dil) → K2SO4 + 2MnSO4 + 3H2O + 5O
C2H2O4+ O → 2 CO2 + H2O ] x5
Overall reaction: 2 KMnO4 + 5C2H2O4 + 3H2SO4 → K2SO4 + 2MnSO4 + 10 CO2 + 8H2O
Or 2MnO4─ + 16H+ + 5 C2O42─ → 2Mn2+ + 8H2O + 10 CO2

(v)It oxidizes nitrite to nitrate

17
 2 KMnO4 + 3 H2SO4 (dil) → K2SO4 + 2MnSO4 + 3H2O + 5O
KNO2 + O → KNO3 ] x5
Overall reaction: 2 KMnO4 + 5 KNO2 + 3H2SO4 → K2SO4 + 2MnSO4 + 5 KNO3+ 3H2O
Or 2MnO4─ + 6H+ + 5 NO2─ → 2Mn2+ + 3H2O + 5 NO3─
(vi) It oxidizes sulphite to sulphate
2 KMnO4 + 3 H2SO4 (dil) → K2SO4 + 2MnSO4 + 3H2O + 5O
K2SO3 + O → K2SO4 ] x5
Overall reaction: 2KMnO4 + 5 K2SO3 + 3H2SO4 → K2SO4 + 2MnSO4 + 5 K2SO4 + 3H2O
Or 2MnO4─ + 6H+ + 5 SO32─ → 2Mn2+ + 3H2O + 5 SO42─
(vii) It oxidizes SO2 to H2SO4
2 KMnO4 + 3 H2SO4 (dil) → K2SO4 + 2MnSO4 + 3H2O + 5O
SO2 + H2O + O → H2SO4] x5
Overall reaction: 2KMnO4 + 5 SO2 + 2H2O→ K2SO4 + 2MnSO4 + 2H2SO4
Or 2MnO4─ + 5 SO2 + 2H2O → 2Mn2+ + 5 SO42─ + 4H+

Q: Explain the oxidising properties of potassium permanganate in neutral or faintly

alkaline medium.
Ans: potassium permanganate in neutral aqueous medium acts as a moderate oxidising
agent because of the reaction:
2 KMnO4 + H2O → 2KOH + 2MnO2 + 3O
Or MnO4─ + 2H2O + 3e─ → MnO2 + 4OH─
(Eq. wt.of KMnO4 = Mol.wt./ 3 = 158 / 3 = 52.67)
eg (i) It oxidizes hot manganous sulphate to MnO2
2 KMnO4 + 3 MnSO4 + 2H2O → K2SO4+ 2H2SO4 + 5 MnO2
Or 2 MnO4─ + 3Mn2+ + 2H2O → 5MnO2 + 4 H+
(ii) It oxidizes thiosulphate to sulphate
8KMnO4 + 3Na2S2O3 + H2O → 3K2SO4+ 3Na2SO4 + 8MnO2 + 2KOH
Or 8MnO4─ + 3S2O3 2─ + H2O → 8MnO2 + 6SO4 2─ + 2OH─
(iii) It oxidizes iodide to iodate ion
2 KMnO4 + KI + H2O → 2 MnO2 + 2KOH + KIO3
Or 2MnO4─ + I─ + H2O → 2MnO2 + 2OH─ + IO3 ─

Q: How does the acidified KMnO4 react with (i) iron(II) ions (ii) SO2 (iii) oxalic
acid? Write the ionic equations for the reactions.

Q: Oxidising properties in alkaline medium:

2 KMnO4 + 2 KOH → 2 K2MnO4 + H2O + O
(Eq. wt.of KMnO4 = Mol.wt./ 1 = 158 / 1 = 158)

 Titrations involving KMnO4 are carried out only in presence of dil H2SO4 but not
HCl or HNO3 because oxygen produced from KMnO4 +HCl is partly used to
oxidize HCl to Cl2 and in case HNO3 is used,it itself acts as oxidising agent and
partly oxidizes the reducing agent.
18
  In MnO4─ ion,Mn has d0 configuration.The deep purple colour of KMnO4 is not
due to d-d transition but due to charge transfer ie. Momentry transfer of charge
from O atom to Mn, reducing the oxidation state of Mn from +7 to +6.

Q: What is meant by disproportionation.Give 2 examples of such reactions in

aqueous solution.
Ans: 1) VI VII IV
3MnO42─ + 4H+ → 2MnO4─ + MnO2 + 2H2O

2) 2 Cu+(aq) → Cu2+(aq) + Cu(s)

Q: What are characteristics of transition metals and why are they called so?
Which of the d-block elements may not be regarded as the transition
elements?

Q: Comment on the statement that the elements of the 1st transition series
possess many properties different from those of heavier transition elements.
Ans: (i) Atomic radii of the heavier transition elements are larger than those of
corresponding elements of 1st transition series though those of 4d and 5d
series are very close to each other.
(ii) for 1st transition series +2 and +3 states are more common whereas for
heavier transition elements,higher oxidation states are more common.
(iii) M.P and B.P. of heavier transition elements are greater than those of 1st
series die to stronger intermatallic bonding.
(iv) Enthalpies of atomization of 4d and 5d series are higher than the
corresponding 1st series elements.
(v) Ionisation enthalpies of 5d series are higher than the corresponding elements
of 3d and 4d series.
(vi)The elements of the1st transition series form low spin or high spin
complexes depending upon the strength of the ligand field.However the
heavier transition elements form low spin complexes irrespective of the
strength of the ligand field.

Q: Compare the general characteristics of 1st series of transition metals with

those of 2nd and 3rd series metals in the respective vertical columns.Give
special emphasis on the following points: (i) electronic configuration (ii)
oxidation state (iii) ionisation enthalpies (iv) atomic size.

Q: Write down the 3d electrons in each of the following ions:

Ti2+, V2 , Cr3+ ,Mn2+, Fe2+, Fe3+, Co2+,Ni2+,Cu2+
Indicate how would you expect the five 3d orbitals to be occupied for these
hydrated ions.(octahedral)

19