CHAPTER 14

“d” and “f” block elements

Q14.1 What do you know about transition elements.
Those elements which have incomplete “d” or “f” orbitals either in their atomic
or in any other oxidation states are called transition elements.
All the transition elements are metals and are present between “s” and “p”
block elements they are further divided into two types
1. d-block elements
Those elements which have partially filled d-orbital. They are also called outer
transition elements
Or
Those elements which have partially filled (n-1) d-orbital.
They are further divided into four series.
(i)3d- series (First transition series)
In this series the 3d- orbital is being progressively filled. This series starts
from scandium (21) and ends at copper (29). They lie in 4th period.
(ii) 4d- series (2nd transition series)
In this series 4d orbital is being progressively filled. It starts from yttrium (39)
and ends at argentums (47). They lie in 5th period.
(iii) 5d-series (3rd transition series)
It has partially filled 5d-orbiral. It starts from Lanthanum (57) and ends at
hafnium (72). They are present in 6th period.
(iv) 6d-series (4th transition series)
This series has partially filled 6d-orbital. This series is incomplete. It includes
actinium (89) and Rutherfordium (104) to Metnerium (109).
2. f-BLOCK ELEMENTS.
Those elements which have incomplete f-orbital. In other words, in these
elements (n-2)f orbital is being progressively filled. They are also called inner
T.Es. They have given a separate place at the bottom of periodic table. They
are further subdivided into two types
(i) 4f- series (ii) 5f- series
Q14.2 Explain characteristic properties of transition elements.
1.ELECTRONIC STRUCTURE.
The electronic configuration of pre-transition element i-e calcium is [Ar]
1 2
3d ,4s .While of scandium, the first transition metal has the electronic
configuration [Ar] 3d1 , 4s2.
The addition of electrons in “3d” subshell continues until it is filled in a case of
zinc i-e Zn30= [Ar] 3d10, 4s2 except two irregularities i-e chromium and copper.
Cr 24 = [Ar]3d5 ,4S
Cu 29 = [Ar]3d10 ,4S

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The 2nd, 3rd and 4th transition metal series correspond to the filling of 4d,5d
and 6d subshell respectively The electronic configuration of d-block is
(n-1)d1----10, ns0,1,2 .
In Lanthanides and actinides, the valence electron enters into “4f” and “5f”
orbitals respectively.
2.ATOMIC RADII, IONIC RADII AND DENSITY.
The atomic and ionic radii of the first transition series (3d series) decreases
slightly from left to right in a period. This decrease is due the increase of
nuclear charge which results into grater attractive forces between the nucleus
and valence electrons. Copper shows a slight increase in atomic radii which
is due to repulsion between the outer electrons. The transition elements
(T.Es) also has high density due to greater mass to volume ratio.
3. BINDING ENERGY.

The energy that is responsible for mechanical strength of T.Es is called

binding energy. Transition elements are tough and have greater mechanical
strength due to the presence of strong metallic bonding as well as the
participation of both s-electrons and d-electrons in binding. The binding
energy increases from left to right up to group VB due to increase of unpaired
electrons and then decreases up to IIB due to decrease of unpaired
electrons. For example in 3d-series binding energy increases up to vanadium
and then decreases up to zinc.
4. VARIABLE OXIDATION STATES.

The T.Es show variable oxidation state in their compounds by losing one or
more electrons, because in addition to s-electrons and (n-1)d electrons are
also involved in bond formation. The common oxidation states of 3d-series is
+2 or +3 or both. The highest oxidation state is +7 for “Mn”. After “Mn” the
oxidation state decreases due to pairing up of electrons in the 3d orbital.
5. CATALYTIC PROPERTIES.
Most of the T.Es and their compounds act as catalyst, both for organic and
inorganic reactions. The catalytic properties are either due to use of d-orbital
or the formation of interstitial compounds which absorb and activate the
reactants Since transition metals have variable oxidation state therefore with
the help of catalyst, they form intermediate compounds .This help the
formation of desired products. For example
i. V2O5 is used in the manufacture of H2SO4 by contact process.
ii. Finely divided iron is used for synthesis of NH3 by Haber-Bosch
process.
iii. Oxidation NH3 to nitric for synthesis of HN3 by Ostwald’s process.
iv. TiCl4 is used for the polymerization of ethene to polythene.
v. Ni, Pt or Pd is used for hydrogenates of unsaturated hydrocarbons.
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 vi. Copper is used in the Oxidation of ethyl alcohol to acetaldehyde.
6. MAGNETIC BEHAVIOUR.
The magnetic properties are classified into.
(i) Paramagnetism (ii) Diamagnetism (iii) Paramagnetism.

(i) PARAMAGNETISM
Substances which are weakly attracted by a strong magnetic
field are called paramagnetic.

ORIGIN OF PARAMAGNETISM.
The paramagnetic behavior is due presence of unpaired electrons in the
d-orbital. Such substances when placed in a magnetic field are attracted. This
attraction is due to interaction of magnetic field, Produce by spinning electron
with the external field. The paramagnetic moment can be determined as.
η = n(n + 2)
Where “n” is number of unpaired electrons.
Examples:
The paramagnetic behaviour is the strongest for “Fe2+ and “Mn2+ and
decreases on both sides of the first transition series, because Fe 2+ and Mn2+
have five unpaired electrons, while in rest of the members of 3d series, the
number of unpaired electrons decrease.
(ii) DIAMAGNETISM.
Those substances which are weakly repelled by magnetic field are called
diamagnetic and the process is called diamagnetism.

ORIGIN OF DIAMAGNETISM.
If the two electrons with opposite spin are paired in the same orbital, then the
magnetic field produced by one electron is cancelled by other and thus the
substances become diamagnetic. It is temp independent.
7. ALLOY FORMATION.
Transition metal atoms have similar structure and almost same size.
Therefore they are able to replace one another in metallic lattice and form
alloys.For example
(i) Brass ( Cu=60-80%, Zn=20-40%)
Used in domestic utensils, cartridges casting, condensers.
(ii) Bronze(Cu=75-90%, Sn=10-25%)
Used for Statues, coins, bells, blades machine parts
(iii) STEEL.(Fe=90-95%, and C=0.1-2%)
Used in cutlery, car bodies, bridges, utensils.
(iv) GOLD (18 CARAT)
(Au=70-75% and 20-35%),Used in jewelry, statues, tooth filling.
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Q14.3 Write note on complex ion complex ion?
A complex ion is composed of metal ion that is surrounded by ligands
(negative ion or neutral molecules).
For example when NH3 is added to a solution of Cu (II) ions, a pale blue
precipitate of cupric hydroxide is formed. If more NH3 is added to cupric
hydroxide then a deep blue solution is formed with a formula.
[Cu (H2O)2 (NH3)4]2+
Q14.4 .Write down various rules for naming complex Compounds.
The nomenclature of complex compound is based upon the recommendation
by the inorganic nomenclature committee of IUPAC. The rules for naming the
complex compounds are as follows.
1) The cations are named before anions like common salts e-g
K4[Fe(CN)6] potassiumhexacyanoferrate (II).
2) In naming the co-ordination sphare, the ligands are named first in
alphabetical order followed by the name of central metal atom.
e-g [Fe(H2O)6]SO4 hexaaquairon (II) sulpate.
3) The nature of ligands is indicated by a suffix.
i. Positively charged ligands have the suffix “ium”e-g NH2-+NH3
(hydrazinium), NO+ - (nitrosylium)
ii. Negative ligands have the suffix “O” e-g cyano (CN-) nitro (NO-2) nitrito
(ONO-) chloro (Cl-).
iii. Neutral ligands have no suffix e-g aqua (H2o), amine (NH3), carbonyl
(CO), nitrosyl (NO)
4) The ligands are named in a definite order, according to the charge
they carry. Negative ligands are named first, then neutral and finally
positive ligands. The names are not separated by spaces or hypens.
e-g NH4[Cr(NCS)4(NH3)2] is named as
ammoniumtetrathiocyanatodiaminechromate(II).
[Co(NH3)3(NO2)3]=Trinitrotriaminecobalt (II).
5) The number of individual ligands are indicated by prefixes mono, di,
tri, tetra.
The chelate ligands are named by prefixes bis, tris, tetrakis etc.
[Co(NH3)4Cl2]Cl=Dicholrotetraaminecobalt (III) chloride
[Co(NH3)3(en)2]Cl3=Diaminebisethylenediamine cobalt (III) chloride
[Co(en)3](so4)3=Trisethylenediamine cobalt (II) sulphate.
Fe(CN)2(CH3NC)4 =Dicyanotetrakismethylisocyanideiron (II)
6) The oxidation state is indicated by a Roman numeral in parentheses
at the end of the name of the complexes.
Na3[Co(No2)6] =Sodiumhexanitrocobaltate (III)
Na3[Fe(CN)6] =Sodiumhexacyanoferrate (III)

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 In cationic and neutral complexes, the name of metal remains the same
while in anionic complexes, the name if metal is followed by “ate” e-g Cr
become chromate, Fe is ferrate, Co is cobaltate, Cu as cuperate, Ag as
argentate.
Examples
K4 [Ni (CN)4)=Potassiumtetracyanonicklate (0)
Ca2[Fe(CN)6] =Calciumhexacyanoferrate (II)
Na[Co(CO)4] =Sodiumtetracarbonylcobaltate (-1)
K2[Cu(CN)4]=Potassiumtetracyanocuperate(II)
Na[Al(OH)4]=Sodiumtetrahydroxoalumimate (III)
Ni[CO]4 =Tetracarbonylnicklate (o)
Na2[Sn(OH)6]=Sodiumhexahydroxostannate (IV)
[Ag(NH3)2] Cl=Diaminesilver(I)chloride
[Cr(H2O)6](NO3)3=Hexaminechromium(III)nitrate
[Cr(NH3)6]Cl3=Hexaminechromium(III)chloride.
[Pt(NH3)5Cl]Cl3=Chloropentaamineplatinum(ivchloride
[Co(NH3)5Cl]Cl2 =Chloropentaaminecobalt(III)chloride.
Fe(CO)5 =Pentacarbonyliron (O)
[Co(en)2Br2]+1=Dibromobisethylenediaminecobalt (III) ion.
[Cr(NH3)3Cl3]=Trichlorotriaminechromium (0)
[Cr(H2O)4Cl2]Cl=Dichlorotetraaquacobalt (III) chloride
[Co(NH3)4Cl2]+=Dichlorotetraominecobalt (III) ion
_
[Fe(en)(CH3COO)4]2 =Tetroacetoethylenediamineferrate (II) ion
[Co(NH3)4 H2O Cl] Cl=Chorotetraomineaquacobalt (II) chloride.
[Co(en)2Cl2]Cl=Dichlorobisethylenediaminecobalt (III) chloride
[Zn(OH)4]2- =Tetrahydroxozincate (II) ion
[Cr(H2O)5Cl]Cl2=Chloropentaaquachromium (III) chloride
[Cu(Br)4]-2 =Tetrabromocuperate (II) ion.
Q14.5 Write note on the followings
1. Shapes of complex ions
2. Colour of complexes

1. SHAPE OF COMPLEX IONS.

Co-ordination compounds have definite geometrical shapes, because the

bond formed between central metal atom and ligands are directional in
nature. The geometry of complexes depends upon the number of ligands and
type of hybridization taking place in central metal atom. Complexes with co-
ordination number four and six are very common.
Complexes having co-ordination number four occur in tetrahedral and square
planar shape while having co-ordination number six exist in octahedral
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shape. Complexes with co-ordination number five are less common. They
occur in trigonal bi-pyramidal and square pyramidal shapes.
(i).Four co-ordinated complex ions.
The four co-ordinated complexes are formed by either sp3 hybridization or
dsp2 hybridization. A complex formed by sp3 hybridization gives rise to
tetrahedral structure and the complex formed by dsp2 hybridization result into
square planar.
(ii)Tetrahedral complexes.
A tetrahedral complex has four bonds from the ligands to the metal ion. The
ligands lie at the corner of tetrahedron. Its symmetry is three dimensional. For
example copper (II) and cobalt (II) ion have four chloride ions bonded to them
rather than six, because the chloride ions are too big to fit any more around
the central metal ion.

a) SQUARE PLANAR COMPLEX.

In square planer complex, there are also four bonds from ligands to the
metal ion. The metal ion and ligands both lie in the same plane.
For example cisplatin which is used as anti-cancer drug.

2. SIX CO- ORDINATION COMPLEX IONS.

These complexes are formed by d2sp3 hybridization. They have octahedral
shape. An octahedral complex results when there are six bonds to the central
metal ion. This can happen if there are six mondentate ligands, three
bidentate ligands or other combination that give the six bonds. Out of the six
ligands, four are in one plane, with 5th one above and 6th on below the plane.
For example

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3. COLOUR OF COMPLEXES.
The ionic and covalent compounds of transition elements are mostly colored.
This is either due to the presence of unpaired electrons or electrons which
have the ability to absorb certain wave lengths of light in the visible region
(4000-7000A0) and jump from low energy levels to high energy level and
emitting the remaining portion of light which appears as coloured.
The ions which have completely filled or empty d-orbital are colourless e-g
Cu+, Zn2+, Sc3+,Ti4
Cr3+ = Green Mn2+ = Green
2+ 3+
Fe = Green Fe = Yellow

Q14.6 Write note on vanadium.

Vanadium is silvery white metal having atomic number 23. It was discovered
by Andres Manuel del Rio in 1801 in Mexico, but it was mistaken for a form of
chromium. It was rediscovered in 1830 by Swedish chemist Nils Gabriel
sefstorm. The word vanadium is derived from vanadis , goddess of beauty
and love in Scandinavian mythology.

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1. OXIDATION STATE OF VANADIUM.
Vanadium shows +2,+3,+4 and +5 oxidation states in its compounds. The
compounds in lower oxidation states are ionic in nature, coloured and good
reducing agents. The compounds in higher oxidation are generally colourless
(vanadyl ion VO+2= 4 which can be reduced and turns blue (V+2=3d3,4s) then
green (v+3+=3d2,4s) and finally violet (v+2=3d3,4s0). vanadium also shows
0,+1,-1 oxidation states in V(CO)6, [V(dipy)3]+1 where dipy = dipyridine, and
[V(CO)6]-1 respectively.
2.CATALYST.
Vanadium as V2O5 used as a catalyst in the manufacturing of sulphuric acid
by contact process.
2 SO2  O2 
V2 O5
 2 SO3
SO3  H 2O 
 H 2 SO4
V2O5 is also used as a catalyst in the oxidation of alcohols and
hydrogenation of olefins.

Q14.7 Write note on chromium and its compounds.

Chromium is shiny metallic element, hard and corrosion resistant having
atomic number 24. It is the important component of stainless steel and also
used to coat the surfaces of other metals to prevent them from corrosion. It
was discovered in 1797 by a French chemist Louis Nicolas Vauquelin, who
named it chromium (Greek Chroma = colour) because it forms large number
of coloured compounds. Its m.p is 1907C0, b.p is 2672C0 and specific gravity
is 7.2.

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ORES OF CHROMIUM.
Chrome iron stone (FeO.Cr2O3)
Chrome ochre (Cr2O3)
Crocite (PbCrO4)

OXIDATION STATES.
The most common oxidation states of chromium are +2, +3 and +6. The
chromium in +3 oxidation state is more stable. The compounds in lower
oxidation state (Cr+2) act as strong reducing agent and ionic in nature i-e
CrO3, K2 CrO4. The acidic character of oxides increases with increase of
oxidation state i-e CrO(+2) is basic,Cr2O3(+3) is amphoteric and CrO3(+6) is
acidic chromium compounds in which the oxidation state of chromium is +3
are called chromic compounds. They are considered to be derived from
chromic oxide (Cr2O3) e-g Cr Cl3, Cr2(SO4)3.18 H2O. They are formed either
by oxidation of Cr+2 or by reduction of Cr+6 compounds. The chromium
compounds in which chromium has +2 oxidation state are called chromus
salts. They are unstable and oxidize to Cr+3 when exposed to air e-g CrCl2,
CrS, CrCO3 CrSO4 etc.
Equilibrium between chromate and dichromate.
When solid K2CrO4 is dissolved in water it forms yellow solution. This yellow
colour is due Cro-24 ions. Similarly when K2Cr2O7 is dissolved in water it forms
orange solution, the colour is due to Cr2O72- ions. These ions are actually in
dynamic equilibrium which is sensitive to acidity or basicity. According to Le-
Chatelier principle. The addition of an acid to reactants shifts the equilibrium
in forward reactants shifts direction and to yield more dichromate (orange
colour).
2 CrO42− + 2 H+ Cr2O72− + H2O
While addition of a base promotes the conversion of dichromate to chromate.
2 CrO42− Cr2O72−
Yellow orange

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Reduction of chromate (VI) ions by zinc and an acid.
Dichromatic ions (K2Cr2O7) can be reduced to Cr+3 and Cr+2 ions by using
zinc and dilute H2SO4 or dil HCl. The reaction occur in the following manner
Cr2 2O7  2Zn  14 H  
 2Cr 3  2 z 2  7 H 2O
2Cr 3  Zn 
 2Cr 2  Zn 2

Q. Explain the oxidizing nature of K2Cr2O7 .

1. IN ORGANIC CHEMISTRY
Acidified solution of K2Cr2O7 is used as oxidizing agent in organic chemistry.
For example

CH3OH  O 
 H  CHO  H 2O
O
||
H  C  H  O  
 H  COOH
Tertiary alcohols are not oxidized by K2Cr2O7.
2. IN TITRATIONS.

In redox titration, a standard solution of K2Cr2O7 is used to determine the

unknown concentration of Fe2+ solution.
6 FeSO4 + K2Cr2O7 + 7 H2SO4 → 3 Fe2(SO4)3 + K2SO4 + Cr2(SO4)3 + 7 H2O
Q14.8 Write note on manganese and its compounds.
The word manganese comes from Latin word “magnes” meaning magnet
because its pyrolusite ore is magnetic. It is slivery white and brittle metal,
having atomic number 25. It was isolated in 17874 by the Swedish chemist
Johan Gottieb Gahn. Its m.p and b.p is 1245C0and 2061C0 respectively.
ORES OF MANGANESE.
It does not occur in free state except in meteors. Its ores are
pyrolusite( ),rhodochrosite ,franklinite,psilomelane
and manganite

OXIDATION STATE.
The manganese shows +2,+3,+4+6,+7 oxidation state in its compounds
(KMnO4) with oxidation state +7 are act as powerful oxidizing agents. The
compounds of Mn3+ are called manganic compounds, of Mn6+ are
manganates. The most stable oxidation state is +2 due to half-filled
3d- orbital and its compounds called manganous compounds.
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OXIDIZING AGENT.
1.Organic chemistry
Potassium manganate (+7) oxidize ethene to glycol in the presence of
an acid.

5CH 2  CH 2  2 H 2O  2Mn O4  6 H  

 5CH 2OH  CH 2OH  2Mn 2
In the presence of alkaline condition, the Mn7+ ions first reduced to green
Mn4+ ions. Further addition result into dark brown solid of MnO2.

2.Titration.
KMnO4, on reduction change from purple to colourless form in the
presence of strong acid.

KMnO4 is also used to find the unknown concentration of. Fe2+ ion in a
solution.

Q14.8 Write note on iron and its compounds.

Iron is the 2nd most abundant metal after aluminum. It is found in meteors,
rocks, minerals, plants and animals. It has two characteristically coloured
compounds e-g Fe2+ salts (pale green) Fe3+ salts (yellow or brown)
ORES OF IRON.
It rarely occurs in free state. Its important ores are
i. Red haematite (Fe2O3)
ii. Brown haematite or limonite(2Fe2O3.3H2O)
iii. Magnetite (Fe3O4)
iv. Fool’’ gold (Iron pyrite) FeS2

Iron is commercially available in three forms which differ in carbon content.

1. Cast iron or pig iron (2-3%C)
2. Wrought or malleable iron (0.1-0.25%C)
3. Steel (0.25-2%C)

OXIDATION STATES OF IRON

Iron shows +2,+3,+4,+5 and +6 oxidation states in its compounds. The most
common oxidation states are +2 and+3 while +6 is very rare.
FORMATION OF AMMONIA WITHOUT CATSLYST.
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 1. In Haber process of NH3, iron is used as a catalyst. Without a catalyst
the reaction proceeds very slowly in the following steps.
N 2  H 2 
 N 2 H 2 H  ive
N 2 H 2  H 2 
 N2 H 4
N 2 H 4  H 2 
 2 NH 3

FORMATION OF AMMONIA IN THE PRESENCE OF CATSLYST.

The breaking of N2 is very difficult and needs a catalyst. In the presence of
iron catalyst, H2 and N2 are adsorbed on the surface of iron. The H2
immediately splits into its component atoms by sharing or exchange of
electrons with a surface of a catalyst. The N2 molecules also split into its
component atoms and adsorbed on the surface of iron. This is slowest step
and rate determining step.
H 2 
 2H  adsorbed 
N 2 
 2N  adsorbed 
The H-atoms then react with N-atoms on the surface of iron to form ammonia.
These ammonia molecules are then desorbed from. The surface of iron in the
form of a gas.
N  ad   H  ad  
 NH  ad 
NH  ad   H  ad  
 NH 2  ad 
NH 2  adsorbed   H  adsorbed  
 NH 3  ad 
NH 3  ad  
 NH 3  g 
Iron (Fe2+) also acts a catalyst in the reaction between persulphate and iodide
ions.
2
S2O82  2 I  
Fe
 2SO42  I 2
The step wise reaction is
2
S 2O82  2 Fe 2 
Fe
 2 SO42  2 Fe3
2 Fe 2  2 I  
 2 Fe 2  I 2

Reactions of hexa-aqua iron (II) (III) with H2O and NH3

1.WITH WATER.
Hexa-aqua iron complex ions ( Fe2+, Fe3+)undergo acid- base reaction with
water to reduce a solution of PH less than seven (Acidic). These are not
redox reaction because the oxidation state of iron remains same.
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 For example
Reaction of iron (II)
[Fe(H2O)6]2+(aq) + H2O(l) Fe(H2O)5(OH)]+(aq) + H3O+(aq)
Less acidic
Reaction of iron (III)

More acidic
3+ 2+
Fe gives more acidic solution than Fe ions. In a case of alkaline
solution OH- ions remove H3O+ - forward direction until ppt is formed.

[Fe(H2O)6]3+(aq) + 3OH-(aq) [Fe(H2O)3(OH)3]0(aq) + 3H2O(l)

In a case of Fe2+ complex, the reaction in alkaline medium does not proceeds
because it is energetically unfavorable.
2. WITH AMMONIA
NH3 acts as a base and thus removes H+ from the complex.
[Fe(H2O)6]2+ + 2OH- [Fe(H2O)4(OH)2] + 2H2O
[Fe(H2O)6] +3NH3→[Fe(H2O)3(OH)3]+3NH+4
3+

REACTIONS OF IRON IONS WITH CARBONATE IONS.

Hex aqua iron (II) complex reacts with carbonate ions to form a precipitate of
ferrous carbonate.
Fe+2 + CO2−3→FeCO3 (ppt)
The hex aqua iron (III) ions react with carbonate ions to form a neutral
complex and CO2 gas is released.
2[Fe(H2O)3+6+3CO2−3→2[Fe(H2O)3(OH)3]+3CO2+3H2O
TEST OF Fe3+ IONS.
A solution containing Fe3+ ions when reacts with thiocyanate ions (SCN-,
NaSCN, KSCN etc). As a result an intense blood red solution is formed which
shows the presence of Fe3+ ions.
[Fe(H2O)6]3+ + SCN− → [Fe(H2O)5(SCN)]2+
Q14.9 Write note on copper and its compounds.
The word copper is derived from Cyprus. It is brownish red metallic copper
was probably the first metal form which useful articles were made. It was
known to prehistoric people.
ORES OF COPPER
(i) Malachite, CuCO3. Cu(OH)2
(ii) Azurite, 2CuCO3. Cu(OH)2
(iii) Chalcocite, Cu2S
(iv) Copper pyrite CuFeS2

OXIDATION STATES OF COPPER

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The principal oxidation states of copper are +1 and +2.
 Copper (I) compounds are colourless and diamagnetic. e-g Cu2O, CuCl,
CuBr etc.
 Copper (II) ions are usually more stable in aqueous solution and
coloured. e-g CuO, CuF2, CuCl2, CuCO3, CuSO4 etc.
 copper (III) is mostly found in oxide states e-g KCuO2(blue black solid)
and cuperate super conductors.
 Yttrium barium copper oxide (YBaCu3O7) contain both Cu (II) and
Cu(III) ions .Similarly in K3CuF6 , copper has +3 and in Cs2CuF6
,copper has +4 oxidation state.

REACTIONS OF HEXA -AQUA COPPER (II) IONS.

1.With hydroxide ions
Hydroxide ions remove H+ ions from ligands (H2O) attached to copper ion. to
form an insoluble neutral complex
Cu  H 2O 6   Cu  H 2O 4  OH 2   2 H 2O
2_
 2OH  
(Blue ppt)
2. WITH AMNIONIA
When a small amount of ammonia is added to a solution of copper (II) ions
blue ppt is formed which dissolves by adding excess of ammonia
2
Cu  H 2O 6   Cu  H 2O 4  OH 2   2 N 1H 4
 2OH 
Blue ppt

Blue ppt
3. WITH CARBONATES
The hexaaqua copper (II) ions react with carbonates to form a
precipitate of metal carbonate.
Cu+2 + CO2−3→CuCO3

EXERCISE
Choose the correct answer from the given choices in each case
1.The transition metals, copper and ______ are best electrical conductors.
(a).Iron (b).vanadium (c).chromium (d).Manganese
2. Transition elements are usually exhibit___________ valencies
(a).Variable (b).normal (c).permanent (d).unchangeable
-2
3. The co-ordination compounds exist in _________shapes.
(a).Tetrahedral (b).octahedral (c).square planer (d).rhombic
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4.The oxidation state of chromium in CrO2Cl2 is ________
(a).2 (b).3 (c).4 (d).6
5.A compound Potassium dichromate is used in dying and
____________industry.
(a).Tanning (b).cement (c).paper (d).glass
6.Acidified Potassium permanganate acts as an __________agent
(a).oxidizing (b).reducing (c).Bleaching (d).colouring
7.The paramagnetic nature of a substance depends on
(a).The number of electrons in the outermost orbit
(b).The number of electrons that are easily ejected
(c).The number of unpaired electrons
(d).The number of lone pair of electrons
8.V2O5 is used as catalyst in the
(a).Manufacture of ammonia (b).oxidation of ammonia to nitric acid
(c).polymerization of ethene to polyethene
(d).manufacture of sulphuric acid
9.Select element which is not ferromagnetic
(a).Fe (b).Co (c).Sb (d).Ni
-4
10.The co-ordination number of iron in is
(a). 9 (b).3 (c).4 (d).6
11.Select ligand which is bidentate.
(a).H2O (b).NH3 (c).CO (d).
12. Salt solution is blue in colour due to transition of electron from
(a).s to p orbital (b).d to d orbital (c).p to d orbital (d).p to p orbital
13.Potassium dichromate acts as a strong
(a).oxidizing agent (b).reducing agent
(c).bleaching agent (d).dehydrating agent
14.When solid potassium chromate , is dissolved in water it forms a
______solution.
(a).Yellow (b).pink (c).red (d).violet
15.Which one is used as catalyst in the reaction between persulphate ions
and iodide ions.
(a).Lead (b).iron (c).copper (d).chromium
SHORT QUESTIONS
(i)What is meant by transition elements?
Ans. Those elements which have incomplete “d” or “f” orbitals either in their
atomic or in any other oxidation states are called transition elements.
All the T.Es are metals and are present between “S” and “P” block elements
they are further divided into two types
1. d-block elements

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Those elements which have partially filled d-orbital. They are also called outer
transition elements Or Those elements which have partially filled (n-1) d-
orbital.
They are further divided into four series.
1. f-BLOCK ELEMENTS.
Those elements which have incomplete f-orbital. In other words, in these
elements (n-2)f orbital is being progressively filled. They are also called inner
T.Es. They have given a separate place at the bottom of periodic table. They
are further subdivided into two types
(i) 4f- series (ii) 5f- series
(ii).Write the electronic configuration of first transition series.
Ans.

(iii).Comment on the electronic configuration of chromium and copper.

Ans. The expected electronic configuration of chromium and copper is
Expected configuration of Cr24=1s2,2s2,2p6,3s2,3p6,3d4,2s2
Expected configuration of Cu24=1s2,2s2,2p6,3s2,3p6,3d9,2s2
While the observed electronic configuration of chromium and copper is
Expected configuration of Cr24=1s2,2s2,2p6,3s2,3p6,3d5,2s1
Expected configuration of Cu24=1s2,2s2,2p6,3s2,3p6,3d10,2s1
The above configurations are verified through the spectroscopic analysis.
Because elements having half-filled or completely filled orbitals are more
stable. Thus chromium and copper in 3d5,2s1 and3d10,2s1are more stable
than 3d4,2s2 and 3d9,2s2.
(iv).Explain the catalytic behaviour of transition elements.
Ans. Most of the transition elements and their compounds act as catalyst,
both for organic and inorganic reactions. The catalytic properties are either
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due to use of d-orbital or the formation of interstitial compounds which absorb
and activate the reactants Since transition metals have variable oxidation
state therefore with the help of catalyst, they form intermediate compounds
.This help the formation of desired products. For example
i. V2O5 is used in the manufacture of H2SO4 by contact process.
ii. Finely divided iron is used for synthesis of NH3 by Haber-Bosch
process.
iii. Oxidation NH3 to nitric for synthesis of HN3 by Ostwald’s process.
iv. TiCl4 is used for the polymerization of ethene to polythene.
v. Ni, Pt or Pd is used for hydrogenates of unsaturated hydrocarbons.
vi. Copper is used in the Oxidation of ethyl alcohol to acetaldehyde.
(v).How co-ordination compounds are formed by transition elements.
Ans. A co-ordination compound (or coordination complex) consists of a metal
cation or neutral atom to which neutral or negatively charged ligands have
bonded. The number of ligand atoms attached to the metal center is called
co-ordination number and this number is always greater than the regular
valence or oxidation number of the metal. The coordination complex can be
negatively charged. For example, [AuCl4 ]− , [PtCl 6 ] 2− , [Co(NO2)6] 3− , and
[Fe(CN)6 ] 3− ; neutral, for example, [Fe(CO)5], [Ni(PF3)4 ], and [Rh(NH3)3Cl3];
or positively charged, for example, [Cu(NH3)4 ] 2+ , [Mn(H2O)6 ] 2+ , and
[Pt(NH3)5Cl]3+ . TiCl 4 and UF6 are neutral molecules (in which oxidation
number. = coordination number), they are not coordination compounds;
whereas [AlCl4] − and [FeF6] 3− are co-ordination complexes in which the
coordination number exceeds the oxidation number. The chromate anion,
CrO42−, is not a coordination complex; the oxidation number of the Cr-atom is
6, but only four O-atoms are bonded to it.
(vi).Write a short note on the variable oxidation state.
Ans. The transition elements show variable oxidation state in their
compounds by losing one or more electrons, because in addition to
s-electrons and (n-1)d electrons are also involved in bond formation. The
common oxidation state of 3d-series is +2 or +3 or both. The highest
oxidation state is +7 for “Mn”. After “Mn” the oxidation state decreases due to
pairing up of electrons in the 3d-orbital.
(vii).What is the oxidation state of Fe in FeCl3.
Ans. FeCl3=0 Fe+3Cl=0 Fe+3 x -1=0 Fe=3
(viii). What is the oxidation state of Cr in [Cr(H2O)6]3+.
Ans. [Cr(H2O)6]3+
Cr +6H2O=3
Cr+6 x 0=3
Cr=3

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