Anda di halaman 1dari 26

1.

INTRODUCTION 2
2. ELECTRONIC CONFIGURATIONAND IRREGULARITIES 2
3. GENERAL CHARACTERISTICS 2
4. COLOUR 3
5. COMPLEX FORMATION 3
6. CHROMATE -DICHROMATE 4
7. MANGANATE & PERMANGANATE 5
8. SILVER AND ITS COMPOUND 6
9. ZINC COMPOUNDS 8
10 .COPPER COMPOUNDS 9
11. IRON COMPOUNDS 10
12. INNER TRANSITION ELEMENTS 11
13. LANTHANIDE CONTRACTION 12
1
CONTENTS
S.NO. TOPIC PAGE NO
d & f - block
1. INTRODUCTION
In these elements the last electron enters (n1)d orbitals of atom of an element is called d-block
elements.
ELECTRONIC CONFIGURATIONAND IRREGULARITIES
The valence shell configurations of these elements can be represented by (n 1)d
110
ns
0,1,2
.
All the dblock elements are classified into four series viz 3d , 4d , 5dand 6d series corresponding to the
filling of 3d, 4d , 5dand 6d orbitals of (n1)
th
main shell orbitals of (n1)
th
main shell. Each Series has
10 element s. Cr(3d
5
, 4s
1
) , Cu(3d
10
, 4s
1
), Mo(4d
5
, 5s
1
), Pd(4d
10
, 5s
0
), Ag(4d
10
, 5s
1
)
anAu(5d
10
, 6s
1
) clearlyshowthe irregularities inthe configurations
These are explained on the basis of the concept that half filled and completely filled dorbitals are
relativelymore stable thanother dorbitals.
GENERAL CHARACTERISTICS
(i) Metallic character: They are all metal and good conductor of heat &electricity
(ii) Electronic configuration: (n1)d
110
ns
12
2.
3.
Cr

Maximum

lowest m.p. (iii) M.P. Zn


Cd
Hg
` `

Mo

)
6 no. of unpaired e s due to no unpaired e

)
W are involved in metallic bonding for metallic bonding
(iv) Variation inatomic radius:
Sc Mn Fe Co Ni Cu Zn

decreases remains increases


same
(v) Variable oxidation states possible
again
Sc Ti V Cr Mn Fe Co Ni Cu Zn
+1 +1
+ 2 + 2 + 2 + 2 + 2 + 2 + 2 + 2 + 2
+ 3 + 3 + 3 + 3 +3 + 3 + 3 +3
+ 4 + 4 + 4 + 4 + 4 + 4 + 4
+ 5 +5 +5
+ 6 + 6 + 6
+ 7
Colour : (aquated)
Sc
3+
Ti
4+
Ti
3+
V
4+
V
3+
V
2+
Cr
2+
Cr
3+
colourless
colourless
purple
blue
green
violet
blue
green
Mn
3+
violet
Mn
2+
light pink
Fe
2+
Fe
3+
light green
yellow
Co
2+
pink
Ni
2+
green
Cu
2+
blue
Zn
2+
colourless
2
d & f - BLOCK
d & f - block
4. COLOUR
Substances appear coloured whentheyabsorb light of a particular wavelength in the visible regionof the
spectrumand transmit light of other wavelengths. The colour whichwe see is the colour of the transmitted
wavelengths. In other words, the colour of the compound observed by us is the complmentary colour
of the colour absorbed by the compound.
In the s- and p-block elements there cannot be any d-d transitions and the energy needed to promote s
or p electronto a higher level is much greater andmaycorrespond to ultraviolet region, inwhichcase the
compound will not appear coloured to the eye.
Relationship between colour and wavelength
Wavelength absorbed in nm
<400
400435
435480
480490
490500
500560
560580
580595
595605
605750
> 750
Colour absorbed
UVregion
Violet
Indigo
Green-blue
Blue-green
Green
Yellow-green
Yellow
Orange
Red
Infra-red
Colour observed
White/colourless
Yellow-green
Yellow
Orange
Red
Purple
Violet
Indigo
Green-blue
Blue-green
White/colourless
Magnetic Properties: When a substance is placed ina magnetic field of strength H, the intensityof the
magnetic field inthe substance maybe greater than or less than H.
diamagnetic, Substances whichare weakly repelled bya magnetic field
paramagnetic the substances whichare weaklyattracted bythe magnetic field andlose their
magnetism when removed fromthe field .
Paramagnetism is expressed bymagnetic moment,
= n(n+ 2)
B.M.
n =number of unpaired electrons
B.M. =Bohr Magneton, unit of magnetic moment
5. COMPLEX FORMATION
In the case of transition metals in lowoxidation states, the electrons in the d orbitals become involved in
bonding with ligands.The bonding between the ligand and the transition metal ion can either be
predominantlyelectrostatic or covalent or inmanycases intermediate between the two extremes. Some
of the typical complexes of the transition meals are [Fe(CN) ]
3
,[Ni(NH ) ]
2+
,[Cu(CN) ]
3
,
6 3 4 4
[Cu(NH ) ]
2+
etc.
3 4
Formation of alloys :
Transition elements have almost similar atomic sizes. Therefore , these elements can mutually
substitute their positions in their crystal lattice. The alloys are hard and have high melting points as
compared to the most metal.
Catalytic Properties: Manytransition metals andtheir compounds have catalytic properties.
some example
TiCl
3
V
2
O
5
MnO
2
Used as the Ziegler-Natta catalyst in the production of polythene.
Converts SO
2
to SO
3
in the contact process for making H
2
SO
4
.
Used as a catalyst to decompose KClO
3
to give O
2
.
3
d & f - block
Fe
H
2
O
2
Pd
Pt/Rh
Promoted iron is used in the Haber-Bosch process for making NH
3
.
Used as Fentons reagent for oxidizing alcohols to aldehydes.
Used for hydrogenation (e.g. phenol to cyclohexanone).
Formerly used in the Ostwald process for making HNO
3
to oxidize NH
3
to NO.
Ni Raney nickel, numerous reduction processes (e.g. manufacture of hexamethylenediamine,
production of H
2
from NH
3
, reducing anthraquinone to anthraquinol in the production of H
2
O
2
).
IonisationEnergies
Ionisation energies-(i) of 5d elements are higher than those of the 3d and 4d elements. This is due to
greater effective nuclear charge actingon outer valence electrons because of the weak shieldingof the
nucleus by 4f electrons. The ionisation energies of the 3dand 4d elements are irregular.
Common oxidation states for each element include +2 and +3 or both. The +3 oxidation states are more
stable at the beginning of the series, whereas towards the end +2 oxidation states are more stable.
Ionisation energy increases gradually fromleft to right. However the third ionisation energies, when an
electron is removed from 3d orbital, increases more rapidly than the second and third ionisation
energies. Because it takes more energyto remove the third electron fromthe metals near the endof the
row than from those near the beginning, the metals near the end tends to form M
2+
ions rather than
M
3+
ions.
6. CHROMATE -DICHROMATE
Preparation :
4FeO . Cr
2
O
3
+ 8Na
2
CO
3
+ 7O
2
Rosting
8Na
2
CrO
4
+ 2Fe
2
O
3
+ 8CO
2

in air
chromate ore
The roasted mass is extracted with water when Na
2
CrO
4
goes into the solution leaving behind insoluble
Fe
2
O
3
. The solution is treated with calculated amount of H
2
SO
4
.
2Na
2
CrO
4
+ H
2
SO
4
Na
2
Cr
2
O
7
+ Na
2
SO
4
+ H
2
O
The solutionis concentrated when less soluble Na
2
SO
4
crystallises out. The solutionis further concentrated
when crystals of Na
2
Cr
2
O
7
are obtained. Then a hot saturated solutionof Na
2
Cr
2
O
7
is treated with KCl
when reddish orange crystals of K
2
Cr
2
O
7
are obtained on crystallisation.
K
2
Cr
2
O
7
is preferred to Na
2
Cr
2
O
7
because Na
2
Cr
2
O
7
is hygroscopic but K
2
Cr
2
O
7
is
not.
* Other props &test of CrO
2
& Cr O
2
:Already discussed
4 2 7
* Similarities between hexavalent Cr &S-compounds:
(i) SO
3
& CrO
3
both acidic.
4
d & f - block
(ii) CrO
2
& SO
2
are isomorphous
4 4
OH
2 2
(iii) SO
2
Cl
2
& CrO
2
Cl
2
SO
4
& CrO
4
respectively.
OH

2 2
(iv) SO
3
Cl & CrO
3
Cl SO
4
& CrO
4
O

O O
|| || ||
(v) CrO
3
&|(SO
3
) has same structure Cr O Cr O Cr
||
O
||
O
||
O
(vi) Potassiumdichromate reacts withhydrochloric acid and evolves chlorine.
K
2
Cr
2
O
7
+ 14HCl 2KCl + 2CrCl
3
+ 7H
2
O + 3Cl
2

(vii) It acts as a powerful oxidising agent in acidic medium(dilute H


2
SO
4
)
Cr
2
O
7
+ 14H + 6e 2Cr
3
+ 7H
2
O. (E = 1.33 V)
The oxidation state of Cr changes from+6 to +3.
Uses
(i) As a volumetric reagent inthe estimationof reducing agents suchas oxalic acid,
ferrous ions, iodide ions, etc. It is used as a primary standard.
(ii) For the preparation of several chromiumcompounds such as chrome alum, chrome
yellow, chrome red, zinc yellow, etc.
(iii) In dyeing, chrome tanning, calico printing photographyetc.
(iv) Chromic acid as a cleansing agent for glass ware.
2 + +
7. MANGANATE & PERMANGANATE
Preparation
This is the most important and well known salt of permanganic acid. It is prepared fromthe pyrolusite
ore. It is prepared by fusing pyrolusite ore either with KOH or K
2
CO
3
in presence of atmospheric
oxygenor anyother oxidising agent suchas KNO
3
. The mass turns greenwith the formationof potassium
magnate, K
2
MnO
4
.
2MnO
2
+ 4KOH + O
2
2K
2
MnO
4
+ 2H
2
O
2MnO
2
+ 2K
2
CO
3
+ O
2
2K
2
MnO
4
+ 2CO
2

The fused mass is extracted withwater. The solution is nowtreated with a current of chlorine or ozone
or carbondioxide to convert magnate into permanganate.
2K
2
MnO
4
+ Cl
2
2KMnO
4
+ 2KCl
2K
2
MnO
4
+ H
2
O + O
3
2KMnO
4
+ 2KOH + O
2

3K
2
MnO
4
+ 2CO
2
2KMnO
4
+ MnO
2
+ 2K
2
CO
3

Props : The above green solution is quite stable in alkali, but in pure water and in presence of acids,
depositing MnO
2
and giving a purple solution of permanganate.
3K
2
MnO
4
+ 2H
2
O 2KMnO
4
+ MnO
2
+ + 4KOH
purple
= 2.26 V
drak brown
E
o
E
o
Prob. : ; = 0.56 V
MnO
2
/ MnO
2

MnO
2
/ MnO

4 4 4
Prove that MnO
2
will disproportionate in acidic medium.
4
Another Method of Prep
n
. : 3K MnO + 2H SO 2KMnO + MnO + + 2K SO + 2H O
2 4 2 4 4 2 2 4 2
or 3K
2
MnO
4
+ 2H
2
O + 4CO
2
2KMnO
4
+ MnO
2
+ 4KHCO
3
5
d & f - block
1
But in the above method of Mn is lost as MnO
2
but when oxidised either by Cl
2
or by O
3
3
2K
2
MnO
4
+ Cl
2
2KMnO
4
+ 2KCl [Unwanted MnO
2
does not form]
OR
2K
2
MnO
4
+ O
3
+ H
2
O 2KMnO
4
+ 2KOH + O
2

200C
Heating effect : 2KMnO
4
green
K
2
MnO
4
+ MnO
2
+ O
2
Black

t r

ed
2K
2
MnO
4
2K
2
MnO
3
+ O
2
hot
Oxidising Prop. of KMnO
4
: (in acidic medium)
(i) MnO

+ Fe
+2
+ H
+
Fe
+3
+ Mn
+2
+ H O
4 2
(ii) MnO

+ H O + H
+
Mn
+2
+ O + H O
4 2 2 2 2
(iii) MnO

+ H S Mn
2+
+ S + + H O
4 2 2
In alkaline solution : KMnO
4
is first reduced to magnate and then to insoluble manganese dioxide.
Colour changes first frompurple to greenand finallybecomes colourless. However brownishprecipitate
is formed.
2KMnO
4
+ 2KOH
2K
2
MnO
4
+ 2H
2
O
2K
2
MnO
4
+ H
2
O + O
2MnO
2
+ 4KOH + 2O
alkaline
2KMnO
4
+ H
2
O 2MnO
2
+ 2KOH + 3[O]

or 2MnO
4
+ H
2
O 2MnO
2
+ 2OH + 3[O]
Oxidising Prop. in neutral or weakly acidic solution:
in presence Zn
+2
or ZnO
(i) 2KMnO
4
+ 3MnSO
4
+ 2H
2
O 5MnO
2
+ K
2
SO
4
+ 2H
2
SO
4
Conversion of Mn
+2
to MnO

:
4
(i) PbO
2
(ii) Pb
3
O
4
+ HNO
3
(iii) Pb
2
O
3
+ HNO
3
(iv) NaBiO
3
/ H
+
(v) (NH
4
)
2
S
2
O
8
/ H (vi) KIO
4
/ H
+ +
8. SILVER AND ITS COMPOUND
(I) MetallicAg
In the same way in presence of O
2
, Ag complexes with NaCN/ KCN.
4Ag + 8KCN + 2H
2
O + O
2
4K[Ag(CN)
2
] + 4KOH
6
d & f - block
AgNO
3
(Silver Nitrate)
Properties.: (i) It is called as lunar caustic because incontact with skinit produces burning sensation like
that of caustic soda withthe formation of finely devided silver (black colour)
(ii) Thermal decomposition:
(iii) Props. ofAgNO
3
: [Already done in basic radical]
6AgNO
3
+ 3I
2
+ 3H
2
O 5AgI +AgIO
3
+ 6HNO
3
(excess)
(iv) Ag
2
SO
4
A

2Ag + SO
2
+ O
2
(v) A(AgNO
3
) white ppt appears quickly
B
added
`
Explain
It takes time to give white ppt. )

added

B(Na
2
S
2
O
3
)
(vi) Ag
2
S
2
O
3
+ H
2
O

Ag
2
S + H
2
SO
4
AgCl . AgBr.AgI (but not Ag
2
S) are soluble in Na
2
S
2
O
3
forming
[Ag(S
2
O
3
)
2
] complexes
(vii)AgBr : AgNO
3
K

Br

AgBr + + KNO
3
Pale yellow
ppt.
3
2AgNO
3
2

12

2AgNO
2
+ O
2
2AgNO
2
5

00

2Ag + 2NO + O
2
Heating effect:
(viii)
Ag
2
O + H
2
O
2
2Ag + H
2
O + O
2
K
2
S
2
O
8
+ 2AgNO
3
+ 2H
2
O 2AgO + 2KHSO
4
+ 2HNO
3
Note:
(1) AgOsupposed to be paramagnetic due to d
9
configuration. But actuallyit is diamagnetic and exists
asAg
I
[Ag
III
O ]
2
(2) Reaction involved indeveloper :
K
2
Fe (C
2
O
4
)
2
+AgBr KFe (C
2
O
4
)
2
+Ag+ + KBr
II III
7
d & f - block
9. ZINC COMPOUNDS
(1) Zinc oxide, ZnO(Chinese white orphilosopher's wool)
Its foundinnature as zincite or red zinc ore.
Preparation :
(i) 2Zn + O
2
2ZnO
A
(ii) ZnCO
3
ZnO + CO
2

A
(iii) 2Zn(NO
3
)
2
2ZnO + 4NO
2
+ O
2

A
(iv) Zn(OH)
2
ZnO + H
2
O

(a) Physical Properties : It is white powder becomes yellow onheating again turns white oncooling ,
insoluble inwater, sublimes at 400C.
(b) Chemical Properties :
(i) ZnO + H
2
SO
4
ZnSO
4
+ H
2
O
(iii) ZnO + 2NaOH Na
2
ZnO
2
+ H
2
O
A

400 C

(iv) ZnO + H
2
(v) ZnO + C
Zn + H
2
O
Zn + CO
ZnCl
2
(Zinc Chloride)
Preparation: ZnO + 2HCl ZnCl
2
+ H
2
O
ZnCO
3
+ 2HCl ZnCl
2
+ H
2
O + CO
2
`
It crystallis es as ZnCl
2
2 H
2
O
Zn(OH) + 2HCl ZnCl + 2H O
2 2 2
Anh. ZnCl
2
cannot be made by heating ZnCl
2
2H
2
Obecause
ZnCl
2
2H
2
O Zn(OH)Cl + HCl + H
2
O
A

A
Zn(OH)Cl ZnO+ HCl
To get anh. ZnCl
2
:
Zn + Cl
2
ZnCl
2
Zn + 2HCl(dry) ZnCl
2
+ H
2
or Zn + HgCl
2
ZnCl
2
+ Hg
Properties:
(i) It is deliquescent white solid (when anhydrous)
(ii) ZnCl
2
+H
2
S ZnS
"
"
+ NaOH Zn(OH)
2
e

xce

ss

Na
2
[Zn(OH)
4
]
+ NH
4
OH Zn(OH)
2
e

xce

ss

[Zn(NH
3
)
4
]
2+
Uses:
1]
2]
3]
Used for impregnating timber to prevent destruction byinsects
As dehydrating agent when anhydrous
ZnOZnCl
2
usedindental filling
ZnSO
4
(Zinc Sulphate)
Preparation:
Zn + dil H
2
SO
4
ZnSO
4
+ H
2
ZnO + dil H
2
SO
4
ZnSO
4
+ H
2
O
ZnCO
3
+ dil H
2
SO
4
ZnSO
4
+ H
2
O+ CO
2
8
d & f - block
ZnS+ 2O
2
ZnSO
4
3
ZnS + O ZnO + SO
`
parallel reaction
2
2 2
ZnS + 4O
3
ZnSO
4
+ 4O
2
>70C >280C 3970C
Props. 1] ZnSO
4
7H
2
O

ZnSO
4
6H
2
OZnSO
4
H
2
O
ZnSO
4
1
2
O
2
+ SO
2
+ ZnO
Uses: 1]
2]
in eye lotion
Lithophone making (ZnS + BaSO
4
) as white pigment
COMPOUNDS
10. COPPER
CuO :
A
Preparation: (i) CuCO
3
.Cu(OH)
2

2CuO+ H
2
O + CO
2
(Commercial process )
Malachite Green
(native Cu-carbonate)
1
2Cu + O
2
2CuO & Cu
2
O +
2
O
2
2CuO (ii)
A
(iii)
(iv)
Cu(OH)
2
CuO + H
2
O
2Cu(NO
3
)
2
2

50

2CuO + 4NO
2
+
O
2
Properties: (i)
(ii)
CuOis insoluble in water
Readily dissolves in dil. acids
CuO + H
2
SO
4
CuSO
4
+ H
2
O
HCl CuCl
2
HNO
3
Cu(NO
3
)
2
It decomposes when, heated above 1100C
4CuO 2Cu
2
O + O
2
CuOis reduced to Cu by H
2
or Cunder hot
condition
CuO + C Cu + CO |
CuO + H
2
Cu + H
2
O |
(iii)
(iv)
CuCl
2
:
Preparation: CuO+ 2HCl(conc.) CuCl
2
+ H
2
O
Cu(OH)
2
CuCO
3
+ 4HCl 2CuCl
2
+ 3H
2
O + CO
2
Properties: (i)
(ii)
It is crystallised as CuCl
2
2H
2
Oof Emerald green colour
dil. solutioninwater is blue in colour due to formation of
[Cu(H
2
O)
4
] complex.
conc. HCl or KCl added to dil. solution of CuCl
2
the colour changes
into yellow, owing to the formation of [CuCl
4
]
The conc. aq. solutionis greenincolour having the twocomplex ions in
equilibrium 2[Cu(H
2
O)
4
]Cl
2
l [Cu(H
2
O)
4
] + [CuCl
4
] + 4H
2
O
CuCl
2
CuCl byno. of reagents
2+
(iii)
2
(iv)
2+ 2
(v)
9
d & f - block
A
(a) CuCl
2
+ Cu-turnings 2CuCl
(b) 2CuCl
2
+ H
2
SO
3
+ H
2
O 2CuCl + 2HCl + 2H
2
SO
4
(c) 2CuCl
2
+ Zn/HCl 2CuCl + ZnCl
2
(d) CuCl
2
+ SnCl
2
CuCl + SnCl
4
** CuF
2
2H
2
Olight blue
CuCl
2
2H
2
Ogreen
CuBr
2
almost black
CuI
2
does not exist

Anh. CuCl
2
is dark brown mass obtained

by heating CuCl
2
2H
2
O at 150C in presence

of HCl vap.

50

HCl gas
CuCl
2
2H
2
O CuCl
2
+ 2H
2
O
CuSO
4
:
Preparation: CuO + H
2
SO
4
(dil) CuSO
4
+ H
2
O Cu(OH)
2
+
H
2
SO
4
(dil) CuSO
4
+ 2H
2
O Cu(OH)
2
CuCO
3
+
H
2
SO
4
(dil) CuSO
4
+ 3H
2
O + CO
2
1
Cu + H
2
SO
4
+
2
O
2
CuSO
4
+ H
2
O [Commercial scale]
(Scrap)
Cu + dil. H
2
SO
4
no reaction {Cu is a belowHin electrochemical series}
It is crystallised as CuSO
4
5H
2
O
Properties:(i)
(ii) CuSO
4
5H
2
O
Blue
CuSO
4
3H
2
O
Pale blue
CuSO
4
H
2
O
Bluish white take places
CuSO
4
(anh.)
white
(iii) Revisionwithall others reagent
11. IRON COMPOUNDS
FeSO
4
7H
2
O:
Preparation: (i) Scrap Fe + H
2
SO
4
FeSO
4
+ H
2
|
(dil.)
FromKipp's waste
FeS + H
2
SO
4
(dil) FeSO
4
+ H
2
S|
7
FeS
2
+ 2H
2
O +
2
O
2
FeSO
4
+ H
2
SO
4
(ii)
(iii)
Properties: (i)
It undergoes aerial oxidation forming basic ferric sulphate
4FeSO
4
+ H
2
O + O
2
4Fe(OH)SO
4
FeSO
4

h

gh
Fe O +SO +SO
300C
(ii) FeSO
4
7H
2
O

anh. white
2 3 2 3
temp.
(iii) Aq. solution is acidic due to hydrolysis
FeSO
4
+ 2H
2
O l Fe(OH)
2
+ H
2
SO
4
weak base
10
d & f - block
(iv) It is a reducing agent
(a) Fe
2+
+ MnO

+ H
+
Fe
3+
+ Mn
2+
+ H O
4 2
(b) Fe
2+
+ Cr O
2
+ H
+
Fe
3+
+ Cr
3+
+ H O
2 7
(c) Au
3+
+ Fe
2+
Au + Fe
3+
(d) Fe
2+
+ HgCl Hg Cl + + Fe
3+
2
2 2 2
white ppt.
(v) It forms double salt. Example (NH
4
)
2
SO
4
FeSO
4
6H
2
O
FeO(Black):
FeC O
A
FeO + CO + CO
Prep
n
:
2 4 2
in absence of air
Props: It is stable at high temperature and on cooling slowly disproportionates into Fe
3
O
4
and
iron
4FeO Fe
3
O
4
+ Fe
FeCl
2
:
Prep
n
:
h

eated

in

a current of HCl
OR
Fe + 2HCl FeCl + H
2 2
A
2FeCl
3
+ H
2
2FeCl
2
+ 2HCl
(i) It is deliquescent in air like FeCl
3
(ii) It is soluble in water, alcohol and ether also because it is sufficientlycovalent in nature
(iii) It volatilises at about 1000Cand vapour density indicates the presence of Fe
2
Cl
4
.
Above 1300Cdensity becomes normal
(iv) It oxidises onheating in air
12FeCl
2
+ 3O
2
2Fe
2
O
3
+ 8FeCl
3
(v) H
2
evolves on heating in steam
3FeCl
2
+ 4H
2
O Fe
3
O
4
+ 6HCl + H
2
(vi) It can exist as different hydrated form
FeCl
2
2H
2
O colourless
FeCl
2
4H
2
O pale green
FeCl
2
6H
2
O green
Props:
FeCl
3
:
Prep
n
: Anhydrous ferric chloride is prepared byheating metallic ironina streamof drychlorine gas.
(i) FeCl
3
solid is almost black. It sublimes at about 300C, giving a dimeric gas.
(ii) FeCl
3
dissolves in bothether and water, giving solvated monomeric species.
(iii) Iron (III) chloride is usuallyobtained as yellow-brown lumps of the hydrate FeCl
3
6H
2
O.
(iv) This isverysoluble inwater andis usedbothas anoxidizing agent, andas a mordant indyeing.
(v) FeCl
3
is also used in the manufacture of CCl
4
.
12. INNER TRANSITION ELEMENTS
The elements in which the additional electrons enters (n2)f orbitals are called inner transition elements.
The valence shell elect ronic configuration of these element s can be represent ed as
(n2) f
0,2...14
(n 1)d
0,1,2,
ns
2
. These are also called f-blockelements because the extra electron goes
to f-orbitals which belongs to (n2)th main shell. 4f-block elements are also called lanthanides or rare
earths. Similarly5f-block elements are called actinides or actinones. The name Lanthanides and actinides
have been given due to close resemblance with Lanthanum and actiniumrespectively. Lanthanides
constitutes the first inner transition series while actinides constitutes secondinner transition series.
11
d & f - block
General Characteristics:
1. Electronic Configuration
[Xe] 4f
n +1
5d
0
6s
2
or [Xe] 4f
n
5d
1
6s
2
Oxidation state: Theyreadilyform
M
+3
ionssome of themalso exhibit oxidationstate of +2 and +4.
Colouration: Ions of Lanthanides andactinides are coloured inthe solid state as well as inaqueous
2.
3.
solution because of absorbation of light due to ff transitionsince theyhave partly filled f-orbitals.
13. LANTHANIDE CONTRACTION
In lanthanides, the additional electron enters 4f-sub shell but not in the valence-shell namelysixth shell.
The shielding effect of one electron in4f-sub-shell by another in the same sub-shell is verylittle, being
even smaller thanthat of d-electrons, because the shape of f-sub shell is very much diffused, while there
is no comparable increase inthe mutual shielding effect of 4f-electrons. This results inthat electrons in the
outermost shell experience increasing nuclear attraction fromthe growing nucleus. Consequently the
atomic and ionic radii go on decreasing as we move fromLa
57
to Lu
71
.
Consequence of Lanthanide contraction
1. Atomic and ionic radii of post-Lanthanide elements: The atomic radii of second rowtransition
elements are almost similar to those ofthe third rowtransitionelement because the increase insize on
moving downthe group fromsecond to third transition elements is cancelled bythe decrease insize
due to lanthanide contraction.
High density of post lanthanide elements: It is because of very small size due to lanthanide
contraction.
Basic strength of oxides and hydroxides: Due to lanthanide contraction the decrease in size of
2.
3.
lanthanides ions, from to increases the covalent character (i.e. decreases the ionic
La
3+
Lu
3+
character) between Ln
+3
and OH

ions in Ln(III) hydroxides (Fajans rules). Thus La(OH) is the


3
most basic while Lu(OH)
3
is the best basic.
Similarly, there is a decrease inthe basic strength of the oxides.
Seperation of Lanthanides: Due to the similar size (Because of lanthanide contraction) of the
lanthanides, it is difficult to separate them. But slight variationintheir properties is utilizedto separate
4.
Consequences of Lanthanide Contraction
(i) Separationof Lanthanides. Separationoflanthanides is possibleonlydue tolanthanide contraction.
All the lanthanides have quite similar properties anddue to this reason theyare difficult to separate.
However, because of lanthanide contraction their properties (such as ability to formcomplexes)
varyslightly. This slight variationinproperties is utilized inthe separationof lanthanides byionexchange
methods.
(ii) Variation inbasic strength of hydroxides. The basic strength of oxides andhydroxides decreases
fromLa(OH)
3
to Lu(OH)
3
. Due to lanthanide contraction size of M
3+
ions decreases and there is
increase inthe covalent character inMOHbond.
(iii) Similarity of second and third transitionseries. The atomic radii of second rowof transition
elements are almost similar to those of the third rowof transition elements. For example, among the
elements of group 3, there is normal increase in size fromSc toYto La. But after lanthanides the
atomic radii fromsecond to third transitionseries do not increase as shown belowfor group 4 and
group 5 i.e., for Zr Hf andNbTa pairs which have element same atomic radii. After group 5 the
effect of lanthanide contraction is not so predominant.
12
d & f - block
5. Colour. The lanthanide metals are silverywhite metals and the trivalent lanthanide ions are coloured
both inthe solid state and inthe aqueous solution.
La
3+
(4f
0
) and Lu
3+
(4f
14
) having no unpaired electron do not show 6. Magnetic properties.
paramagnetism while all other tripositive ions of lanthanides are paramagnetic.
They have lowionisation energy and are highly electropositive. Their ionisation energy values are
quite comparable withthose of alkaline earth metals particularlycalcium.
These metals donot have much tendencyto formcomplexes.
The lanthanides are highlyreactive. Thisis inagreement withthe lowvalues oftheir ionisationenergies
and electronegativity.
7.
8.
9.
10. The solubilityof compoundsof lanthanides followthe same order as group 2elements. Their fluorides,
oxides, hydroxides, carbonates are insoluble inwater. However halides (except fluorides), nitrates,
acetates are soluble in water.
General Characteristics ofActinides 5f Block Series Second InnerTransition Series
1.
2.
These are silverywhite metals withhigh melting and boiling points.
Besides the most common oxidation state of +3, actinides show+4, +5 and +6 oxidation states in
certainelements.
All the actinides are radioactive in nature.
All the actinides are highlyelectropositive and as such are strong reducing agent.
Actinides have a strong tendency towards complex formation and formoxocations like UO
2
2
+
,
PuO
2
2+
, UO
+
etc.
Most of the cations of actinides are coloured.
Actinides showactinide contraction i.e., decrease inionic radii along the series.
3.
4.
5.
6.
7.
13
d & f - block
Ex.1 On what basis can you say that scandium
(Z = 21) is a transition element but since
(Z =30) is not.
On t he basis of i incomplet ely filled
3d - orbitals in case of scandium atom in its
ground state 3d
1
), it is regarded as a transition
element. On the other hand, zinc atom has
completelyfilled d- orbitals (3d
10
) in its ground
state as well as in its oxidised state, hence it is
not regarded as transition element.
(b) because Ce (IV) has extra stabilitydue to
empty f
0
orbital.
Ce
3+
Ce
4+
+ e

[Xe] 4f
1
5d
0
6s
0
Sol.
(c) In Mn
2+
d
5
configuration leas to extra
stability of half filled configuration , so Mn
2+
/
Mn
2+
(d
4
) tends to get converted to stable d
5
,
configuration of Mn
2+
, by accepting an electron
so Mn
3+
/Mn
2+
redox couple has more positive
potential than Fe
3+
/Fe
2+
(d
14
) couple.
(d) Due to more negative enthalpy of hydration
of Cu (aq) than Cu (aq) which compensates
or second ionizationenthalpyof copper.
(e) In the third transition series after lanthanum
their is lanthanoid contraction due to ineffective
shielding by intervening f-orbital electrons and
hence second and third transition series
elements have similar atomic radii.
Ex.2 What is the effect of increasing pHon K
2
Cr
2
O
7
solution?
In aqueous solution, we have
2+
+
Sol.
Cr
2
O
7
+ H
2
O
2
2CrO
4
+ 2H .
2 +
When pH < 4 (acidic medium), it exists as
Cr
2
O
7
and the colour is orange.
When pH> 7 (basic medium), it exists as
CrO
4
and the colour is yellow.
What is the basic difference between the
electronic configurations of transitionandinner
transitionelements.
General electronic configuration of transition
element = [ Noblegas] (n 1) d
110
ns
12
and
for inner transition elements
= (n 2) f
114
(n 1)d
01
ns
02
. Thus , in transition
elements, last electron enters d-orbitals of the
penultimate shelll while in inner transition
elements, it enters f- orbital of the penultimate
shell.
2
2
Ex.5 Whyis Cr
2+
reducing andMn
3+
oxidising when
both have d
4
configuration?
Cr
2+
is reducing as its configuration changes
formd
4
to d
3
, the later has half filled t level.
Ex.3
Sol.
2g
Againthe change fromMn
2+
to Mn
3+
results in
the half filled (d
5
) configurationwhichhas extra
stability.
Sol.
Ex.6
Sol.
Cu
+
ionis not stable inaqueous solution. Why?
Cu
2+
(aq) is much more stable than Cu
+
(aq).
This is because although second ionization
enthalpyof copper is large but A
Hfor Cu
2+
hyd
(aq) is much more negative than that for Cu
+
(aq) and therefore it more than compensates
for the second ionization enthalpy of copper.
Thus many copper (I) compounds ar unstable
in aque o us so lu t io n and und er go es
disproportional as follows.
2Cu
+
(aq) Cu
2+
(aq) + Cu(s)
Ex.4 Give reasons for the following
(a) Transition metals have high enthalpies of
atomizations.
(b) Among the lathanoids, Ce(III) is easily
oxidised to Ce (IV)
(c) Fe
3+
| Fe
2+
redox couple has less positive
electrode potential thanMn
3+
| Mn
2+
couple.
(d) Copper (I) has configuration , still
copper (II) has d
9
configurationstill copper (II)
is more stable inaqueous solutionthancopper
(I).
(e) The second and third transition series
elements have almost similar atomic radii.
(a) Due to strong interatomic interaction
between valence electrons.
d
10
Ex.7 Why is the E value for the M
3+
/ M
2+
couple
much more positive than that of Cr
3+
/Cr
2+
or
Fe
3+
/Fe
2+
? Explain.
Much larger third ionization energy of Mn
(Where the required change is d
5
tod
4
) is mainly
responsible for this. This also explains whythe
+3 state of Mn is of little importance.
Sol.
Sol.
14
SOLVEDEXAMPLES
d & f - block
Ex.8 Why does Mn (II) ion show the maximum Q.13 Arranged the following inincreasing order of
acdic character:
CrO , CrO, Cr O
paramagnetic behvavious among bivalent ions
of the first transition series.?
The electronic configurations of Mn and Mn
(II) ionare
25
Mn : 1s 2s 2p 3s 3p 3d 4s ,
Mn
+2
: 1s
2
,2s
2
2p
6
3s
2
3p
6
3d
2
4s
0
The Mn
+2
ion has five unpaired electrons in its
3d subshell which is the maximumvalue for a
transition metal ion. Hence, Mn (II) shows the
maximum paramagnetic behaviour (due to
unpaired electrons) among bivalent ions of the
first transition series.
2
CrO< Cr O <
3 3
Sol.
Sol. CrO . Higher the oxidation
2 3
e
3
dic character. state , mor will be ac
2 2 6 2 6 2 2
Q.14 In the series Sc (Z = 21) to Zn (Z = 30), the
enthalpy of atomization of zinc is the lowest,
i.e. 125 kJ mol
1
. Why?
In theformation of metallic bond, no electrons
from3d-orbitals are involved in case of zinc
while in all other metals of the 3d series,
electrons from the d-orbitals are always
involvedintheformationofmetallicbonds. That
is why, the enthalpy of atomisation of zinc is
the lowest in the series.
Sol.
Ex.9 K
2
[PtCl
6
] is a will known compound whereas
the corresponding Nicompound is not known.
State reasonfor it.
The oxidation state of Pt in K
2
[PtCl
6
] is +4,
whichis a stable oxidation state for Pt. The +4
oxidation statefor Ni is verydifficult to achieve
because the sum of the first four ionization
energies is veryhigh. Hence, the corresponding
Ni (II) compound is not formed.
Sol.
Q.15 In transitionseries, with an increase inatomic
number, the atomicradius doesnot change very
much . Whyis it so?
With increase in atomic number along a
transition series the nuclear charge increases
which tends to decrease the size of the atom.
But the addition of electrons inthe d subshell
increases the screening effect which
counterbalances the increased nuclear charge.
Hence alonga transitionseries theatomic radius
does not very much.
Sol.
Ex.10 What is mean by disproportionation of an
oxidation state? Give anexample.
Whena particular oxidationstate becomes less
stable relative to other oxidation states, one
loser one higher, it is said to undergo
disproportionation. For example manganese
(VI) becomes unstable relative to managanese
(VII) and manganese (IV) in acidic solution.
3Mn
VI
O
2
+ 4H
+
Sol.
Q.16 Account for the following :
(i) Cerium(atomic number =58) forms tetra
positive , Ce
4+
inaqueous solution.
(ii) The second and third members in each
group of transitionelement have similar atomic
radii.
(i) The electronic configuration of Ce (Z=58)
is Ce = [Xe]4f
1
5d
1
6s
2
4
2Mn
VII
O

+ Mn
IV
O + 2H O
4 2 2
Ex.11 Whichmetalinthefirst seriesoftransitionmetals
exhibits +1 oxidationstate most frequencyand
why?
Copper metal (Cu, Z=29) show+1oxidation
state, i.e. exists as Cu
+
in large number of
copper compounds .e.g. cuprous oxide
(Cu
2
O), cuprous sulphide (Cu
2
S), cuprous
chlor ide ( Cu
2
Cl
2
) et c. The elect r onic
configuration Cu
+
is [Ar] 3d
10
4s
0
.
All the five 3dorbitals are fullyfilled therefore
this is a verystable configuration.
Whyis Ti
+2
ionparamagnetic in nature?
Ti
+2
is paramagnetic because of the presence
of two unpaired electrons in 3d-orbitals.
Sol.
Sol.
58
C umcan lose four electrons (4f
1
eri 5d 6s ) in
1 2
aqueous solutiontoacquire stableconfiguration
of rate gas xenon. Moreover due to small size
and high charge , Ce
4+
ionhas high hydration
energy.
(ii) The second and third members in each
group of transition elements have very similar
atomic radii due to lanthanoid contration. It
arises due to poor shielding effect of Af
electrons.
Ex.12
Sol.
22
Ti :
Ti
+2
:
1s 2s 2p 3s 3p 3d 4s ,
2 2 6 2 6 2 2
1s
2
,2s
2
2p
6
3s
2
3p
6
3d
2
4s
0
15
d & f - block
Ex.17 For the first rowtransition metals the E values are:
E V Cr
0.91
Mn
1.18
Fe
0.44
Co
0.28
Ni
0.25
Cu
+0.34 (M
2
+ /M) 1.18
Explain the irregularityin the above values.
The E (M
2+
/M) values are not regular whichcan be explained fromthe irregular variation of ionisation
entthalpies (AH+AH ) andalos the sublimation enthalpies which are relativelymuchless for maganese
Sol.
i l i 2
and vanadium.
Ex.18
Sol.
The E (M
2+
/M) value for coppers is positive ( +0.34V), What is possiblythe reasonfor this ?
E (M
2+
/M) for anymetal is related to the sumof the enthalpychange taking place inthe following steps:
M(s) + A H M(g)
M
2+
(g)
M
2+
(aq) + D H
(A H=Enthalpyof atomisation)
a
M(g) + AH
a
(A H=Ionization enthalpy)
i
M
2+
(g) + aq
a
(A H=Hydration enthalpy)
hyd hyd
Copper has high enthalpyof atomisation and lowenthalpy of hydration . So E (Cu
2+
/Cu) is positive.
The high energy to transformCu(s) to Cu
2+
(aq) is not balanced by it s hydration enthalpy.
Ex.19 (a) Complete the following chemical equation of for reactions:
(i) MnO

(aq) + S O
2
(aq) + H O(l)
4 2 3 2
(ii) CrO

(aq) + H (g) + H
+
(aq)
7 2
(b) Give anexplanation for each of the following observation:
(i) The gradual decrease insize (actinoid contraction) fromelement to element is greater among the
actionod is thanthat among the lanthanoids (lanthanoids contraction).
(ii) The greatest number of oxidation states are exhibited bythe members in the middle of a transi-
tion series.
(iii) With the same d- orbital configuration (d
4
) Cr
2+
ion is a reducing agent but Mn
3+
ion is an
oxidisngagent.
Sol. (a) (i) In neutral or faintlyalkaline solutions
MnO

+ 2H O + 3e

MnO + 2H P + 4O

H] 8
4 2 2 2
S O
2
+ 10O

H 2SO
2
+ 5H O + 8e

] 3
2 3 4 2
8Mn O
2
+ 10O

H + H O 8 MnO + 6SO
2
+ 2O

H
3 2 2 4
(ii) In acidic solutions
Cr O
2
+ 14H
+
+ 6e

2Cr
3+
+ 7H O
2 7 2
H S S + 2H
+
+ 2e

] 3
2
Cr O
2
+ 3H S+ 8H
+
2Cr
3+
+ 3S + 7H O
2 7 2 2
(b) (i) This due to poor shielding by 5f electrons from element to element in actinoid than by 4f
electrons inlanthanoids series.
This is due to involvement of both (n1) d and ns electrons in bonding, which are unpaired in
maximumnumber at the middle of series.
(ii)
(iii) Cr
2+
has the configuration d
4
and easily changes to Cr
3+
which has half t configuration and
2g
hence move stable. Therefore Cr
2+
is reducing. On the other hand, the change fromMn
3+
to
Mn
2+
results inthe halffilled, d
5
configurationwhichhasextrastability. Therefore Mn
3+
inoxidising.
16
d & f - block
Ex.20 (a) Complete the following chemical reaction equations:
(i) MnO

(aq) + C O
2
(aq) + H
+
(aq)
4 2 4
(ii) Cr O
2
(aq) + F
2+
(aq) + H
+
(aq)
2 7
(b) Explainthefollowing observation about the transition/inner transition elements:
(i) There is general an increase in densityof element formtitanium(Z=22) to copper (Z= 29).
(ii) There occurs much more frequent metal-metal bonding in compounds of heavy transition
elements (3
rd
series).
(iii) the members in the actinoid series exhibit a large number of oxidation states than the
corresponding members inthe lanthanoid sereis.
Sol. (a) (i) Inacidic medium:
MnO

+ 8H
+
+ 5e

Mn
2+
+ 4H O] 2
4 2
C O
2
2CO + 3e] 5
2 4 2
2MnO

+5C
2
+ 16H
+
2M
2+
+ 10 CO + 5H O
4 4 n 2 2
(ii) In acidic medium
Cr O
2
+ 14H
+
+ 6e

2Cr
3+
+ 7H O
4 7 2
Fe
2+
Fe
3+
+ e

] 6
Cr O
2
+ 6Fe
2+
+14H
+
2Cr
3+
+ 6Fe
3+
+ 7H O
4 7 2
(b) (i) Onmoving fromtitaniumto copper in general atomic mass increases where as atomic size
decreases, therefore densityincreases in general
(ii) The frequent metal-metal bonding incompounds of heavytransition elements is due to their
highenthalpyof atomization.
(iii) Thisisduetoverysmall energygap between5f, 6dand7sorbitalsintheactinoidsseries.
Ex.21 Complete the followingchemical reaction equations:
(i)
(ii)
(i)
MnO

(aq) + C O
2
(aq) + H
+
(aq)
4 2 4
Cr O
2
(aq) + Fe
2+
(aq) + H
+
(aq)

2 7
MnO

+ 8H
+
+ 5e

Mn
2+
+ 4H O] 2 Sol.
4
2
2
2CO +2e

] 5 C O
2 4 2
2MnO

+ 5C O
2
+ 16 H
+
2Mn
2+
+ 10CO + 8H O
4 2 4 2 2

(ii) Cr O
2
+14H
+
+ 6e

2Cr
3+
+ 7H O
2 7
Fe
2+
2
Fe
3+
+e

] 6
Cr O
2
+ 6F
2+
+ 14H
+
2Cr
3+
+6Fe
3+
+ 7H O
2 7 2
17
Electronic
Element Possible O.S. More Stable O.S.
conf iguration
3d
2
4s
2
Vanadium + 2, +3, + 4, + 5
+5
3d
5
4s
2
Manganese + 2, +3, + 4, + 5,
+2+7
3d
6
4s
2
Iron + 2, +3, + 4, +6,
+2+3
d & f - block
Ex.22 (a) What may be the possible oxidation states of the transition metals with the following d-electronic
configuration inthe ground state oftheir atoms.
3d
3
,s
2
,3d
5
,4a
2
and 3d
6
4s
2
. Indicate relative stability of oxidation states in each case.
(b) Write steps involved in the preparation of
(i) Mn CrO fromchromite ore and
2 4
K MnO frompyrolusite ore. (ii)
2 4
Sol. (a)
(b) (i) Chromite ore is fused with sodiumcarbonate inexcess of air.
4FeCr O + 8Na CO + 7O 8Na CrO + 2Fe O + 8CO
2 4
chromite ore
2 3 2 2 4
Sod. chromate
2 3 2
(ii) Pyrolusite ore (MnO ) is fused with KOH in the presence of O or oxidising agent such as
2 2
KNO .
3
2MnO + 4KOH + O 2K MnO + 2H O
2
Pyrolusite ore
2 2 4
Postassium magnate
2
18
d & f - block
Why are Mn
2+
compounds more stable than
Fe
2+
towards oxidation to their +3 state?
Q.11 Explainthefollowing observations :
(a) The elements of the d-series exhibit a larger
number of oxidation sates than the elements of
f-series.
(b) The Cu
+
salts are colurless while Cu
2+
salts
are coloured.
Q.1
Q.2 Write complete equation for
Oxidationof Fe
2+
byCr O
2
inacidic medium.
2 7
Q.3 Answer thefollowing questions:
(i) Whichelement inthe first series of transition
elements does not exhibit variable oxidation
states and why ?
(ii) Whydo actinoids, ingeneral exhibit a greater
range of oxidationstates thanthelanthanoids ?
Q.12 Mention the direct consequence of the
following factors on the chemical behavior of
the transitionelements :
(i) They have incompletely d-orbitals in the
ground state or in one of the oxidised states of
their atoms.
(ii) Theycontribute more valence electrons per
atominthe formation of metallic bonds.
Q.4 Explain briefly how +2 state becomes more
and more stable in the first half of the first row
transition elements with increasing atomic
number? Q.13 What are the characteristics of the transition
elements and why are they called transition
elements? Which of the d-block elements may
not be regarded as the transition elements?
Q.5 Write chemical equations for the reactions
involved in the manufacture of potassium
permanganate frompyrolusite ore.
Q.14 How would you account for the following
situations ?
(i) the transitionmetals generallyformcoloured
compound .
Q.6 What is misch metal ? Mention its two
important uses.
(ii) With 3d
4
configuration, Cu
2+
acts as a Q.7 To what extent do the electronic configurations
decide the stability of oxidation states in the
first series of the transition elements? Illustrate
your answer with examples.
reducing agent but Mn
3+
acts asoxidizingagent
(iii) The actinides exhibit a larger number of
oxidation states than the corresponding
lanthanides.
Q.8 (a) Name two properties of the central metal
ion which enable it to form stable complex
entities.
(b)Account for the following : Zinc salts are
while Cu
2+
salts are coloured.
Q.15 Howwouldyou account for the following :
(i) The transition elements have high enthalpies
of atomisation.
(ii) The transition metals and their compounds
are found to be good catalysts in many
processes. Q.9 Howdo you account for the following :
(a)All scandiumsalts are white ?
(b) The first ionization energies of the 5d
transition elements are higher than those of the
3d and 4d transition elements in respective
groups ?
Q.16 Explaingiving reasons:
(i) Transition metals and many of their
compounds showparamagnetic behaviour.
(ii) The enthalpies of atomisation of the
transition metals are high.
(iii) The transition metals generally form
coloured compounds.
(iv) Transit ion met als and their many
compounds act as good catalyst.
Q.10 What maybe the stable oxidation state of the
transitionelement withthe followingdelectron
configurations inthegroundstate oftheir atoms
: 3d
3
, 3d
5
, 3d
8
and 3d
4
?
19
EXERCISE- I
d & f - block
Q.17 Give reasons for each of the following :
(i) Size of trivalent lanthanoid cations decreases
with increase inthe atomic number
(ii) transition metal fluorides are ionic nature,
whereas bromides and chlorides are usually
covalent innature.
(iii) Chemistry of all the lanthanoids is quite
similar.
Q.24 Use Hunds rule to derive the electronic
configuration of Ce
3+
ion, and calculate its
magnetic moment on the basis of spin-only
formula.
Describe the preparation of potassium
dichromate fromironchromite ore. What is the
effect of increasing pH on a solution of
potassiumdichromate?
Q.25
Q.18 Discuss the general characteristics of the 3d
series of the transition elements with special
reference to their.
(i) atomic sizes,
(ii) enthalpies of atomisation
(iii) tendencyfor complexformation.
Q.26 Assign reasonfor the following :
(i) The enthalpies of atomisation of transition
metals are high.
(ii) The transition metals and many of their
compounds act as catalysts.
(iii) From element to element, the actinides
contraction is greater than lant hano id
contraction.
(iv) The E value for Mn
3+
/Mn
2+
couple is much
more positive thanthat for Cr
3+
/Cr
2+
.
(v) Scandium(Z=21) does not exhibit variable
oxidation states and yet it is regarded as
transition element.
Q.19 Predict whichof the following will be coloured
in aqueous solution? Ti
3+
, V
3+
, Cu
+
, Sc
3+
,
Mn
3+
, Fe
3+
and Co
3+
. Give reasons for each.
Q.20 Write down electronic configuration of the
following below:
(a) La
3+
(c) Eu
2+
(e) Ru
2+
(b) Gd
3+
(d) Zn
4+
(f) Ce
4+ Q.27 Describe the oxidising action of potassium
dichromate and write the ionic equations for
its reaction with:
(i) iodide (ii) iron(II) solution and (iii) H
2
S
(a) Describe the general trends in the following
properties of the first series of the transition
elements :
(i) Stability of +2 oxidation state (ii) Formation
of oxometal ions.
(b)Assignreason for each of the following :
(i) Transition elements exhibit variable oxidation
states.
(ii) Transition metal ions are usuallycoloured
(a) Write the steps involved in the preparation
of:
(i) K Cr O fromNa CrO
Q.21 What are alloys? Name an important alloy
whichcontains some of the lanthanoid metals.
Mention its uses.
Q.28
Q.22 (a) Give one example each of amphoteric and
acidic oxides of transition metals.
(b) Describe the trends in the following cases:
(i) Meltingpoints of elements inthe3dtransition
series.
(ii) Atomic sizes of elements inthe 4f transition
series.
Howwouldyou account for the following ?
(i) Sc, the first member of first transition series
does not exhibit variable oxidation state.
(ii) K
2
PtCl
6
is well-known compound whereas
corresponding compound of nickel is not
known.
(iii) Only transition metals for complex
compounds with ligands suchas CO.
Q.23
Q.29
2 2 7
fromK
2 4
nO (ii) KMnO
4 2
M
4
(b) What is meant bylanthanoid contraction ?
What effect does it have onthe chemistry of
the elements whichfollowlanthanoids ?
Q.30 For same of first rowof trnasition elements the E values are :
Give suitable explanationfor the irregular treand in these values.
20
V Cr Mn Fe Co Ni Cu
1.18V 0.91V 1.18V 0.44V 0.28V 0.25V + 0.34V
d & f - block
Q.1 Explainwhythegreenishsolutionof potassium
manganate turns purple when CO
2
is bubbled
in the solution.
Q.11 Acomplex has the formula Pt Cl
4
.2KCl. The
electrical conductance of the compound shows
that each formula unit has 3 ions. AgNO
3
on
treatment with the complex does not give a
precipitate ofAgCl. What should be the correct
formula of the complex?
Q.2 Explainwhymercurous compounds areformed
when mercury is oxidised in a limited amount
of an oxidising agent whereas with an excess
of oxidising agent mercuric compounds are
formed.
Q.12 [Ni Cl
4
] and [Ni (CO)
4
] both are tetrahedral
inshapebut [Ni Cl
4
] is paramagnetic whereas
[Ni(CO)
4
] is diamagnetic. Explain the
difference in magnetic behaviour of both the
complexes.
2
2
Q.3 Explain why [Co(NH
3
)
6
] is diamagnetic and
[CoF
6
] is strongly paramagnetic.
What happens when NaOH or NH
4
OH are
added in excess toAlCl
3
and ZnCl
2
?
3+
3
Q.13 FeSO
4
solution is mixed with (NH
4
)
2
SO
4
in
the molar ratio 1:1. It gives test of Fe . When
CuSO
4
is mixed with liquid ammonia (in the
ratio 1:4) the mixture does not give test of Cu
2+
.
Explain the difference.
Q.4
2+
Q.5 Whyis zinc oxide used inpaints instead of lead
salts?
Q.6 Identify from[A] to [E]. Q.14 (A), (B), and (C) are three complexes of
Cr(III). Its formula is H
12
O
6
Cl
3
Cr. All the three
complexes have water and chloride ions as
ligands. (A) does not react withconc. H SO
NaOH
Colourless salt [A]
+ Ag NO
3
[E] white
precipitate
[B] (white precipitate)
dissolves in NaOH
2 4
whereas (B) and (C) lose 6.75%and 13.5%
of their original weight respectivelyontreatment
with conc. H
2
SO
4
. Find [A], [B], and [C].
A metal complex having composition Cr
(NH
3
)
4
Cl
2
.Br. has been isolated in two forms
(A) and (B). (A) reacts with AgNO
3
to give a
whiteprecipitatesolubleindiluteammoniawhile
(B) gives a pale yellow precipitate soluble in
concentrated ammonia. Write the formulae of
(A) and (B) and hybridisation state of Cr in the
compounds.
[C]
Pass H
2
S
[D] (white precipitate)
Q.15
Q.7 Why are melting and boiling points of zinc,
cadmium, and mercury lower than those of
other transition metals?
Q.8 Why is HCl not used to acidify KMnO
4
for
volumetric estimations?
? Q.9 Colourless salt (A) (B) + (C) gas.
(B) dissolves both in acid and alkali solution.
(C) turns lime water milky and acidified
K
2
Cr
2
O
7
solution green.
(A) gives white precipitate (D) with H
2
S when
the solutionis alkaline. Identify[A] to [D].
Q.16 Amonomeric compound of cobalt gives the
following data on quantitative analysis:
Co
3+
: 21.24%; NH : 24.77%; Cl

: 12.81%;
3
SO
2
: 34.65%; H O: 6.53%.
4 2
Deduce the empiric l formula of the complex a
and the possible isomers.
Q.10 (a) K
2
MnO
4
in acidic medium changes to
MnO
2
and KMnO
4
. What would be the
equivalent weight of K
2
MnO
4
.
(b) Drawthe structures of MnO
4
and CrO
4
ions.
2
21
EXERCISE- II
d & f - block
Single Correct Questions
Q.8 During estimation of oxalic acid Vs KMnO
4
,
self indicator is
Q.1 The number of moles of acidified KMnO
4
required to convert one mole of sulphite ion
into sulphate ionis
(A) KMnO
4
(C) K
2
SO
4
(B) oxalic acid
(D) MnSO
4
(A) 2/5
(C) 4/5
(B) 3/5
(D) 1
Q.9 Acompound of mercury used in cosmetics, in
Ayurvedic andYunani medicines and known
as Vermilon is
Q.2 N
2
( g) + 3H
2
( g)
Habers process, Mo is used as
(A) a catalyst
(B) a catalytic promoter
(C) anoxidising agent
(D) as a catalytic poison
2NH
3
( g) ; (A) HgCl
2
(C) Hg
2
Cl
2
(B) HgS
(D) HgI

Org.

.solvent

Q.10 Acidified chromic acid +H O


2 2
X +Y, XandYare
(A) CrO
5
and H
2
O
(C) CrO
2
and H
2
O
(B) Cr
2
O
3
and H
2
O
(D) CrOand H
2
O
O
2
2CrO
2
, X and Y are Q.3 Cr
Q.11 Transition elements are usually characterised
by variable oxidation states but Zn does not
showthis property because of
(A) completion of np-orbitals
(B) completion of (n1)d orbitals
(C) completion of ns-orbitals
(D) inert pair effect
2 7 4
respectively
(A) X = OH

, Y= H
+
(B) X = H
+
, Y= OH

(C) X = OH

, Y= H O
2 2
(D) X = H
2
O
2
, Y= OH

Q.4 CrO
3
dissolves in aqueous NaOHto give
Q.12 (NH ) Cr O (Ammoniumdichromate) is used
4 2 2 7
in fire works. The green coloured powder
blown in air is
(A) Cr
2
O
7
2
(B) CrO
4
2
(C) Cr(OH)
3
(D) Cr(OH)
2
(A) Cr
2
O
3
(C) Cr O
(B) CrO
2
(D) CrO
Q.5 Anornamental of gold having 75%of gold, it
is of .............. carat.
2 4 3
(A) 18
(C) 24
(B) 16
(D) 20
Q.13 The d-block element whichis a liquid at room
temperature, having high specific heat, less
reactivitythanhydrogenandits chloride (MX
2
)
is volatile onheating is

Q.6 Solution of MnO


4
is purple-coloured due to
(A) d-d-transition
(B) charge transfer fromOto Mn
(C) due to both d-d-transition and charge
transfer
(D) none of these
(A) Cu
(C) Ce
(B) Hg
(D) Pm
Q.14 Coinage metals showthe properties of
(A) typical elements
(B) normal elements
(C) inner-transition elements
(D) transition element
Q.7 Transition elements having more tendency to
formcomplex than representative elements
(s and p-block elements) due to
(A) availabilityof d-orbitals for bonding
(B) variable oxidation states are not shown by
transition elements
(C) all electrons are paired in d-orbitals
Q.15
Iron becomes passive by ..................... due
to formation of .....................
(A) dil. HCl, Fe O
2 3
(B) 80% conc. HNO , Fe O
3 3 4
(C) conc. H SO , Fe O
2 4 3 4
(D) f-orbitals are available for bonding (D) conc. HCl, Fe
3
O
4
22
EXERCISE- III
d & f - block
Q.16 Bayers reagent usedto detect olifinic double
bond is
(A) acidified KMnO
4
(B) aqueous KMnO
4
(C) 1%alkaline KMnO
4
solution
(D) KMnO
4
in benzene
The transition metal used in X-rays tube is
Q.23 1 mole of Fe
2+
ions are oxidised to Fe
3+
ions
with the help of (in acidic medium)
(A) 1/5 moles of KMnO
4
(B) 5/3 moles of KMnO
4
(C) 2/5 moles of KMnO
4
(D) 5/2 moles of KMnO
4
The metals present ininsulin andhaemoglobin
are respectively
Q.24
Q.17
(A) Mo
(C) Tc
(B) Ta
(D) Pm
(A) Zn, Hg
(C) Co, Fe
(B) Zn, Fe
(D) Mg, Fe
Q.18 Cu + conc. HNO
3
Cu(NO
3
)
2
+ X(oxide
of nitrogen); then Xis
Q.25 Therustingof ironis formulatedas Fe O xH O
2 3 2
whichinvolves the formation of
(A) N
2
O
(C) NO
(B) NO
2
(D) N
2
O
3
(A) Fe O (B) Fe(OH)
2 3 3
(C) Fe(OH) (D) Fe O +Fe(OH)
2 2 3 3
Q.19 When KMnO
4
solution is added to hot oxalic
acid solution, the decolourisation is slowinthe
beginning but becomes instantaneous after
some time. This is because
(A) Mn
2+
acts as auto catalyst
(B) CO
2
is formed
(C) Reactionis exothermic
(D) MnO
4
catalyses the reaction.
CuSO
4
solution reacts with excess KCN to
give
Q.26 Metre scales are made-up of alloy
(A) invar
(C) elektron
(B) stainless steel
(D) magnalium
Q.27 Ametal Mwhichis not affectedbystrongacids
like conc. HNO
3
, conc. H
2
SO
4
and conc.
solution of alkalies like NaOH, KOH forms
MCl
3
whichfindsuse for toninginphotography.
The metal Mis

Q.20 (A)Ag
(C)Au
(B) Hg
(D) Cu
(A) Cu(CN)
2
(C) K
2
[Cu(CN)
2
]
(B) CuCN
(D) K
3
[Cu(CN)
4
]
Q.28 Solid CuSO
4
5H
2
Ohaving covalent, ionic as
well as co-ordinate bonds. Copper atom/ion
forms ................. co-ordinate bonds with
water.
Q.21 The higher oxidation states of transition
elements are found to be in the combination
withAand B, which are
(A) 1
(C) 3
(B) 2
(D) 4
(A) F, O
(C) O, Cl
(B) O, N
(D) F, Cl
KMnO
4
+ HCl H
2
O + X(g), X is a
(acidified)
(A) red liquid
(B) violet gas
(C) greenish yellowgas
(D) yellow-brown gas
Q.29
Q.22 Pick out the incorrect statement:
(A) MnO
2
dissolves in conc. HCl, but does
not formMn
4+
ions
(B) MnO
2
oxidizes hot concentrated H
2
SO
4
liberating oxygen
(C) K
2
MnO
4
is formed when MnO
2
in fused
KOH is oxidised by air, KNO
3
, PbO
2
or
NaBiO
3
(D) Decomposition of acidic KMnO
4
is not
catalysed bysunlight.
Q.30 Purple of cassius is:
(A) Pure gold
(B) Colliodal solution of gold
(C) Gold(I) hydroxide
(D) Gold (III) chloride
23
d & f - block
Q.31 Amongst the following species, maximum
covalent character is exhibited by
Multiple Correct Question
Q.38 Potashalumisadoublesalt, itsaqueous solution
shows the characteristics of
(A) FeCl
2
(C) HgCl
2
(B) ZnCl
2
(D) CdCl
2
(A) Al
3+
ions
2
(B) K
+
ions
(C) SO
4
ions
(D)Al
3+
ions but not K
+
ions
Q.32 Number of moles of SnCl
2
required for the
reduction of 1 mole of K
2
Cr
2
O
7
into Cr
2
O
3
is
(in acidic medium)
Q.39 Addition of non-metals like B and C to the
interstitial sites of a transition metal results the
metal
(A) of more ductability (B) of less ductability
(A) 3
(C) 1
(B) 2
(D) 1/3
Q.33 The aqueous solution of CuCrO
4
is green
because it contains
(A) green Cu
2+
ions
(B) green CrO
4
ions
(C) blue Cu
2+
ions and green CrO
2
ions
(C) less malleable (D) of more hardness
Q.40 Mercury is a liquid at 0Cbecause of
(A) veryhigh ionisation energy
(B) weak metallic bonds
(C) highheat of hydration
(D) highheat of sublimation
2
4
(D) blue Cu
2+
ions and yellow CrO
2
ions
4
Q.34 Manganese steel is used for making railway
tracks because
(A) it is hard with high percentage of Mn
(B) it is soft with highpercentage of Mn
(C) it is hard with small concentration of
manganese withimpurities
(D) it is soft with small concentration of
manganese withimpurities
Q.41 The ionisation energies of transition elements
are
(A) less than p-block elements
(B) more than s-block elements
(C) less than s-block elements
(D) more than p-block elements
Q.42 The metal(s) whichdoes/do not formamalgam
is/are
Q.35 In nitroprusside ion, the ironexists as Fe
2+
and
NO as NO
+
rat her than Fe
3+
and NO
(A) Fe
(C) Zn
(B) Pt
(D)Ag
respectively. These formsofionsareestablished
with the help of
(A) magnetic moment in solid state
(B) thermal decomposition method
(C) by reaction with KCN
(D) byaction with K
2
SO
4
Transition elements inlower oxidation states
act as Lewis acid because
(A) theyformcomplexes
(B) theyare oxidising agents
(C) theydonate electrons
(D) they do not showcatalytic properties
Q.43 The highest oxidation state among transition
elements is
(A) + 7 by Mn
(C) + 8 by Ru
(B) + 8 by Os
(D) + 7 by Fe
Q.44 Amphoteric oxide(s) is/are
Q.36
(A) Al
2
O
3
(C) ZnO
(B) SnO
(D) Fe
2
O
3
Q.45 Interstitial compounds are formed by
(A) Co
(C) Fe
(B) Ni
(D) Ca
Q.37 The Ziegler-Natt a cat alys t used for
polymerisation of ethene and styrene is TiCl
4
+
(C
2
H
5
)
3
Al, the catalysing species (active
species) involved inthe polymerisation is
Q.46 The catalytic activityof transition elements is
related to their
(A) variable oxidation states
(B) surface area
(C) complexformation ability
(D) magnetic moment
(A) TiCl
4
(C) TiCl
2
(B) TiCl
3
(D) TiCl
24
d & f - block
Q.47 In the equation: M+8CN

+2H O+O
Statement Type Question
2 2
4[M(CN)
2
] + 4OH , metal M is

Questions given below consist of two
statements each printed as Assertion (A) and
Reason (R); while answering these questions
you are required to choose any one of the
following four responses:
(A) if both (A) and (R) are true and (R) is the
correct explanationof (A)
(B) if both (A) and (R) are true but (R) is not
correct explanationof (A)
(C) if (A) is true but (R) is false
(D) if (A) is false and (R) is true
Statement-1: K CrO has yellowcolour due
(A)Ag
(C) Cu
(B)Au
(D) Hg
Q.48 An element of 3d-transition series shows two
oxidation states x and y, differ bytwo units then
(A) compounds in oxidation state x are ionic if
x > y
(B) compounds in oxidation state x are ionic if
x < y
(C) compounds inoxidationstate yare covalent
if x < y
(D) compounds inoxidationstate yare covalent
if y< x
Q.56
2
to charge transfer
4
.
Statement-2: CrO
2
ion is tetrahedral in Q.49 To anacidified dichromate solution, apinchof
Na
2
O
2
is added and shaken. What is observed:
(A) blue colour
(B) Orange colour changing to green
(C) Copious evolution of oxygen
(D) Bluish- green precipitate
4
shape.
Q.57 Statement-1: The highest oxidation state of
chromiuminits compounds is +6.
Statement-2: Chromiumatomhas onlysix
electrons in ns and (n1) d orbitals.
Q.50 Amongst CuF
2
, CuCl
2
and CuBr
2
(A) only CuF
2
is ionic
(B) both CuCl
2
and CuBr
2
are covalent
(C) CuF
2
and CuCl
2
are ionic but CuBr
2
is
covalent
(D) CuF
2
, CuCl
2
as well as CuBr
2
are ionic
CuSO
4
(aq) + 4NH
3
X, then Xis
Q.58 Statement-1 :
meltingpoint.
Statement-2 :
compound.
Tungsten has a very high
Tungsten is a covalent
Q.51
Q.59 Statement-1: Equivalent mass of KMnO is
(A) [Cu(NH
3
)
4
]
2+
4
equal to one-third of its molecular mass w n he
(B) paramagnetic
(C) coloured
(D) of a magnetic moment of 1.73 BM
it acts asanoxidisinggent inanalkaline medium.
Statement-2:
in KMnO
4
.
Statement-1:
Statement-2:
Oxidationnumber of Mnis +7
Q.52 Amphoteric oxide(s) of Mn is/are
(A) MnO
2
(C) Mn
2
O
7
(B) Mn
3
O
4
(D) MnO
Q.60 Cu ionis colourless.
+
Four water molecules are
coordinated to Cu
+
ion.
Q.53 Acidified KMnO
4
can be decolourised by
(A) SO
2
(C) FeSO
4
(B) H
2
O
2
(D) Fe
2
(SO
4
)
3
Q.54 The lanthanide contraction is responsible for
the fact that
(A) Zr and Hf have same atomic sizes
(B) Zr and Hf have same properties
(C) Zr and Hf have different atomic sizes
(D) Zr and Hf have different properties
Ion(s) havingnonzero magnetic moment (spin
only) is/are
Q.55
(A) Sc
3+
(C) Cu
2+
(B) Ti
3+
(D) Zn
2+
25
d & f - block
EXERCISE - II

Q.1
Q.2
Q.3
Formation of MnO
4
2+
Due to disproportionation of Hg
2
NH
3
- strong ligand causes pairing of electrons. So complex is diamagneitc. F

is a weak ligand and so


pairing is not possible.
[Al (OH)
3
and NaAlO
2
; Zn(OH)
2
and Na
2
ZnO
2
] also [Zn(NH
3
)
4
]
2+
[Zn Sis white but PbSis black].
[A] = ZnCl
2
; [B] = Zn(OH)
2
; [C] = Na
2
ZnO
2
; [D] = ZnS; [E] = AgCl
l
All the three elements have d
10
See text for the reaction of HCl and KMnO
4
.
[(A) = ZnSO
3
; (B) = ZnO ; (C) = SO
2
; (D) = ZnS]
3/2 M
K
2
[Pt Cl
6
]
Cl

is a weak ligandso no pairing of electrons. CO is a strong field ligand and, therefore, causes
pairing of electrons.
In the first case, a double salt is formed. In the second case, a complex is formed. So no test.
(A) = [Cr(H
2
O)
6
]Cl
3
; (B) = [CrCl(H
2
O)
5
]Cl
2
H
2
O(C) = [Cr Cl
2
(H
2
O)
4
]Cl
2
.2H
2
O
(A) = [Cr(NH
3
)
4
Cl Br]
+
Cl

and (B) = [Cr(NH


3
)
4
Cl
2
]
+
Br

.
[Co(NH
3
)
4
Cl(H
2
O)] SO
4
;[Co(NH
3
)
4
(SO
4
)(H
2
O)]Cl [Co(NH
3
)
4
(SO
4
)(Cl)] H
2
O
Q.4
Q.5
Q.6
Q.7
Q.8
Q.9
Q.10
Q.11
Q.12
Q.13
Q.14
Q.15
Q.16
EXERCISE - III
Q.1
Q.6
Q.11
Q.16
Q.21
Q.26
Q.31
Q.36
Q.41
Q.46
Q.51
Q.56
A
B
B
C
A
A
C
A
A,B
A,B,C
A,B,C,D
B
Q.2
Q.7
Q.12
Q.17
Q.22
Q.27
Q.32
Q.37
Q.42
Q.47
Q.52
Q.57
B
A
A
A
D
C
A
B
A,B
A,B
A,B
A
Q.3
Q.8
Q.13
Q.18
Q.23
Q.28
Q.33
Q.38
Q.43
Q.48
Q.53
Q.58
A
A
B
B
A
D
D
A,B,C
B,C
B,C
A,B,C
C
Q.4
Q.9
Q.14
Q.19
Q.24
Q.29
Q.34
Q.39
Q.44
Q.49
Q.54
Q.59
B
B
D
A
B
C
A
B,C,D
A,B,C
A,C
A,B
B
Q.5
Q.10
Q.15
Q.20
Q.25
Q.30
Q.35
Q.40
Q.45
Q.50
Q.55
Q.60
A
A
B
D
D
B
A
A,B
A,B,C
A,B
B,C
C
26
ANSWERKEY