4 MEGACOSM

coGIONS PRIVATE LbaE

Catalytic Properties
Many transition metals and their compounds have catalytic properties. For e.g. V,O,, Fe. FeCl, Ni, Pd
This
etc. property of transition elements is due to their variable oxidation states. In some cases the transition
metals with their variable valency may form variable unstable intermediate compounds. In other cases the
transition metal provides a suitable reaction surface.
NON STOICHIOMETRY
Another feature of the transition elements is that they sometimes form non stoichiometric compounds.
example Fe, s 0. It is mostly due to th
These are compounds of indefinite structure and proportions. For
is caused by defects in the solis
variable valency of transition elements. Sometimes, non stoichiometry
structures.
ALLOY FORMATION
obtained by melting the components and
Alloys are homogeneous solid solutions of two or more metals
then cooling the melt. These are formed by metals whose atomic radii differ by not more than 15% so that
crystal lattice of the other. Since transition
the atoms of one metal can easily take up the positions in the
metals have similar atomic radii, they form alloys very readily.
STUDY OF SOME IMPORTANT COMPOUNDS
() Copper (ll) Sulphate pentahydrate or blue vitriol, CuSO4.5H,0
Preparation
hydroxide or cupric carbonate in dil ute
In the laboratory, it is prepared by dissolving cupric oxide, cupric
H,SO4.
CuO + H,SO4 ’ CuSO4 + Hz0
Cu(OH); + H,SO. ’ CuSO4 + 2H,0
CuCO, + H,SO4 ’ CuSO + H,0 + CO,
when crystals of blue vitriol.
The solution of CuSO. thus obtained is concentrated and cooled acid on scrap
CuSO4.5H,0 separates out. Commercially it is prepared by the action of hot dilute sulphuric
copper in the presence of air.
2Cu +2H,SO, +0, ’2CuSO, +2H,0
Properties
1. Action of heat
CuSO, strong
CuSO,.5H,O 373KCuSO, H,0 423K
heating
CuO+ SO,
(white)
5" one is
In CuSO,.5H,0, four H,O molecules are coordinated to the central Cu ion. While the
thus
attached between SO and H,0 molecule by hydrogen bonding. This fifth H,O molecule is
deep inside the crystal lattice and is not easily lost.
2. Action of alkalis
CuSO, +2NaOH ’Cu(OH), +Na,SO,
With NHOH it forms tetraamminecopper (ll) sulphate
CuSo, +4NH,OH ’Cu(NH,), Jso, +4H,0
3. Reaction with KI
CuSO, +2KICul, +K,SO,
2Cul, ’2Cul +, estimate
used to
The liberation of iodine in this reaction is quantitative. Therefore, this reaction is
copper volumetrically.
 MEGACOSM
cOGNITIONS PRIVATE LIMITEO
5
Uses

() It is used as an electrolyte in
(i) It is used in reservoirs and electroplating, electrotyping and refining of copper.
swimming pools to
(n) It is used as a fungicide under the name of prevent the growth of weeds.
Bordeaux mixture, which is a mixture of CuSO, and slaked
lime Ca(OH)2.
(iv) Anhydrous CuSO, is used for detection of
moisture in organic liquids such as alcohol, ether etc.
Silver Nitrate, AgNO,
Preparation
It is prepared by the action of dilute nitric acid on silver and then
crystallization. evaporating the soluton to
3Ag +4HNO, ’3AgNO, +NO‘ +2H,0
Properties
1. Action of heat
It decomposes on heating.
2AgNO, A2Ag+ 2NO, +O,
2. On Coming into contact with organic matter like skin or clothes, it is reduced to finely divided silver,
giving a black stain.
3. Precipitation reactions
It gives precipitates with some salt solutions which help in the detection of acid radicals. Some of the
precipitation reactions are:
NaCl+ AgNO, ’AgCi +NaNO,
Na,PO, +3AgNO, ’Ag,PO, +3NaNO,
K,CrO, +2AgNO, ’Ag,CrO, +2KNO,
Na,S + 2AgNO, ’Ag,S +2NaNO,
Na,S,O, +2AgNO, ’Ag,S,0, +2NaNO,
Na,C,0, +2AgNO, ’Ag,C,O, +2NaNO,
Na,BO, +3AgNO,Ag,BO, +3NaNO,
Uses
It is used for
1. Preparing silver halides used in photography.
2. For making inks and hair dyes.
3. In qualitative and quantitative analysis.
4. For silvering of glass, i.e. preparation of mirrors.
Halides
1. Silver halides (AgF, AgCI, AgBr &Agl)
Preparation
Silver halides are prepared by the action of sodium or potassium halide on silver nitrate solution (except
for AgF)
AgNO, +NaXAgX +NaNO,
Silver fluoride is prepared by the action of HF on silver (1) oxide.
2HF +Ag,0- ’2AgF +H,0

P-2224-P7-CBSE-CHEMISTRY-TRANSITION ELEMENTS &CO-ORDINATION COMPOUNDS

 6
MEGACOSM
Properties
() Agci is white solid, AgBr is apale yellow solid and Agl is a yellow solid.
(ii)) AgF is soluble in water whereas other halides are insoluble in water. AgCl dissolves in
form a complex. ammonia to
AgCl+ 2NH,OH ’[Ag(NH,),]ci+2H,0
AgBr is partially soluble and Agl is insoluble in NH,OH.
() All the silver halides dissolve in potassium cyanide and Na, S,O, solution to form complexes.
AgCl+ 2KCN K[Ag(CN),]+KCI
AgCl+ 2Na,S,O, Na, (Ag(S,0,), ]+NaCI
Uses
Allsilver halides (particularly AgBr) are photosensitive and hence are widely used in photography.
2. Mercury halides
(a) Mercury () chloride or mercurous chloride or calomel, HgzCl2
Preparation
0 tcan be prepared by mixing a chloride solution with a mercury () salt solution.
Hg, (NO, ), +2NaCI- Hg,Ci, +2NaNO,
calomel

(i) Itcan also prepared by heating a mixture of mercuric chloride and mercury in an iron vessel.
HgCl, +Hg Hg,Cl,
Properties
(0) It is a white power insoluble in water but soluble in chlorine water.
Hg,Cl, +Cl, ’2HgCi,
(i) Itdecomposes on heating to HgCl,
Hg,Cl, HgCl, +Hg
(iii)) On treatment with ammonia, if turns black due to the formation of finely divided mercury.
Hg,Cl, + 2NH, ’ Hg +Hg(NH, )Cl +NH,CI
(black)
Uses

(i) In making standard calomel electrode

(ii) As a purgative in medicine.
(b) Mercury (l) chloride HgCl,
1. It is prepared by passing dry chlorine over heated mercury.
Hg +Cl, AHgCl,
2. It is also obtained by treating HgO with HCI
HgO+ 2HCI- HgCl, +H,0
3. Commercially, it is prepared by heating a mixture of HgSO, and NaCI in the
presence of MnO2
HgSO, +2NaClHgCi, +Na,SO,
Properties
1. It is a white crystalline solid sparingly soluble in cold water but soluble in hot water. Its solubility can
be increased by adding CI.
HgCi, +2C1 -[HgCi,

P-2224-P7-CBSE-CHEMISTRY-TRANSITION ELEMENTS &CO-ORDINATION COMPOUNDS

 MEGACOSM
coGNITIONS PRTVATE LMTED
7

2. It is readily soluble in organic solvents suggesting its covalent nature.

3. When treated with SnCl, it is reduced to
mercury.
2HgCl, +SnCl, ’ SnCl, + Hg,Cl,
Hg,Cl, +SnCl, ’2Hg +SnCi,
4. When Cu turnings are placed in its contact a shining grey film of mercury deposits over them.
HgCi, + Cu- >Hg +CuCI,
Uses

It is used for preserving wood and for making fungicides.

(c) Mercury (ll) lodide
Preparation
It is prepared by treating HgCl, with KI.
HgCi, +2KI- ’ Hgl, +2KCI
(scarlet red)
Properties
1. Mercuric iodide exists in two forms, i.e. red and yellow. The yellow form is stable above 400 K white
the red form is stable below this temperature.
>400K
Hgl, <400K Hgl,
(red) (Yellow)
2. It readily dissolves in KI forming a complex
Hgl, + 2KI’ K[Hgla]
An alkaline solution of KHgl.] is called Nessler's reagent and is used to detect the presence of NH with
which it gives a brown precipitate due to the formation of iodide of Million's base.
Uses
It is used to prepare Nessler's reagent and for making ointments for treatment of skin infections.
Potassium Dichromate, K,Cr,0,
Preparation
It is prepared from the ore called chromate or ferrochrome or chrome iron, FeO.Cr,03. The various steps
involved are

(a) Preparation of sodium chromate

4FeO.Cr,0, +O, +2Fe,O, + 4Cr,0,
4Na,CO, +2Cr,O, + 3 0 , ’4Na,CrO, +4CO,
(b) Conversion of sodium chromate into sodium dichromate.
2Na,CrO, +H,SO, ’Na, Cr,O, + Na, SO, +H,0
(c) Conversion of sodium dichromate into potassium dichromate.
Na,Cr,O, + 2KCI. ’K,Cr,O, + 2NaCI
Properties
It forms orange red crystals. It is moderately soluble in cold water but freely soluble in hot water.
1. Action of heat
When heated, it decomposes to its chromate
4K,Cr,O, 4K,CrO, +2Cr,O, +30,
2. Action of alkalis
With alkalis it is converted into chromate which on acidifying gives back dichromate.
K,Cr,0, +2KOH- ’2K, CrO, +H,0

P-2224-P7-CBSE-CHEMISTRY-TRANSITION ELEMENTS &CO-ORDINATION COMPOUNDS

 8 MEGACOSM
coCNTIONS 9RTatt LMIE
2K,CrO, +H,SO, >K,Cr,0, +K,SO, +H,0
In dichromate solution the Cr.0 ions are in equilibrium with CrO ions at pH = 4.
Cr,0 +H,0P2cr0; +2H
orange red yellow
3. Action of conc. H,SO, solution
(a) In cold conditions
K,Cr,0, +2H,SO, ’2CrO, +2KHSO, +H,0
(b) In hot conditions
2K,Cr,0, +8H,SO, ’K,SO, +2cr, (SO, ), +8H,0+30,
4. Oxidising properties
It is a powerful oxidising agent. In the presence of dil. H,SO, it furnishes 3 atoms of available oxygen
K,Cr,0, +4H,SO, K,SO, +Cr, (SO, ), +4H,0 +30
Some of the oxidizing properties of K,Cr,0, are
(a) It liberates I, from KI
K,Cr,0, +7H,SO, +6KI 4K,SO, +Cr, (SO, ), +31, +7H,0
(b) Itoxidises ferrous salts to ferric salts
K,Cr,0, +7H,SO, +6FeSO, K,so, +Cr,(SO,), +3Fe, (S0,), +7H,o
(c) It oxidises S to s
K,Cr,0, +4H,SO, +3H,S K,SO, +Cr, (S0,), +7H,0 +3S
(d) It oxidises nitrites to nitrates
K,Cr,0, +4H,SO, +3NaNO, K,SO, +Cr, (SO,), +3NaNO, +4H,0
(e) It oxidises SO, to SO;
K,Cr,0, +H,SO, +3SO, K,SO, +Cr, (SO,), +H,0
(f) It oxidises ethyl alcohol to acetaldehyde and acetic acid.
5. Chromyl chloride test
When heated with conc. HCI or with a chloride in the presence of sulphuric acid,
of chromyl chloride are obtained. reddish brown vapours
K,Cr,0, +4KCl+6H,SO, ’20r0,Ci, +6KHSO, +3H,0
This reaction is used in the detection of chloride ions in qualitative analysis.
Uses
1. In volumetric analysis for the estimation of Fe and I.
2. In chrome tanning in leather industry.
3. In photography and in hardening gelatin film.
Potassium Permanganate, KMnO4
Preparation on a large scale
It is prepared from the mineral pyrolusite, MnO2. The
preparation involves the following steps
(i) Conversion of MnO, into potassium manganate.
When finely powdered MnO, is fused with KOH. K,MnO4 is obtained.
2MnO, +4KOH+0,- ’2K,MnO, +2H,0
(i0) Oxidation of potassium manganate into permanganate
(a) Chemical oxidation
KMnO is oxidised to KMnO, by bubbling CO, or Cl, or ozone into
the former.
3K,MnO, +2C0, ’2KMnO,+MnO, +2K,Co,

P-2224-P7-CBSE-CHEMISTRY-TRANSITION ELEMENTS &CO-ORDINATION COMPOUNDS

 MEGACOSM
coGNITIONs PRrATE LMIED

(b) Electrolytic oxidation

The manganate solution is electrolysed between iron electrodes. The oxygen evolved at anode
converts manganate into permanganate.
2K,MnO, +H,0+0 ’2KMnO, +2KOH
Properties
KMnO4 exists as deep purple prisms. It is moderately soluble in water at room temperature and its
solubility in water increases with temperature.
(0) Action of heat
When heated it decomposes to K,MnO4.
2KMnO, K,MnO, +MnO, +O,
(ii) Action of conc. H,SO,
With cold conc. H,SO, it gives Mn,O, which on warming decomposes to MnO2.
2KMnO, +2H,SO, >Mn,0, +2KHSO, +H,0
2Mn,0,4MnO, +30,
With hot Conc. H,SO4, O, is evolved
4KMnO, +6H,SO, ’2K,SO, +4MnSO, +6H,0+50,
(ii) Oxidising properties
KMnO, is a powerful oxidizing agent. The actual oxidizing action depends upon the medium i.e.
acidic, basic or neutral.
(a) In neutral solution, it acts as moderate oxidizing agent.
2KMnO, +H,0 ’2KOH+ 2MnO, +3O
Some oxidizing properties of KMnO, in neutral medium are
8KMnO, + 3Na, S,O, +H,0 3K,SO, +8MnO, +3Na,SO, +2KOH
2KMnO, +4H,S- ’2MnS +S +K,SO, +4H,0
(b) In strong alkaline solution, it is converted into MnO
2KMnO, + 2KOH ’2K,MnO, +H,0 +0
Some reactions in alkaline medium are
2KMnO, +H,0 +KI2MnO, +2KOH +KIO,
(c) In acidic medium, Mn is converted into Mn*?
2KMnO, +3H,SO, >K,SO, +2MnSO, +3H,0+50
Some other reactions are
(i) 2KMnO, +3H,SO, +5H,S K,SO, +2MnSO, +8H,0 +5S
(i) 2KMn0, +5S0, +2H,0’K,SO, +2MnSO, +2H,SO,
(i) 2KMno, +3H,SO, +5KNO, K,SO, +2MnSO, +3H,0 +5KNO,
(iv) 2KMn0, +3H,SO, +5C,H,0, K,SO, +2MnSO, +8H,0 +10C0,
(v) 2KMnO, +8H,S0, +10FeSo, K,SO, +2Mn SO, +5Fe, (s0,), +8H,o
(vi) 2KMnO, +3H,SO, +10HIK,S0, +2MnSO, +8H,0 +51,
Uses
() It is used in volumetric analysis for the estimation of ferrous salts, Oxalates, iodides and H,O,.
laboratory as well as in industry.
(ii) It is used as oxidizing agent in the gemicide.
(ii) It is also used as disinfectant and

P-2224:P7-CBSE-CHEMISTRY-TRANSITION ELEMENTS &CO-ORDINATION COMPOUNDS