Genius Students Academy

D AND F – BLOCK ELEMENTS [NOTES]

XII – CHEMISTRY
D-Block elements (transition elements)
(n - 1)d1-9ns2

Metals of S – Block Non-Metal of P-Block

D-Block elements are those where electrons enter D – orbitals successively.
All transition elements are D – Block elements but all D – Block elements are not transition elements.
Characteristics of D-Block Elements
(i) Incomplete d – subshell (ii) Should have unpaired e- s
(iii) Shows variable oxidation state. (iv) Shows paramagnetic behaviour. (v) d – d transition
Transition elements have partially filled d-subshell in the elementary form or in their commonly occurring
oxidation state e.g. Cu, Ag, Au.
General electronic configuration → (n – 1)d1–10 ns 0 – 2 & (n-1)d 1-10 ns 1-2 .
Transition series: - The transition elements consist of three complete rows of ten elements and one incomplete
row. These rows are called first, second and third transition series which involves the lining of 3d, 4d and 5d
orbitals. These series are called transition series.
First Transition Series: - Scandium (21) to zinc (30). 3d- orbitals are gradually filled.
Second Transition Series: - Ytterium (39) to cadmium (48). 4d- orbital are gradually filled.
Third Transition Series: - Lanthanum (57) to mercury (80). 5d orbitals are gradually filled.
Fourth Transition Series:- The series starts from actinium (89) and is incomplete. It will include elements from
at no 104 onwards (6d orbitals are gradually filled)
❖ Palladium is an exception as its atom has no e— in s – subshell sc3+ , y3+ - d ] Group - 3
❖ Zn, Cd and Hg are often not regarded as transition elements because d-orbitals in these elements are
completely filled in the ground state and in their common oxidation states. [Gp -12]
❖ Group – 3 & Group 12 are exceptions because of d & d10 configuration.
Q. On what basis can you say that Sc(z = 21) is a transition element but Zn (z= 30) is not?
Ans. In case of Sc 3d orbitals is incompletely filled & at +3 becomes 3d.
Properties of transition elements
(1) Physical Properties
(a) Have high tensile strength, ductility, malleability, high thermal and electrical conductivity and metallic
luster. Except Hg which is liquid at room temperature other transition elements have metallic character
due to following reasons:
(i) Due to smaller ionic radii. They are associated with strong force of attraction.Tr. metals have high enthalpy
of atomization.
(ii) They are electropositive in nature
(iii) They are associated with strong inter-metallic bonding
(iv) Tr. Metals have high heat of atomization & high mp & Bp.

(b) Their mp and bp are very high due to (high enthalpy of atomisation) 9.11 (b)
(i) Smaller ionic radii. They are associated with strong force of attraction.
(ii) Due to large surface area, they are associated with strong vanderwall forces.
(iii) Due to electropositive character, they are associated with strong intermetallic bonding.
(iv) Due to unpaired orbitals or incomplete subshell they undergo d - d overlapping or undergo multiple
bonding(metal – metal bonding or interatomic interaction force).

(v) All paired(Zn, cd) and all unpaired (Mn,Tc) produce greater repulsion but all unpaired produce more
repulsion than all paired.
Sc (inc.) Cr (dec.) Mn (inc.) Fc (dec.) Zn
d5
Reason for Mn & Zn:
S. E increase, ENC decrease, IMB low, radii increases high polarity, low I.E, low E° redn , high
reactivity.
(vi) They crystallize in a close pack lattice i.e ccp, hcp, bcc, fcc.
Trend of MP
ccp
inc. (bcc) dec. (hcp) inc. dec.
Sc Cr Mn Fe Zn(hcp)
inc. (bcc) dec. (hcp) inc. dec.
Y Mo TC Ru Cd(hcp)
inc. dec.
La W Hg
Due to increase in unpaired e- (s) magnitude of d - d overlapping. Increase(s) later due to pairing of d-
subshell, d - d overlapping decrease(s). Exceptionally, Mn and Tc shows low MP and BP due to weak inter-
metallic bonding and low density bigger size & high volatility, presence of unpaired electrons and weak metal –
metal bonding.
(2) Atomic Radii(decrease irregularly across the period)
Sc Ti V Cr Mn Fe Co Ni Cu Zn

dec. Almost Constant Large at radius

(due to all paired)radii
Dec. in atomic radii in beginning is due to the increase in ENC with the increase in at no. However with increase
in no of election in (n – 1) d-subshell the SE also increase which neutralize the effect of increase ENC and as such
at radii remain almost constant in the middle of series. The pairing of e-(s) in the d-orbitals of the penultimate
shell occurs only after d-subshell is half filled. The repulsive interactions b/w the paired e-(s) in d-orbital become
dominant towards end of series and thereby increase in atomic size.
d5 e— of Mn produces greater shielding. Mn has bigger size.
❖ The at radii increase (s) while going down the group the at radii of transition metal of second series have
large value than those of the first transition series.
It is because the e-(s) in the atoms of second transition series element occupy energy levels farther from
the nucleus with the increase in no. of outermost shell, size

Q. Ist IE of 5d element is higher than 3d and 4d elements

Or
st
I IE of Pt is higher than Pd.
Ans. This is due to Lanthanide contraction and poor shielding of 4f e-(s). As a result the 5d orbitals also
produces poor shielding effect. Therefore, magnitude of effective nuclear charge acting on the other e -
increase (s). Thus IE increase (s)
5 d&4f electrons give poor shielding effect.
SHIELDING EFFECT: - It is a repulsive force produced towards outer e-(s) by inner e-(s) by forming a screen
outside the nucleus or it is the shielding of outer e-(s) by inner e-(s) by forming a shield around the nucleus.
Shielding Effect  Atomic size
1
Shielding Effect 
Effective nuclear ch arg e / I.E. / E.A.

Cause: - The addn of shell or e-(s) leads to e- – e- repulsions. As a result, the far lying e-(s) move further apart and
close lying e-(s) move closer. As a result, a shield is formed around the nucleus due to which the ENC or attraction
of nucleus on outer e-(s) decrease (s).

(3) Ionic radii: - Ionic radii decrease with oxidation state. For the same oxidation state, the ionic radii
generally decrease (s) with increase in nuclear charge.
(a) If magnitude of SE is more than ENC, size increase (s).
(b) If magnitude of SE is less than ENC, size decrease (s).
(c ) If magnitude of both SE and effective nuclear charge counter balance each other equally.  size remain
same.
Q. Cr to Cu size (ionic radii) remains same.
Ans. If magnitude of both SE and ENC counter balance each other equally  size remains same.

Q. Why at size decrease in the order: S>d>P.

Ans. Due to addition of subsequent e– to the same shell, the increase in ENC is much more than se.

Q. 5d element have unexceptionally smaller ionic radii?

Ans. Due to lanthanoid contraction and poor shielding of 4f e–(se)

(4) Metallic Character: - All the transition elements are metals. They exhibit all the characteristics of metals.
They all have high density, hardness, high MP’s and BP’s, high density strength, ductility, malleability,
high tensile and electrical conductivities and luster.
(5) Ionisation Energy/ Enthalpy: -
❖ The first IE of d-block elements are higher than those of s-block element but are lesser than those of p-
block elements. The IE increase (s) as we move across each series, though not quite regularly. In a
particular series, the difference in I.E b/w any two successive d-block elements is much less as compared
to the difference in case of successive s-block elements.
❖ The first I.E of third transition series is higher than those of first and second one. It is because the atoms
of transition series are filled in 4f orbitals which have very poor S.E. As a result, the outer e–s are tightly
held with the nucleus.  their I.E. are higher.
❖ It has comparatively high value of I.E because it has a symmetrical and stable configuration due to
presence of all filled orbitals.
❖ Smaller the I.E of a metal greater will be the thermodynamics stability of the compound e.g. Pt(iv) is more
stable than Ni (IV) as first four I.E of Pt is less than that of Ni. due to small ionic radii of Ni. Due to poor
S.E. & lanthanoid contraction of 4f and 5d, the sum of IE, and IE2 of Pt is more than Ni.
Energy required for taking out 4 electrons is not compensated by Ni. Therefore Ni 4+ compounds are not
stable. Therefore Ni(II) compounds are more stable than pt(II).

Q. K 2 PtCl6 exists while analogous Ni compounds does not exist. Why?

Ans. In K 2 PtCl6 Pt exists in +4 (stable) oxidation state.
(6) The trend in std. Redn potentials is not regular.
(a) Except Cu, all other elements have –ve redn pot value. This means that they should liberate hydrogen quite
readily from dilute acids but the rate of liberation of H 2 is very poor due to the formation of a protective
inert oxide film on their surface.
(b) Except Cu, all of them are expected to be a good reducing agent but their reducing character is less as
compared to S-block metals because of high enthalpy of sublimation, enthalpy of ionization and poor
enthalpy of ionization and poor enthalpy of hydration of their ions.
Lesser the sum of Ionisation enthalpies of a metal, more the size, more chemically reactive and hence
more stable.
Transition metals are less reactive and also poor reducing agents. (E reduction increase, reactivity decrease)
Q. E0 values (M2+/ M) for first row transition metals are given below:
Elements V Cr Mn Fe Co Ni Cu Zn
E0(M2+/ M) — 1.18 —0.91 —1.18 —0.44 —0.28 —0.25 0.34 —0.76
(in volts)
In Mn reactivity increase because of all unpaired electrons(half filled configuration). In Zn reactivity increase
because of all paired electrons. (Fulfill configuration)
There is no regular trend in the values of their reduction potentials as the ionization energy (IE1 + IE2) &
Sublimation energies of these metals do not show any regular trend.
Mn has weak IMB, low density, low  H atom & low IE.
(7) Oxidation states: - Transition elements show variable oxidation states due to the participation of ns and
(n – 1)d subshells are almost equal for e.g. Sc has the electronic configuration 3d‘ 4s 2. It exhibits an
oxidation state of +3 when it uses both of its 4s e–(s) and 3d-e–(s) as they possesses comparatively similar
I.Es The highest oxidation states are found in compounds of fluorine and oxygen because fluorine and
oxygen are most electronegative element., small size , high charge density & strong oxidising power.
Oxoanion are more stable due to the formation of  bond (p - d overlapping). Oxygen can form II –
bond but fluorine doesn’t .

Important Conclusion Regarding Oxidation States Of Transition Elements

(a) With in a group, oxidation increase with increase in at no, reaches a maximum in the middle and then
starts decrease (ing) e.g. Mn → maximum oxidation state = +7.
(b) Except Sc the most common oxidation of first tran-series is +2 which arise due to loss of two 4S2 Electrons.
(c ) For the first 5 members of each of each transition series the highest oxidation state shown is generally
equal to the sum of ns and (n – 1) de–(s). For the remaining five elements, the maximum oxidation state
is not related to their electric configuration.
(d) In +2 and +3 oxidation states, transition elements generally form ionic bonds. On the other hand, in higher
oxidation state, the bonds formed are essentially covalent but these higher oxidation states are attained by
elements of high electro negativity e.g F and 0.
(e) Some transition elements also show oxidation state of zero in some of their compounds e.g. in [Ni(CO) 4],
oxidation of Ni is zero.Egs. of compounds showing 0 or +1 or –1 ixd, state. :
+1 : U2O, [Ag (NH3)2]+ Ag2O
0 : [Ni(CO)4 ] [Fe(CO)5]
-1 : [Co(Co)4]—
Group 3 inc. Group 7 Group 8 dec. Group 12
Sc Mn Fe Zn
(+3) (+7) (+3) (+2)
Y Tc Ru (Cd)
(+3) (+8) (+2)
La Re Os Hg
(+3) (+8) (+19+2)
Due to increase in unpaired e–(s), later due to pairing of e–(s),
Oxidation state increase(s) oxidation state decrease (s)
Higher the oxidation number, smaller the radii, higher will be the charge density and polarization power, greater
will be the covalent character, form acidic oxide, act as oxidizing agent.
Lowest oxidation state show electropositive character, form ionic salts and form basic oxides and act as reducing
agent.
At moderate oxidation state, form amphotheric oxides.

Trend of Oxidation state: -

Observations: -
(a) In first series the highest oxidation state is +7 given by Mn while +8, higher oxidation state is given by
Ru, Os. At +8 oxidation state, compounds behave as oxidizing but at lower, compounds are reducing in
nature.
(b) At lower oxidation, they form ionic compound and basic oxides (Mn2+).
(c ) At higher oxidation, they form covalent compounds and acidic oxides [Mn+7] e.g. MnO4–.
(d) At moderate state, they form amphoteric compound or oxides. Mn 4+ e.g. MnO2.
(e) They show catalytic properties due to variable oxidation states.
Stability of oxidation state: - When an element exists in more than one oxidation states, std. Electrode potential
data provide a due to the relative stabilities of different states with respect to oxidation.
Factors Governing Stability: -
(i) Lower I.E (iii) Lower Eo redn value
(ii) High Hydration enthalpy (iv) Stable configuration →d°,d5 , d10
But cr 3+ → d3 (more stable than d5 ).
Electrode Potential Data: - (Born Haber Cycle)
M(s) → M(g) H atom or H sublimation = +ve (endo)
M (g) → M (g) n+
H I.E = +ve (endo)
Mn+(g) → Mn+ (aq) Hnyd. = –ve(exo)
M (aq) → std. Electrode potential value (Eored)
n+

In aqueous state hydration enthalpy and in gaseous state lattice enthalpy compensates the energy required for
removal of electron and formation of stable compounds. (or to overcome H atom or H I.E).
Lower the sum of I.E or high Hydration enthalpy or lower the Ered., value, higher the reactivity towards
oxidation and greater the stability of oxidation state.
Stable the configuration, greater will be the stability of oxidation state as a result, compound formed will be stable.
(d, d10 , d5 & Cr +3 (d 3 ) (t 2 g half filled extra stable)
Give Reason Why: -
Cu2+ compounds are more stable than Cu+ ions.
Co3+ compounds are more stable than Co2+ ions.
Cr3+ compounds are more stable than Cr2+ ions.
E Cu+/Cu = +0.52v ECu2+ / Cu = +0.34v
Cu has lower stability of the compounds +1 oxidation state than+ 2 because Cu2+ has lower E redn value
& high hydration enthalpy compensates the energy required for removal of successive electrons.
(Same answer for Co3+, Cr3+)
Fe is more stable than Fe2+
3+

Fe3+ = 3d5 Fe2+ = 3d6

3d5 is half filled stable configuration  forms stable compounds than Fe2+(3d6). Fe3+ is also associated with lower
Htotal due to high hydration energy.
Fe2+ / Fe = –.4V , Fe3+ / Fe2+ = +0.08V
Mn2+ / Mn = –1.2V , Mn3+ / Mn2+ = +1.5V
Comment on the relative stabilities of +2 and +3 oxidation state of Fe and Mn.
Which of the two metals may be easily oxidized to +2 state?
At +2, Mn forms stable compounds due to lower E redn value and stable 3ds configuration, whereas, at +3 Fe
forms stable compounds due to lower E red value and stable 3d5 configuration.
Fe2+ 3d6 Mn2+ 3d5
3+ 5
Fe 3d Mn3+ 3d4
Mn2+ / Mn : stronger reducing agent.
Mn is easily oxidized as compared to Fe.

Formation of coloured ions: - Most of the transition elements are coloured in solid form or in solution form.
At d salts are colourless Sc3+, Ti4+, V5+
10
At d salts are colourless Zn2+, Cd2+, Hg2+, Cu+, Ag+, Au+

Requirement : Unpaired electron in aqueous state ( water acting as weak ligand – not causing pairing.
d/d10 – diamagnetic / colourless
d1-9 – paramagnetic / coloured
Due to d – d transition absorb white light and reflect complementary wavelength (colour).

REASON: - Due to incomplete d-subshell, unpaired e–(s), d – d transition the d-orbital undergoes spiliting into
sets of orbitals – lower energy orbital and high energy orbital in presence of strong field ligands. The difference
of their energies is called as crystal field splitting energy (). If this energy lies in visible spectrum it imparts
characteristic colour of that region.
When white light falls on such a transition element, Some light energy corresponding to certain colour is absorbed
and one or more e–(s) are raised from lower energy set of orbitals to high energy. With the absorption of radiation
from white light, a complementary colour is observed.
Magnetic Properties: - are a measure of number of unpaired e–(s) present. There are two main types of
substances: -
Paramagnetic Subs: - Which are weakly attracted by magnetic field are called Paramagnetic subs and this
character a rise due to presence of unpaired e– in the at orbitals.
Diamagnetic Subs: - Which are repelled by magnetic field are called diamagnetic subs and this character a rises
due to presence of paired e– in the at orbitals. Most of the compounds of transition elements are paramagnetic

Large the numbers of unpaired e– → greater is paramagnetic character → larger is the magnetic moment.
The magnetic moment is expressed in Bohr magneton (B.M) and can be calculated from the relation:
Spin only  = n(n + 2) n → no. of unpaired e–(s)
eh
formula  → magnetic moment. B.M = 4 me
Fe and Fe oxide are highly magnetic about 1000 time more than the ordinary metals. These are called
ferromagnetic substance.
Magnetic behavior

Diamagnetic Para Ferro Antiferro Ferrimagnetic

Reason - Due to incomplete d-subshell and presence of unpaired e–(s), behave as paramagnetic.
At ground Sc Ti Cr Mn Fe Co Ni Cu Zn
V
State n 3d1422 3S24s2 3d54s1 3d54s2 3d64s2 3d74s2 3d84s2 3d104s1 3d104s2
1
3d34s
1 2 3 6* 5 4 3 2 1 0

At + 2 (Mn2+)
3d1 3d2 3d3 3d4 3d5 3d6 3d7 3d8 3d9
3d10

n 1 2 3 5(Mn2+)* 4 3 2 1 0
4

* High paramagnetic behavior

Calculate the Mag. Moment of Cr3+ if each e— produce 1.1 BM magnetic moment
Cr3+ = 3d3 (n = 3)

Cr3+ = 3d3
1.1  3 = 3.3 BM
At ground state Cr(3d54s1) show maximum paramagnetic behaviour and at +2 Mn2+ (3d5, n=5) shows maximum
paramagnetic behaviour.

Group 12 metals form dia and colourless compounds due to filled d-subshell and absence of d – d transition.
Q. [ Sc(H2 O) 6 ]3+ is dia and colourless while [Ti(H2O)] 3+ is coloured and para?
Sc3+ = 3do Ti3+ = 3d1
No unpaired 
No d – d transition Shows d – d transition
Due to se in unpaired electons the paramagnetic behaviour se. Later due to pairing of es— paramagnetic
behaviour ses across the period.
At ground state Cr (3d5 4S1) shows more paramagnetic behaviour At +2 Mn2+ (3d5 n = 5) shows max
paramagnetic behaviour.
At ground state At + 2 state
Cr = 3d5 4s1 n=6 Cr2+ = 3d4 n=4
5 2
Mn = 3d 4s n=5 Mn2+ = 3d5 n=5
Paramagnetism  ses due to  ses umpaired e s . Later due to pairing of orbitals unpaired e—s se.
—

gp 12 metals form dia and colourless compounds.

At do and d10 compounds are diamagnetic

d0 — Sc3+, Ti4+, v5+
d10 — Cu+, Hg2+, Zn2+, cd2+

Q. Calculate the mag. Moment of Mn, Cr.

Mn = 3d5
n=5
 =  5(5+2)
=57 = 35
= 5.8BM

Formation of complex compounds: Complex compounds are those in which the meta1ions bind a no. of
anions or neutral complex giving complex spp. E.g. [fe (CN)6]2–
[Cu (NH3)4]2+, [Ag (NH3)2]2+ etc. The e– donor spp are known as ligands. Transition metals form a large
number of complex compounds due to their
❖ Comparatively small size
❖ High ionic charge
❖ High nuclear charge/ ENC & high charge density
❖ Availability of vacant orbitals for bond formation. (incompletely filled d – orbital)
1) Formation of Interstitial compounds (Inters. Alloys → metal to non-metals)
Inters. Compounds are those which are formed when small atoms like H, N or C are trapped inside the
crystal lattices of metals. They are non-stoichiometric and are neither ionic nor covalent. Some
important charactertistics of these compounds are;
❖ Have high MP’s than pure metal.
❖ They are very hard, some borides approach diamond in hardness
❖ They retain metallic conductivity.
❖ They are chemically inert.

Conditions: Metal lattice should have small interstitial spaces

Difference in radii

Alloy formation: (Comparable radii – intermetallic alloys) Transition elements form a large number of alloys.
Mn dissolves in molten iron to form manganese steel. Such alloys are hard, have high MP and are most resitant
to corrosion than parent metal.
Explanation → The transitionmetals are quite similar in size and , the atoms of one metal can substitute the
atom of other metal in crystal lattice. Thus on cooling a mixture solution of two or more transition metals, solid
alloys are formed.

Catalytic properties: The catalytic ability of the transitional elements is described to their ability to adopt
multiple oxidation states and to form complexes. Fe, Co, Ni, V, Cr, Mn, Pt etc are very common catalysts.
Reasons for showing catalytic behaviour:
1. Due to incomplete d-subshell variable oxdn state and d-d transition they produce large no. of unstable
intermediate compounds. Therefore, adsorb large amount of reactant thereby enhanced catalytic
behaviour.
2. Due to low reactivity and large surface area they adsorb large amount of reactant.
3. Due to presence of vacant spaces and free valency they readily combine with the reactive molecules and
carry out the Rxn without itself undergoing any permanent change.

Vanaduim pentoxide (V2O5) is used in contact process for the manufacture of sulphuric acid (as a catalyst) due
to variable oxdn state.
Finely divided iron and molybdenum are used in Habee process for the manufacture of ammonia.
Ni powder is used in hydrogenation of unsaturated compounds
MnO2 is used as a catalyst in decomposition H2O.
Co salts catalyse the decomposition of bleaching powder.

Comparison of Ist Row Transition Metals Through d- Electron Configuration in the stable compounds.
(Q. 8.5 page no. 234)
The do configuration : - Only SC3+ is known to have this configuration. This configuration occurs for those
metals in which formed oxidation states equal the total number of 3d and 4s e– e.g
Ti (IV), V (VI) and Mn (VII).
1
The d configuration: - Except V(IV), all others with this configuration are either reducing or undergo
disproportionation e.g. this process. Occurs for Cr(V) and Mn(VI)
3CrO4 + 8H → 2 CrO4 + Cr3+ + 4H2O
3– 2–

3MnO42– + 4H → 2 MnO4– + MnO2 + 2H2O

The d2 configuration: -
3
The d configuration: -
4
The d configuration: -
5
The d configuration: -
6
The d configuration: -
The d7 configuration: -
The d8 configuration: -
The d9 configuration: -
The d10 configuration: -
The given configurations i.e. d, d1, …… d10 are in the stable state and not in ground state.
This configuration ranges from TiIIwhich is very strongly reducing to FeVI which
is very strongly oxisdising. V(III) is also reducing.
Cr(III) is the important spp with this configuration which is stable and form
complex.
These are really no stable spp. With this configuration. The Cr(II) is strongly
reducing and Mn(III) disproportionation.
The two important spp with this configuration are Mn2+ and Fe3+.
Fe (II) and Co (III) are important spp with this configuration iron(II) is quite
stable although a mild reducing agent.
The spp with this configuration is Co(II) which is is share in aq solution (s) but
gets oxisdised to form CO(III) complex in presence of strong ligands.
Ni (II) is the most important species.
This configuration is found in Cu2+ compounds.
The two spp Cu+ and Zn2+ are important one.

General Transition in group in d-block elements.

Ques. 8.35 page 236
Group 3 - (n — 1) d1ns2 Sc, Y, La and Ac

❖ Oxdn state: +3 and are used in alloy formation.

❖ Compounds of sc and Y are colourless and diamagnetic.
 ❖ They react with H2O and evolve hydrogen.

Group 4 – Ti + 3 state is stable., Zr and Hf (hafnium) (n – 1)d2 ns2

❖ They are silvery white metals with high MP.[Hf 4+, Zr4+ due to nearly same size]
❖ They are less electropositive than 4f metals.
❖ Oxdn state- 4 do = compounds are colourless and diamagnetic.
❖ Upon ,they combine with halogens, hydrogen and oxygen etc to form corresponding halides,
hydrides & oxides .
❖ Oxides of both occur in minerals together & exhibit similar properties.

Group 5 – V, Nb and Ta (tantalum)

❖ They are shiny silvery metals and slightly less electropositive.

❖ Nb and Ta are nearly identical in size due to lanthanoid contraction and hence have nearly similar
properties.
❖ Oxdn state, V= + 4, +3, +2, +5.
❖ Most stable Oxdn state, Nb and Ta = + 5.
❖ Chief use of V is to se the strength and toughness of steel.
❖ Ta owing to its high resistance to corrosion, is used in surgical vessels, analytical weights of high
precision.
❖ Nb → Alloys are used in jet engines.

Group 6 – Cr, Mo and W(tungsten)

❖ They are silvery, lustrous and fairly soft and form colourless compounds.
❖ Oxdn state = + 6 (common for all)
❖ Cr (most stable) = + 3 (a q and complexes)
❖ Cr (II) is strongly reducing.
❖ Cr is used in leather and in manufacture of stainless steel and chrome plating.
❖ Mo and W compounds are employed are catalysis.
❖ Mo is used in X – ray tubes and Tungsten is used as catalyst.

Group 7 – Mn, technetium (Te) and rhenium (Re).

❖ Tc is radioactive and is obtained from fission waste.
❖ Re is rare and closely resembles Te.
❖ Mn is a good constituent of all steels.
❖ Mn exhibit are Oxdn state from +2 to +7 of which the ump ones are +2 , +4 and +7
❖ Re is used in electronic filaments, high temperature thermocouples and in flash bulbs

Group 8 – Fe, ruthenium (Ru) and Osmium (Os)

❖ Fe is corrodect by atm while the other two elements are resistant to corrosion.
❖ Fe fails to attain an Oxdn state of +8 while other two elements can achieve the same.
❖ +2 and +3 Oxdn states are very common for Fe but are rare for the other elements.
❖ Fe is the backbone of many ind’s.
❖ Other elements are used as alloys. Noble metals: (very low reactivity & rare earth metals) [Re, Ru, Os,
Pt, W, Au]

Group 9 – Co, Rhodium (Rh) and iridium(Ir)

❖ Oxdn state for Co is +2 and +3 white Rh and Ir generally exibit +3oxdn states.
❖ Co in Oxdn +3 form a laioe no. of co-ordination complex especially with lioands having niliogen.
❖ Co is less reactive than Fe.
❖ Co is used in ceramic, paint ind’s and also catalyses a variety of P xn(S)
 ❖ An alloy of Rh – Pt is used in thermocouples and in crucibles.
❖ Ir – Pt alloy is used in manufacturedof measuring scales.

Group 10 – Ni, Pd and Pt.

❖ All are resistance to atom corrosion under normal condn (s).
❖ Pt is regarded as a noble metal due to its reactive metals whereas both Niand Pd combine with some
non-metals.
❖ Oxdn state, Ni and Pd = +2 .
❖ Ni is used as hydrogenation catalyst.
❖ Noble Metals: very low reactive metal & rare earth metals : Re, Ru, Os, Pt, W, A

Group 11-Cu, Ag and Au.

❖ The reactivity ses down the gp and in its intertness gold resembles platinum.
❖ Oxdn states, Cu= +2 , Ag = +1 and Ac = +3.
❖ Ag has the lowest first, Ie the sum of Ist and IInd is lowest for Cu and sum of Ist and IIIrd is lowest for
Au.
❖ Cu and Ag are used in alloys whereas Au is used in jewellry.(coingage metals)

Group 12 – Zn, Cd and Hg.

❖ All of them have completely filled d-orbitals.

❖ Oxdn state = +2.
❖ Hg exist as a dimer Fe as Hg22+ in which two Hg+ion is involved having Oxdn state +1.
❖ Zn is used for the galvanization of Fe and Zn dust is a powerful reducing agent.
❖ Cd is used for electroplating Fe.
❖ Hg is used in scientific instruments, barometers and thermometers. The alloy of mercury are called
amalgams.

Oxides and Oxometal ion

Potassium dichromate (K2Cr2O7) Dichromates are generally prepared from chromates.
a) Preparation:
1) Chromates are formed by fusion of chromite ore [FeCr2O4] with Na or potential carbonate in excess of
air (FeO.Cr2O3).
fusion
4FeCr2O4 + 8Na2CO3 + 7O2 8Na2CrO4 + 2Fe2O3 + 8CO2
2) The yellow solution of Na chromate is filtered and acidified with sulphuric acid to give a solution from
which orange sodium dichromate, Na2Cr2O7.2H2O can be crystallyes.

2Na2CrO4 + 2H+ Na2Cr2O7 + 2Na + Na2SO4 + H2O

(H2SO4)
3) Sodium dichromate is more soluble than potassium dichromate. Potassium dichromate is prepared by
treating solution of sodium dichromate with potassium chloride when orange crystals of potassium
dichromates crystallis out.
Na2Cr2O7 + 2KCl K2Cr2O7 + 2NaCl

b) Properties: -
1) Physical State: - Potassium dichromate forms orange red crystal which melts at 69k. It is moderately
soluble in cold water but freely soluble in hot water.
2) Action of heat: - When heated strongly, it decompose with the evolution of oxygen
 4K2Cr2O7 4K2CrO4 + 2Cr2O3 + 3O2
pot. Dichromate pot. Chromate chromic oxide
3) Action of alkalies: - when an alkali is added to an orange red solution containing dichromate, a yellow
solution is obtaines due to the formation of chromate ions e.g. (at higher pH)
K2Cr2O7 + 2KOH 2 K2CrO4 + H2O
4) Action of conc. H2SO4: - In cold, red crystal of chromic anhydride (CrO3) are formed.
K2Cr2O7 + 2H2SO4 2CrO3+ 2KHSO4 + H2O
5) Oxidising properties: - Potassium dichromate is a powerful oxidizing agent. In presence of dil H2SO4,
K2Cr2O7. Liberates nascent oxygen and act as an oxidizing agent.

K2Cr2O7 + 4H2SO4 K2SO4 + Cr2 (SO4)3 + 4H2O + 3 [O]

Or
Cr2O72- + 14H+ + 6e- 2Cr3+ + 7H2O --------------(1)
Some of the oxidizing Rn(s) of K2Cr2O7 with different reducing agent are.
i) Potassium Iodine (KI)
Cr2O72- + 14H+ + 6e- → 2Cr3 + 7H2O
3x 2I- → I2 + 2e-

CrO72- + 14H+ + 6I- → 2Cr3+ + 3I2 + 7H2O

ii) Oxalic acid
Cr2O72- + 14H+ + 6e- → 2 Cr3+ + 7H2O
COO - → 2CO2 + 2e-
3 x |
COO -

Cr2O72- + 3Sn2+ + 14H+ → 2Cr3+ + 3Sn4+ + 7H2O

iii) Stannous chloride (SnCl2)

Cr2O72- + 14H+ + 6e- → 2Cr3+ + 7H2O
3x [ Sn2+ → Sn4+ + 2e-
Cr2O72- + 14H+ + 3Sn2+ → 2Cr3+ + 3Sn4+ + 7H2O

iv) Sulphur dioxide

Cr2O72- + 14H+ + 6e-→ 2Cr3+ + 7H2O
3[ SO2 + 2H2O → SO42- + 4H+ + 2e—]

Cr2O72- + 3SO2 + 2H+ →2Cr3+ + 3SO42- + 5H2O

v) Ferrous sulphate
Cr2O72- + 14H+ + 6e- → 2Cr3+ + 7H2O
6 [Fe2+ → Fe3+ + Ie-

Cr2O72- + 6fe2+ + 14H+ → 2Cr3+ + 6fe3+ + 7H2O

vi) Hydrogen sulphite (H2S)

Cr2O72- + 14H+ + 6e- → 2Cr3+ + 7H2O
3[S2- → S + 2e-
Cr2O72- + 14H+ + 3S2— → 2Cr3+ + S + 7H2O
vii) Sodium sulphite
 Cr2O2-7 + 14H+ + 6e- → 2Cr3+ + 7H2O
3[ SO32- + H2O → SO42- + 2e- + 2H+

Cr2O72- + 3SO32- + 8H+ → 2Cr3+ + 3SO42- + 4H2O

viii) Pot. Nitrite

Cr2O72- + 14H+ + 6e— → 2Cr3+ + 7H2O
3x [ NO2- + H2O → NO3 + 2H+ + 2e]

Cr2O72- + 3NO2- + 8H+ → 2Cr3+ 3NO3- + 4H2O

ix) Halogen acids
Cr2O72- + 14H+ + 6E- → 2Cr3+ 7H2O
3 [ 2Cl- → Cl2 + 2e-

Cr2O72- + 14H+ + 6Cl- → 2Cr3+ + Cl2 + 7H2O

6) Chromyl Chloride test : - When pot. Dichromate is heated with conc. HCl or CONC. H 2SO4 or with a chloride,
reddish brown vapours of chromyl chloride are obtains which when passed through NaOH turns it yellow. To this
yellow solution, a few drops of active acid followed by lead acetate is added and a yellow ppt. of lead chromate
is obtained
i) K2Cr2O7 + 4NaCl + 6H2SO4 (conc.)→ 2KHSO4 + 4NaHSO4 + 2CrO2Cl2 + 3H2O
ii) CrO2Cl2 + 2NaOH → Na2CrO4 + 2HCl
(sodium chromate)
iii) Na2CrO4 + Pb (CH3COO)2 → PbCrO4 + 2CH3COONa
(yellow ppt.)

7) Rxn with HCl: - pot. Dichromate reacts withHCl and evolves chlorine
K2Cr2O7 + 14HCl → 2KCl + 2CrCl3 + 7H2O + 3Cl2 
8) Action with H2O2: - forms a deep blue colour due to formation of CrO5
K2Cr2O7 + H2SO4 + 4H2O2 → 2CrO5 + K2 SO4 + 5H2O
The blue colour fades away gradually due to decomposition of CrO5 into Cr3+ ions and oxygen.

Q. Na2Cr2O7 cannot be used as oxidizing agent. Explain .

 Because it is hydroscopic in nature and has high solubility in water. It’s a secondary std. solution.
Cr3+ CrO42- Cr2O72-
Chromic ion Chromate ion dichromate
(green) (yellow) (orange)

Uses: -
In volumetric analysis, K2Cr2O7 is used for the estimation of ferrous (Fe2+), iodine(I-), sulphite(SO32-)
ions etc.
❖ In calico printing and dyeing.
❖ In chrome tanning in leather industry.
❖ In photography for hardening of gelatin film.
❖ In the preparation of other compounds such as chrome alum, K2SO4.Cr2 (SO4)3.24H2O, chrome yellow,
PbCrO4, chrome red PbcrO4.PbO, zinc yellow, ZnCr4 etc.
❖ Chromic acid (mixture of K2Cr2O7) and conc. H2SO4 is used as a cleaning agent for glass wares in the
laboratory.
❖ As an oxidizing agent in a organic synthesis.
STRUCTURE OF CHROMATE AND DICHROMATE IONS
The chromate ion has a tetrahedral structure in which four oxygen atoms around the central chromium
atom are oriented in a tetraheral arrangement.

Dichromate ion consists of two tetyahedral sharing an oxygen atom at a common corner (Bond angle →
126)

The chromate and dichromate ions exist in equilibrium and are interconvertible by altering the pH of the
solution.
2CrO42- + 2H+ 2HCrO4− Cr2O72- + H2O
chromate hydrogen dichromate
(yellow) chromate (orange)

6) Potassium permagante [KMnO4]

a) Preparation: - Potassium permagnet is prepared from mineral pyrolusite (MnO2). The preparation
involves 3 steps: -
i) Conversion of pyrolusite into potassium maganate(green): Pyrdusite is fused with KOH or K 2CO3 in
presence of air or an oxidizing agent like KNO3 and a green fused mass of K2MnO4 is obtained
2MnO2 + 4KOH + O2 → 2K2MnO4 + 2H2O
(green)
ii) Conversion of potassium manganate into potassium permanganate: - The fused mass is extracted with
water and solution after filteration is converted into potassium permaganate either by chemical oxidation
or by electrochemical oxidation. (disproportionation)
3K2 MnO4 + 2CO2 → 2KMnO4 + MnO2 + 2K2CO3
(a) Chemical oxidation: - is carried but by bubbling CO2 a chlorine or ozonised oxygen through green fused
mass.
(b) Electrolytic oxidation: - Industrially, it is prepared by this method. In this methos green coloured solution
containing potassium maganate is electrolysed using Ni anode and iron as cathode. The potassium
maganate solution is taken in anodic compartment, while dil KOH solution is taken in the cathodic
compartment. When current is passed through the green solution manganate ions are oxidized to purple
coloured permanganate ions at the anode and H2 gas is liberated at cathode.
At anode: 2Mno42- → 2Mno4- + 2e-
At cathode: 2H2O + 2e- → 2OH- + H2

2Mno42- + 2H2O → 2Mno4- + 2OH- + H2

K+ + OH- → KOH
electrolytic
2K2MnO4 + 2H2O 2KMnO4 + 2KOH + H2
After oxidation is complete the purple coloured solution is filtered and concentrated by evapouration.
The less soluble potassium permagnet crystallizes out cooling the conc. Solution.
c) Properties:-
i) Potassium permagnet exists as dark purple black prismatic crystal having a greenish metallic luster.
ii) It’s Mp is 523k.
iii) It is moderately soluble in water giving a purple solution. However, its solubility se with se in
temperature.
iv) Action of heat: when heated strongly to a temperature above 745k, it readily decompose giving oxygen.

2KMnO4→ K2MnO4 + MnO2 + O2
v) Oxidising nature: potassium permagnet acts as a powerful oxidizing agent in neutral, alkaline or acidic
media.
vi) In neutral solution: - It acts as a moderately powerful oxidizing agent.
MnO4- + 2H2O + 3e- → Mno2 + 4OH-
Some oxidizing properties of KMno4 is neutral solution are: -
(i) Hydrogen sulphide
2x [MnO4- + 2H2O + 3e- → MnO2 + 4OH-
3x [ S2- → S + 2e-

2MnO4- + 2H2O + 3S2- → 2MnO2 + 8OH- + 3S

(ii) Sodium thiosulphate

2KMnO4 + H2O → 2MnO2 + 2KOH– + 3 [O]
3[Na2S2O3 + [O] → Na2SO4 + S

2KMnO4 + H2O + 3Na2S2O3 → 2KOH + 2MnO2 + 3Na2SO4 + 3S

OR
2MnO4 + H2O + 3S2O32– → 2OH– + 2MnO2 + 3SO42– + 3S
–

(b) In alkaline solution :- In presence of conc. Alkali, purple coloured permanganate ions are coloured
manganate ions with evolution of oxygen.

reduced to green.
4MnO4– + 4OH– → 2MnO42– + 2H2O + O2
 OR
2MnO4 + H2O → 2MnO2 + 2OH– + 3 [O]
–

(i) Pot. Iodide.

2MnO4– + H2O → 2MnO2 + 2OH– + 3 [O]
I– + 3[O] → IO3–
2MnO4 + H2O + I– → 2MnO2 + 2OH– + IO3–
–

(c) In acidic medium :- It is frequently used as a strong oxidizing agent.

2KMnO4 + 3H2SO4 → K2SO4 + 2MnSO4 + 3H2O + 5[O]
OR
MnO4– + 8H+ + 5e– → Mn2+ + 4H2O
(i) Ferrous sulphate.
MnO4– + 8H+ + 5e– → Mn2+ + 4H2O
5 [ Fe2+ → Fe3+ + e– ]
MnO4– + 8H+ + 5Fe2+ → Mn2+ + 5Fe3+ + 4H2O
(MnO4– + 8H+ + 5Fe2+ → Mn2+ + 5fe3+ + 4H2O )

(ii) Oxalic acid.

2 [ MnO4– + 8H+ + 5e– → Mn2+ + 4H2O
5[ COO– → 2CO2 + 2e–


COO–
2MnO4– + 5COO– + 16H+ → 2Mn2+ + 10CO2 + 8H2O

COO–
(iii) Hydrogen sulphide.
2[ MnO4– + 8H+ + 5e– → Mn2+ + 4H2O
5[ S2– → S+ 2e– ]
2MnO4– + 16H+ + 5S2– → 2Mn2+ + 5S + 8H2O

(iv) Sulphur dioxide.

2x [ MnO4– + 8H+ + 5e– → Mn2+ + 4H2O
5x [ SO2 + 2H2O → SO42– + 2e– + 4H+
2MnO4– + 5SO2 + 2H2O → 2Mn2+ + 5SO42– + 4H+

(v) Pot. Iodide.

2x [ MnO4– + 8H+ + Se– → Mn2+ + 4H2O
5x [ 2I – → I2 + 2e–
2MnO4– + 16H+ + 10I– → 2Mn2+ + 5 I2 + 8H2O

(vi) H2O2.
MnO4– + 8H+ + 5e– → Mn2+ + 4H2O } x2
H2O2 → O2 + Ze– + ZH + } x5
2MnO4— + 6H+ + 5H2O2 → 2Mn2+ + 5O2 + 8H2O

(c) Uses :
(i) Used as a powerful oxidizing agent.
(ii) Used to disinfect water in wells and tanks.
(iii) Used in qualitative analysis for detecting halides, sulphites and oxalates.
 (iv) It is also used in quantitalive analysis for the estimation of ferrous stlts, oxalic acid or oxalates
etc.
F- BLOCK ELMENTS OR INNER TRANSITION ELEMENTS
(n – 2) f 1 –14 (n – 1) d o – 1 ns2
F – block elements

Lanthanoids Actinoids
(14 elements following La) (14 elelments followingAC)
Lanthanoids(Ln)
The series involving filling of 4f orbitals following La is called lanthanoid series.
Ce (58) Lu (71)
(Cerium) (Lutetium)
Electronic configuration of Lanthanoids (4f 1-14 5d0-16s2) and oxdn state.
Element Atomic No. Oxdn state Outer Electronic Configuation
Lan thanum(La) 57 +3 [xe] 5d1 6s2
Cerium(Ce) 58 +3 , +4 [xe] 4f1 5d1 6s2
Prase dymium(Pr) 59 +3 , +4 [xe] 4f3 5d0 6s2
Neodymium(Nd) 60 +2 , +3 [xe] 4f4 5d0 6s2
Promethium(Pm) 61 +3 [xe] 4f5 5d6 6s2
Samarium(Sm) 62 +2 , +3 [xe] 4f6 5d0 6s2
Europium(Eu) 63 +2 , +3 [xe] 4f7 5d0 6s2
Gadolinium(Gd) 64 +3 [xe] 4f7 5d1 6s2
Terbium(Tb) 65 +3 , +4 [xe] 4f9 5d0 6s2
Dysprosium(Dy) 66 +3 [xe] 4f10 5d0 6s2
Holmium(Ho) 67 +3 [xe] 4f11 5d0 6s2
Erbium(Er) 68 +3 [xe] 4f12 5d0 6s2
Thuluim (Tm) 69 +2 , +3 [xe] 4f13 5d0 6s2
Ylterbium(Yb) 70 +2 , + 3 [xe] 4f14 5d0 6s2
Lutetium(Lu) 71 +3 [xe] 4f14 5d1 6s2

+2 Eu2 = 4f7 f 0, f 7 & f 14 are extra stable configurations

Yb2+ = 4f14 +3 is the most common oxdn state.

oxidizing agent

+3  La 3+ = 4f0
Gd 3+ = 4f7
Lu3+ = 4f14
Reducing agent
+4  Ce4+ = 4f0
Tb4+ = 4f7

Generally lanthanoids in +4 oxdn state act as strong oxidizing agents eg Ce2+ ion. While in +2 oxdn state they act
as strong reducing agents eg: Sm2+, Eu2+ and Yb2+ ion.(because +3 is most stable oxidation state in whole
series)
If intervening electrons give more shielding effect then electrons bring more shielding effect and vice versa
Chemical Reactivity of Lanthanoids
A few imp. Chemical characteristics are:
i) They tarnish readily on exposure to air
(ii) in finely divided state, all burn in air to form oxide of formula
 Ln2o3 (Ln Lanthanoid ) except Ce which gives CeO3
(iii) Lanthanoids react with H2O slowly in cold but rapidly on heating liberating H2 gas and
forming Ln(OH)3. The basic character es with se in atomic no.
(iv) Ln react with hydrogen at 575K-675K giving LnH3.

Lathanoid Contraction
The steady  se in ionic as well as at radii of elements of Lanthanoid series in moving form left to right is called
Lanthanoid contraction.
Cause : In moving from left to right, ENC se (s) and this se is expected to be compensated by se in the
magnitude of SE by the 4f-e-(s). However the f – electrons orbitals have very poor SE b’coz of their shapes. This
means that f-electrons are not able to exert as much SE as expected consequently the at and ionic radii se from
left to right.

Actinoid Contraction
The size of the atoms or ions ses regnlarly along the series as in lanthanoid series. The steady decrease in ionic
radic with increases in at no is called actinide contraction. This in analongous to lanothanoid contraction & is
due to poor shielding of nuclear charge.

Consequences of Lanthanoid Contraction:-

(1) Separation of Ln is difficult only due to Ln contraction. All the Lanthanoids have quite similar properties
and due to this they are difficult to separate.
(2) The basic strength of oxides and hydroxides se (s) from La(OH)3 to Lu(OH)3. Due to Ln contraction size
of M3+ ions se (s) and thus there is a corresponding se covalent character of M-OH bond.
(3) It is clear that the difference in at radii of Y and La is quite large as compared to difference in the values
for Zr and Hf. This is on account of intervening f-block element in third series due to Ln contraction.
(4) Due to Ln contraction there is a small but steady se in Std redn potential for the redn process.
(5) The first Ionisation enthalpy of 5d elements is more than their corresponding 3d and 4d elements.
(6) Various physical properties like mp, bp, hardness etc se with se in at no. This is b’coz the attraction
forces b/w the atoms se as the size se.

Colour and Paramagnetism

Many trivalent lanthanoid ions are coloured both in solid state and in aq.soln(s). Colour of these ions may be
attribute to the presence of f electrons. Neither La3+ not Lu3+ ions show any colour but rest do so.

The Lanthanoid ions other than the fo type (La3+ and Ce4+ ) and the f14 type (Yb2t ND Lu3t) are all paramagnetic.
The paramagnetism rises to max. in neodymium.

Uses of Lanthanoids
(1) It is used for prodn of alloy steels for plates and pipes
(2) 3% Misch metal(pg – 230 2nd para) : It is an alloy of kare earth metals containing cerium (up to 50%), La
& Nd [up to 40%), Fe (10%). Traces of other elements like C, S, Ca, Al & etc. Mg mixed with 3% of
mosch metal is used for making jet engine parts. mixed with Mg is used for making jet engine parts,
bullets, shells etc.
(3) Mixed oxides of Ln are employed as catalysts in petroleum cracking.
(4) Some individual Ln oxides are used as phosphors in television screens and similar fluorescing surface.
(5) Nd and Pr oxides are used for making coloured glasses.

In lactanoids, 4f , 5d, 6s have comparable energies and hence they show variable oxidation state
In d block elements 3d and 4s have comparable energies.
In actinoids 5f, 6d, 7s have comparable energies.
Actinoids (pg- 231)
 5f 1-14 6do-1 7S2
Electronic Configuration and Oxdn state
Element At.No. Electronic Configuration OxDn State

Actinium (Ac) 89 [Rn] 6d1 7s2 +3

Thorium (Th) 90 [Rn] 5f 1 6d1 7s2 (+ 3) , + 4
Protactinium (Pa) 91 [Rn] 5f 2 6d1 7s2 (+ 3), (+ 4), + 5
Uranium (U) 92 [Rn] 5f 3 6d1 7s2 + 3, + 5, + 6
Neptunium (Np) 93 [Rn] 5f 4 6d1 7s2 + 3, + 4, + 5, + 6,+7
Plutonium (Pu) 94 [Rn] 5f 6 6d0 7s2 + 3, + 4, + 5, + 6,+7
Americium (Am) 95 [Rn] 5f 7 6d0 7s2 + 3, (+ 4) ,+ 5, + 6
Curium (Cm) 96 [Rn] 5f 7 6d1 7s2 + 3, (+ 4)
Berkelium (Bk) 97 [Rn] 5f 9 6d0 7s2 + 3, + 4
Californium (Cf) 98 [Rn] 5f 10 6d0 7s2 +3
Einsteinium (Es) 99 [Rn] 5f 11 6d0 7s2 +3
Fermium (Fm) 100 [Rn] 5f 12 6d0 7s2 +3
Mendelevium (Md) 101 [Rn] 5f 13 6d0 7s2 +3
Nobelium (No) 102 [Rn] 5f 14 6d0 7s2 + 2, + 3
Lawrencium (Lr) 103 [Rn] 5f 14 6d1 7s2 +3
(Less stable oxdn states are given in brackets)
Radioactivity : All these elements are radioactive. The half life of transuranic elements are so short that they
have long ceased to exist on earth. Man made series is called Neptunium series.
Physical Properties : All these elements are silvery white metals with high mp and bp. All the actinoids except
thorium and americium have high densities.
Oxidation States: There is a greater range of oxidation states, which is in part attributed to the fact that the 5f,
6d and 7s levels are of comparable energies. The actinoids show in general +3 oxidation state. The elements, in
the first half of the series frequently exhibit higher oxidation states. For example, the maximum oxidation state
increases from +4 in Th to +5, +6 and +7 respectively in pa, U and Np but decreases in succeeding elements. The
actinoids resemble the lanthanoids in having more compounds in +3 state than in the +4 state. However, +3 and
+4 ions tend to hydrolyse. Because the distribution of oxidation states among the actinoids is so uneven and so
different for the earlier and latter elements, it is unsatisfactory to review their chemistry in terms of oxidation
states.
Coloured ions: Cations of actinoids are coloured both in crystalline state, as well as in their aq. solns

Cations of actinoids which contain only paired e-(s) are diamagnetic.

Chemical reactivity: All the actinoid metals are highly electropositive and act as strong reducing agents.

Actinoids show actinoids contraction, which is very similar to lanthanoid contraction due to poor shielding of
nuclear charge by 5f e-(s).

Uses of Actinoids:
(i) Th is used as a nuclear fuel in atomic reactor.
(ii) Th oxide is used in prepn of incandescent gas mantles
(iii) U is used as a nuclear fuel and its salts are used in ceramic industry, textile ind., chemical analysis etc.
(iv) Plutonium also finds use as nuclear fuel in atomic reactors and in atomic weapons.
Lanthanoids Actinoids
(1) Besides most common oxdn state of + 3, Ln (1) Besides the most common oxdn state of +3,
show +2 and +4 oxdn states in case of certain actinoids show +4, +5, and +6, oxdn states.
elements.
(2) Ln have less tendency towards complex (2) Stronger tendency
 formn
(3) Except promenthium, all are non radio active (3) All of them are radioactive
(4) Their mag. Properties can be easily explained. (4) Their mag. Properties are not easy to explain.
(5) Ln do not form oxocations. (5) They form oxocations like UO22+ ,UO+ etc.

(6) Oxides and hydroxides of Ln (s) are less basic. (6) more basic

USES OF LANTHANOIDS:

The pyrophoric (pyro = heat) alloys containing rore earth metals are used in the preparation of ignition devices
such as tracer bullets & shells, flints for lighters composition → cerenium (40.5%), La & Mo (44%), fe (4.5%),
Al (0.5%) & traces of other elements like Ca, Si & C. Such an alloy produces sparkces when rubbed & thus can
be used to ignite.
Similarties b/w Lanthanoid and actinoid
(1) Both show a dominant oxdn state of +3.
(2) Both are electropositive and act as strong reducing agents.
(3) Cations with unpaired e-(s) in both of them are paramagnetic.
(4) Most of their cations are coloured.
(5) Both show a steady  se in their ionic radii along the series.

Q1 Why group 12 metals is not considered transition metals by some scientists?

(# Dissimilarities with Tr. Metals) (n-1)d104s2
(i) They have filled d-subshell, doesn’t show variable oxidation state & d-d transition
(ii) They form diamagnetic and colourless compound.
(iii) They have relatively bigger ionic radii, lower IE lower e’red value and lower H total, therefore, show
high chemical reactivity, that is why Zn gets tarnished in air.
(iv) They form divalent compounds which are predominantly covalent in nature and covalent character
further increases down the group.
(v) They have weak intermetallic bonding, fairly electropositive in nature, absence of d-d
overlapping,bigger ionic radii and weaker force of attraction. Therefore group 12 metals have low MP
and BP, low heat of atomization, volatile and soft in nature. Even Hg exist in liquid state at room
temperature.

(Similarties with transition metals) ( X = F, Cl, Br, I)

(1) They form complexes but only sp3 hybridised

(Cdx4)2-, (ZnX4)2-, (HgI4)2-
(ii) They show catalytic properties like amalgams (Hg alloys)
(Zn-amalgam) ZnO in methanol preparation.
(iii) They form alloys like brass and amalgams.
(iv) They are electropositive therefore shows properties similar to transition metal i.e. oxides,
sulphides and halides.
ZnO - White pigment
CdO - yellow pigment Zns and Cds flourescent screen
Q. What is meant by ‘disproportionation’ of an oxidation state? Give an example.
Ans When a particular oxidation state becomes less stable relative to other oxidation states, one lower, one
higher, by self reduction and self oxidation it is said to undergo disproportionation. For example,
manganese (VI) becomes unstable relative to manganese (VII) and manganese (IV) in acidic solution.
3MnVIO4 2– + 4 H+ = 2MnVIIO4– + MnIVO2 + 2H2O
 OCCURRED AND EXTRACTION OF SOME TRANSITION METALS(UNIT -6)

Iron, 26 = Is2 2s2 2p6 3s2 3p6 us2 3d6

Occurrence:- The chief ores of uion are:

Haematite ; Fe2o3
Limonite ; Fe2o3. 3H2o
Magnetite ; Fe3o4
Siderite ; FeCo3
Ironpyrites ; Fes2
b) Varities of Iron

Cast or Pig Fe Wrought iron Steel .15 – 1.5% C,

most impure form, purest form, .2 – .5% C, also contains Mn, Cr, Ni,
contains 2.5 – 4.5% C malleable, ductile and soft. P, S etc.
with Mn, Si, P and S,
hard and brittle.

c) Extraction of Pig Iron [from haematite]

1. Concentration of ore: The ore is crushed into small pieces with the help of jaw crushers and is washed
repeatedly with water to remove the impurities of clay and sand.

Calcination: The concentrated ore is calcined in limited supply of air when the following changes occur:
Moisture is removed.
Impurities of s, As and P are converted to their volatile oxides.
S8 + 8O2 → 8SO2
P4 + So2 → P4O10
2As + So2 → As2O5
Ferrous oxide get oxided to ferric oxide.
Ore becomes porous and can be easily reduced to metallic form by redn.
Smelting : The calcined ore along with coke and limestone are fedinto the top of the blast of air
Preheated at about 100 kelvin is blown by means of narrow tubes (tuyeres) at the base of furnace. This initiates
the combustion of coke to Co2 (Zone of heat absorption)
C + O2 CO2
 Co2 gas moves upwards and comes in contact with more of coke and is reduced to CO.
(Zone of heat absorption)
Co2 + C 2Co.

Co reduces berric oxide to spongy iron (Zone of redn)

Fe2O3 +3Co 2Fe + 3Co2
FeO + Co Fe + Co2

This iron and lime stone pass through middle zone, limestone decomposes to form lime and Co2. Lime acts as a
basic flux and removes silica which is the major impurity present in the major impurity present in the ore as slag
(Zone of slag formn)
Caco3 Cao + Co2

Cao + Sio2 Casio3

(Basic flux) (impurity) (slag)
Themolten iron framed in the lowest zone of blast furnace rundown to the base from where it can be collected .

Prepation of wrought iron:

Wrought iron is prepared from cast iron by heating with haematitewhich oxidizes C to Co.
Fe2O3 +3C 2Fe + 3Co.

Limestone is added as flux and Si, S and P are oxidized and passed into the slag. The metal is removed and
freed from the slag by passing through rollers.

Copper, 29= 1s2 2s2 2p6 3s2 3s2 3p6 4s1 3d10
Occurrence of Cu : Chief ore of Cu are
Copper pyrities ; Cufec2
Copper glance ; Cu2S
Cuprite : Cu2O
Malachite ; Cu(OH)2 . Cuco3
Azurite ; Cu(OH)2 . Cuco3

Extaction of Cu (framCufeS2)
Crushing and concentration of ore = The ore is crushed into fine particles and is then concentrated by froth
floatation process.
Roating = The cone ore is roasted in presence of excess of air when following changes occur.

❖ Moisture is removed.
❖ Impurities of S, P, As and Sb are removed as their volatile oxides.
❖ Cu pyrities is decomposed and both Cu2S and FeS are patially oxidesed.
2CuFeS2 + O2 → 2Cu2S + 2Fes + So2
2FeS + 3O2 → 2FeO + 2So2
❖ Cu2S + 3O2 → 2Cu2O + So2
III Smelting = The roasted ore is mixed with sand and coke and is heated strongly in blast furnace. A blast of
hot air is led and following changes are observed.
Most of the ferrous sulphide is converted into ferrous oxide which forms slag with sand.
2FeS + 3O2 2FeO + 2So2
FeO + SiO2 FeSiO3(slag)

Some cuprous sulphide may also be converted into cuprous oxide but it is formed again by reducing with
ferrous sulphide.
2Cu2S + 3O2 2Cu2O + So2
Cu2O + FeS Cu2S + FeO
FeO + SiO2 FeSiO3

Two separate layers are formed the lower layer known as matte, contains Cu2S and small amt of ferrous sulphate
while upper layer is of slag.

IV Bessemerisation: Molten matte is transferred to Beesemer converter. A blast of hot air and sand is led and
any impurities present will be converted into volatile oxides which escapes. The remaining iron sulphide
is converted into iron (II) oxide which slag’s off as silicate and the copper (I) sulphide is reduced to Cu.
(auto-reduction)
FeO + SiO2 FeSiO3(slag)
2Cu2s+ 3O2 2Cu2O + 2SO2
Cu2S + 2Cu2O → 6Cu + SO2
When metal being heavy falls below tuyeres and escapes oxdn by air So 2 escapes slowly. However, some
bubbles of gas get wrapped and look like blisters. The metal obtained is called Blister Cu.

V Refining of Cu : Blister Cu is electrolytically refined using impure metal as anode while cathode consists
of pure Cu. The electrolyte is a mixture of Cuso4 and H2so4 and the net result of eletrolysis is the transfer
of Cu in pure from anode to cathode and the impurition are deposit as anode mud.

SOME IMPORTANT ALLOY OF COPPER

Alloy % Age Composition Uses
Cubronze Cu =80, Zn =10, Sn =10 For making statues, coins utensils etc.
Brass Cu =80, Zn= 10 For making utensils parts of machinery, wire
Constantan Cu= 60, Ni= 40 etc.
 For making heating elements
Al bronze Al= 95, Cu= 5 of electrical appliances
Coins, picture frame, cheap jwellery.
Silver, 47=[kr]4d10 5S1

a) OCCURRENCE : Main ores of silver are

Argentic or silver glance: Ag2S

Horn silver ; Agcl
Pyraroyrite or ruby silver : Ag3Sb S3
Prousite : Ag3As S3

b) Extraction (cyanide process)

❖ concentration of ore : by forth floatation process.

❖ Treatment with sodium cyanide: The one ore isleached with sodium cyanide solution (.5% or less conc)
and air is continuously passed through the solution silver goes into the solution as complex cyanide and
sodium sulphide gets oxidized to sodium sulphate.
Ag2S + 4NaCN 2Na [Ag(CN2)] + Na2S
4Na2S + 5O2 + 2H2O 2Na2SO4 + 4NaoH + 2S (ppt)

❖ Precipitation of Silver : The complex cyanide thus formed is treated with Zn dust. This is known as
hydrometallurgy. The ppt of silver is filtered.
2Na [Ag(CN2)] + Zn Na2[Zn(CN)4] + 2Ag(ppt)

Refinine of silver: Is done by electrofining impire silver is made anode while a their sheet of pure silver is made
cathode. The electrolyte is aq. AgNO3 with 1% HNO3. On passing current Ag deposit at cathode, impurition of
zn and Cu pass into the solution as soluble salts while gold gets collected as anode mud. KNO3 is added to
remove Zn & Pb.
Silver is also removed by desilverisation of lead obtained from argentiferrous leod through concentration &
sruelting process.
c) USES OF SILVER
Used in making jewellery, coins and decorative objects.
Used in silvering of mirror’s and in silver plating
AoBr is used in photography.
Thin silver amalgam is employed in filling teeth.

Zinc, 30 =1s2 2s2 2p6 3s2 3p6 4s2 3d10

Occurrence of zn: The chief ores of zn are=

Zn blende or zinc sulphide, zns
Calamine = ZnCO3
Zincite or zn oxide : ZnO
Extraction of zn (from ZnS)

Concentration of ore : by froth floating process.

Roasting : The concores is roasted with excess of air when ZnS gets oxided to ZnO.

2ZnS + 3O2 2ZnO +2So2

ZnCO3 ZnO +CO2
Reduction : Zn oxide is then converted into Zn by heating with coke invertical retorts. The vapours of Zn
escape from the funnle and upon cooling give soild mass.
ZnO + C 1673k Zn + CO
fumel
Refining : Zn is refined by two methods
By fractional distillation = Pure metal itself boils. The impure metal is distilled when Zn and Cd distill over
leaving behind iron and lead which are high boiling.
The mixture of zn andcd are again subjected to fractional distillation when Cd distilled off leaving behind Zn.

By electrorefining = Improve Zn is made as anode white a plate of pure Zn act as cathode.

The electrolyte consist of ZnSO4 solution with small amt of dil sulphuric acid. On passing current, Zn form the
electrolyte gets deposited at cathode.