COMPLEX COMPOUNDS

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COMPLEX COMPOUNDS
 Secondary valency (Non-Ionisable valency)
SYNOPSIS
i) It is satisfied by anions or neutral molecules
Co-ordination Compounds or rarely with cations. The groups satisfying
 Double Salt : secondary valencies are called ligands.
1) Double salts exist only in solid state and ii) The number of secondary valencies is equal
dissociate into ions in water to coordination number.
2) They lose their identity in solution. iii) It is represented by thick lines while writing
3) The properties of double salt are essentially the structure of the complex.
the same as those of the constituent compounds  In some complexes the same groups satisfies
4) In double salts, metal ion exhibit their normal both primary and secondary valencies.
valency.  The ligands are directed in space around the
5) Double salts contain ionic bonds central metal atom in different ways. This leads
to a definite geometry to the molecule.
Ex: i) KCl . MgCl2 .6 H 2O (Carnallite)
ii) K 2 SO4 . Al2 ( SO4 )3 .24 H 2O (Potash alum) Colour Formula
No. of ions
in solution
iii)FeSO4 . (NH4)2 SO4 . 6H2O (Mohr’s salt)
 Coordination compound : Yellow CO NH 3 6  3Cl 
3
4 ions
1) They exist in the solid state as well as in
solution. Purple COCl NH 3 5  2Cl 
2
3 ions
2) They donot completely lose their identity in
solution. COCl2 NH 3 4  Cl 

Green 2 ions
3) The properties of coordinate compounds are
different from the constituent compounds. 
Violet COCl2 NH 3 4  Cl  2 ions
4) In coordination compound, metal ion is
surrounded by a number of anions or neutral
molecules. The metal ion exhibits more than Complex
No. of
6 Werner structure
ligands
its normal valency. Octahedral
5) Coordinate comounds may have ionic as well –
1. Three Cl ions satisfy primary valency NH3 NH3 NH3
2. Six NH3 species satisfy secondary valency
as coordinate bonds. COCl36NH3 6
3. Ions in solution = 4 Cl– CO
+3
Cl–

Ex: K4[Fe(CN)6], K3[Fe(CN)6], Na3  Ag  S 2O3 2  4. AgCl molecules precipitated on adding

AgNO3 = 3 AgCl = 3
NH3 NH
3
NH3
–
Cl
 The transition metal ions form co-ordinate –
5. Ionisable Cl = 3

compounds because Octahedral

–
1. Two Cl satisfy primary valency
i) They have small size. COCl35NH3 6
–
2. One Cl satisfy both primary and NH3 NH3 NH3
ii) They have high nuclear charge secondary valency
– +3 –
3. 5NH3 satisfy secondary valency Cl CO Cl
iii) They have vacant d-orbitals 4. No of ions in solution = 3
iv) They can accept lone pairs of electrons. 5. AgCl molecules precipitated on adding
Cl–
NH3 NH3

 Werner’s Theory: According to Werner AgNO3 = 2

6. Ionisable Cl– = 2
(father of Co-ordination chemistry) transition 1. Octahedral NH3 NH3
metals possess two types of valencies. –
2. 2Cl & 4NH3
3. One Cl satisfies
a) Primary valency (Ionisable valency) COCl34NH3 6
4. No of species in
Cl– CO+3 Cl–

b) Secondary valency (non ionisable valency) 5. AgCl molecules

– NH3 NH3
Cl

–
6. Ionisable Cl = 1
Primary Valency (Ionisable Valency)
1. Octahedral NH3 NH3
i) It is referred to as oxidation state. –
2. The three Cl ions and 3NH3 satisfy secondary
ii) It is satisfied by only anions. COCl33NH3 6 valency Cl
–
CO
+3
Cl
–

3. No. of species in solution = 1

iii) It is represented by dotted lines while writing 4. AgCl molecules precipitated = nil
– NH3
the structure of complex. 5. Ionisable Cl– = 0 Cl
 COMPLEX COMPOUNDS
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Defects in Werner’s Theory Definitions of Some Important Terms
 This theory does not relate the electronic in co-ordination Compounds
configuration of metal with the formation of the Oxidation number of central atom: The
complex. oxidation number of the central atom in a
 It is known now that the metal tries to acquire complex is defined as the charge it would carry
the nearest inert gas configuration during the if all the ligands are removed along with the
formation of complex electron pairs that are shared with the central
 This theory does not explain the reason for the atom. It is also called primary valency.
colour of the complex  The oxidation number is represented by a
 This theory does not explain the magnetic Roman numerical in parenthesis after the name
behaviour of complexes. of the metal.

W.E-1:When excess of silver nitrate solution is Coordination number: The coordination

added to aqueous solution containing 0.1 number (CN) of a metal ion in a complex can
be defined as the number of ligand directly
molar CoCl3 .xNH 3 . If 43.05 g of silver bonded to metal ion through coordinate bonds
chloride precipitated, then x value is (or)  bonds.
43.05  The co-ordination number is generally 2, 4 (or)
Sol. nAgCl   0.3 6, ocassionally 8 (in Osmium complexes).
143.5
 It is equal to the number of monodentate ligands
0.1 mole of CoCl3 .xNH 3 gives 0.3 mole of which are bound to central metal atom or ion
AgCl . through a dative bond. It is also called secondary
valency.
1 mole of CoCl3 .xNH 3 gives 3 mole of AgCl  Shape of the complex species depends on its
IV is 3. SV of Co 3 is 6 and PV is 3. co-ordination number.
So, IV = PV, Hence x =6. Co-ordination Shape of the
IV=Ionisable valency, PV=primary valency Number Complexes
2 Linear
W.E-2: The secondary valence of Co  3 is 6. 3 Trigonal planar
Calculate the number of moles of AgCl Tetrahedral (or)
4 square planar
precipitated, when excess of AgNO3 solution
Square pyramidal (or)
is added to 1.5lit of 0.2M. CoCl3 .5 NH 3 5 trigonal bipyramidal
solution.
6 Octahedral
Sol. SV of Co  3 is 6 and it will be satisfied by five Pentagonal
7
NH 3 and one Cl  the remaining 2Cl  ions bi-pyramidal

satisfy IV so fomula is CoCl  NH 3 5  Cl2 .  Co-ordination Entity or Co-ordination

1 mole of this complex gives 2 mole of Cl  sphere: A coordination entity constitutes a
ions central metal atom or ion bonded to a fixed
number of ions or molecules. It is enclosed in
1.5 x 0.2 mole gives how many moles of Cl 
square bracket and is collectively termed as the
ions. coordination sphere. The ionisable groups are
1.5  0.2 written outside the bracket and are called
 2  0.6moles counter ions
1
 COMPLEX COMPOUNDS
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 A molecule or ion which donates only one pair
 In CoCl  NH 3 5  Cl2 complex,
of electrons is called monodentate ligand. The
CoCl  NH 3 5  is coordination sphere and monodentate ligand is said to have only one
co-ordinating center.
2Cl  ions are counter ions. Ex: CN  , HO  , NH 3 , H 2O
 Co-ordination entities are mainly two types.  A molecule or ion which donates two lone pairs
They are of electrons is called bidentate ligand. The
a) Mononuclear complexes bidentate ligand will have two co-ordinating
centers.
Ex: K 4  Fe  CN 6  , CrCl  H 2O 5  Cl2 Ex: 1) Oxalate ion 2) Glycinate ion
b) Polynuclear complexes 3) Ethylene diamine
 Bidentate ligand: contains two donor atoms
Ex:  Co 2  NH 3  6  OH  3  Cl3 Ex :- oxalate, ethylenediamine, DMG, carbonate,
 
glycinate
 Mono nuclear complexes are three types.  Tridentate ligand: contains three donor atoms
1) Neutral complexes : Diethylene triamine, iminodiacetate, 2,2’,2’’-
complex donot posses charge terpyride

Ex: Co  NH 3 3 Cl3  ;  Pt  NH 3 2 Cl4 
Tetradentate ligand: contains four donor
atoms. Triethylene tetramine
2) Cationic complexes :  Pentadentate ligand: contains five donor
Complex posses positive charge atoms. Ethylene diamine triacetate (EDTA)-3
Ex : Cu  NH 3 4  SO4 ; Co  NH 3 6  Cl3
3) Anionic complexes :
complex posses negative charge

Ex: K 4  Fe  CN 6  , K 3 CoCl6 
 Hexadentate ligand: contains six donor
Based on ligands types of complexes: atoms. (EDTA)-4 (ethylene diamine tetra acetate)
 Homoleptic complex: The complex in which
the central metal atom (or) ion bound with only
one kind of ligand.
4 3
Ex:  Fe  CN 6  ,  Co  H 2 O  6 
 Heteroleptic complex: The complex in which  Ambidentate Ligand: It contains two donor
the central metal atom (or) ion bound with more atoms but both atoms can’t form dative bond in
than one kind of ligand. single compound.
2
Ex: CO  NH 3 5 Cl  O
Ligand: An ion or a molecule which can donate M N M O N O
a pair of electrons to a metal atom or a metal O
ion and can form dative bond is called ligand. nitrito-N nitrito-C
They are Lewis acids.
M SCN
 Ligands are three types M NCS
Negative ligands Eg: Cl-, SO4-2, CN-, C2O4-2; etc., thiocyanato isothiocyanato
Neutral ligands Eg: H2O, NH3 etc., EDTA can acts a penta and hexa dentate ligand.
Positive ligands Eg : NO+, NO2+ So., it is called felxi dentate ligand.
COMPLEX COMPOUNDS
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 Chelating ligands: A multi dentate ligand  No characteristics suffix for neutral
simultaneously coordinate to metal ion through ligands.
more than one sigma bond, a ring like structure Ex: NH CH CH NH - Ethylene diammine
2 2 2 2
obtained. which is called Chelate and ligand is
called Chelating ligand. C6 H 5 N - Pyridine
 Chelating effect: Due to this stability of PH 3 - Phosphine
 C6 H 5 3 P
complex increases.
- Triphenylphosphine
2
Ex : Cu  en 2  is less stable because it forms H 2O - aqua (or) aquo
1
only two rings.  Fe  EDTA   is more stable
NO - Nitrosyl
NH 3 - ammine
because it forms five rings.
CS - Thiocarbonyl
Chelate contains 6 donor atoms are less stable
due to steric hinderance. CO - Carbonyl
NS - Thionitrosyl
 Importance of Chelates: Chelates used in  Suffix for negative ligand is ‘o’.
(i) softening of hard water
Ex: Cl  - Chloro, OH  - hydroxo
(ii) separation of lanthanides and actinides.
(iii) estimation of Ni +2 , Mg +2 , Cu +2 ions NO2 - Nitrito, CO32 - Carbonato
qualitatively.
C2O42 - Oxalato, C6 H 5COO  - Benzoato
 Central atom/ion: In a coordination entity, the
Br  - Bromo, I  - Iodo, F  - Flouro
atom/ion to which a fixed number of ions/groups
are bound in a definite geometrical arrangement SO42 - Sulphato, O22 - Peroxo,
around it, is called the central atom or ion.
H  - Hydrido, NH 2 - amido,
 For example, the central atom/ion in the
coordination entities: [NiCl 2(H 2 O) 4 ], NH 2 - Imido C2O42 - Oxalato etc..
[CoCl(NH 3 ) 5 ] 2+ and [Fe(CN)6 ] 3– are Ni2+ ,  Suffix for positive ligand is ‘ium’.
Co3+ and Fe3+, respectively. These central atoms/
ions are Lewis acids. Ex: NO2 - Nitronium, Cl  - Chloronium

IUPAC nomenclature NO  - Nitrosonium, N 2 H 5 - Hydrazinium
 Order of Naming of Ions: The positive ion  Order of Naming Ligands:If more than one
is named first followed by the negative ion. different kinds of ligands are present in a
compound, their names should be written in
4
Ex: K 4  Fe  CN 6   4 K    Fe  CN 6  alphabetical order.

Potassium hexacyano Ferrate (II) Ex :  Pt  Br  Cl  NO2  NH 3   is named
 Name of the non ionic (or) neutral complex must as ammine bromo chloro nitro platinate (II) ion.
be written in one word.  Numerical prefixes to indicate number of
Ex :  Ni  CO 4  - tetra carbonyl nickel (O). ligands: If more than one same kind of ligands
are present they are labled as di, tri, tetra, penta
 Naming the Co-ordination Entity: In
etc. Ex : Cr  NH 3 6  Cl3 -
naming the coordination entity, the ligands are
named first and then central metal ion. Hexaamminechromium(III) chloride.
 2
Naming of ligands : ligands are 3 types  Ni  CN 4  - Tetracyanonickelate(II)ion.
 COMPLEX COMPOUNDS
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 If the same ligand can donate lone pairs from  Point of Attachment: When a ligand can
more than one centre, they are named as coordinate through more than one atom, then
bidentate, tridentate etc, depending on the the point of attachment of the ligand is indicated
number of lone pairs donated. by putting the symbol of the atom through which
Ex: NH 2CH 2CH 2 NH 2 . coordination occurs, after the name of the ligand.
 The number of bidentate, tridentate etc ligands Sometimes, different names are used for
is mentioned with bis, tris, tetrakis, etc. If they alternative modes of attachment.
already contain di, tri, tetra etc. in their names. Ex: NO2 can co-ordinate through -N (or) -O.
Ex:  Pt Br2  NH 2 CH 2 CH 2 NH 2 2  Cl2 is If it co-ordinates through N, it is called nitrito
-N (or simply as nitro). On the other hand, if
named as dibromobis (1, 2-ethane diamine) it co-ordinates through -O, (-ONO-), it is called
Platinum(IV) chloride. nitrito-O.
 Ending Names: When the complex is anionic,
the name of the central metal atom ends with -  NO2 (through N) ONO  (through -O)
ate. For cationic and neutral complexes the Nitrito -N (or) Nitrito-O (or)
name of the metal is written without any Simply nitro Simply nitrito
characteristic ending.  SCN  (through -S)  NCS  - (through -N)
Ex: Cationic complex : thio cyanato (or) isothio cyanato (or)
Co  NH 3 6  Cl3 -Hexamminecobalt(III) thio cyanato-S thio cyanato-N
 
chloride Cationic Complexes
Ex :Neutral complex :  Co  NH 3 6  Cl3
 
 Ni  CO 4  - Tetracarbonylnickel(0) Hexamminecobalt (III) chloride
Ex :Anionic complex :
  Pt  Cl  NH   Cl
K  Pt Cl5  NH 3   -
 3 5
 3
Pentaamminechloroplatinum (IV) chloride
Potassium amminepentachloroplatinate(IV)
 If the complex is anion, the name of the metal  CrCl  NO2  NH 3 4  NO3
should be taken from latin language. Tetraamminechloronitrochromium(III) nitrate
Ex : Cu - Cuprum – Cuprate
  Pt  NH 3 6  Cl4
Sn - Stannum – Stannate  
Fe - Ferrum – Ferrate Hexammineplatinum(IV) chloride.
Pb - Plumbum – Plumbate
 Co  NH3   H 2O  Cl  Cl2
Ag - Argentum – Argentate  4 
Au - Aurum – Aurate Tetraammineaquachlorocobalt(III) chloride.

Cr - Chromium – Chromate
 Cr  H 2O 4 Cl2 
Ni - Nickel – Nickelate
Tetraaquodichlorochromium(III)ion.
Oxidation State of Central Metal ion:
The oxidation state of the central metal ion is   Ag  NH 3 2  Cl Diamminesilver(I) chloride.
designated by a Roman numerical (such as II,
III, IV) in the brackets at the end of the name of  Ti  H 2O 6  Cl3
 
the metal of the complex. Hexaaquotitanium(III) chloride.
Ex : CoCl  NH 3 5  Cl2 -  Cr  NH 3 6  Cl3
 
Pentaamminechlorocobalt(III) chloride. Hexaamminechromium(III) chloride.
COMPLEX COMPOUNDS
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  Cu  en  2  SO4 Neutral Complex
 Co  NH 3 3 Cl3 
Bis(ethylenediamine)copper(II) sulphate.  
 Cu  NH 3 4  SO4 Triamminetrichlorocobalt(III)
  Pt  NH 3  Br2Cl2 
Tetraamminecopper(II) sulphate  2 
Diamminedibromodichloroplatinum(IV)
  Fe  H 2O 4  C2O4   SO4
2
 Cr  H 2O 3 Cl3  .3H 2O
Tetraaquaoxalatoiron(III) sulphate.  
Triaquotrichlorochromium(III)trihydrate.
  Fe  H 2O  NO   SO4
 5   Fe  CO 5 Pentacarbonyliron(O)
Pentaaquanitrasonium(I) sulphate
 Co  NH 3 3  NO2 3 
Anionic Complexes  
Triamminetrinitrocobalt (III)
 K 4  Fe  CN 6 
Isomerism in Complexes: Substances
Potassium hexacyanoferrate(II) having the same molecular formula but have
 Na2  Zn Cl4  Sodium tetrachlorozincate(II) different structures (or) properties are known as
isomers. The phenomenon of the existence of
 K 3  Fe  CN 5 NO  isomers is known as isomerism. It is two types
1) Structural isomerism 2) Stereo isomerism
Potassium pentacyanonitrosylferrate(II)
 Structural Isomerism: This isomerism arises
 K 3  Fe  CN 6  due to the difference in the structures of
complexes.
Potassium hexacyanoferrate(III)
 Ionisation Isomerism: Complexes which
 K 3 Cr  C2O4 3  have the same molecular formula but gives
different ions in solution are called Ionisation
Potassium trioxalatochromate(III)
isomers and the phenomenon is called ionisation
 K 3 CoCl2  C2O4 2  isomerism.
Potassium dichlorodioxalatocobaltate(III) Ex: Co  NH 3 5 SO4  Br and Co  NH 3 5 Br  SO4
 K2  HgI4  Potassium tetraIodomercurate(II).  Ionisation isomers are formed by the interchange
K 2  Pt Cl6 
of the position of ligands inside (or) out side
 the coordination sphere.
Potassium hexachloroplatinate(IV)  Ionisation isomerism arises, when the counter
 Na  Ag  CN 2  ions in a complex compound can also function
as ligands.
Sodium dicyanoargentate(I)  In the ionic complex compounds, the ion having
2 an opposite charge to that of the complex ion is
  Ni  CN 4  called counter ion.
Tetracyanonickelate(II) ion. i) K in K 4  Fe  CN 6 
 K 3 Cr  CN 6 
ii) Cl ions in Co  NH 3 6  Cl3
Potassium hexacyanochromate(III)
 The following pairs of compounds give different
 K 3 Co  CN 6  ions in solutions.
Potassium hexacyanocobaltate(III)  Co  NO3  NH 3 5  SO4 gives sulphate ions
 
 Na3  Ag  S 2O3 2  while Co  SO4  NH 3 5   NO3  gives nitrate
Sodium bis(thio sulphato)argentate(I) ions.
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 Linkage Isomerism: Complex with
 Co  NO3  NH 3 5  SO4 gives white
  ambidentate ligands shows this type of
precipitate with BaCl2 solution. isomerism. A mono dentate ligand with two (or)
more donar atoms is called ambidentate ligand.
Co  SO4  NH 3 5   NO3  cannot give white Ex: Co( NO )( NH ) 2 &
  
Co(ONO)( NH 3 )5 
2
2 3 5
precipitate with BaCl2 solution.
 Co-ordination Isomerism: It arises due to
  Pt Cl2  NH 3 4  Br2 gives Br ions. So it
 the mutual exchange of ligands between anionic
and cationic spheres.
can give light yellow precipitate with aqueous
AgNO3 solution. Ex: Co( NH 3 )6 Cr (CN )6  &

  PtBr2  NH 3  4  Cl2 gives Cl  ions. So it Co(CN )6 Cr ( NH 3 )6 

 Ligand Isomerism: This type of isomerism
can give white precipitate with aqueous AgNO3
arises due to the presence of isomers of the
solution.
ligands in different isomers of the complex
 Co  SO4  NH 3 5  Br is red coloured and it compound.
 
3
gives Br  ions, where as Co Br  NH 3 5  SO4 Ex :  Co  H 2 NCH 2 CH 2 CH 2 NH 2  3 
is violet coloured and it gives sulphate ions.
3
 Hydrate Isomerism: Hydrate isomerism is a  Co  CH 3CH - CH 2  
&   | |  
special type of ionization isomerism. This type
  NH 2 NH 2  3 
of isomerism arises due to the presence of water
molecules in and outside the coordination  Stereo Isomerism: Isomers which have the
sphere. same position of atoms (or) groups but differ in
 This type of isomers differ in number of water the spatial arrangements around the central atom
molecules as ligands and as hydrated molecules. are called stereo isomers and the phenomenon
Ex : CrCl3 .6 H 2O molecular formula has four is called stereo isomerism. It is classified into
possible isomers. They are two types.
(a) Geometrical isomerism
Cr  H 2O 6  Cl3 - violet coloured;
  (b) optical isomerism.
Cr  H 2O 5 Cl  Cl2 .H 2O - light green Geometrical Isomerism: Geometrical
 
isomerism is due to ligands occupying different
coloured
positions around the central metal atom (or) ion.
CrCl2  H 2O 4  Cl.2 H 2O - dark green  When two identical ligands occupy adjacent
coloured positions, the isomer is called cis-isomer.
 When two identical ligands occupy opposite
CrCl3  H 2O 3  .3H 2O - brown coloured
  positions, the isomer is called trans-isomer.

In the same manner CoCl3  H 2O 6 complex
Geometrical isomerism is very much common

in coordination number 4 and 6 complexes.
has the isomers  Tetrahedral complexes cannot exhibit
CoCl  H 2O 5  Cl2 .H 2O ; geometrical isomerism.
 Square planar complexes of the type
CoCl2  H 2O 4  Cl.2 H 2O
Ma4 , Ma3b, Mab3 do not exhibit geometrical
and CoCl3  H 2O 3  .3H 2O . isomerism.
 COMPLEX COMPOUNDS
Jr Chemistry E/M
 Square planar complexes of the type
Ma2b2 , Ma2bc and Mabcd exhibit CH3 CH3
geometrical isomerism. C – NH2 NH2– C
H H and
Pt

Ex :  Pt  NH 3 2 Cl2 
CH3 CH3
C – NH2 NH2– C
H CH3

H CH3
Cl  Cl  C – NH2 NH2– C
CH3 H
Pt
H CH3
C – NH2 NH2– C
CH3 H

Cl  Cl
 Octahedral complexes
L1

L5 L2
L4 L1
M
M

L4 L3
L3 L2
L6
Cis Positions : 1,2; 2,3; 3,4; 1.4 Cis Positions : 1,2; 1,3; 1,4; 1,5; 2,3; 2,5;
Trans Positions : 1,3; 2,4 3,4; 4,5; 2,6; 3,6; 4,6; 5,6
Trans Positions: 1,6; 2,4; 3,5
 Mabcd type of complexes will have 3
geometrical isomers i.e. 2cis and 1 trans isomer  octahedral complexes of the type Ma6 , Ma5b ,
 Square planer complex having unsymmetrical Mab5 do not exhibit geometrical isomerism.
bidentate chelating ligands with general  Octahedral complexes of the type
n
formula  M  AB 2  exhibit geometrical Ma4b2 , Ma4bc and Ma3b3 complexes exhibit
isomerism geometrical isomerism.

Ex : CoCl2  NH 3 4 

NH3 Cl–

Ex: NH3 Cl– H3N NH3

CO3+ CO3+

 Square planer complex having symmetrical

bidentate ligands with general formula NH3 Cl– H3N NH3
n
 M  AA 2  can also exhibit cis-trans NH3 Cl–
isomerism Cis-isomer Trans-isomer

Ex:  Pt II  NH 2 CH  CH 3  CH  CH 3  NH 2 2 
2
 Ma3b3 type of complexes exhibits maridian and
facial type of isomers
 COMPLEX COMPOUNDS
Jr Chemistry E/M
b
NH3 NH3
a b
Pt Pt
M NO2
H2O NO2 H2O
a Cl Cl
b
d-form Mirror l-form
a  A pair of optical isomers which are non super
facial imposable mirror images are called enantiomers
or enantiomorphs.
b  An equimolar mixture of d-forms and l-forms
is called racemic mixture. Racemic mixtures
a a are optically inactive.
 Optical Isomers have almost identical physical
M and chemical properties.
 The optical isomers can be distinguished only
a b by their rotation of the plane polarised light.
 Optical isomers are also generally provided by
the octahedral coordination compounds having
b bidentate (or) polydentate ligands.
 Octahedral complexes with general formula  3
n n Ex: CoCl2  en  2  , Cr  C2O4 3  ,
 M  AA 2 a2  ,  M  AA 2 ab  ,
 2
n
 M  AA  a2b2  can exhibit geometrical Cr  NH 3  Cl2en  ;  Pt Cl2  en  
 2   2

isomerism. Here ' en ' represents H 2 NCH 2CH 2 NH 2

 Octahedralcomplexexcontaining unsymmetrical  Optical isomerism is shown by the complexes
bidentate chelating ligands with general formula having chiral structures. They rotate the plane
n
 M  AB 3  can exhibit geometrical of polarised light in opposite directions.
a) Complexes with C.N. = 4
isomerism.  Square planar complexes do not show optical
 Optical Isomerism: The compounds having isomerism.
Tetrahedral complexes with formula M  AB 2
same molecular formula but differ in the rotation

of plane polarised light are called optical isomers
and the phenomenon is called optical isomerism. can exhibit optical isomerism.
 The isomer which rotates the plane polarised  Octahedral complexes with general formula
 Ma2b2c2  ,  Ma2b2 cd  ,  Ma2bcde 
light to the right direction is called dextro (d)- n n n
and
form while the isomer which rotates the plane
 Mabcdef 
n
polarised light to left direction is called laevo can exhibit optical isomerism.
( l )-form.  Octahedral complexes containing symmetrical
 Co-ordination number four, tetrahedral bidentate ligands with general formula
complexes of the type ( M abcd ) exhibit optical n n
 M  AA 3  ,  M  AA 2  BB   can exhibit
isomerism.
optical isomerism.
Ex :  Pt  NH 3  H 2O  Cl  NO2  
 COMPLEX COMPOUNDS
Jr Chemistry E/M
Type of Geometry of Examples
Py 2+ Py 2+ hybridization complex

Cl Py Py Cl sp Linear or  Ag  NH 3 2  ,
Pt Pt
 4s 4 p 

Cl NH3 Cl diagonal  Ag  CN 2 
H3N
NH3 NH3 CN  2
Mirror
cis-l-isomer
 HgI 3 

cis-d-isomer
sp 2 Trigonal planar
 Octahedral complexes containing  4s 4 p  2

unsymmetrical bidentate ligands with formula

CN  3
n
 M  AB 3  ( both Cis & Trans ) can exhibit sp3 Tetrahedral  Ni  CO 4 
0

optical isomerism.
 4s 4 p  3
 Zn  NH 3 4 
2

 Octahedral complexes containing symmetrical

 ZnCl4 
2
bidentate and monodentate ligands with CN  4
CuX 4 
2
n
general formula Cis   M  AA 2 a2  ,
 MnX 4 
2
n
Cis   M  AA 2 ab  ,
 NiX 4 
2

n
Cis   M  AA  a2b2  , and X  Cl  , Br  , I 
2
Cis   M  AA  BB  a2 
n
are optically active. dsp 2 Square planar  Ni  CN 4 

 Octahedral complexes containing polydentate 3d x2  y 2

4 s 4 pz 4 p y   Ni  NH 3 4 
2

ligands are optically active. 2

CN  4 Cu  NH 3 4 

Ex: Co III  EDTA   .
CuCl5 
3
dsp 3 Trigonal

W.E-3: The number of stereo isomers of the given  3d z2

4s 4 p3  bipyramidal  Fe  CO 5 
0

compound is CN  5

Co  C2O4   NH 3 2  NO2 2  .


sp 3 d  SbF5  , IF5
2
Square

Sol. Four  4s, 4 p 4d  pyramidal

3
x2  y 2

CN  5
3
VBT of Co-ordination Compounds: d 2 sp 3 Inner orbital Cr  NH 3 6 
 The central metal atom or ion makes available
a number of empty s, p and d atomic orbitals 3d x2  y 2 
3d z 2 4s 4 p 3 octahedral  Mn  CN 6 
3

3
equal to its coordination number. These vacant CN  6  Fe  CN 6  etc
orbitals hybridise together to form hybrid
 FeF6 
3
orbitals. These hybrid orbitals are vacant, sp 3d 2 Outer orbital
equivalent in energy and have definite geometry.
The most common hybridizations in complex  4 s 4 p 4d 3
x2  y 2 
4d z 2 octahedral Co  H 2O 6 
2

are given. 2
CN  6  Ni  NH 3 6 
 COMPLEX COMPOUNDS
Jr Chemistry E/M
 Each ligands have atleast one sigma orbital Examples of Complexes
containing alone pair of electrons. 4
1.  Mn  CN 6 
 Vacant hybrid orbitals of the central metal atom
C o m p l e x / i o n :

or ion overlap with the filled (containing lone Electronic configuration and hybridisation of Mn 2 :
pair of electrons) sigma orbitals of the ligands
to form metal-ligand sigma bond. This bond is 3d5 4s 4p
coordinate bond. ×× ×× ×× ×× ×× ××
 If d orbitals are involved in the hybridisation
than that may be either inner (i.e., (n-1) d-orbital) d2sp3-hybridisation
or the outer (i.e., nd-orbital). Geometry : Octahedral
 If (n - 1)d orbitals are used for hybridization [Link] unpaired electrons/paramagnetic
along with ns and np orbitals, such complex is character: 1-Paramagnetic.   1.76BM
called inner orbital complex. If nd orbitals are
3
used for hybridisation along with ns and np 2. Complex/ion :  Fe  CN   Fe3
 6
orbitals then it is called outer orbital complex.
Electronic configuration and hybridisation:
 Some times the unpaired (n-1) d-electrons
undergoes rearrangement and provides more 3d5
number empty orbitals, which is possible in ×× ×× ×× ×× ×× ××
presence of strong ligands such as
CO, CN  , NO2  , en, NH 3 , Py and EDTA. d2sp3-hybridisation
 The non-bonding electrons of central metal atom Geometry : Octahedral
or ion remain unaffected and do not take part in No. of unpaired electrons/paramagnetic
chemical bonding. character: 1-Paramagnetic.   1.76BM
 During complex formation, the Hund’s rule of 3

maximum multipliciy is strictly followed. 3. Complex/ion :  Fe  H 2O 6  Fe3

However, under the influence of strong ligands,
the electrons may be forced to pair up against Electronic configuration and hybridisation:
Hund’s rule (but only for (n-1)d orbits) 3d
5

 Complex containing unpaired electron (unpaired ×× ×× ×× ×× ×× ×× ××

electron of central metal atom or ion) is 3 2
sp d -hybridisation
paramagnetic in nature. If all the electrons of
metal atom or ion are paired, the complex is Geometry : Octahedral
diamagnetic in nature. No. of unpaired electrons/paramagnetic
Inner orbital complex, low spin complex, spin character: 5-Paramagnetic.   5.86BM
paired complex or covalent complex 4
4. Complex/ion :  Fe  CN 6  Fe 2
Hyperligated complex
Electronic configuration and hybridisation:
Outer orbital complex, high spin complex, spin
free complex, or ionic complex, Hypo ligated 3d6
complex ×× ×× ×× ×× ×× ××
 The spin only magnetic moment of the complex
can be calculated by the formula d2sp3-hybridisation
S  n  n  2  BM Geometry : Octahedral
No. of unpaired electrons/paramagnetic
( n = number of unpaired electrons ) character: 0-Diamagnetic
 COMPLEX COMPOUNDS
Jr Chemistry E/M
2
Complex/ion :  Zn  NH 3 4  Zn 2
2
5. Complex/ion :  Fe  H 2O 6  Fe2 9.
Electronic configuration and hybridisation: Electronic configuration and hybridisation:
6
3d
×× ×× ×× ×× ×× ××

3 2
sp d -hybridisation

Geometry : Octahedral Geometry : Tetrahedral

No. of unpaired electrons/paramagnetic No. of unpaired electrons/paramagnetic
character: 4-Paramagnetic.   4.85BM character: 0-Diamagnetic
2

Complex/ion : Co  NH 3 6 
3
3 10. Complex/ion :  Ni  CN 4  Ni 2
6. Co
Electronic configuration and hybridisation:
Electronic configuration and hybridisation:

3d6 4s 4p
×× ×× ×× ×× ×× ××

d2sp3-hybridisation
Geometry : Square Planar
Geometry : Octahedral No. of unpaired electrons/paramagnetic
No. of unpaired electrons/paramagnetic character: 0-Diamagnetic
character: 0-Diamagnetic
11. Complex/ion :  NiCl4  Ni 2
2

7. Complex/ion: CoF6  Co3

3
Electronic configuration and hybridisation:
Electronic configuration and hybridisation:
6
3d
×× ×× ×× ×× ×× ××

3 2
sp d -hybridisation
Geometry : Tetrahedral
Geometry : Octahedral [Link] unpaired electrons/paramagnetic
No. of unpaired electrons/paramagnetic character:
character: 4-Paramagnetic.   4.85BM 2-Paramagnetic
  2.8BM
8. Complex/ion: CuCl4  Cu 2
2

12. Complex/ion :  Ni  CO 4  Ni 0
Electronic configuration and hybridisation:
Electronic configuration and hybridisation:

Geometry : Tetrahedral
Geometry : Tetrahedral
No. of unpaired electrons/paramagnetic
No. of unpaired electrons/paramagnetic
character:1-Paramagnetic.   1.75BM character: 0-Diamagnetic
 COMPLEX COMPOUNDS
Jr Chemistry E/M
2
13. Complex/ion :  Pt  CN 4  Pt 2 Hence hybridisation is dsp 2 (square planar). But
Electronic configuration and hybridisation: Cl is weak field ligand. So, rearrangement of
d-electrons is not possible. Hence the

configuration of Ni 2 is
3d8
then hybridisation is sp3 (tetrahedral).
Geometry : Square Planar Effective atomic number (EAN)
No. of unpaired electrons/paramagnetic
 Effective atomic number (EAN) concept was
character: 0-Diamagnetic
introduced by Sidgwick to explain the stability
Limitations of VBT of complexes.
 It gives only the qualitative explanations for  The resultant number of electrons with the metal
complexes. atom or ion after gaining electrons from the
 It does not explain the detailed magnetic donar atoms of the ligands in a complex is called
properties of complexes. effective atomic number (OR)
 This thoery does not explain the spectral The total number of electrons present around
properties of coordination compounds. central metal ion in a complex is called effective
 It does not explain the thermodynamic and atomic number.
kinetic stabilities of different coordination  Sidgwick proposed that complex ion is stable.
compounds.
If EAN is equal to the atomic number of the
 It does not distinguish between weak and strong
nearest noble gas element.
ligands.
 EAN of a central metal can be calculated by the
 It does not make exact predictions regarding
terahedral or square planar coordinations entities following formula.
with co-ordination number is 4.  EAN  Z  x  n  y
x = charge of metal ions
W.E-3: The spin only magnetic moment of n = co-ordination number ; y =2
 FeBr4 

is 5.92 BM. Predict the geometry of Ex. (1)In K  Fe  CN   complex
4 6
complex ion.
EAN of Fe  26  2  6  2  36 .
Sol. Secondary valence of Fe 3 ion is 4. So,
3
complex is square planer  dsp  or tetrahedral
2 2)In Co  NH 3 6  complex ion

 sp  .
3
Br is weak field ligand so,
EAN of Co  27  3  2  6  36
rearrangement of d-electrons is not possible. 3)In  Ni  CO 4  complex
Hence complex is tetrahedral ( sp -3
EAN of Ni  28  0  2  4  36
hybridization). 2
4)In  Ni  CN  4  complex ion
2
W.E-4:  Ni  CN 4  is inner complex but
EAN of Ni  28  2  2  4  34
 NiCl4 
2
is outer complex. Give the reason. 3
5)In  Fe  CN 6  complex ion
2
Sol. CN  is strong field ligand. So. in  Ni  CN 4  EAN of Fe  26  3  2  6  35
6)In K 2  Pt Cl6  complex
ion Ni 2 configuration is
EAN of Pt  78  4  2  6  86  Rn 
8
3d
 COMPLEX COMPOUNDS
Jr Chemistry E/M
 In some complexes, the EAN is not equal to the  In a free metal atom, all five orbitals of d-sub
atomic number of the nearest inert gas. Yet they shell have same energy. They are called
are stable. degenerated orbitals.
2 When ligands approach the central metal atoms,
Ex: K 3  Fe  CN 6  ,  Ni  CN 4  . the electrons of d-orbitals of metal suffer
repulsions by lp of ligands as a result digeneracy
W.E-5: If  AuCl6 
y
follows EAN rule, then the
is broken and d-orbitals are split into two sets
oxidation state of Au is (At. no. of Au =79 of orbitals.
and At. no. of Rn =86).  a) Three of d-orbitals i.e., d xy , d yz and d zx which
Sol. EAN = Z - x + n x y are oriented in between the co-ordinate axes are
86 = 79 - x + 6 x 2 ; x = +5
called t2 g -orbitals.
W.E-6: If Ni  CO  x follows EAN rule, then x -  b) The other two d-orbitals i.e., d x2  y 2 and d z 2
value is which are oriented along the axes are called
Sol. EAN = Z - x + n x y
eg -orbitals.
36 = 28 - 0 + n x 2 ; n = 4.
 This spliting of d-orbitals of metal ion under
Formula of compound is  Ni  CO  4  . the influence of approaching ligands is called
crystal field spliting. It is designated by  and
Crystal Field Theory (CFT) is called crystal field splitting energy.
 This theory is based on theoretical work of Bethe  The decreasing order of field strength among
& Van Vleck on interaction of ionic crystals. some of the ligands are
 Ligands are either anion or neutral molecule Weak field ligand
containing atleast one lone pair of electron. The
anions are regarded as negative point charges. I   Br   SCN   Cl   S 2  NO3
The neutral ligands are regarded as point dipoles.  F   OH   ox 2  O 2  H 2O
 The neutral ligands are polarised by positive
charges of metal ion. Strong Field ligands
NCS   Edta 4  py  NH 3  en
 dipy  o  phen  NO2   CN   CO
 Central metal ion is surrounded by anions or
neutral ligands. For d 4 ions, two possible patterns of electron
distribution.
+
+ 1) If  0  p, the fourth electron enters one of
– – –
–
the eg orbital giving the configuration t2g
3 1
eg .
– M
+
– M
+

–
– Ligands for which  0  p are known as weak
– – + field ligands and form high spin complexes.
+ –
2) If  0  p , it becomes more energetically
+
favourable for fourth electron to occupy a t2 g
 The electrostatic attraction between nucleus of
orbital with configuration t2g
4 0
eg . Ligands which
cation and negative charge of ligands.
 Repulsive forces arise between lp of ligands, produce this effect are known as strong field
ligands and form low spin complex.
electrons of d-orbitals of central metal atom.
 COMPLEX COMPOUNDS
Jr Chemistry E/M
Crystal Field Splitting in octahedral In this situation, the t2 g set of orbital lie
and tetrahedral complexes relatively nearer to the approaching ligands and
 In octahedral complexes, the six ligands therefore t2 g set of d-orbitals have higher energy
approach the central metal ion along the co-
than eg set of orbitals.
ordinate axes i.e., the axes of d x2  y 2 and d z 2
 Relationship between  t and  0 is given as ;
orbitals. Consequently, the eg set of orbitals has
higher energy than t2 g orbitals. t 
4
o
9
 In tetrahedral complex, four ligands may be
imagined to occupy the alternate corners of the  While entering electrons into d-orbitals after
cube and the metal ion at the centre of the cube. splitting in ligand field, Hunds and pauli’s
principle to be followed.

weak

W.E-7:Arrange the following in the increasing d 10  6  0.4  4  0.6  0 0

order of stabilization energy of following in d 10  d 9  d 2  d 4  d 5
presence of strong field ligands.
Sol. d 2  2  0.4  0  0.6  0.8 0 W.E-8: Give the stabilization energy of d 7
electrons in presence of strong and weak field
d  3  0.4  0  0.6  1.2 0
3
ligands.
Sol. Strong field ligands
d 4  4  0.4  0  0.6  1.6 0
SE  6  0.4  1  0.6  1.8 0
d  5  0.4  0  0.6  2 0
5
Weak field ligands
d 9  6  0.4  3  0.6  0.6 0 SE  5  0.4  2  0.6  0.8 0
COMPLEX COMPOUNDS
Jr Chemistry E/M
Factors Determining the Magnitude of Colouring Coordination Compounds
the Orbital Splitting Energy  : The  most of the transition metal complexes are
following factors influence the magnitude coloured in their solid or solution form. The
of  . transition metals have the property to absorb
Nature of ligand: certain radiations from the visible region of the
spectrum and as a result, the transmitted or
 The  value depends upon the nature of the
reflected light is coloured.
ligand.
 In the case of transition metal complexes,the
 The CFSE depends on the tendency of ligand to
energy difference between two sets of d-orbitals
interact with the central metal ion.
is very small. When visible light falls on them,
 The ligands which cause only small  value the electron gets raised from lower set of orbitals
are called weak field ligands while those which to higher set of orbitals.
cause a large  value are called strong field  In case of octahedral complexes the electron
ligands.
goes from set of d xy , d yz , d zx to set of d x2  y 2 and
 The ligands can be arranged in the increasing
field strength in spectrochemical series. d z 2 [Link] a result of absorption of some
Oxidation state of the metal ion: selected wavelength of visible light
 Higher the ionic charge on the central metal ion, corresponding to energy difference between
the greater the value of  . these sets of energy levels, the transmitted light
gives colour to complexes,
 The metal ion with higher oxidation state causes
larger  than is done by the ion with lower  3
For example, the complex Ti  H 2O 6  is
oxidation state.
purple.
  for the entity [Co(H2O)6] will be more than
3+

 In this complex, the metal ion has d 1

 for the entity [Co(H2O)6]
2+

because oxidation state of cobalt is +3 in the configuration. The electron in t2 g orbital is

first and +2 in the second. excited to one of the eg


Nature of the metal ion:
For the analogous entities within a group, 
d x2  y 2 
or d z 2 orbital by absorbing light equal

values differ. The  value for similar complexes to  0 .

in the same oxidation state increases by 30-50%
This may be expressed as
on going from 3d series (first transition series)
to 4d series (second transition series). This t2 g1eg 0  t2 g 0 eg1
increase is almost of the same amount (30-50%)
 The energy corresponding to this transition
on going from 4d-series (second transition
corresponds to green and yellow lights which
series) to 5d-series (third transition series). As
are absorbed from the white light, while the blue
a consequence of this, coordination entities of
and red portions are emitted. the solution of
second and third transition series have a greater
3
tendency to form low spin complexes as comlpex Ti  H 2O 6  , therefore, looks
compared to the first transition series.
purple.
Geometry of the coordination entity
 In octahedral complexes  vary from one metal
 The  value for tetrahedral coordination entities
ion to another and the nature of the ligands.
is about half the  value for octahedral entities
 Different complexes absorb different amounts
4
i.e.  t   0 of energies from visible region and exhibit
9 different colours.
 COMPLEX COMPOUNDS
Jr Chemistry E/M
 For example, three complexes of Co 3+ as 2 2
 Ni  H2O4 en aq  enaq  Ni  H2O2 en2  aq  2H2O
[Co(H2O)6]3+ ,[Co(NH3)6]3+ and [Co(CN)6]3-.
According to spectrochemical series, the crystal blue / purple
field splitting energies will be in the order of 2 2

Ni  H2O2 en2  aq  enaq  Ni en3  aq  2H2O
ligands as H 2O  NH 3  CN
Violet
[CO(H2O)6]3+ [CO(NH3)6]3+ [CO(CN)6]3+
These colour changes are observed due to the
0 value small Intermediate Large presence of different ligands in the complexes.
Excitation Rules for Writing the Formulae of
small Intermediate Large
energy(
Absorption Co-ordination Compounds
wavelength large Intermediate small  All mononuclear complex entities contain a
(
single central metal atom, which is symbolised
Colour Orange first.
Blue Violet
absorbed
 If more than one ligand of each type is present,
Colour Yellow
Blue Yellow they represented in the following order.
transmitted orange
negative, neutral, positive
Colour of Ex:-
Wave length Colour of
Coordination coordination
of light light
in correct formula :  Fe  NO    CO 3 Cl 
entity entity 2
absorbed(nm) absorbed (transmitted)
3–
[CO(CN)6] 310 Violet Pale yellow 2
Correct formula :  FeCl  CO 3 NO   .
3+
[CO(H2O)6] 475 Blue Yellow orange
 Complete co-ordination entity is enclosed in
[CO(H2O)
Blue green
square brackets. Different species present in the
3+ 500 Red
(NH3)5] formula are written continuously without
[Ti(H2O)6]
3+
510 Blue green Purple leaving space.
 Charge of anionic or cationic complex is
[COCl(NH3)5] Violet
4+
53.5 Yellow indicated outside the square brackets as a right
superscript.
[Cu(H2O)6]3+ 600 Red Blue
3
W.E-9:In Ti  H 2O 6  complex Ti 3 has only
 It may be noted that in the absence of ligands,
the crystal field splitting does not occur and one electron in 3d-orbital. Its spectrum shows
hence the substance is colourless. For example, a single absorption peak of 5000 A0 then
removal of water from [Ti(H2O)6]Cl3, on heating corresponding energy is
makes it colourless. Similarly, anhydrous CuSO4
N 0 .hc
is white but CuSO4.5H2O is blue in colour. Sol. E 
 The effect of the ligand on the colour of a 
complex may be illustrated by taking the
6.023 1023  6.63  1034  3  108
example of [Ni(H2O)6]2+. This is formed when =
nickel chloride dissolved in water. The aqueous 5 107
solution of the complex has green colour. If the = 239 kJ / mol
bidentate ligand, ethane-1,2-diamine (en) is
progressively added in the molar ratio of en : Ni Metal Carbonyls
as 1 : 1, 2 : 1 and 3 : 1, the following series of  Class of coordination compound known as metal
reactions occur resulting different colour carbonyls in which carbon monoxide (CO) acts
changes as : as ligand.
2 2  These are also called homoleptic carbonyls
 N i  H 2 O  6   a q   en  a q    N i  H 2 O  4 en   2 H 2 O
P a le b lu e
(compounds containing carbonyl ligands only).
COMPLEX COMPOUNDS
Jr Chemistry E/M
 These compounds contain both (ii) There is a  -overlap involving donation of
 and  character.. electrons from filled metal d-orbitals into vacant
Structure of metal carbonyls anti-bonding  * molecular orbitals of CO. This
 Tetracarbonyl nickel (0) is tetrahedral. results into the formation of M  C  bond.
 Pentacarbonyl iron (0) is trigonal bipyramidal. This is also called back donation or back
 Hexacarbonyl chromium (0) is octahedral. [Link] metal to ligand bonding creates a
 Some carbonyls have metal-metal bonds. synergic effect which strengthens the bond
 Decacarbonyl dimanganese (0) is made up of between CO and the metal.
two square pyramidal Mn(CO)5 units joined
by Mn-Mn bond. Stability of Coordination
 Octacarbonyl dicobalt (0) has a Co-Co bond  Compounds in Solution: The stability of a
bridged by two CO-CO groups. complex in solution refers to the degree of
association between the two species involved
CO CO
OC in the state of equilibrium.
 The magnitude of the (stability or formation)
Ni Fe CO
equilibrium constant for the association,
OC CO OC quantitatively expresses the stability.
CO CO  we have a reaction of the type:
Ni(CO)4 Fe(CO)5
Tetrahedral Trigonal bipyramidal M  4 L  ML4 then the larger the stability
constant, the higher the proportion of ML4 that
exists in solution. Free metal ions rarely exist
CO in the solution so that M will usually be
CO CO CO CO
CO CO surrounded by solvent molecules which will
Cr compete with the ligand molecules, L, and be
OC Mn Mn CO successively replaced by them. we generally
OC CO
CO CO CO ignore these solvent molecules and write four
CO CO stability constants as follows:
Cr(CO)6
[Mn(CO)10]
Octahedral M + L  ML K1=[ML]/[M][L]

ML+L  ML2 K2=[ML2]/[ML][L]

ML2+L  ML3 K3=[ML3]/[ML2][L]

ML3+L  ML4 K4=[ML4]/[ML3][L]

where K1, K2, etc., are referred to as stepwise
stability constants.
Alternatively, we can write the overall stability
constant thus:
Bonding in Metal Carbonyls: The
bonding in metal carbonyls is described by the
M + 4L  ML4  4 = [ML4]/[M][L]4
following steps:  The stepwise and overall stability constant
(i) There is a donation of lone pair of electrons are therefore related as follows:
of carbon (of CO) into the suitable empty orbital  4 = K1 × K2 × K3 × K4 or more generally,,
of the metal atom. This is a dative overlap and
forms a sigma M  C bond.  n = K1 × K2 × K3 × K4 ....... Kn
 COMPLEX COMPOUNDS
Jr Chemistry E/M
2
W.E-10: Zn 2  2 NH 3   Zn  NH 3 2  ; K1  2 103 K 4  Fe  CN 6   4 K    Fe  CN 6 
4

2
 Zn  NH 3 2   2 NH 3  K 2  1.5  103 
Find out the instability constant ? Ex : Fe  6CN 
2

Sol. K C  K1.K 2  2  10 3  1.5  10 3  3  10 6  feebly dissociated 

Instability constant is inverse of stability
Imperfect or normal complexes: These are
constant
the compounds in which complex ion is less
1 1 stable and is reversibly dissociated to give
  3.3  105
K C 3  106 enough simple ions.
2
Application of Complexes: CuSO4 K 2 Cd  CN 4   2 K   Cd  CN 4 
solution, when mixed with aqueous ammonia, 
gives a deep blue complex soluble in water. This Ex : Cd 2  4CN 
is used in the identification of Cu 2 ion. It is  appreciably dissociated 
due to the formation of the complex
2
Based on reactivity complex are two types
Cu  NH 3 4   Labile complexes : Those complexes are
 Ammonium salts are identified by Nessler’s highly reactive, i.e., in which ligands can be
readily replaced by other ligands are called labile
reagent. It is a complex K 2  HgI 4  -a colourless complexes.
solution.  Inert complexes : Those complexes are less
 Fe(III) ion in group III is identified as reactive, i.e., in which the ligands cannot be
[Fe(NCS)6]3- ion which has blood red colour. readily replaced by other ligands are called inert
 In Photography the developing of negative is complexes.
based on complex formation.
C.U.Q
AgBr  2 Na2 S 2O3  Na3  Ag  S 2O3  2   NaBr
WERNER’S THEORY
 The extraction of silver, gold from their ores
1. The following does not give a precipitate
makes use of a complex compound formed by
either with AgNO3 or BaCl2
leaching their ores with NaCN solution.
1) [Co (NH3)5 Cl] SO4 2) [Co (NH3)3 Cl3]
 In the electroplating of Ag, large amounts of
silver are held as the complex, K[Ag(CN)2]. 3) [Co (NH3)4 Cl2]Cl 4) Co NH 3 2 Cl4 Cl
 Haemoglobin is a complex which contains Fe+2 2. Which of the following has highest molar
ions. conductivity?
 Chlorophyll is a complex which contains Mg+2 1) [Co (NH3)6] Cl3 2) [Co (NH3)5Cl] Cl2
ions. 3) [Co (NH3)4 Cl2] Cl 4) [Co (NH3)3 Cl3]
 Vitamin - B12 is a complex which contains Co3+ 3. Transition elements form complexes readily
ions. because
ADDITIONAL TOPICS i) Small size of cation ii) Large ionic Charge
iii) Vacant d orbitals
 Based on stability complexes are two types
The correct statements is / are:
Perfect or penetrating complexes These are
the compounds in which complex ion is fairly 1) i only 2) ii only 3) i & ii 4) i,ii,iii
stable and is either not dissociated or feebly 4. The ionizable valency of Ni in Ni(CO)4 is
dissociated in solution. e.g., 1) 2 2) 4 3) 0 4) 1
 COMPLEX COMPOUNDS
Jr Chemistry E/M
5. According to Werner’s theory transition 16. Which of the following is cationic complex
1) K 4  Fe  CN 6  2)  Ni  CO  4 
metals possesses
1) only one type of valency
2) two types of valencies 3)  Co  NH 3 3 Cl3  4)  Cu  NH 3 4  SO 4
3) three types of valencies 17. The no. of moles of AgCl obtained when
4) four types of valencies excess AgNO 3 is added to one mole of
6. The primary valency of the metal ion is [Cr(NH3)4Cl2]Cl
satisfied by 1) 1 2) 2 3) 3 4) 4
1) neutral molecules 2) positive ions 18. Ligand in a metal carbonyl complex is
3) negative ions 4) all the above 1) NH3 2) CO 3) CN- 4) SCN-
7. No of ionizable & non-ionizable Cl ions in 19. The no. of moles of AgCl precipitated when
excess of AgNO3 is mixed with one mole of
CoCl3 5 NH 3 representively aree [Cr(NH3)3 Cl3] is
1) 3, 0 2) 2, 1 3) 1, 2 4) 0, 3 1) 0 2) 1 3) 2 4) 3
8. Central metal ion in complex compound acts NOMENCLATURE
as
1) Lewis acid 2) Lewis base 20. IUPAC name of the complex CoCl3 5 NH 3 is
3) Arrhenius acid 4) Arrhenius base 1) Cobalt trichloride penta amonium
9. Which one of the following acts as a Lewis 2) Penta amine carbonyl chloride
base in complexes 3) Trichloro penta amino cobalt
1) CO2 2) BF3 3) NH3 4) BCl3 4) Pentaaminechlorocobalt  III  chloride

DEFINITION OF ISOMERISM IN COMPLEXES

CO-ORDINATION COMPOUNDS 21. The property of possessing atleast one atom
that is attached to four non-identical groups
10. Potassium ferrocyanide is an example for
is called
1) Complex salts 2) Normal salts 1. polarisation 2. chirality
3) Double salts 4) Basic salts 3. enantiomerism 4. meridionity
11. Example for a coordination compound is 22. A racemic mixture has a net rotation
1) KCl . Mg Cl2 . 6H2O 1. to right of original plane
2) K2 SO4.Al2(SO3).24 H2O 2. to left of original plane
3) CoCl3 . 6N H3 3. toright or left of original plane
4) Fe SO4 . (NH4)2 SO4 . 6 H2O 4. zero
12. In which of the following transition metal 23. Optical isomer have
complexes does the metal exhibit zero 1) property of chirality
oxidation state 2) almost identical chemical properties
1) [Co (NH3)6] Cl3 2) [Fe (H2O)6] SO4 3) almost identical physical properties
3) [Ni (CO)4] 4) [Fe (H2O)6] Cl3 4) all the above
13. The number of moles of ions produced when EFFECTIVE ATOMIC NUMBER
one mole of Potassium Ferricyanide is 24. The effective atomic number of iron in
dissolved in water is
3
1) 2 2) 4 3) 5 4) 6  Fe  CN 6  is
 
14. Metal-Isothiocyanato is indicated by
1. 34 2. 36 3. 37 4. 35
1) M-SCN 2)M-NCS 3)M-CNS 4)M-CSN
25. Which doesnot obey EAN rule
15. Number of chlorides satisifying secondary
valency in CoCl3 .4 NH 3 1) Fe  CO 5 2) K 4  Fe  CN 6 
1) 2 2) 3 3) 4 4) 1 3) Cu  NH 3  4  SO4 4) Co  NH 3 6  Cl3
 COMPLEX COMPOUNDS
Jr Chemistry E/M
26. The effective atomic number of central metal CFT
ion is wrongly calculated in the following 35. Which of the following system has maximum
complex? number of the unpaired electrons in an inner
1. In  Ni  CO 4  the EAN of Ni is 36
octahedral complex ?
1) d 4 2) d 9 3) d 7 4) d 5
2. In K 2  Ni  CN 4  the EAN of Ni is 36 36. In an octahedral crystal field, the correct set
of low energy orbitals are
3. In K 3  Fe  CN 6  the EAN of Fe 35 1) d xy , d xz , d x2  y 2 2) d x2  y 2 , d z 2

4. In Cr  NH 3 6  Cl3 the EAN of Cr is 33 3) d xy , d xz , d yz 4) d xy , d x2  y 2

27. According to Sidgwick’s effective atomic 37. For the same metal, stabilisation energies of
number rule the central metal acquires tetrahedral and octahedral complexes are
1. inert gas configuration related in presence of strong field ligands is
2. octet 3. duplet 4. quartet 1)  t   0 2)  t  4   0  6
VALENCE BOND THEORY AND SHAPES 3)  t  9   0  4 4)  t  6   0  4
OF CO-ORDINATION COMPOUNDS 38. The orbitals having lower energy in
28. The shape of the complex species will be tetrahedral complexes according to CFT are
square planar if its coordination number is
1) d xy , d yz , d z 2 2) d xy , d yz , d x2  y 2
1) 2 2) 6 3) 5 4) 4
29. Which of the following is outer orbital 3) d xy , d yz , d zx 4) d x2  y 2 , d z 2
complex
APPLICATION OF COMPLEXES IN
1) CoF6 
3
2) [Cu ( H 2O ) 6 ]2 QUALITATIVE ANALYSIS AND METAL
3) [Co( NH 3 ) 6 ]2 4) Both 1 and 2 CARBONYL COMPOUNDS AND STABILITY
OF CO-ORDINATION COMPOUNDS
30. sp 3d 2 hybridisation is present in 39. The metal which does not form poly nuclear
1)  CoF6  2) [ N i  C O  4 ]
3 carbonyl is
1) Mg 2) Fe 3) Cr 4) Co
2
3) [Co( NH 3 ) 6 ] 2
4)  Ni  CN 4  40. Nessler’s reagent is
31. The type of hybridisation present in 1) K 2 HgI 4 2) K 2 HgI 2 3) K 2 HgCl4 4) HgI 2
2
41. Among the following metal carbonyls, the
Cu  NH 3 4  ion is C-O bond order is lowest is
2)  Fe  CO 5 

1) sp3 2) dsp 2 3) sp 3 d 4) sp 3d 2 1) V  CO 6 
32. The shape of  CoF6 
3
3) Cr  CO 6 
is 
4)  Mn  CO 6 
1) Square Planar 2) Trigonal bipyramidal
3) Octahedral 4) Tetrahedral
33. The hybridisation of metal atom & geometry C.U.Q - KEY

of complex in  Ag  NH 3 2  aree 1) 2 2) 1 3)4 4) 3 5) 2 6) 3 7) 2
8) 1 9) 3 10) 1 11) 3 12) 3 13) 2 14) 2
1) sp, linear 2) sp2, linear
3) sp2, trigonal planar 4) sp, angular 15) 1 16) 4 17) 1 18) 2 19) 1 20) 4 21) 2
2 22) 4 23) 1 24) 4 25) 3 26) 2 27) 1 28) 4
34. The magnetic moment of  Ni  Cl 4  is
29) 4 30) 1 31) 2 32) 3 33) 1 34) 1 35) 1
1) 2.85 BM 2) 1.83 BM
36)3 37) 3 38) 4 39) 1 40) 1 41) 1
3) 4.86 BM 4) 5.95 BM
 COMPLEX COMPOUNDS
Jr Chemistry E/M
C.U.Q - HINTS 35. In an inner orbital complexes :

1. Co  NH 3 3 Cl3  cannot ionise. d 4  t24g eg0 , so two unapired electrons

2. Co  NH 3 6  Cl3 gives more number ions. d 9  t26g eg3 , so one unpaired electron
7. 2, 1 d 7  t26g e1g , so one unpaired electron
8. In any complex central metal ion acts as Lewis
acid {electron pair acceptor) and Ligands acts d 5  t25g eg0 , so one unpaired electron
as Lewis base {electron pair donar)
4
9. NH 3 acts as ligand. 37.  t  0
9
12. In metal carbonyl compounds the oxidation
number of metal is zero because CO is neutral. 40. Formula of Nessler’s reagent is K 2 HgI 4 .
3 41. As increase of electron density back bonding
13. K 3  Fe  CN 6   3K    Fe  CN 6  tendence of  bond increases, so C-O bond
= 4 moles order decreases.

17. Cr  NH 3 4 Cl2  Cl ionises gives one Cl  ion. LEVEL-I (C.W)

So it gives 1 mole AgCl ppt.
20. Pentaamminechlorocobalt(III) chloride. WERNERS THEORY
21. Chirality property 1. Which of the following is not a draw back of
22. Racemicmixture contains equimolar proportions Werner’s theory
of d and l forms. So net rotation is zero. 1) does not explain the valency of metal ions in
the complex
23. Optical isomers are differ towards rotation of
plane polarised light. 2) does not give any explanation for the colour
of complex compounds
24. EAN=[Z-oxidation number of central ion + 2 x
number of ligands] 3) does not explain the magnetic behaviour of
complex compounds
= 26 - 3 + 2 x 6 = 35
4) does not correlate electronic configuration of
25. EAN = 29 - 2 + 2 x 4 = 35
the metal with the formation of complex
So, it does not obeys EAN rule.
26. EAN = 28 - 2 + 2 x 4 = 34 DEFINITION OF
27. According to Sidgwick’s EAN rule. The central CO-ORDINATION COMPOUND
metal atom acquires inert gas configuration. 2. Which is a coordination compound ?
28. Shape of complex depends on coordination 1) Ferrous ammonium sulphate 2) Carnallite
number. If coordination number = 4, shape is
3) Potassium ferrocyanide 4) Gypsum
tetrahedral (or) square planar.
3. A q u e o u s

2
O)5 SO4]Cl gives
s o l u t i o n o f [ C o ( H

29. NH 3 strong field ligand,so it forms inner orbital precipitate with

complex. 1) BaCl2 (aq) 2) AgNO3 (aq)
30. F  is weak field ligand so it forms outer 3) both 1 and 2 4) neither 1 nor 2
complex. 4. Silver Chloride dissolves in excess ammonia
32. Coordination number 6. So shape is octahedral. due to the formation of a soluble complex
34. Cl  is weak field ligand so rearrangement of whose formula is
1) [Ag (NH3)] Cl 2) [Ag (NH3)2] Cl
electron is not possible. Hence Ni 2 ion
3) [Ag (NH3)3]Cl 4) [Ag (NH3)4] Cl
contains two unpaired electrons.
 COMPLEX COMPOUNDS
Jr Chemistry E/M
+2
5. Zn dissolves in excess of NaOH due to the VBT AND SHAPES OF
formation of COORDINATION COMPOUNDS
1) Soluble Zn (OH)2
2) Soluble Na2 [Zn (OH)4] 13. The hybrdisation of the complex [ NiCl4 ]2 is
3) Soluble Na [Zn (OH)3] 4) ZnO 1) sp3 2) dsp 2 3) sp 3 d 4) sp 3d 2
6. Example of neutral complex compound in the
2
following is 14. The complex Fe H 2O  5 NO   is formed
 
1) CoCl3 .6 NH 3 2) CoCl3 .5 NH 3
in the brown ring test for nitrates when
3) CoCl3 .4 NH 3 4) CoCl3 .3NH 3 freshly prepared FeSO 4 solution is added to
7. Which of the following releases metal slowly
aqueous solution of NO 3  followed by
which gives uniform coating in electroplating
is addition of con.H 2SO 4 . Select correct
1) metal salts 2) double salts statement about this complex.
3) complex salts 4) alums 1) Colour change is due to charge transfer
NOMENCLATURE 2) it has iron in +1 oxidation sate and
8. IUPAC name for the complex nitrosonium as NO 
 Cu  NH 3 4  SO 4 is 3) it has magnetic of 3.87 BM confirming three
unpaired electrons in Fe
1) cuprammonium sulphate 4) it has iron in +2 oxidation sate and
2) copper sulphate tetraammonia
nitrosonium as NO 
3) tetraamminecopper   sulphate
II 15. Which of the following is paramagnetic ?
4) copper ammonium  IV  sulphate 1) Ni  CO  4
2) Fe  CO  5

ISOMERISM 3) V  C O  6 4) Cr  CO 6
9. Which of the following does not exhibit 16. The number of ions formed when
optical isomer ? cupraammonium sulphate is dissolved in
1) Co  NH 3 3 Cl3  2) Co  en 3  Cl3
    water
1) 1 2) 2 3) 4 4) zero
3) Co  en 2 Cl2  Cl 4) Co  en  NH 3 2 Cl2  Cl
CFT
10. Co-ordination compounds  Pt  NH 3 3  NCS   17. Which of the following is correct
arrangement of ligands in terms of field
and  Pt  NH 3 3  SCN   are example of -- strength
isomerism
1) Cl   F   NCS   NH 3  CN 
1) Co-ordination 2) Ionization
3) Linkage 4) Optical 2) NH 3  F   Cl   NCS   CN 
11. Geometrical isomerism is observed in
1) Tetrahedral complex 3) Cl   F   NCS   CN   NH 3
2) Square planar complex 4) NH 3  CN   NCS   Cl   F 
3) Tined complexes 18. In which of the following octahedral
4) Planar triangle complexes complexes of cobalt (atomic number = 27) will
EFFECTIVE ATOMIC NUMBER the magnitude of  0 be the highest ?
12. Stable complex based on EAN rule
3 3
1) Co  C2O4 3  2) Co  H 2O 6 
1) K 4  Fe  CN 6  2) Co  NH 3 5 Cl  Cl2
3 3
3) Co  NH 3 6  4) Co  CN 6 
3)  Ni  CO 4  4) all the above
 COMPLEX COMPOUNDS
Jr Chemistry E/M
19. If 0  P , the correct electronic 8. IUPAC name of complex Cu  NH 3  4  SO4 is
configuration for d 4 system will be tetraamminecopper(II) sulphate.
( P =pairing energy)
12. EAN of  Ni  CO  4  = 28 - 0 + 2 x 4 = 36, So it
1) t24g eg0 2) t23g e1g 3) t20g eg4 4) t22g eg2
is stable
APPLICATION OF COMPLEXES IN 13. It is outer orbital complex. Coordination
QUALITATIVE ANALYSIS AND METAL number is 4. Shape is tetrahedral.
CARBONYL COMPOUNDS AND STABILITY 18. Strength of ligands
OF CO-ORDINATION COMPOUNDS C2O42  H 2O  NH 3  CN 
20. Ammonium ions are detected with
1) Nessler’s reagent 2) Borsch reagent 19. Weak field ligand
3) Tollen’s reagent 4) Fehling’s solution 23. K  K1.K 2 .
21.  Ph3 P 3 RhCl  is a familiar catalyst used in
1) hydrogenation of oils LEVEL-I (H.W)
2) hydrogenation of alkenes
3) dehydration of alcohols WERNERS THEORY
4) dehydration of aldehydes 1. The complex formed by the combination of
22. Metals those can be extracted with aqueous calcium ions and ethylene di amine tetra
solution of sodium cyanide as complexes are
acetate.  EDTA  Number of moles of
4
1) Au and Ag 2) Fe and Ag
3) Au and Hg 4) Hg and Fe calcium ions produced by disulving of one
23. Ag   NH 3  Ag  NH 3  ; K1  3.5  10 3
 mole of that complex in excess of water is

1) one 2) two 3) four 4) five
A g  N H 3   N H 3   A g  N H 3  2  ; K 2  1 .7  1 0  3


Then, the formation constant of DEFINITION OF

 CO-ORDINATION COMPOUND
 Ag  NH 3 2  from Ag  and NH 3 is
2. Which is a double salt?
1) 1.7  10 3 2) 5.92  10 6 1) Carnallite 2) Potassium ferrocyanide
3) 1.8  103 4) 1.7  107 3) Potasium ferricyanide 4) Nessler’s reagent
3. Bonds present in K4 [Fe (CN)6] are
LEVEL-I (C.W) - KEY 1) Only ionic 2) Only covalent
1) 1 2) 3 3) 2 4) 2 5) 2 6) 4 7) 3 3) Ionic and Covalent
8) 3 9) 1 10) 3 11) 2 12) 4 13) 1 14) 2 4) Ionic, covalent and coordinate covalent
15) 3 16) 2 17) 1 18) 4 19) 2 20) 1 21) 2 4. Copper sulphate solution forms blue
coloured complex with excess of ammonia.
22) 1 23) 2
Its formula is
LEVEL-I (C.W) - HINTS 1) [Cu (NH3)4]+3 2) [Cu (NH3)4]+2
3) [Cu (NH4)3]+2 4) [Cu (NH4)3]+3
3. Co  CN 4 SO4  Cl ionises and gives Cl  ion.
5. Which of the following cannot act as a ligand
Ag   Cl   AgCl  ppt  1) BF3 2) NH3 3) NO  4) CN 

4. AgCl  2 NH 3   Ag  NH 3  2  Cl 6. Alum in aqueous solution gives positive test

for
5. Zn 2  2 NaOH  Na2 ZnO2  H 2 A) K  B) Al 3 C) SO42 
Na2 ZnO2  2 H 2O  Na2  Zn  OH 4  1) A only 2) B only 3) A and B 4) A, B and C
 COMPLEX COMPOUNDS
Jr Chemistry E/M
7. Chelates are used in VBT AND SHAPES OF
1) Analytical chemistry 2) Water softning COORDINATION COMPOUNDS
3) Removal of Pb2 from the blood 14. The following solutions requires three moles
of AgNO3 for the complete precipitation of
4) All of these all the chloride ions present in it
NOMENCLATURE 1) One litre of 1M [Co (NH3)6] Cl3
2) Three litres of 1M [Co (NH3)4 Cl2] Cl
8. Hexaaquotitanium  III  Chloride is 3) One litre of 1.5M [Co (NH3)5 Cl] Cl2
represented as 4) All the above
15. AgCl dissolved in excess of NH 3 , KCN and
1)  Ti  H 2 O 6  Cl3 2)  Ti Cl 3  6H 2 O Na 2S 2O 3 solutions the complex produces
ions.
3)  Ti  H 2 O 5 Cl  Cl 2 4) Ti  H 2 O 3 Cl3 
  3
1.  Ag  NH3 2  ,  Ag  CN 2  &  Ag  S2O3 2 
9. IUPAC name of Li[AlH4] is
2 3 2
1) Lithium aluminium hydride 2.  Ag  NH 2  2  ,  Ag  CN  2  &  Ag 4  S 2 O3  5 
2) Lithium tetrahydrido aluminate [III] 2  2
3.  Ag  NH 3  2  ,  Ag  CN  2  &  Ag 2  S 2 O3  2 
3) Tetrahydride aluminium lithionate
 3 2
4) Aluminium lithium hydride 4.  Ag  N H 3  4  ,  Ag  C N  4  &  Ag 2  S 2 O 3  2 
16. The secondary valency of chromium in
ISOMERISM
10. Dipole moment will be zero in the complexes Cr  en 3  Cl3 is
2 1) 6 2) 3 3) 2 4) 4
1) Ni  CN  
 4
CFT
2) Cis  Pt NH 3  2 Cl 2  17. Stabilisation energy of octahedral complex
with d 7 configuration
3) Trans  Pt NH 3  2 Cl 2  4) Both 1 and 3 A) 1.8  0 with one unpaired electron
11. The number of geometrical isomers of B) 1.8  0 with three unpaired electrons
Co  NH 3 3  NO3 3  is
C) 0.8  0 with one unpaired electron
1) 0 2) 2 3) 3 4) 4 D) 0.8  0 with three unpaired electrons

12. For the given comlex CoCl2  en  NH 3 2  , 1) A and D 2) A and B 3) C and D 4) B and C
18. If  0  P , the correct electronic
the number of geometrical iosmers, the
number of optical isomers and total number confuguration for d 4 system will be ( p =
of isomers of all type possible respectively are pairining energy)
1) 2, 2 and 4 2) 2, 2 and 3 1) t24g eg0 2) t23g e1g 3) t20g eg4 4) t22g eg2
3) 2, 0 and 2 4) 0, 2 and 2
APPLICATION OF COMPLEXES IN
EFFECTIVE ATOMIC NUMBER QUALITATIVE ANALYSIS AND METAL
13. Which does not obey EAN rule? CARBONYL COMPOUNDS AND STABILITY
OF CO-ORDINATION COMPOUNDS
1) K 4  Fe  CN 6  2) K 3  Fe  CN 6  19. The ligand used in the identification of cupric
copper in the laboratory
3) Co  NH 3 6  Cl3 4)  Ni  CO 4  1) NH 3 2) I  3) CN  4) S 2O32
 COMPLEX COMPOUNDS
Jr Chemistry E/M
20. The cofiguration of an element ‘X’ is 4 s 3d .
1 10 ADDITIONAL QUESTIONS
The wrong statement regarding the element 1. Type of Pair of examples
‘X’ is isomerism
1) it forms complexes
A)Ionisation (a) Cr  H 2O 6  Cl3 and
2) it exhibits variable velency
3) it forms paramagnetic ions only
Cr  H 2O 5 Cl  Cl2 .H 2O
4) It can form coloured salts  
21. In the qualitative analysis of group 3 cations
Cr  NH 3 6  Co  CN 6 
blood red colouration is a test for B) Linkage (b)   
1) iron using cyanide as ligand & Co  NH 3 6  Cr  CN 6 
2) chromium using cyanide as ligand
3) iron using thiocyanide as ligand Co  NH 3 5  NO2   Cl2
 
C)Coordination (c)
4) chromium using thiocyanide as ligand & Co  NH 3 5  ONO   Cl2

LEVEL-I (H.W) - KEY Co  SO4  NH 3 5  Br

 
1) 2 2) 1 3) 4 4) 2 5) 1 6) 4 7) 4 D)Hydrate (d)
& Co  Br  NH 3 5  SO4
8) 1 9) 2 10) 4 11) 2 12) 2 13) 2 14) 4
15) 1 16) 1 17) 1 18) 1 19) 4 20) 3 21) 3 The correct match is
A B C D A B C D
LEVEL-I (H.W) - HINTS 1. a b c d 2. b a d c
formula of the compound is  Ca2  EDTA 
3. d c b a 4. d b c a
1.
2. COLUMN-I COLUMN-II
4. CuSO4  4 NH 3  Cu  NH 3 4  SO4 (Complex) (Geometry)
A)  Ni (CN )6 2  p) Tetrahedral
5. BF3 Lewis acid. It can’t donate the lone pair of
electrons. B)  ZnCl4 2  q) Trigonal
8. Hexaaquotitanium(III) chloride is given as
C) Co(en)3 3 r) Sqaure planar
Ti  H 2O 6  Cl3 .
D) Cu ( NO2 ) 4 4  s) square pyramid
13. EAN = Z  x  n  y ; Z=At number of metal ion,
t) Octahedral
x=charge of metal ion, n= secondary valency
A B C D A B C D
14. n = M x V
1) r p t p 2) r p t q,t
15. AgCl  2 NH 3   Ag  NH 3  2  Cl 3) p q r s 4) p t q s
3. COLUMN-I COLUMN-II
AgCl  2 KCN  K  Ag  CN  2   KCl
(Equivalent (formula)
AgCl  2 Na2 S 2O3  Na3  Ag  S 2O3 2   KCl conductance)
17. For strong field ligands - A) 229 p)  Pt ( NH 3 )5 Cl  Cl3

CFSE   6  0.4  1 0.6   1.8 0 B) 97 q)  Pt ( NH 3 )3 Cl3  Cl

one unpaired electron C) 404 r)  Pt ( NH 3 )4 Cl2  Cl2
For weak field ligands D) 523 s)  Pt ( NH 3 )6  Cl4
CFSE   5  0.4  2  0.6   0.8 0 A B C D A B C D
three unpaired electrons 1) s p q r 2) r q s p
18. Strong field ligand. 3) r q p s 4) s p r q
 COMPLEX COMPOUNDS
Jr Chemistry E/M
4. COLUMN-I COLUMN-II 8. Match the lists I and II and pick the correct
(Complex) (  effective) matching from the codes given below
A) K3  MnF6  p) 1.70 List - I List - II
(complex) (Structure and magneticmoment)
B) K3 VF6  q) 2.8 
a)  Ag  CN 2  1) square planar and 1.73 BM
C) K2  Mn(CN )6  r) 3.8
3
D) K3 TiF6  s) 4.9 b) Cu  CN 4  2) Linear and zero
A B C D A B C D 4
c) Cu  CN 6  3) Octahedral and zero
1) s q r p 2) q s r p
2
d) Cu  NH 3 4  4) tetrahedral and zero
3) s q p r 4) p q r s
5. Match the following.
4
Set -I Set -II e)  Fe  CN 6  5) octrahedral and 1.73 BM
A) Co-ordination number 3 1) Pentagonal
bipyramidal 1) a-2,b-4,c-5,d-1,e-3 2) a-5,b-4,c-1,d-3,e-2
B) Co-ordination number 2 2) Trigonal 3) a-1,b-3,c-4,d-2,e-5 4) a-4,b-5,c-2,d-1,e-3
bipyramidal ASSERTION & REASON TYPE
C) Co-ordination number 5 3) Linear Two statements ‘A’ and ‘R’ are given below:
D) Co-ordination number 7 4) Trigonal planar Select your answers to these items using the
The correct matching is codes given below :
A B C D A B C D 1) Both A and R are correct and R is the correct
1) 4 3 2 1 2) 1 2 3 4 explanation of A
3) 4 3 1 2 4) 3 1 2 4 2) Both A and R are correct and R is not a correct
6. COLUMN-I COLUMN-II explanation of A
(Complex Ions) (No. of unpaired 3) A is true but R is false
electrons) 4) A is false but R is true
9. Assertion (A) : Among the cobalt (III)
A) CrF6 4  p)One 3
complexes Co  NH 3 6  is a diamagnetic but
B)  MnF6 4
q) Two
CoF6 
3
is paramagnetic.
C) Cr (CN )6  4
r) Three
3

D)  Mn(CN )6  4
s) Four Reason (R) : Hybridisation of Co  NH 3 6  is
t) Five sp 3d 2 where as hybridisation of Co in
A B C D A B C D
CoF6 
3
is d 2 sp 3 .
1) s t q p 2) q r s t
3) t q s p 4) p q r s 10. Assertion (|A) : The complex ion

7. COLUMN-I COLUMN-II cis  Co  en 2 Cl2  is optically active
(Complex) (O.N. of Co)
Reason (R) : It is an octahedral complex
A) Co( NCS )( NH 3 )5  (SO3 ) p) -1
11. Assertion (A) :  Ni  CO 4  is diamagnetic and
B) Na Co(CO)4  q) 0
tetrahedral in shape
C) Na4 Co( S2O3 )3  r) 1 Reason (R) : Hybridisation of the complex is
D) Co2 (CO)8 s) 2 dsp 2 .
t) 3
ADDITIONAL QUESTIONS - KEY
A B C D A B C D
1) 3 2) 1 3) 3 4) 1 5) 1 6) 1 7) 1
1) t p s q 2) q t s p
3) p t s q 4) q r s t 8) 1 9) 3 10) 2 11) 3
 9. COMPLEX COMPOUNDS JEE-MAIN-SR-CHEM-VOL-II
Jr Chemistry E/M
ISOMERISM
LEVEL-II (C.W)
7. The complexes Co ( NH 3 )6  Cr (C2O4 )3 
DEFINITION OF and Cr ( NH 3 )6  Co (C2O4 )3 
CO-ORDINATION COMPOUND 1) Geometrical isomerism
2) Ionization energy
1. Oxidation number of cobalt in K Co (CO )4  3) Co-ordination isomerism
is 4) Linkage isomerism
1) +1 2) +3 3) -1 4) -3 8. Which of the following complex or the
complex ion will show geometrical
[ EDTA]
4−
2. is a isomerism?
−
1) Monodentate ligand 2) Bidentate ligand 1)  Pt ( NH 3 )2 Cl2  2)  Pt ( NH 3 ) Cl5 
3) Quadridentate ligand 4) Hexadentate ligand
3+
3. ‘en’ is an example of a 3)  Pt ( NH 3 )5 Cl  4) Co ( NH 3 )6  Cl3
1) Monodentate ligand 2) Bidentate ligand 9. Which isomerism is exhibited by
3) Tridentate ligand 4) Hexadentate ligand Co ( NH 3 )3 ( H 2O )3  Cl3
NOMENCLATURE 1) Geometrical isomerism
2) Linkage isomerism
4. IUPAC name of K 2 [ PtCl6 ] is 3) Coordination isomerism
1) Potassiumhexachloroplatinum 4) Ionization isomerism
2) Potassiumhexachloroplatinum(IV) 10. Co ( NH 3 )4 ( NO2 )2  Cl exhibits
3) Potassium hexachloroplatinate(IV) 1) Linkage isomerism, ionization isomerism and
4) Dipotassium hexa chloro platinum geometrical isomerism
5. IUPAC name of 2) Ionisation isomerism, geometrical isomerism
and optical isomerism
 Pt ( NH 3 )3 Br ( NO2 ) Cl  Cl is 3) Linkage isomerism, geometrical isomerism
1) Triamminechlorobromonitroplatinum (IV) and optical isomerism
chloride 4) Linkage isomerism, ionization isomerism and
optical isomerism.
2) Triamminebromonitrochloroplatinum (IV)
11. Which one of the following is an example of
chloride
coordination isomerism?
3) Triamminebromochloronitroplatinum (IV)
chloride 1) Co ( NH 3 )5 Br  SO4 and
4) Triamminenitrochlorobromoplatinum (IV) Co ( NH 3 )5 SO4  Br
chloride
6. Tetrammine diaqua copper (II) hydrox 2) Co ( NH 3 )5 NO2  Cl2 and
ide is given by the formula
 Co ( NH 3 )5 ONO  Cl2
1) Cu ( NH 3 )4  (OH )2 .2 H 2O
3) Cr ( H 2O )6  Cl3 and
2)  Cu ( NH 3 )4 (OH )2  .2 H 2 O
Cr ( H 2O )5 Cl  Cl2 .H 2O
3)  Cu ( NH 3 )4 ( H 2O )2  (OH )2
4) Cr ( NH 3 )6  Co (CN )6  and
4)  Cu ( NH 3 )4 ( H 2O )(OH )2  Co ( NH 3 )6  Cr (CN )6 
JEE-MAIN-SR-CHEM-VOL-II COMPLEX COMPOUNDS
Jr Chemistry E/M
VBT CFT
20. For an octahedral complex, which of the
[ FeF6 ]
3+
12. has Fe atom .... hybridized with following d electron configuration will give
unpaired ........ electrons. maximum crystal - field stabilisation energy
1) d 2 sp 3 , 4 2) d 2 sp 3 ,5 1) High spin d 6 2) Low - spin d 4
3) sp 3 d 2 ,5 4) sp 3 d 2 ,3 3) Low spin d 5 4) High - spin d 7
13. How many EDTA molecules are required to APPLICATION OF COMPLEXES IN
make an octahedral complex with a Ca +2 QUALITATIVE ANALYSIS AND METAL
ion? CARBONYL COMPOUNDS AND STABILITY
1) two 2) six 3) three 4) one OF CO-ORDINATION COMPOUNDS
14. Which of the complexes will exhibit the 21. Chromium compound widely used in tanning
minimum paramagnetic behaviour of leather is
+2 +2 1) Cr2O3 2) Cr2O2Cl2 3) Cr2O3
1)  Fe ( H 2O )6  2)  Mn ( H 2O )6 
4) K2 SO4Cr2 ( SO4 )3 24H 2O
+2 +2
3) Cr ( H 2O )6  4)  Ni ( H 2O )6 
22. Wilkinsons catalyst,  Rh ( Ph3 P )3 Cl  is used
15. The expected spin only magnetic moments for for
4−
 Fe (CN )6  and [ FeF6 ] are
3− 1) Hydrogenation of oils
2) Hydrogenation of alkynes
1) 1.73and1.73 B.M 2) 1.73and 5.93 B.M 3) Hydrogenation of alkenes
3) 0.0 and1.73 B.M 4) 0.0 and 5.92 B.M 4) Polymerisation of alkenes
23. Coordination compounds have great
16. The volume (in mL) of 0.1M AgNO3 required importance in biological systems. In this
for complete precipitation of chloride ions context which of the following statements is
present in 30 mL of 0.01M solution of incorrect?
1) Chlorophylls are green pigments in plants and
Cr ( H 2O )5 Cl  Cl2 as silver chloride is close contain calcium.
to 2) Haemoglobin is the red pigment of blood and
1) 3 2) 4 3) 5 4) 6 contains iron.
17. Among the following ions which one has the 3) Cyanocobalamin is B12 and contains cobalt.
highest paramagnetism: 4) Carboxypeptidase-A is an enzyme and
3+ 2+
1) Cr ( H 2O )6  2)  Fe ( H 2O )6  contains zinc.

2+ 2+ LEVEL-II (C.W) - KEY

3) Cu ( H 2O )6  4)  Zn ( H 2O )2 
1) 3 2) 4 3) 2 4) 3 5) 3 6) 3 7) 3
18. Which of the following complexes is an outer 8) 1 9) 1 10) 1 11) 4 12) 3 13) 4 14) 4
orbital complex?
15) 4 16) 4 17) 2 18) 4 19) 2 20) 3 21) 4
4− 4−
1)  Fe (CN )6  2)  Mn (CN )6  22) 3 23) 1
3+ 2+
3) Co ( NH 3 )6  4)  Ni ( NH 3 )6  LEVEL-II (C.W) - KEY
EFFECTIVE ATOMIC NUMBER
2. (CH COO )
3
−
2
− N − CH 2 − CH 2 − N −
19. The EAN of cobalt in the complex ion (CH COO )
3
−
2
+
Co (en )2 Cl2  is 12. F − is weak field ligand so, its forms outer
1) 27 2) 36 3) 33 4) 35 complex.
 COMPLEX COMPOUNDS JEE-MAIN-SR-CHEM-VOL-II
Jr Chemistry E/M
14. H 2O is weak field ligand so, rearrangement 2. Which of the following is not chelating agent?
electron is possible 1) Thiosulphato 2) Oxalato
3) Glycinato 4) Ethylene diamine
1) n = 4 → µ = 4.85 BM
2) n = 5 → µ = 5.92 BM NOMENCLATURE
3) n = 4 → µ = 4.85 BM 3. IUPAC name of Na3 CoCl ( NO2 )5  is
4) n = 2 → µ = 2.8 BM 1) Sodium chloropentanitrocobaltate(III)
16. 1 - 2 2) Sodium cobaltnitrate
0.3 - ? 3) Trisodium chloropentanitro cobalt
0.3 4) Pentanitrocobalt (III) trisodium complex
× 2 = 0.6
1 4. The IUPAC name of the Wilkinsons catalyst
0.6  RhCl ( P Ph3 )3  is
0.6 = 0.1× X ; X = 0.1 = 6ml
1) Chlorotris (triphenylphopshine) rhodium (I)
17. 1) −n = 3 2) n = 4 3) n = 1 4) n = 0 2) Chlorotris (triphenylphosphine) rhodium (IV)
18. Ni +2 − 4 s 0 3d 8 rearrangement of electron is not 3) Chlorotris (triphenylphosphine) rhodium (0)
possible. So, hybridisation is sp 3 d 2 . 4) Chlotrotris (triphenylphosphine) rhodium (VI)
5. IUPAC name for the compound
20. High spin d 6 : t24g eg2
Co ( NH 3 )5 ( NO2 ) Cl2 is
CFSE = [0.4 × 4 − 0.6 × 2] ∆ 0
1)Nitrito-N-pentaammine cobalt (III)chloride
Low spin d 4 : t24g eg0 2)Nitrito-N-pentaammine cobalt (II) chloride
3) Pentaammine nitrito-N-cobalt (II) chloride
CFSE = [0.4 × 4] = 1.6∆ 0
4) Pentaammine nitrito-N-cobalt (III)chloride
Low spin d 5 : t25g eg0
ISOMERISM
CFSE = [0.4 × 5] ∆ 0 6. Both geometrical and optical isomerism are
shown by
High spin d 7 : t25g eg2 + 2+
1) Co (en )2 Cl2  2) Co ( NH 3 )5 Cl 
CFSE = [0.4 × 5 − 0.6 × 2] ∆ 0
+ 3−
22. Wilkinson’s catalyst is ( Ph3 P )3 RhCl 3) Co ( NH 3 )4 Cl2  4) Cr (ox )3 
(transform)
LEVEL-II (H.W) 7. Which of the following is not optically active?
3+ 3−
1) Co (en )3  2) Cr (ox )3 
DEFINITION OF
+
CO-ORDINATION COMPOUND 3) cis − CoCl2 (en )2 
1. An ambidentate ligand is one which
+
1) is linked to the metal atom at two points 4) trans − CoCl2 (en )2 
2) has two donor atoms but only one of them
has the capacity to form a coordinate bond. 8. Cis-trans isomerism is found in square planar
3) has two donor atoms but either of the two complexes of the molecular formula: (a and
can form a co-ordinate bond b are monodentate ligands)
4) forms chelate rings 1) Ma4 2) Ma3b 3) Ma2b2 4) Mab3
 JEE-MAIN-SR-CHEM-VOL-II COMPLEX COMPOUNDS
Jr Chemistry E/M
9. Which of the following isomeric pairs shows 14. A solution containing 2.675g of CoCl . 6NH
3 3
ionization isomerism?
−
(molar mass = 267.5 g mol ) is passed
1
1) Co ( NH 3 )6  Cr (CN )6  and
through a cation exchanger. the chloride ions
Cr ( NH 3 )  Co (CN ) 
 6  6 
obtained is solution were treated with excess
of AgNO3 to give 4.78 g of AgCl (molar mass
2) Cr ( H 2O )6  Cl3 and
= 143.5 g mol −1 ). The formula of the complex
Cr ( H 2O )5 Cl  Cl2 .H 2O is
(At. mass of Ag = 108 u)
3)  Pt ( NH 3 )2 Cl 2  and
1) CoCl3 ( NH 3 )3  2) CoCl ( NH 3 )5  Cl2
 Pt ( NH 3 )4  [ PtCl4 ]
3) Co ( NH 3 )6  Cl3 4) CoCl2 ( NH 3 )4  Cl
4) Co ( NH 3 )5 Br  SO4 and
2+
Co ( NH 3 )5 SO4  Br 15. The complex  Pt ( NH 3 )4  has... structure

VBT 1) square planar 2) tetrahedral

10. List - I List - II 3) pyramidal 4) pentagonal
A) Ti +3 1) Charge transfer phenomenon\ CFT
B) MnO4− 2) Impurities 16. Crystal field stabilization energy for high
spin d 4 octahedral complex is
C) F2 3) s-s transition
D) Gems 4) d-d transition 1) 0.6∆ 0 2) 1.8∆ 0 3) 1.6∆ 0 4) 1.2∆ 0
5) Excitation of electron \
APPLICATION OF COMPLEXES IN
The correct match which is responsible for
colour QUALITATIVE ANALYSIS AND METAL
1) A - 4, B - 1, C - 2, D - 5 CARBONYL COMPOUNDS AND STABILITY
2) A - 4, B - 1, C - 5, D - 2 OF CO-ORDINATION COMPOUNDS
3) A - 4, B - 5, C - 1, D - 2 17. Which of the following is antidote for lead
4) A - 5, B - 2, C - 3, D - 4 poisoning?
11. Co-ordination number of Cr is 6.A complex
1) CoCl3 2) Cis-platin 3) EDTA 4) DMG
entity with C2O4−2 en, superoxide as ligands
18. EDTA is used for the estimation of
is Cr (C2O4 )x (en ) y (O2 )z  . The ratio of x : y 1) Na + and K + ions 2) Cl − and Br − ions
: z is 3) Cu 2 + and Ag + ions 4) Ca 2 + and Mg 2+ ions
1) 1 : 1 : 2 2) 1 : 1 : 1 3) 1 : 2 : 2 4) 2 : 1 : 1 19. Wilkinson’s catalyst used as a homogeneous
12. The geometries of Ni (CO )4 and catalyst in the hydrogenation of alkenes
contains
Ni ( PPh3 )2 Cl2 are 1) iron 2) aluminium
1) both square planar 3) rhodium 4) cobalt
2) tetrahedral and square planar 20. Ziegler - Natta catalyst is
3) both tetrahedral
4) square planar and tetrahedral 1) Solution of SnCl4 + trialkylaluminium
13. What are the magnetic moment (in BM) for 2) Solution of TiCl4 + trialkylaluminium
Ni(II) ion in square planar and octahedral
geometry, respectively? 3) Solution of TiCl4 + trialkylchromium
1) 0 and 2.83 2) 2.83 and 2.83
4) Solution of SnCl4 + Tollen’s reagent
3) 0 and 1.73 4) 2.83 and 0
 COMPLEX COMPOUNDS JEE-MAIN-SR-CHEM-VOL-II
Jr Chemistry E/M
LEVEL-II (H.W) - KEY 3. A coordinate complex contains CO +3 , Cl −
1) 3 2) 1 3) 1 4) 1 5) 4 6) 1 7) 4 and NH 3 when dissolved in water, one mole
8) 3 9) 4 10) 2 11) 1 12) 2 13) 1 14) 3 of this complex gave a total of 3 moles of ions.
15) 1 16) 1 17) 3 18) 4 19) 3 20) 2 The complex is [EAM-2012]

LEVEL-II (H.W) - HINTS 1) Co ( NH 3 )6  Cl3 2) Co ( NH 3 )5 Cl  Cl2

11. C2O4−2 and en are bidentate ligands O2− is
3) Co ( NH 3 )4 Cl2  Cl 4) Co ( NH 3 )3 Cl3 
monotente ligand.
4. Identify the correct set [EAM-2013]
12. Hybridisations are sp3 and dsp 2
Molecule Hybridisation Shape
13. For square planar
1) PCl5 dsp 3 square pyramidal
→n=0 −2
2)  Ni (CN )4  sp3 tetrahedral
For octahedral
3) SF6 sp 3 d 2 octahedral
→n=2
4) IF3 dsp 3 pyramidal
2.675
14. Moles of the complex = = 0.01 5. Match the following [EAM-2014]
267.5
List-I List-II
4.78
moles of AgCl precipitated = = 0.033 3−
143.5 A) sp3 I) Co ( NH 3 )6 
Thus, 1 mole of the complex will precipitate
0.033 B) dsp 2 II)  Ni (CO )4 
AgCl = 3moles
0.01
C) sp 3 d 2 III)  Pt ( NH 3 )2 Cl2 
That means 1 molecule of the complex contains
3 ionizable Cl.
IV) (CoF6 )
−3
D) d 2 sp 3
Hence, the formula is Co ( NH 3 )6  Cl3
16. Weak field ligand V)  Fe (CO )5 

d 4 → t 23g , e1g 1) A-II, B-III, C-IV, D-I

2) A-II, B-III, C-I, D-V
CFSE = 3 × 0.4 − 1× 0.6 = 0.6∆ 0
3) A-III, B-II, C-IV, D-I
PREVIOUS EAMCET QUESTIONS 4) A-V, B-II, C-IV, D-III
1. CO ( NH 3 )5 SO4  Br and CO ( NH 3 )5 Br  SO4
6. Ti ( H 2O )6  Cl3 has Ti atom ___ hybridized
are a pair of ____ isomers [EAM-2008]
with unpaired ___ electrons. [EAM-2010]
1) Ionization 2) Ligand
3) Coordination 4) Hydrate 1) d 2 sp 3 ,1 2) d 2 sp 3 , 4
2. The solution of X having excess of caustic
potash is used to detect ammonia. Which of 3) sp 3 d 2 ,1 4) sp 3 d 2 ,3
the following is X [EAM-2011]
1) K 2 [ HgI 4 ] 2) CO ( NH 3 )6  Cl3 PREVIOUS EAMCET - KEY

3) K 3  Fe (CNS )6  4) CO ( NH 3 )5 SO4  Br 1) 1 2) 1 3) 2 4) 3 5) 1 6) 3

JEE-MAIN-SR-CHEM-VOL-II COMPLEX COMPOUNDS
Jr Chemistry E/M
6. Among the following which are ambidentate
LEVEL-III lignads ?
WERNER’S THEORY a) NO 2b) NO
−
c) EDTA
3
− 4-

1. One mole of the complex compound d) C O

2 e) SCN
4
2−
f) H NCH CH NH
−
2 2 2 2

Co ( NH 3 )5 Cl3 gives 3 moles of ions on 1) (a) and (b) 2) (c) and (d)
dissolution in water. One mole of the same 3) (a) and (f) 4) (a) and (e)
complex reacts with two moles of AgNO3 7. The number of donor sites in dimethyl
glyoxime, glycinato, diethylene triamine and
solution to yield two moles of AgCl ( s ) . The EDTA are respectively
structure of complex is 1)2,2,3 and 6 2) 2,2,3 and 4
1) Co ( NH 3 )4 Cl  Cl2 .NH 3 3) 2,2,2 and 6 4) 2,3,3 and 6

2) Co ( NH 3 )5 Cl  Cl2
NOMENCLATURE
8. The IUPAC name of the coordination
3) Co ( NH 3 )3 Cl3  [Link] 3
compound K 3  Fe (CN )6  is
4) Co ( NH 3 )4 Cl2  [Link] 3 1) potassium hexacyanoferrate (II)
2. The primary and secondary valencies of 2) potassium hexacyanoferrate (III)
chromium in the complex ion, 3) potassium hexacyanoiron (II)
dichlorodioxalatochromium (III), are 4) tripotassium hexacyanoiron(II)
respectively
1) 3,4 2) 4,3 3) 3,6 4) 6,3 ISOMERISM
3. In the complex with formula MCl3 .4 H 2O the 9. Which one of the following has largest
co-ordination number of the metal M is six number of isomers?
and there is no molecule of hydration in it. + 2+
1)  Ru ( NH 3 )4 Cl2  2) Co ( NH 3 )5 Cl 
The volume of 0.1M AgNO3 solution needed
2+ +
to precipitate the free chloride ions in 200ml 3)  Ir ( Ph3 )2 H (CO ) 4) Co (en )2 Cl2 
of 0.01M soltuion of the complex is
1) 40ml 2) 20 ml 3) 60 ml 4) 80 ml (R=alkyl group, en=ethylenediamine)
4. The molar ionic conductances of octahedral 10. Which of the following compounds shows
complexes. optical isomerism?
I) PtCl4 .5 NH 3 II) PtCl4 .4 NH 3 3− 3−
1) Cr (C2O4 )3  2) Co (CN )6 
III) PtCl4 .3 NH 3 IV) PtCl4 .2 NH 3
2+
3) Cu ( NH 3 )4  4) [ZnCl4 ]
2−
1) I<II<III<IV 2) IV<III<II<I
3) III<IV<II<I 4)IV<III<I<II
11. In which of the following pairs both the
DEFINITION OF complexes do not show optical isomerism?
CO-ORDINATION COMPOUND −3
5. The coordination number of a central metal 1) cis − Cr (C2O4 )2 Cl2  ,
atom in a complex is determined by
1) the number of ligands around a metal ion trans − Co ( NH 3 )4 Cl2 
bonded by sigma bonds
2) the number of ligands around a metal ion 2) Co (en )3  Cl3 , Cis − Co (en )2 Cl2  Cl
bonded by π -bonds
3)  PtCl2 ( en ) , [ NiCl2 Br2 ]
−2
3) the number of ligands around a metal ion
bounded by sigma and pi bonds both.
4) the number of only anionic ligands bonded 4) Co ( NO3 )3 ( NH 3 )3  , cis −  Pt (en )2 Cl2 
to the metal ion.
 COMPLEX COMPOUNDS JEE-MAIN-SR-CHEM-VOL-II
Jr Chemistry E/M
12. Of the following configurations, the optical 17. The correct order of magnetic moments (spin
isomers are only values in bohr magneton) among is
4−
1) [MnCl4 ] > [CoCl4 ] >  Fe (CN )6 
2− 2−

4−
2) [MnCl4 ] >  Fe (CN )6  > [CoCl4 ]
2− 2−

4−
3)  Fe (CN )6  > [MnCl4 ] > [CoCl4 ]
2− 2−

4−
4)  Fe (CN )6  > [CoCl4 ] > [MnCl4 ]
2− 2−

(Atomic numbers: Mn = 25, Fe = 26, Co = 27)

18. Which one of the following cyano complexes
would exhibit the lowest value of
paramagnetic behaviour?
3− 3−
1)  Fe (CN )6  2) Co (CN )6 
3− 3−
3) Cr (CN )6  4)  Mn (CN )6 

1) I and II 2) I and III 19. Which of the following statemants is not

3) II and IV 4) II and III correct ?
2−
13. The type of isomerism shown by 1) The complexes [ NiCl ] and  Ni (CN )  4
2−
4

Co ( NH3 )4 Br2  Cl is differ in their magnetic properties.

2− 2−
1) Optical and ionisaton 2) The complexes Ni (Cl )4  and  Ni (CN )  differ
4

2) Geometrical and optical in the state of hybridisation of nickel.

3) Geometrical and ionisation 2− 2−
4) Only geometrical 3) the complexes Ni(Cl)  and  Ni (CN )  differ
4 4

14. Which of the following doesn’t have optical in geometry.

isomer? 2− 2−
4) The complexes Ni (Cl )4  and  Ni (CN )  differ
1) Co (en )3  Cl3 2) Co ( NH 3 )3 Cl3 
4

in primary valancies of nickel.

3) Co (en )2 Cl2  Cl 4) Co (en )( NH 3 )2 Cl2  Cl 20. The species having tetrahedral shape is
2− 2−
1) [PdCl ]  Ni (CN 4 )  Pd (CN 4 ) 4) [ NiCl ]
2− 2−

VBT AND SHAPES OF 4

2) 3) 4

COORDINATION COMPOUNDS 21. 2−

 Ni (CN )4  , [MnBr4 ]
2−
and [FeF ] . Geometry, 6
3−

15. The complex K 3  Fe (CN )6  should have a hybridisation and magnetic moment of the
ions respectively are
spin only magnetic moment of
1) Tetrahedral ,square planar, octahedral :
1) 48BM 2) 2 5BM 3) 35BM 4) 6BM
sp3 , dsp 2 , sp3d 2 :5.9,0,4.9
16. Which one of the following complexes is an
outer orbital complex? 2) Tetrahedral ,square planar, octahedral :
4− 4− dsp 2 , sp3 , sp3d 2 :0,5.9,4.9
1)  Fe (CN )6  2)  Mn (CN )6 
3) Square planar, tetrahedral ,octahedral :
3+ 2+
3) Co ( NH 3 )6  4)  Ni ( NH 3 )6  dsp 2 , sp3 , d 2 sp 3 :5.9,4.9,0
4) Square planar, tetrahedral ,octahedral :
[Atomic numbers: Mn = 25, Fe = 26, Co = 27,
Ni = 28] dsp 2 , sp3 , sp3d 2 :0,5.9,4.9
JEE-MAIN-SR-CHEM-VOL-II COMPLEX COMPOUNDS
Jr Chemistry E/M
CFT 27. In Fe (CO )5 the Fe − C bond possess
22. Cr ( H 2O )6  Cl3 has a magnetic moment of 1) π − character only
3.83BM. The correct distribution of 3d 2) σ character only
electrons in chromium present in the complex 3) ionic character only
is 4) Both σ and π character
1
1
1) 3 d xy , 3 d 1yz , 3 d zx1 2) 3 d xy , 3 d 1yz , 3 d z12
LEVEL-III - KEY
1 1 1 1 1 1
3) 3d ( x2 − y 2 ) ,3d ,3d
4) 3d ,3d ( x2 − y 2 ) ,3d
z2 xz xy yz 1) 2 2) 3 3) 2 4) 2 5) 1 6) 4 7) 1
23. In which of the following octahedral 8) 2 9) 4 10) 1 11) 3 12) 3 13) 3 14) 2
complexes will the magnitude of ∆ 0 be the 15) 3 16) 4 17) 2 18) 3 19) 4 20) 4 21) 4
highest 22) 1 23) 1 24) 1 25) 1 26) 1 27) 4
3− 3−
1) Co (CN )6  2) Co (C2O4 )3 
LEVEL-III - HINTS
3+ 2. 3+ Primary valecy corresponds to oxidation
3) Co ( H 2O )6  4) Co ( NH 3 )6 
state and secondary valecy corresponds to
24. Which of the following is a correct Irving- coordination number primary=3, secondary=6.
Williams order? (Tendency of complex
formation) 3. Formula of complex is  MCl2 ( H 2O )4  Cl .
1) Mn 2 + < Fe 2 + < Co 2 + < Ni 2 + Ionisable Cl − atoms are only one.
2) Ni 2 + < Co 2 + < Fe 2 + < Mn 2 + M1V1 = M 2V2
3) Fe 2 + < Mn 2 + < Ni 2 + < Co 2 + 4. IV of four complexes
2+
4) Co < Mn < Fe < Ni 2+ 2+ 2+
(1) is 3, (2) is 2, (3) is 1, (4) is 0
25. Which order is correct in spectrochemical 6. are ambidentate ligands which
− NO2 − and − SCN
series of ligands? have two donor atoms.
1) Cl − < F − < C2O42− < NO2− < CN −
The complex [Co(en) 2 Cl2 ] shows geometrical
+
9.
2) CN − < C2O42− < Cl − < NO2− < F − as well as optical isomerism.

3) C2O42− < F − < Cl − < NO2− < CN − 15. µ = n ( n + 2 ) where n =5.

4) F − < Cl − < NO2− < CN − < C2O42− 17. For Mn +2 → n = 5

For Co +2 → n = 3
APPLICATION OF COMPLEXES IN
QUALITATIVE ANALYSIS AND METAL For Fe +2 → n = 4
CARBONYL COMPOUNDS AND STABILITY 18. For Fe +3 and Mn +2 → n = 5
OF CO-ORDINATION COMPOUNDS
26. Which of the following ligands is called π -
For Co +3 → n = 4
acceptors? For Cr +3 → n = 3
CO, CN − , NO + 19. Cl is weak field ligand and ( N − is strong field
(I ) ( II ) ( III ) ligand so, in [ NiCl4 ]
−2
hybridisation is sp3 in
1) I,II,III 2) I, II only −2
3) I,III only 4) III only  Ni (CN )4  hybridisation is dsp 2 .
 COMPLEX COMPOUNDS JEE-MAIN-SR-CHEM-VOL-II
Jr Chemistry E/M
PREVIOUS AIEEE QUESTIONS 2. Aqueous solution of Ni contains [ Ni ( H 2 O)6 ]2 +
2+

1. Which one of the following has an optical and its magnetic moment is 2.83 B.M. when
isomer [AIEEE-2010] ammonia is added in it, the predicted change
2+ 2+ in the magnetic moment of solution is :
1)  Zn (en )2 
 (
2)  Zn en ( NH 3 )  )2  1) It will remain same
3+ 3+
2) It increases from 2.83 B.M.
3) Co (en )3  4) Co ( H 2O )4 en  3) It decreases from 2.83 B.M.
4) It can not be predicted theoretically.
2. Which of the following facts about the 3. Which of the following complexes is a
complex Cr ( NH 3 )6  Cl3 is wrong. paramagnetic complex ?
[AIEEE-2011] 1) K 2  Ni (CN )4  2)  Ni ( H 2 O )6  ( NO3 ) 2

1) The complex innvolves d 2 sp3 hybridisation 3) [Co( NH 3 )6 ]Cl3 4) [ Pt ( NH 3 )4 ]Cl2

4. Which of the following are paramagnetic ?
and is octahedral shape
2) The complex is paramagnetic 1) K 4 [ Fe(CN )6 ] 2) K3 [Cr (CN )6 ]
3) The complex is an outer orbital complex 3) K3 [Co(CN )6 ] 4) K 2 [ Ni(CN )4 ]
4) The complex gives white precipitate which 5. Which of the following pairs of d-electron
silver nitrate solution. configuration exhibit both low and high spin
3. The magnetic moment (spin only) of tetrahedral complex
[ NiCl4 ]2− [AIEEE-2011] 1) d 1 , d 2 2) d 3 , d 4 3) d 7 , d 8 4) d 9 , d 10
1) 1.8BM 2) 5.86 BM 6. Assign the hybridisation, shape and magnetic
3) 2.82 BM 4) 3.82 BM moment of K 2 Cu (CN )4 
4. Which among the following will be named
1) sp 3 , tetrahedral, 1.73 BM
as dibromidobis (ethylene diamine)
chromium III bromide [AIEEE - 2012] 2) dsp 2 , square planar, 1.73 BM
+ − −
2) CrBr2 ( en )2 
3) sp 3 , tetrahedral, 2.8 BM
1) CrBr2 (en )2 
 
4) dsp 2 , square planar, 2.8 BM
+ +2
3) CrBr2 ( en ) 4) CrBr2 (en ) 7. Which of the following is most stable.
3+ 3−
5. Which of the following complex species is not 1)  Fe ( H 2O )6  2)  Fe (CN )6 
expected to exhibit optical isomerisim
3−
[MAINS-2013] 3)  Fe (C2O4 )3  4) [ FeCl6 ]3−
+
1) Co (en )2 Cl2  2) Co ( NH 3 )3 Cl3  COMPREHENSION TYPE QUESTIONS
+ 3+
Comprehension-1: Valence bond theory
3) Co (en ) ( NH 3 )2 Cl2  4) Co (en )3  successfully explains the magnetic behaviour of
complexes. The substances which contains
PREVIOUS AIEEE QUESTIONS - KEY unpaired electrons are paramagnetic and
1) 3 2) 3 3) 3 4) 1 5) 2 paramagnetic character increases as the number
of unpaired electrons increases. Magnetic
moment of a complex can be determined
LEVEL-IV experimentally and by using formula n(n + 2)
and we can determine the number of unpaired
1. Which is low spin complex ? electrons in it. This information is important in
1) [ Fe(CN )6 ]3− 2) [Co( NO2 )6 ]3− writing the electronic structure of complex
which in turn is also useful in deciding the
3) [Mn(CN )6 ]3− 4) All of these geometry of complex.
 JEE-MAIN-SR-CHEM-VOL-II COMPLEX COMPOUNDS
Jr Chemistry E/M
8. The magnetic moments (spin only) of [ NiCl4 ]2 − Comprehension-3: When degenerate
2−
d -orbitals of an isolated metal atom/ion come
and  Ni (CN )4  are: underinfluence of magnetic field of ligands,
1) 0, 0 2) 2.82 B.M., 2.82 B.M. the degeneracy is lost. Two sets of orbitals
3) 0, 2.82 B.M. 4) 2.82 B.M., 0 are obtained in case of octahedral and
9. There are four complexes of Ni. Select the tetrahedral complexes. The energy difference
complex/es which will be attracted by between these two set of orbitals is known as
magnetic field : crystal field splitting energy.
2− 15. The value of ∆ depends on
(I)  Ni (CN )4  (II) [ NiCl4 ]2 − 1) the nature of the metal cation
(III) Ni (CO )4 (IV)  Ni ( H 2 O )6 
2+ 2) nature of the ligands
3) geometry of the complex 4) all of these
1) I only 2) I and IV 16. The splitting power of the ligands in
3) II, III and IV 4) II and IV decreasing order is as follows :
10. The magnetic moments of complexes given
below are in the order : 1) CN − > NO2− > NH 3 > H 2O

(I) Ni (CO ) (II)  Mn (CN ) 

4−
2) CN − > NH 3 > NO2− > H 2O
4  6 
(III) [Cr ( NH 3 )6 ]
3+
(IV) [CoF6 ] 3− 3) NH 3 > CN − > NO2− > H 2O
1) I > II > III > IV 2) I < II < III < IV 4) H 2O > NH 3 > NO2− > CN −
3) IV > II > I > III 4) IV < II < I < III 17. Which of these species has same number of
11. The magnetic moment of [Cu ( NH 3 ) 4 ] was
2+
unpaired electrons with weak field as well as
found to be 1.73 B.M. The number of with strong field ligands.
unpaired electrons in the complex is : 1) Ti 2+ 2) Cr 3+ 3) Ni 2+ 4) all of these
1) 0 2) 1 3) 2 4) 3
LEVEL-IV - KEY
Comprehension - 2: When two or more
simple salts are mixed in storchiometric 1) 4 2) 1 3) 2 4) 2 5) 2 6) 2 7) 3
proportions and allowed to crystallised 8) 4 9) 4 10) 2 11) 2 12) 3 13) 4 14) 4
together, crystals of new compounds are 15) 4 16) 1 17) 4
formed. The new compound is known as
addition compound. LEVEL-IV - HINTS
12. The addition compound is a 5. d 3 and d 4 systems have e 2t12g and e 2t2g2
(high
1) double salt only
2) coordination compound only spin state) configuration. In weak field are e3t2g
0

3) either double salt or coordination compound

4) mixture of two salts and e 4t2g
0
(low spin state) configurations.
13. Mohr’s salt on dissociation in water gives 7. Complexes having more rings in structure will
1) positive test for Fe 2 + be more stable.
2) positive test for Fe 2+ and SO42 − 8. On the basis of VBT structure, [ NiCl4 ]2 − and
2−
3) positive test for Fe3+ , SO42 − and NH 4⊕ Ni (CN )4  have two and zero unpaired electrons

4) positive test for Fe 2+ , NH 4+ and SO42 − and magnetic moment is equal to n(n + 2) .
14. Complex compound is made up of 9. II and IV contain unpaired electrons.
1) simple cation and complex anion 10. The number of unpaired electrons in I, II, III &
2) complex cation and simple anion IV are 0, 1, 3 and 4 respectively.
3) complex cation and complex anion 11. The hybridisation is dsp 2 with one unpaired
4) all of these electron.
 SR-MAIN-CHEM-VOL-II
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TRANSITION ELEMENTS
SYNOPSIS  IIB elements have a d10 configuration both in
elemental form and in their stable oxidation
General Introduction: In the modern states.
periodic table elements are classified on the  d-block elements are present as 3d, 4d, 5d and
basis of their electronic configuration into 6d series in the periodic table.
 3d series starts with Sc [Z = 21] ends with Zn
s, p, d and f block elements. [Z = 30]
 The elements whose differentiating electron  4d series starts with Y [Z = 39] ends with
enters in (n-1) d sub-level are called d-block Cd [Z = 48]
elements.  5d series starts with La [Z = 57], Hf ( Z  72)
 The d-block elements in which the atoms or ions ends with Hg[Z = 80].
have incomplete d-orbitals are called transition  6d series is incomplete
elements.  Technitium is the first man made element.
 A typical transition element shall have an  Elements in VIIIB group
incompletely filled d  sublevel either in its Fe, Co, Ni ; Ru , Rh, Pd ; Os, Ir , Pt ; Hs, Mt , Ds
elemental form or in any of its chemically Lattice Structures of Transition Metals
significant oxidation states.  Sc, Ti, Mn & Fe group elements have hcp
 All d  block elements are not transition structures.
elements.  V & Cr group elements have bcc structures.
Ex: Zn, Cd & Hg are not transitional elements  Co, Ni & Cu group elements have ccp structures.
 The general outer electronic configuration of d- Note: Zn, Cd, Hg & Mn have one or more typical
metallic structures at normal temperatures.
block elements is (n-1)d1-10 ns0 (or) 1 (or) 2
 The transition elements are placed in between Electronic Configurations
the electropositive (or) metallic elements (s-  The elements with exceptional configuration in
block) and the electronegative (or) non-metallic 3d series are Cr (24) [Ar] 3d5 4s1 and Cu (29)
elements (p-block) [Ar] 3d10 4s1
 The properties of these elements are in between  The elements with exceptional configuration in
4d series are
those of highly reactive metallic elements of s-
Nb (41) - [Kr] 4d4 5s1 ; Mo (42) - [Kr] 4d5 5s1
block and those of less reactive non-metallic
Ru (43) - [Kr] 4d7 5s1 ; Rh (45) - [Kr] 4d8 5s1
elements of p-block
Pd (46) - [Kr] 4d10 5s0; Ag (47) - [Kr] 4d10 5s1
 d-block elements are placed in the groups 3 to  The elements with exceptional configuration in
12 (i.e, III B to VIII B and I B & II B ) 5d series are
 The elements of IB group namely Cu, Ag, Au P t (78) [Xe] 4f 14 5d 10 6s 0
are called typical transition elements since in
these elements electrons from completely (or) 4f 14 5d 9 6s1 (or) 4f 14 5d 8 6 s 2
filled inner (n-1)d subshell take part in bond and Au (79) [Xe] 4f 14 5d10 6s1
formation along with outer s-electrons  Atoms of d-block elements having d 5 (half
 IB group elements copper, silver and gold are
filled) and d10 (completely filled) configuration
called coinage elements. In olden days these
metals are used to prepare coins. are more stable because of greater exchange
energies.
 The elements of IIB (Zn, Cd and Hg) are not
considered as transition elements as they do not  ns 2 np 6 nd10 configuration for an ion or atom is
show the properties of transition elements known as pseudo inert gas configuration (or)
because of completely filled d-orbitals. nickel group configuration.
 SR-MAIN-CHEM-VOL-II
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 Examples for atoms / ions having ns 2 np 6 nd10 Zinc Calamine ZnCO3
configuration are Pt, Pd  nickel group  Zinc Blende ZnS
Silver Argentite Ag 2 S
Cu  , Ag  , Au  , Zn 2 ,Cd 2 , Hg 2
Horn silver AgCl
Occurrence of Transition Elements  Pt and Au are almost unreactive.
 3d elements are more widely distributed in  Pt, Au and Ag are called noble metals.
nature than 4d and 5d series.
 3d series elements with even atomic numbers
Characteristics of 3d series: Transition
are largely available in nature than those with elements exhibit horizontal similarities also in
odd atomic numbers. addition to usually existing group similarities.
 The transition elements exhibit typical
 Iron is the fourth most abundant among all
characteristic properties. This is due to their
elements in the earth’s crust.
small atomic sizes, large nuclear charges and
Some Important Minerals of 3d-elements the presence of unpaired d - electrons.
Scandium Thortveitite Sc2  Si2O7  a) Variable oxidation states
b) para and ferro magnetic properties
Titanium Ilmenite FeTiO3 c) formation of coloured hydrated ions and salts
d) alloy formation ability
Rutile TiO2 e) catalytic properties
Vanadium Carnotite 2 K UO2 VO4 .3H 2O f)complex forming ability
Trends in M.P, B.P. & densities:
Vanadinite Pb5 VO4 3 Cl
Transition elements have high melting points.
Chromium Chromite FeO.Cr2O3 High melting points, boiling points and heat of
atomisation values of transition elements are due
Manganese Pyrolusite MnO2 to the involvement of (n - 1)d electrons in
Braunite Mn2O3 addition to ns electrons in the interatomic
metallic bonding.
Manganite Mn2O3 .H 2O  In any series melting points increase upto VI B
group and then decrease.
Hausmannite Mn3O4
 M.P of Mn & Tc are lower than neighbouring
Iron Haematite Fe2O3 elements.
 In any series of d-block, last element (IIB group)
Magnetite Fe3O4 has the least melting and boiling points. This is
Siderite FeCO3 probably becuase the d-electrons do not
participate in metallic bonding.
Limonite Fe2O3 .xH 2O  Among all metals tungston has the highest
melting point. Mercury is a liquid at room
Iron Pyrites FeS2
temperature.
Cobalt Smaltite CoAs2  IIB group elements have very low m.p values
Cobaltite CoAsS due to non involvement of d 10 electrons in
metallic bonding.
Nickel Pentalandite  Ni, Fe, Cu  S  In a period densities increase as the atomic radii
Garnierite  Ni, Mg  SiO3 .xH 2O decrease. Density increases down the group in
transition elements.
Copper Chalcocite Cu2 S  Iridium has the highest density (22.7g cm -3)
among all the elements. Osmium also has a very
Copper Pyrites Cu2 S .Fe2 S3
high density (22.6g cm-3).
 SR-MAIN-CHEM-VOL-II
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 In 3d-series highest density is observed in Cu  nd
In Cr and Cu 2 IP value is almost double the
and least in Sc.
1st IP value due to half filled and completely
filled ‘d’ orbitals in Cr  and Cu  ions
 In a period the increase in IP2 and IP3 values
are predominant than increase in IP1 .
 In IIIB-group ionisation potential decreases from
scandium to lanthanum, but in the remaining
groups trend is not same.
 Atomic radii of Zr = 1.6 A° and Hf =1.59 A°
and their IP values are Zr = 674 kJ/mole and Hf
= 760 kJ/mole. This is due to Lanthanide
contraction.
 IP values of 4d and 5d series are almost equal
due to lanthanide contraction.
 Chromium and copper have unusally high
Atomic and ionic radii of 3d series second ionization energy when compared with
 The atomic radius decreases in a period in the their neighbouring elements.
begining, with the increase in the atomic  Second ionization energy of the zinc is
number. considerinably low because removal of second
 At the end of series, there are increased electron-
electron from zinc leads to the stable d 10
electron repulstions between the added electrons
configuration.
in the same orbitals. These repulsions exceed
 Third ionization energy of Mn is higher than
the attractive forces due to increased nuclear
charge. Therefore, electron cloud expands and the neighbours because of stable d 5
the atomic radius increases at the end of any configuration.
series.  Among 3d, 4d and 5d series of d-block elements,
 The radii of 4d and 5d series are almost equal. first ionization energy is least for lanthanum and
This is due to lanthanide contraction. is highest for mercury.
 Atomic and ionic radii of Cr, Mn and Fe are Oxidation States of 3d Series: Transition
equal. Between Ag and Cd bigger atom is Cd. elements exhibit variable oxidation states.
 The slight irregularities in size have been  Both ns and (n-1)d electrons will participate in
described to crystal field effects. bond formation due to small energy difference
 Atomic radii of Zr is 1.6 A° and Hf is1.59 A° between them.
due to Lanthanide contraction.  Sc, Y, La and Ac do not exhibit variable
 The ionic radii of transition metals decrease with
oxidation states. These elements always exist
increase in oxidation state. in + 3 oxidation state as they acquire octet
Ionization Energies of 3d Series configuration in that oxidation state.
 Their IP values are higher than s block elements,  For transition elements the oxidation state
but less than those of p block elements. ranges between 0 and + 8.
 They are less electropositive than s block  Manganese (Mn) in 3d seires, Technitium (Tc)
elements, but more electropositive than p block in 4d series and Rhenium (Re) in 5d series
elements. exhibit stable +7 oxidation state.
 IP values generally increase from left to right in  The maximum stable oxidation state + 8 is
any series but the increase is less than that of S exhibited by Osmium (Os) of 5d- series and
block elements due to increase in nuclear charge Ruthenium (Ru) of 4d series, but it is unstable
is opposed by screening effect. for Ruthenium.
 SR-MAIN-CHEM-VOL-II
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 In transition elements, across a period from left  VX 5 hydrolysed to give oxo halides VOX 3
to right, the +2 state becomes more stable while
+3 state becomes less stable.  Besides the oxides, oxocations stabilize V 5 as
 Cu, Mo, Ag, W, Au and Hg exhibit stable +1
oxidation state.
VO2 and V 6 as VO22 .
 Chromium also exhibits +1 oxidation state but  Cu forms flourides, chlorides, bromides but not
it is unstable. iodides.
 Ferric ion with d5 configuration is more stable  
Cu 2 oxidises I to I 2
than ferrous ion with d6 configuration.
 The variable oxidation states are also referred 2Cu 2  4 I   Cu2 I 2  s   I 2
as variable valencies.  Cu  compounds disproportionate in aqueous
 The minimum oxidation state exhibited by an
solutions.
element is given by the no. of outer s-electrons
and maximum oxidation state is given by the  Cu 2 compounds are stable due to more
sum of s-electrons of outer most shell and negative enthalpy of hydration.
unpaired d-electrons of penultimate shell.  For example, in group 6, Mo (VI) and W (VI)
 The compounds with lower oxidation state (i.e.,) are found to be more stable than Cr (VI).
+2 exhibit the reducing nature (eg : Cr+2, Fe+2 In Oxides: In oxides of 3d series highest
etc). Their oxides have basic character and also oxidation number in the oxides coincide with
exhibit reducing property. its group number.
 Compounds with lower oxidation states are  In 3d-series after 7th group no higher oxides
ionic and with higher oxidation states are above Fe2O3 are known.
covalent.
 Due to formation of multiple bonds in oxides,
 The compounds of lower oxidation state are
they are more stable than flourides
known as ‘ous’ compounds and those of higher
oxidation states are ‘ic’ compounds. eg: Fe+2 (+2)  Mn2O7 is stable.
Ferrous. Fe+3 (+3) Ferric. Electrode potentials and chemical
 Most stable oxidation states of transition series reactivity
are: Ti  IV  ; V  V  ; Cr  III & VI  ;  S.R.P of M 2 / M values increases from left to
Mn  II  ; Fe  III  ; Co  II & III  ; right as IP values increases. (except Zn)
 Cu cannot displace H 2 from acids because it
Ni  II  ; Cu  II 
has highest S.R.P value which is +0.34 V.
Trends in Stability of Higher Oxidation  Mn, Ni and Zn have more negative S.R.P values
States than expected.
 In 3d series highest oxidation numbers are Reason: Mn & Zn have d 5 & d 10 stable e.c.
observed in TiX 4 , VF5 , CrF6 . Ni has higher hydration energy.
(  H Hyd Ni 2 = -2121 KJ/mole)
 Manganese show +7 state in MnO3 F and in
 Mn 3 and Co 3 are strong oxidising agents due
other halides it is not observed.
to high S.R.P of M 3 / M 2 values.
 Beyond manganese except FeX 3 and CoF3 are
only known trihalides.  EM0 3 / M 2 show varying trends
 Flourides of highest oxidation state are stabilised
 ESc0 3 / Sc2 is low as it gets noble gas configuration
due to high lattice energy or higher bond
enthalpy  EFe
0
3
/ Fe2
is low as Fe 3 has stable d 5
Eg: CoF3 , VF5 , CrF6 configuration
 SR-MAIN-CHEM-VOL-II
Jr Chemistry E/M
EMn  Paramagnetic substances contain unpaired
 0
3
/ Mn2
is high as Mn 2 has stable d 5
electron spins or unpaired electrons.
configuration. Ex : K3[Fe(CN)6], Sc2+, Cr3+ etc
 Mn3  d 4  is less stable than Mn 2  d 5   In paramagnetic substances the magnetic field
of the substance (B) is more than the applied
because the latter has half-filled d-subshell magnetic field strength (H).
stable electronic configuration. Thus Mn3  For paramagnetic substances B>H.
 The substances which are repelled by the
easily reduced to Mn 2 and acts as oxidant.
magnetic field when they are kept in higher
 EMn
0
3
/ Mn2
is more positive than ECr
0
3
/ Cr 2
(or) magnetic field are called diamagnetic substances
(stronger to weaker field.)
EFe
0
3
/ Fe2
due to high 3rd I.E of Mn.  Diamagnetic substances exhibit decrease in
weight in the presence of magnetic field.
 Ti 2 , V 2 and Cr 2 are strong reducing agents
 It is hard for magnetic lines to pass through a
and liberate H 2 from dilute acids. diamagnetic substance than in vacuum.
 If Magnetic field in the substance (B) is less than
 Cr 2 is a stronger reducing agent than Fe 2
external magnetic field (H), then they are said
because its configuration changes from d 4 to to be diamagnetic.
d 3 (a half filled t2 g level). In aqueous solution
EX : Ti+4, V+5 , Sc3+, Zn, Hg, Cd etc
 Mercurous ion is diamagnetic in nature. It exists
d 3 is more stable as compared to d 5.
as Hg 22 .
 Mn 3 is oxidising agent as its configuration  For diamagnetic substances B<H.
changes to d 5  Diamagnetic substances contain electron pairs
E 0 M 3 / M 2 in the 3d series are observed for some with opposite spins.
metals as  Ferromagnetic substances are considered as a
special case of paramagnetic substances.
Co 3 / Co 2  Mn 3 / Mn 2  Fe 3 / Fe 2   Ferromagnetic substances are those in which
Ti 3 / Ti 2  Sc 3 / Sc 2  V 3 / V 2 there are large no. of electrons with unpaired
 At times oxidizing power depends on the spins and whose magnetic moments are aligned
stability of the species formed from the in the same direction.
 For Ferromagnetic substances B  H
oxidizing agent. Ex: VO2  Cr2O72  MnO4 .
 Iron, Cobalt and Nickel are best examples for
W.E-1: Why is E 0 value for Mn 3 / Mn 2 couple ferromagnetic substances.
 Ferromagnetism disappears in the aqueous
much more positive than that for Cr 3 / Cr 2
solution of the substance
or Fe 3 / Fe 2 ? Explain  Paramagnetism of substances (molecules, atoms
Sol. Mn 2 contains stable d 5 configuration. So or ions) is due to the spins of the unpaired
removal of another electron from exactly half- electrons and also due to angular orbital
filled configuration requires more energy i.e., momentum.
greater third IE of manganese is responsible for  The magnetic moment of transition metal ions
the variation. exhibiting paramagnetism is calculated by the
formula.
Magnetic Property of Transition
S  L  4S (S  1)  L( L  1) BM
Metals: The substances which are attracted
into the magnetic field when they are kept in Where S = Sum of the spin quantum numbers
higher magnetic field are called paramagnetic L = Sum of the orbital angular momentum
substances (weaker field to stronger field). quantum numbers.
 SR-MAIN-CHEM-VOL-II
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 For an electron, spin quantum numbers Colours of Transition Metal Ions: Many
s=±½ S= sxn compounds of transition metals are coloured and
Where n = number of unpaired electrons. the compounds of s-block and p-block elements
 The unit of magnetic moment is Bohr Magneton are almost colourless.
eh  The transition metal ions with unpaired
(BM) 1 BM = d-electrons absorb characteristic coloured light
4 mc
from the visible region and transmit its
where e = electron charge; h = Planck’ss
complementary colour in the same region. This
constant, m = mass of electron, c = velocity is responsible for the colour of the ion.
of light. Ex: i) Hydrated Titanium ions (one 3d-electron)
1 BM = 9.273 x 10-24Joule / Tesla . absorbs green light from visible region and
= 9.273 x 10-21 erg / Gauss transmits the purple light.(pink)
ii) Hydrated Cu+2 ions absorb red colour and
Unpaired Magnetic moment transmit blue colour.
Ion Configuration electrons(S)
Calculated Observed iii) Mn2+ ion transmits pink colour
3+ 0
Sc 3d 0 0 0 Colours of visible radiations
Ti
3+
3d1 1 1.73 1.7  1.8 Absorbed Wavelength of Complementary
Tl
2+
3d
2
2 2.84 2.7  2.8
colour colour colour
V
2+
3d
3
3 3.87 3.7  3.9
Violet 400 - 450 nm Yellow-green
Cr
2+
3d 4
4 4.90 8.8  4.9
Blue 450 - 490 nm Yellow
Mn2+ 3d
5
5 5.92 5.7  6.0
Greenblue 480 - 490 nm Orange
Fe
2+
3d
6
4 4.90 5.3  5.5
Co
2+
3d
7
3 3.87 4.4  5.2 Absorbed Wavelength of Complementary
Ni 2+
3d
8
2 2.84 2.9  3.4 colour colour colour
Cu
2+
3d
9
1 1.73 1.8  2.2 Blue green 490 - 500 nm Red
Zn
2+
3d 10
0 0 Green 500 - 560 nm Purple
Yellow green 560 - 575 nm Violet
Yellow 575 - 590 nm Blue
 The contribution of orbital angular quantum Orange 590 - 625 nm Green blue
number towards magnetic moment is low and Red 625 - 750 nm Blue green
hence it can be neglected [ L = 0] for 3d series.  According to crystal field theory, the d-orbitals
But in some cases  exp is higher than calc . e.g. of transition metal ions split into two groups
when ligands or counter ions or solvent
Fe 2 , Co 2 , Ni 2 , Cu 2 molecules attack on them. This is known as d-
 Spin-only magnetic moment is given by orbital splitting (or) crystal field splitting.
  4SS  1 BM  In presence of other ions or molecules five d-
orbitals lose their degeneracy and split into two
 In terms of number of unpaired electrons (n),
the magnetic moment is given by the formula. groups namely t2 g  d xy , d yz , d zx  and eg
 s  nn  2 BM (d x2  y 2 & d z 2 ) of slightly different energies.
if n =1 m= 1.73 BM  As the energy difference between two groups
if n =2 m= 2.83 BM
if n =3 m= 3.87 BM eg & t2 g is small, the energy from visible light
 In 2nd and 3rd transition series (4d & 5d) , the is sufficient for the excitation of electrons.
orbital contribution is significant and so L must  The colour of the transition metal ion depends
be included on the number of electrons undergoing the d-d
transition and the energy difference between
S L  4S(S  1)  L(L  1)BM
these d-orbitals.
 SR-MAIN-CHEM-VOL-II
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Colours of some of the first row  Catalysts at a solid surface binds the reactants.
(aquated) Transition metal ions In which metals utilise (n-1)d and ns electrons
for bonding.
ION Outer electron [Link] Unpaired Colour
Configuration electrons Ex: Iron (III) catalyses the reaction between
iodide and perdisulphate ions.
Sc3+ 3d0 0 Colouress
Ti3+ 3d1 1 Purple 2 I   S 2O82  I 2  2 SO42
V 3+
3d 2
2 Green Mechanism:
Cr 2+
3d 4
4 Blue 2 Fe 3  2 I   2 Fe 2  I 2
2 Fe 2  S 2O82  2 Fe 3  2 SO42
3+ 3
Cr 3d 3 Violet
3+ 4
Mn 3d 4 Violet
3+ 5  TiCl4 with Al  CH 3 3 forms the basis of
Fe 3d 5 Yellow
Mn2+ 3d5 5 Pink Ziegler Natta catalyst used in the manufacture
6+ 1
of polythene.
Mn 3d 1 Green  In the Wacker process the oxidation of ethyne
2+ 6
Fe 3d 4 Green
to ethanal is catalysed by PdCl2 .
Co2+ 3d7 3 Pink
2+ 8
Ex: i)In the manufacture of sulphuric acid by contact
Ni 3d 2 Green process, the catalyst used is V2O5.
Cu2+ 3d9 1 Blue ii) In the synthesis of Ammonia by Haber’s
Cu +
3d 10
0 Colourless process, the catalyst used is a mixture of Iron
Zn 2+
3d 10
0 Colourless and Molybdenum.
 The transition metal ions with empty d-orbitals iii) In the manufacture of HNO3 by Ostwald’s
(or) completely filled d-orbitals are colourless. process, the catalyst used is Platinum.
iv) The catalyst used in the hydrogenation of
Eg: Sc+3 ; Cu+ ; Zn+2 etc
oils is Nickel.
 The metal ions may exhibit different colours in
different oxidation states. v) Fenton’s reagent  FeSO4  H 2O2  is used as
e.g. Mn 2 - Pink an oxidising agent
Interstitial Compounds: Compound
Mn 3 - Blue
formed when atoms with small atomic size like
Mn 6 - Green H, B, C and N are trapped in the holes of
 Anhydrous CuSO4 is almost colourless. But transition metals are called interstitial
hydrated CuSO4 is blue in colour. This is because compounds. The components are not in definite
of the absence of water molecules (ligands), ratios in them. So such compounds are also
there is no splitting of d-orbitals in anhydrous known as non stoichiometric compounds.
CuSO4.  They have metallic nature, hard and brittle with
 The Cr (+6) and Mn (+7) have empty d-orbitals high MP and B.P.
but their compounds are coloured.  The density of these compounds is less than that
 The colours of oxo-ions like Cr2O72 , CrO42 of metals due to expansion of lattice.
 Ti, Zr, Hf, V, Nb, Ta form such compounds.
and MnO4 can be explained by charge transfer  Hydrogen occupies always smaller tetrahedral
phenomenon. holes while C and N occupy larger octahedral
holes.
Catalytic properties of transition
 Oxides and sulphides of T.E with more than one
metals: Transition metals and their compounds oxidation state form these compounds.
act as good catalysts. This is due to the presence
Ex: 1) Fe0.82O , Fe0.94O 2) WO2.88 , WO2.92
of free valencies and also variable oxidation
states. 3) Fe0.89 S , Fe0.96 S
 SR-MAIN-CHEM-VOL-II
Jr Chemistry E/M TRANSITION ELEMENTS
 A stoichiometric compound may become non Physical Properties
stoichiometric compound at high temperature.  It is orange red coloured crystalline solid.
 ZnO is white when cold and yellow when hot,  It is moderately soluble in cold water but freely
because stoichiometric ZnO changes to non- soluble in hot water.
stoichiometric ZnO, when heated.  It’s melting point is 398°C.

Alloy Formation: Alloy is a homogeneous Chemical Properties

 On strong heating it decomposes and gives
mixture of a metal with other metals or
oxygen
metalloids or nonmetals. Alloys are solid in solid
solutions. 3
2 K 2Cr2O7  2 K 2CrO4  Cr2O3  O2
 Since d-block elements are similar in size, they 2
can easily form alloys.  On heating with alkalies it is converted into
 Alloys are generally prepared to modify the chromate [Yellow colour]
properties like malleability, ductility, toughness, K 2Cr2O7  2 KOH  2 K 2CrO4  H 2O
resistance to corrosion.
 In acid medium K 2CrO4 changes into K 2Cr2O7
Potassium dichromate  K 2Cr2O7  2K 2CrO4  H 2 SO4  K 2 SO4  K 2Cr2O7  H 2O
Preparation: Yellow Orange
 It is manufactured from chromite ore  It reacts with HCl and evolves chlorine.
 FeO.Cr2O3  . K 2Cr2O7  14 HCl 
2 KCl  2CrCl3  7 H 2O  3Cl2
 Chromite ore is roasted with Na2CO3 to convert
 In acid medium
into Na2Cr2O7 . It is mixed with KCl gives
Cr2O72  14 H   6e   2Cr 3  7 H 2O
K 2Cr2O7 .
Mwt of K 2Cr2O7
 [Link] of K 2Cr2O7 
O O 6
  It acts as a powerful oxidising agent in acidic
O
O Cr 126
0 Cr medium (dilute H 2 SO4 )
 It oxidises KI to I 2
O O
O
K 2Cr2O7  7 H 2 SO4  6 KI 

 Two CrO units are bonded to sp hybrid
3
3
4 K 2 SO4  Cr2  SO4 3  3I 2  7 H 2O
oxygen atom.
 Cr atom is surrounded by four oxygen atoms  Both Na2Cr2O7 and K 2Cr2O7 are oxidising
tetrahedrally. agents but K 2Cr2O7 is preferred because it is
3
 Cr atom is sp hybrid. not hygroscopic and can be used as primary
 It contains two types Cr  O bonds. standard in volumetric analysis.
 It oxidises ferrous ions to ferric ions
..
 O Cr bond length of sp3 hybrid central K 2Cr2O7  6 FeSO4  7 H 2 SO4 
..

oxygen atom has single bond length ( 179 pm ). 3Fe2  SO4 3  Cr2  SO4 3  7 H 2O  K 2 SO4
 Other oxygen atom surrounding Cr atoms have  It oxidises sulphites to sulphates
intermediate bond length which lies in between K 2Cr2O7  3Na2 SO3  4 H 2 SO4 
single and double bond length ( 163 pm ) due to
resonance. 3Na2 SO4  K 2 SO4  Cr2  SO4 3  4 H 2O
 SR-MAIN-CHEM-VOL-II
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 It oxidises H 2 S to Sulphur.. Structure of Dichromate Ion
K 2Cr2O7  4 H 2 SO4  3H 2 S   Cr2O72 contains eight Cr-O bonds.

K 2 SO4  Cr2  SO4 3  7 H 2O  3S  Cr2O72 contains six equivalent Cr-O bonds.

 In Cr2O72 Cr atom undergoes ‘ sp3 ’
 It oxidises SO2 to H 2 SO4 .
hybridization.
K 2Cr2O7  H 2 SO4  3SO2  Structure of chromate ion
K 2 SO4  Cr2  SO4 3  H 2O  In chromate ion hybridization of Cr is sp3 .
 Shape of chromate ion is Tetrahedral
 It oxidises C2 H 5OH to acetaldehyde and
Potassium Permanganate Preparation:
CH 3CHO to CH 3COOH Potassium permanganate is prepared by the
 It oxidises thiosulphate to sulphate. fusion of MnO2 with alkali metal hydroxide and
 It oxidises nitrites to nitrate.
an oxidaising agent like KNO3
Chromyl Chloride Test
 This is a test of chloride. When a mixutre of a 2 MnO2  4 KOH  O2  2 K 2 MnO4  2 H 2O

metal chloride and K 2Cr2O7 is heated with conc. K 2 MnO4 can be converted into KMnO4 by

H 2 SO4 , orange red vapours of chromyl chloride bubbling CO2 , Cl2 or ozonized oxygen through
are evolved. the given solution.
3K 2 MnO4  2CO2  2 KMnO4  MnO2  2 K 2CO3
K 2Cr2O7  6 H 2 SO4  4 NaCl 
K 2 MnO4 disproportionates in acidic or neutral
2 KHSO4  4 NaHSO4 
solution to give permanganate.
2CrO2Cl2  3H 2O
3MnO42   4 H   2 MnO4  MnO2  2 H 2O
Chromyl chloride 
In the laboratory permanganate ion is obtained
 When chromyl chloride vapours are passed by oxidising Mn (II) salts with peroxodisulphate
through NaOH solution, yellow colour  S O  ion.
2
2
8

 Na2CrO4  is obtained. 2 Mn 2  5S 2O82   8 H 2O 


 When lead acetate is added to yellow coloured 2 MnO4  10 SO42  16 H 
solution, yellow precipitate is formed.
Structure of Permanganate Ion:
Na2CrO4   CH 3COO 2 Pb O

 PbCrO4  2CH 3COONa

Yellow ppt
Mn
Uses: It is used as volumetric reagent in the
estimation of Iodide ions, Fe 2 ions. O O
O
 It is used as a primary standard solution.
 Permanganate ion is diamagnetic but manganate
 It is used for the preparation of chrome alum, ion is paramagnetic with one unpaired
chrome yellow, chrome red, etc., d-electron.
 It is used in dyeing, chrome tanning, calico  The oxidation state of central atom is 7
printing, photography.
Mn undergoes sp 3 hybridization.
 Chromic acid  H 2CrO4  is used as a cleaning
t2 g set of 3d orbitals involve in hybridization.
agent for glass ware.
Shape of species is tetrahedral.
SR-MAIN-CHEM-VOL-II
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Physical Properties: Acidic Medium: To acidify the KMnO4
 It is purple coloured crystalline compound. sulphuric acid to be used but not hydrochloric
 It is fairly soluble in water. acid because it oxidises hydrochloric acid to
 Its solubility increases with increase in chlorine.
temperature.
 2 KMnO4  3H 2 SO4 
Chemical Properties: When heated alone (or)
with alkali gives oxygen. K 2 SO4  2MnSO4  3H 2O  5  O 
2KMnO4  K 2 MnO4  MnO2  O2 (or) Mwt of KMnO4
Eq wt of KMnO4 
4 KMnO4  4 KOH  4 K 2 MnO4  2 H 2O  O2 5
 It oxidises ferrous ion to ferric ions.
 When it treated with conc. H 2 SO4 , it forms
2 KMnO4  10 FeSO4  8 H 2 SO4 
Mn2O7 [explosive compound]
5Fe2  SO4 3  2MnSO4  K 2 SO4  8H 2O
2 KMnO4  2 H 2 SO4  2 KHSO4  Mn2O7  H 2O
 It oxidises KI to I 2 .
 KMnO4 act as an oxidising agent in alkaline,
2 KMnO4  10 KI  8 H 2 SO4 
neutral and acidic solutions.
 In alkaline medium 6 K 2 SO4  2 MnSO4  5 I 2  8 H 2O
Molecular weight of KMnO4  It oxidises sulphite or sulphurous acid to
Eq wt of KMnO4  sulphate or sulphuric acid
3
 In alkaline medium it is reduced to Potassium 2 KMnO4  5 Na2 SO3  3H 2 SO4 
manganate and then to insoluble MnO2 . K 2 SO4  2 MnSO4  5 Na2 SO4  3H 2O
2 KMnO4  H 2O  2MnO2  2 KOH  3  O   It oxidises H 2 S to Sulphur..
 It oxidises iodide to iodate. 2 KMnO4  3H 2 SO4  5 H 2 S 
2 KMnO4  KI  H 2O  2 KOH  2MnO2  KIO3
K 2 SO4  2 MnSO4  5S  8 H 2O
Neutral Medium  It oxidises SO2 to H 2 SO4 .
 In neutral medium
2 KMnO4  5SO2  2 H 2O 
Mwt of KMnO4
Eq. wt of KMnO4  K 2 SO4  2 MnSO4  2 H 2 SO4
3
 It oxidises C2 H 2O4 (Oxalic acid) to CO2 .
2 KMnO4  H 2O  2MnO2  2 KOH  3  O 
2 KMnO4  3H 2 SO4  5C2 H 2O4 
 It oxidises H 2 S to Sulphur..
K 2 SO4  2 MnSO4  10CO2  8 H 2O
2 KMnO4  3H 2 S 
 In acidic medium MnO4 oxidises ferrous ion
2 KOH  2 MnO2  2 H 2O  3S
to ferric ion and oxalate ion to CO2 .
 It oxidises MnSO4 to MnO2
6 KMnO4  10 FeC 2 O4  24 H 2 SO4 
2 KMnO4  3MnSO4  2 H 2O 

3 K 2 SO4  6 MnSO4  5 Fe2 SO4   20CO2  24 H 2 O
K 2 SO4  5MnO2  2 H 2 SO4 3

 It oxidises HX  HCl , HBr, HI  to X 2

 It oxidises Na2 S 2O3 to Na2 SO4 and Sulphur..
(halogens).
2 KMnO4  3 Na2 S 2O3  H 2O  2 KMnO4  3H 2 SO4  10 HX 
2 KOH  2 MnO2  3S  3 Na2 SO4 K 2 SO4  2 MnSO4  8 H 2O  5 X 2
 SR-MAIN-CHEM-VOL-II
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Uses: It is used as an oxidising agent in  The halides of higher oxidation states are the
laboratory and industry. fluorides because metals can be oxidised to
 In laboratory it is used as primary standard higher oxidation states with only fluorine which
solution. is most reactive.
 In titrations KMnO4 is used to estimate the  Bonding in fluorides is mainly ionic.
quantity of reducing agents like oxalic acid,  In chlorides, bromides and iodides, the ionic
Mohr’s salt solutions in acid medium. character decreases with atomic mass of
halogen.
 Dilute H 2 SO4 is used as acidic medium.
 Dilute HCl can not be used as it can be oxidised Sulphides: Transition metals form sulphides
either by direct combination with sulphur or
by KMnO4 to Cl2 .
with H 2 S or Na2 S
 Alkaline KMnO4 is called Bayer’s reagent.  The sulphides are generally coloured or black
 It is used to identify unsaturation in organic and are insoluble in water.
compounds.
 It is used in the manufacture of saccharine, Additional information
benzoic acid, acetaldehyde etc., Alloys: Alloys are generally prepared by
 It is used for detecting halides, sulphides, a) Melting a mixture of the metals or the
oxalates etc., components taken in proper proportions.
 A mixture of sulphur, charcoal and KMnO4 b) Simultaneous electrolytic deposition of metals
forms explosive powder. under suitable conditions.
Compounds of transition metals Oxides c) Amalgam’s are prepared by grinding the metal
 Transition metal oxides are formed by the action with mercury
of oxygen with transition metals at high Ex: Zn, Na, Cu , Ag (or ) Au
temperature. d) two metallic oxides are reduced at a time.
 General formulae of the oxides are
Ex:- Fe, Cr alloy is prepared by reducing
MO, M 2O3 , M 3O4 , MO2 , M 2O5 and MO3 . chromite ore
 The oxides in which the metal is in lower e) Finally powdered metals are compressed at a
oxidation number are basic in nature. temperature slightly below their melting points
 The oxides in which the metal is in higher
Ex: - Mo, W
oxidation state are acidic in nature.
 The oxides in which the metal exhibits f) Quenching: Fe, C alloy is made by sudden
intermediate oxidation states are amphoteric. immersing in oil or water
 Among the oxides of manganese lower oxides  Alloys are in wide use in nuclear engineering,
are basic higher oxides are acidic intermediate dental fillings, manufacture of strongly magnetic
oxides are amphoteric materials.
MnO - basic  Alloys are usually divided into ferrous and non-
Mn2O3 , Mn3O4 and MnO2 - amphoteric ferrous alloys depending on the presence (or)
absence of iron in the alloy.
Mn2O7 - acidic
Ex: Ferrous alloys : Stainless steel, cast iron
Halides: Transition metals react with halogens Non - ferrous alloys: Brass, German silver
at high temperature to form transition metal  Alloy of a metal with Mercury is called an
halides. Amalgam.
The order of reactivity of halogens is Ex : Zn-Hg, Al-Hg, Na-Hg etc.
F  Cl  Br  I .  Fe and Pt do not form amalgams.
 SR-MAIN-CHEM-VOL-II
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Some Ferrous Alloys
Alloy Composition Uses (in making) LEVEL-I (C.W)
1. Invar steel 64% Fe, for pendulum
INTRODUCTION
35% Ni, rods
1.
Element with atomic number 111 might,
Mn & C belong to the following group
in trace amounts 1) Chromium 2) Scandium
2. Nichrome 60% Ni, in heating 3) Copper 4) Titanium
25%Fe, of fire stoves,
2. The following belongs to d-block but it is not
15%Cr furnaces a transition element
1) Mn 2) Fe 3) Zn 4) Cr
Some non-ferrous alloys
3. Which set of elements is transitional in
Alloy Composition Uses (in making) character
1. German Silver 50-60% Cu, Spoons, i) Fe, Co, Ni ii) Ru, Rh, Pd iii) Os, Ir, Pt
10-30% Ni, forks, utensils The correct statements is / are:
20-30% Zn 1) i,ii 2) iii,i 3) iii,ii 4)i,ii,iii
2. Brass 60-80% Cu; Machine parts 4. Which of the following set of elements does
20-40% Zn not belongs to transitional elements?
3. Bronze 75-90% Cu; Utensils, 1) Fe, Co, Ni 2) Cu, Ag, Au
10-25% Sn Coins, Statues 3) Ti, Zr, Hf 4) Ga, In, Tl
4. Gun metal 88% Cu; 5. In the transition elements the incoming
10% Sn; Guns, Bearings electron occupies [n-1]d sublevel in
2% Zn; preference to
5. Bell metal 80% Cu; Bells 1) np 2) ns 3) [n-1]d 4) [n+1]s
20% Sn 6. Catalytic activity of transition elements and
6. Deverda’s 50% Cu; to reduce nitrites their compounds is due to their
alloy 45% Al; (or) nitrates to 1) Small size 2) Vacant d-orbitals
5% Zn NH3 3) Higher densities 4) Colour
7. Duralumin 95% Al; for stressed 7. Transition metals are good electrical
4% Cu; structures conductors because
0.5% Mn; like aircraft 1) They are metals 2) They are solids
0.5% Mg 3) They have free electrons in outer energy levels
8. Magnalium 85-99%Al; in balance beams, 4) They are hard.
1-15%Mg aircrafts parts and 8. Which of the following is a transition element
motor spares 1) Al 2) As 3) Ni 4) Pb
9. Aluminimum 88-90% Cu; in ornaments, 9. The ground state electronic configuration of
Bronze 10-12% Al photoframes etc
chromium is against
1) Hund’s rule 2) Pauli’s principle
10. Wood metal 50% - Bi Automatic
3) Auf-bau principle 4) Boyle principle
25% - Pb fire alarams,
10. The following has pseudo-inert gas
12.5% - Sn sprinklers system
configuration in the (n-1) shell.
12.5% - Cd
1) Typical transition elements
11. Type metal 60-80%-Pb Sharply defined 2) Zinc group elements 3) Both 4) Neither
13-30% - Sb casting
3-10% - Sn ELECTRONIC CONFIGURATION
12. Solder metal 50% - Sn Electrical 11. Which one of the following pairs of ions have
47.5% - Pb appliances the same electronic configuration?
2.5% - Sb 1) Cr 3 , Fe 3 2) Fe 3 , Mn 2
 Steel is an alloy of Iron and Carbon (2%). 3) Fe 3 , Co 3 4) Sc 3 , Cr 3
 SR-MAIN-CHEM-VOL-II
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12. Which one of the following ions has same OXIDATION STATES OF 3D SERIES
number of unpaired electrons as those 19. The following does not show variable valency
present in V 3 ion? (E 2014) 1) Mn 2) Fe 3) Zn 4) Cr
2 2 3
1) Fe 3 2) Ni 3) Mn 4) Cr 20. Element which can show +2, +3, +4 +6 and
+7 oxidation states is
OCCURENCE OF TRANSITION ELEMENTS 1) Cr 2) Mn 3) Co 4) V
13. In the following pair of d-block elements, 21. Maximum oxidation state exhibited by
the first member is a liquid at room Osmium is
temperature and the second member is 1) +8 2) +7 3) +6 4) +5
mostly available in the earth’s crust. The pair ATOMIC AND IONIC RADII OF 3d SERIES
is 22. Which of the following pairs of elements have
1) Hg, Fe 2) Hg, Tc 3) Hg, Zn 4) Hg, Au same radii ?
14. Match the following 1) Zr,Hf 2) Sc, Y 3) La, Ac 4) Zn, Cd
List-I List-II
COLOURS OF TRANSITION METAL IONS
A) Rutile i) Mn2O3 23. Which of the following ion is coloured in its
B) Chromite ii) MnO2 aqueous solution?
1) Cd+2 2) Zn+2 3) Sc+3 4) Ti+3
C) Pyrolusite iii) FeO.Cr2O3 24. Transition metals are coloured due to the
D) Braunite iv) TiO2 following electronic transition
1) d - s 2) d - d 3) s - p 4) f - s
1) A-iv, B-iii, C-ii, D-i 2) A-i, B-ii, C-iii, D-iv
25. In which pair, both ions are coloured in
3) A-i, B-iii, C-iv, D-i 4) A-iv, B-i, C-ii, D-ii
aqueous medium
15. Match the following 1) Sc+3, Zn+2 2) Cu+2, Ti+4
List - I List -II +3
3) Ti , Co +3
4) Cd+2, Mn+2
A) FeCO3 I) Calamine
CATALYTIC PROPERTIES
B) Fe2O3 .xH 2O ii) Chalcocite 26. The catalyst used in the oxidation of 1°
alcohol to aldehydes
C) Cu2 S iii) Limonite
1) FeSO4  H 2O2 2) Fe + Mo
D) ZnCO3 iv) Siderite 3) Pt + Ir 4) Raney Ni
Correct match is 27. The catalyst and promoter respectively used
1) A-iv, B-ii, C-iii, D-iv 2) A-ii, B-iv, C-i,D-iii in the Haber’s process of industrial synthesis
3) A-iv, B-iii,C-ii, D-i 4) A-iii, B-i,C-ii, D-iv of ammonia are (E 2012)
CHARACTERISTICS OF 3d SERIES 1) Mo, V2O5 2) V2O5 , Fe
16. Which element exhibits highest density in 3d 3) Fe, Mo 4) Mo, Fe
series
1) Sc 2) Cr 3) Zn 4) Cu MAGNETIC PROPERTIES
17. The maximum and minimum melting points 28. The ion having maximum magnetic moment
of first and second transition series is
respectively are observed with 1) Co+3 2) Cr+3 3) Ni+2 4) Cu+1
29. The following metal shows ferromagnetic
1) Cr and Zn 2) Cr and Hg
nature
3) Cr and Cd 4) Mo and Cd 1) Co 2) Cr 3) Cu 4) Mn
30. For a paramagnetic substance, the field
IONIZATION ENERGIES OF 3d SERIES
strength of substance ( B ) and applied field
18. The IP of Zr is 674 kJ/mole. The IP of Hf is strength ( H ) are related as
1) 656 kJ 2) 760 kJ 3) 616 kJ 4) 631 kJ 1) B = H 2) B < H 3) B > H 4) B >>>H
 SR-MAIN-CHEM-VOL-II
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Note: 1) Both A and R are true and R is the correct ex- POTASSIUM PERMANGANATE
planation of A
2) Both A and R are true and R is not the correct 39. When KMnO4 reacts with acidified FeSO4
explanation of A
1) Only FeSO4 is oxidised
3) A is true but R is false 4) A is false but R is true
31. Assertion (A) : Magnetic moment of 2) Only KMnO4 is oxidised
 Fe( H 2O)6  SO4 is given by 4(4  2) BM 3) FeSO4 is oxidized and KMnO4 is reduced
Reason(R): In the above complex Iron ion has
four unpaired electrons 4) KMnO4 and FeSO4 oxidised
32. Assertion (A) : The “spin-only” magnetic 40. The number of moles of KMnO4 that will be
moment [in units of Bohr magneton,   B  ] needed to react with one mole of sulphite ion
in acidic solution is
of Ni 2  in aqueous solution would be (atomic
1) 2/5 2) 3/5 3) 4/5 4) 1
number Ni = 28) 2.84BM
Reason(R) : The metal ion has 2 unpaired 41. The product of I  with MnO4 in alkali
electrons. medium is
+2
33. Assertion(A) : Magnetic moment of Ni ions
1) I 2 2) IO3 3) IO  4) IO4
can be very close to that of Ti+2 ions
Reason(R) : both metal ions have equal no. 42. Assertion(A) : The compound formed as a
of unpaired electrons. result of oxidation of ethyl benzene by
INTERSTITIAL COMPOUNDS KMnO4 is benzoic acid
34. Which of the following elements form Reason(R) : The isomer of ethyl benzene is
interstitial compounds? Xylene i.e dimethylbenzene with KMnO4
1) Alkali metals 2) Transition metals
3) Halogens 4) Noble gases gives phthalic acid.
35. Hydrogen occupies the following holes, C and 1) Both A and R are true and R is the correct
N occupy the following holes explanation of A
1) Tetrahedral and octahedral 2) Both A and R are true and R is not the correct
2) Octahedral and tetrahedral explanation of A
3) Octahedral and octahedral 3) A is true but R is false
4) Tetrahedral and tetrahedral 4) A is false but R is true
ALLOY FORMATION POTASSIUM DICHROMATE
36. One of the constituents of an amalgam is
1) Fe 2) Hg 3) Au 4) Os 43. The number of moles of K 2Cr2O7 that will
37. The alloy used in the reduction of nitrites to be needed to react one mole of H 2 S in acidic
ammonia is
medium
1) Gun metal 2) Devarda’s alloy
3) Solder metal 4) Bronze 1) 1/6 2) 1/3 3) 2/5 4) 2/3
38. Assertion(A) : Zinc-copper couple that can 44. Chromyl chloride when dissolves in NaOH
be used as a reducing agent solution gives yellow solution. The yellow
Reason(R) : Zinc copper couple can be solution contains
obtained from zinc coated from copper 1) Cr2O72  2) CrO42 3) CrO5 4) Cr2O3
1) Both A and R are true and R is the correct
explanation of A 45. When chromite ore is fused with NaOH in
2) Both A and R are true and R is not the correct the presence of air, the product formed is
explanation of A 1) Na2Cr2O7 2) Cr2O3
3) A is true but R is false
4) A is false but R is true 3) Na2CrO4 4) K 2Cr2O7
 SR-MAIN-CHEM-VOL-II
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46. Assertion (A) :When a solution of potassium
chromate is treated with an excess of dilute LEVEL-I (H.W)
nitric acid chromate undergo oxidation
Reason (R): Dichromate ions are produced INTRODUCTION
in above process 1.
The following is not a typical transition
element
1) Both A and R are true and R is the correct
1) Cu 2) Ag 3) Au 4) Hg
explanation of A
2.
Which of the following statement regarding
2) Both A and R are true and R is not the correct transition elements is false
explanation of A 1) Their atoms contain partially filled ‘d’ orbitals
3) A is true but R is false 2) They are capable of showing variable
4) A is false but R is true valencies
3) All of their ions are colourless
COMPOUNDS OF TRANSITION ELEMENTS 4) They form complexes readily
47. Cinnabar is an ore of 3. Which of following is a true transition
1) Hg 2) Cu 3) Pb 4) Zn element
1) Zinc 2) Cadmium 3) Aluminium 4) Iron
48. Calomel is
4. The group numbers of transition elements
1) Hg 2Cl2 and Hg 2) Hg 2Cl2 1) 1 to 10 2) 1 to 9 3) 3 to 11 4) 3 to 12
5. Best conductor of electricity is
3) Hg + Hg 2Cl2 4) HgCl 2 1) Cu 2) Al 3) Au 4) Ag
49. Which of the following metals react with 6. Which of the following set of elements are
chlorine to form their respective chlorides? transition elements ?
1) Cu 2) Ag 3) Au 4) All 1) Po, At, Rn 2) Ga, In, Tl
50. Which of the following is not an amphoteric 3) Cs, Ba, La 4) Ac, Ku, Ha
oxide? 7. General electron configuration of d-block
elements is
1) HgO 2) PbO2 3) ZnO 4) SnO2 1) ns2np6nd1-10 2) (n-1)d1-10 ns0-2 np0-6
51. Which of the following iron salts exists as a 3) (n-1)d1-10 ns1-2 4) nd1-9ns0-2
dimer? 8. ns1 electron configuration is not present in
1) Ferric chloride 2) Ferrous chloride 1) Ag 2) Mn 3) Cr 4) Cu
3) Ferrous sulphate 4) Mohr’s salt 9. Which of the following is the stable electron
52. Which oxide of Mn is acidic in nature? configuration of Fe+3 ion
1) 3d64s0 2) 3d5 4s0 3) 3d6 4s2 4) 3d4 4s2
1) MnO 2) Mn2O7 3) Mn2O3 4) MnO2 10. The general configuration (n-1)d 3 ns 2
indicates that particular element belongs to
LEVEL-I (C.W) - KEY the following group
1) 3 2) 3 3) 4 4) 4 5) 1 6) 2 7) 3 1) II B 2) I B 3) V B 4) III B
11. Which of the following ion has same number
8) 3 9) 3 10) 3 11) 2 12) 2 13) 1 14) 1 of unpaired electrons as that of V3+ ion
15) 3 16) 4 17) 3 18) 2 19) 3 20) 2 21) 1 1) Cr+3 2) Mn+2 3) Ni+2 4) Fe+3
22) 1 23) 4 24) 2 25) 3 26) 1 27) 3 28) 1 12. Platinum, palladium and iridium are called
29) 1 30) 3 31) 1 32) 1 33) 1 34) 2 35) 1 noble metals because
1) Alfred Nobel discovered them
36) 2 37) 2 38) 2 39) 3 40) 1 41) 2 42) 2 2) They are inert towards many common
43) 2 44) 2 45) 3 46) 4 47) 1 48) 2 49) 4 reagents
50) 1 51) 1 52) 2 3) The are shining lustrous pleasing to look at
4) They are found in active state7
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ELECTRONIC CONFIGURATION 24. Which of the following element exhibits
13. In which of the following elements, the maximum oxidation state
configuration is against Auf-bau rule ? 1) Mn 2) Co 3) Fe 4) Zn
1) Ni, Pd, Pt 2) Sc, Ti, Zr 25. In which of the following compounds iron has
3) Pd, Pt, Cu 4) Fe, Cr, Mn the lowest oxidation state
14. The configuration of chromium atom in 1) Fe (CO)5 2) Fe2O
ground state is 3) K4 [Fe(CN)6] 4)FeSO4(NH4)2SO4. 6H2O
1) [Ar] 3d4 4s1 2) [Ar] 3d5 4s1 ATOMIC AND IONIC RADII
3) [Ar] 3d6 4s2 4) [Ar] 3d7 4s2 26. The correct order of atomic sizes is
OCCURENCE 1) Sc < Y < La 2) Ti < Zr < Hf
15. The chemical formula of siderite 3) Sc > Y > La 4) Sc>Y<La
1) Fe2O3 2) Fe3O4 3) FeCO3 4) MnO2 COLOUR
16. The mineral of silver is 27. Which of the following cation is colourless in
1) Argentite 2) Horn silver its aqueous solution
3) Sylvine 4) Both 1 and 2 1) Cu+2 2) Sc+3 3) Fe+3 4) Co+3
28. Cuprous ion is colourless while cupric ion is
CHARACTERISTIC OF 3d SERIES
coloured because,
17. Which of the following group elements
1) Cuprous ion has completed d-orbitals while
exhibits high melting and boiling points Cupric ion has an incomplete d-orbitals
1) IVB 2) VB 3) VIB 4) IIB 2) Cuprous ion has exactly half-filled ‘d’ orbitals
18. Which group elements exhibits highest 3) Cupric ion has completely filled ‘d’ orbitals,
densities while Cuprous ion has incompletely filled ‘d’
1) IIIB 2) IVB 3) VIB 4) VIIIB orbitals
19. Which of the following transition metals has 4) Cupric ion has half - filled d-orbitals
the highest melting point? 29. Which of the following pairs of ions are
1) Cr 2) Mo 3) W 4) Hg colourless
20. Transition element which is volatile Co 2 , Fe 3
1) Ti 3 , Cu 2 2)
1) Zn 2) Cd 3) Hg 4) All
3 2 2 3

IONIZATION ENERGIES 3) Sc , Zn 4) Ni ,V
21. The second IP of Cr is high due to 30. Colour of ferrous ion is
1) Red 2) Blue
1) 3d 5 2) 3d 0 3) 3d 10 4) 3d 4
3) Pale green 4) Pale yellow
22. Transition metals are less reactive because 31. Colour in transition metal compounds is
of their attributed to
1) High ionization potential and low melting 1) small size metal ions
point 2) absorption of light in UV region
2) High ionization potential and high melting
point 3) complete  ns  subshell
3) Low ionization potential and low melting 4) incomplete  n  1 d subshell
point
4) Low ionization potential and high melting CATALYTIC PROPERTIES
point 32. Which of the following is used as Catalyst in
OXIDATION STATES the hydrogenation of oils
23. An element M has the electron configuration 1) V2O5 2) Pd 3) Fe 4) Ni
[Ar]3d54s2. Which one of its oxide is unlikely 33. The catalyst used in the polymerisation of
ethylene is
to exist
1) MO 2) M O 3) MO 4) M O 1) R3 Al  TiCl4 2) SnCl4 3) Ni 4) Pt
2 2 3 4 2 7
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MAGNETIC PROPERTIES 44. During estimation of oxalic acid with KMnO4
34. Which of the following pair of transition the self indicator is
metal ions, have the same calculated values of
1) KMnO4 2) H 2C2O4 3) K 2 SO4 4) MnSO4
magnetic moment?
2 2 2 2
1) Ti and V 2) Fe and Cu POTASSIUM DICHROMATE
2 2
3) Cr and Fe 4) Co 2 and Ti 2 45. Number of moles of K 2Cr2O7 reduced by one
35. The following species is repelled by a mole of iodide ions is
magnetic field 1) 3 2) 1/3 3) 6 4) 1/6
1) Hg+2 2) Fe 2 3) Co+3 4) Ni+2 46. Number of moles of K 2Cr2O7 reduced by one
36. The following is not a ferromagnetic mole of Sn 2 ions is
1) Fe 2) Co 3) Y 4) Ni
1) 1/3 2) 3 3) 1/6 4) 6

37. Assertion (A) : Zn is diamagnetic
2
47. The oxoanion in which oxidation state of the
Reason(R): Two electrons are lost from 4s central atom is same as its group number in
orbital to form Zn 2 periodic table.
1) Both A and R are true and R is the correct 1) SO42 2) VO2 3) MnO42 4) Cr2O72
explanation of A
2) Both A and R are true and R is not the correct COMPOUNDS OF TRANSITION ELEMENTS
explanation of A 48. The substance that sublimes on heating is
3) A is true but R is false 1) MgCl2 2) AgCl 3) HgCl2 4) NaCl
4) A is false but R is true
49. Which of the following oxides is least stable
INTERSTITIAL COMPOUNDS at room temperature?
38. Which is not an interstitial compound?
1) CuO 2) Ag 2O 3) ZnO 4) Hg 2O
1) TiH 2) Fe2O3 3) Mn2C3 4) W2C 50. Which of the following metal oxides is white
ALLOY FORMATION in colour but becomes yellow on heating
39. The common metal present in german silver, 1) Ag 2O 2) ZnO 3) FeO 4) MgO
bell metal and brass is 51. Oxide of metal cation which is not
1) Fe 2) Cu 3) Zn 4) Sn amphoteric?
40. Which of the following is an alloy of a metal
1) Al 3 2) Cr 3 3) Fe 3 4) Zn 2
and a non-metal
1) bronze 2) electron 3) nichrome 4) steel 52. Which of the following oxides of chromium
is amphoteric in nature?
POTASSIUM PERMANGANATE
1) CrO 2) Cr2O3 3) CrO3 4) CrO5
41. In permanganate ion MnO4 , manganese has
an oxidation number of +7. Therefore it is LEVEL-I (H.W) - KEY
1) sp d hybridised
3 3
2) sp hybridised
3
1) 4 2) 3 3) 4 4) 3 5) 4 6) 4 7) 3
3) dsp hybridised
2
4) d sp hybridised
3 3
8) 2 9) 2 10) 3 11) 3 12) 2 13) 3 14) 2
42. When KMnO4 acts as oxidising agent in 15) 3 16) 4 17) 3 18) 4 19) 3 20) 4 21) 1
acidic medium, the oxidation number of Mn 22) 2 23) 3 24) 1 25) 1 26) 1 27) 2 28) 1
decreases by 29) 3 30) 3 31) 4 32) 4 33) 1 34) 1 35) 1
1) 1 2) 2 3) 3 4) 5
36) 3 37) 1 38) 2 39) 2 40) 4 41) 2 42) 4
43. An acidified solution of KMnO4 oxidizes
43) 2 44) 1 45) 4 46) 1 47) 4 48) 3 49) 2
1) sulphates 2) oxalates
3) iodine 4) ferric salts 50) 2 51) 3 52) 2
 8. d-AND f- BLOCK ELEMENTS
TRANSITION ELEMENTS
d-BLOCK ELEMENTS
11. Transition metals are often paramagnetic
LEVEL-II (C.W) owing to
1) high melting point and boiling point
IONIZATION ENERGIES OF 3d SERIES 2) the presence of vacant orbitals
1. Maximum IP value in 3d series is 3) the presence of unpaired electrons
1) Zn 2) Cr 3) Cu 4) V 4) malleability and ductility
2. The second IP of Cu is very high due to the 12. Match the following .
configuration of Cu + is Set -I Set -II
A) Ferromagnetism 1) 9.273 x 10 −24 J .Tesla −1
1) 3d 5 2) 3d 0 3) 3d 10 4) 3d 9
B) Paramagnetism 2) Fe, Co, Ni
OXIDATION STATES OF 3d SERIES C) Diamagnetism 3) Cr 2+ , Fe3+ , Mn 2+
3. Variable valency of transition elements is on
account of D) Bohr Magneton 4) Zn +2 , Cu + , Sc +3
1) incomplete p - orbitals The correct matching is
2) incomplete d - orbitals A B C D A B C D
3) completely filled d - orbitals 1) 4 2 3 1 2) 2 3 4 1
4) incomplete p-orbitals 3) 1 2 3 4 4) 3 1 2 4
4. Transition elements show generally positive 13. Match the following
oxidation state due to Set -I Set -II
1) Large atomic size 2) low ionization energy
A) Sc 3+ 1) 5.92 B.M
3) low electronegativity 4) high electronegativity
5. Which one of the transition metal ions have B) V 2 + 2) 1.73 B.M.
no unpaired electrons C) Fe3+ 3) Zero.
1) Ti+4 2) V+4 3) V+3 4) Cr3+ +
D) Cu 2 4) 3.87 B.M
6. The maximum oxidation state of ruthenium
is The correct matching is
1) +6 2) +7 3) +8 4) +5 A B C D A B C D
1) 3 4 1 2 2) 4 1 2 3
COLOURS OF TRANSITION METAL IONS 3) 3 4 2 1 4) 2 1 3 4
7. Which of the following is a correct statement
(E 2010) POTASSIUM PERMANGANATE
1)Aqueous solutions of Cu + and Zn +2 are 14. The mineral from which potassium perman-
ganate is manufactured is
colourless
1) Pyrolusite,MnO2 2) Branuite,Mn2O3
2) Aqueous solutions of Cu +2 and Zn +2 are 3) Hausmannite,Mn3O4 4)Manganite,MnO3.H2O
colourless 15. Which of these react with potassium perman-
3) Aqueous solutions of Fe +2 is green in colour ganate to give oxygen quantitavely
−
4) Aqueous solutions of MnO4 is colourlesss 1) CO2 2) Cl2 3) O3 4) H2O2
16. Which one of the following is not oxidized
8. The metal ion which does not form coloured
by acidified KMnO4
compound is
1) Chromium 2) Iron 3) Zinc 4) Manganese 1) [Link] 2) Pot. iodide
3)Ferrous sulphate 4) Sodium sulphate
9. Mn2+ , Mn+3 , Mn+6 have the colours 17. Which of the following can not reduce
1) pink, blue and green 2) green, blue and yellow
acidified solution of Mn O4− ion
3) blue, yellow and green 4) yellow, blue and green
1. H2C2O4 2. H2 3. H(nascent) 4. Fe2+ions
MAGNETIC PROPERTIES 18. Oxidation of oxalic acid by acidified KMnO4
10. The magnetic moment of an ion in its +3 is an example of autocatalysis, it is due to the
oxidation state is 3.85 BM. The number of presence of
unpaired electrons present in the ion is
1) 1 2) 4 3) 3 4) 5 1. SO42− 2. MnO4− 3. Mn2+ 4. K+
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POTASSIUM DICHROMATE (K2Cr2O7) OXIDATION STATES OF 3d SERIES
19. K2Cr2O7 is preferred to Na2Cr2O7 for use in 3. Zn and Cd do not show variable valency
volumetric ananlysis as a primary standard because
because 1) They are soft
1. Na2Cr2O7 is hygroscopic while K2Cr2O7 is not 2) Their d subshells are complete
2. K2Cr2O7 is hygroscopic while Na2Cr2O7 is not 3) They have only two electrons in outer most
3. K2Cr2O7 is pure while Na2Cr2O7 is impure subshells
4. None of the above 4) Their d subshells are incomplete
20. The deep blue colour produced on adding 4. Oxidation number of chromium in potassium
H2O2 to acidified K2Cr2O7 solution is due to dichromate is
the formation of 1) +4 2) +5 3) +6 4) +3
1. Cr2O3 2. CrO3 3. CrO5 [Link] O42− 5. Manganese exhibits maximum oxidation
state in
21. Mixture of K2Cr2O7 and conc, H2SO4 is called 1) K2 MnO4 2) KMnO4 3) MnO2 4) Mn3O4
[Link] acid 2. Chromic acid 6. The number of unpaired electrons in ferrous
3. Chromium sulphate [Link] of these ion is
22. In the redox reaction involving Cr2 O72 − and 1) 2 2) 3 3) 4 4) 5
Fe2+ ions the number of electrons absorbed COLOURS OF TRANSITION METAL IONS
per each chromium of dichromate is 7. Which of the following ion is coloured ?
1. 1 2. 3 3. 4 4. 6 1) Zn+2 2) Ca+2 3) Cu+2 4) Sc+3
23. CrO4−2 (yellow) changes to Cr2O7−2 in pH = x 8. Which of the following metal ions is colour
less in water
and vice versa in pH = y hence x,y are 1) V+2 2) Cr+3 3) Fe+2 4) Sc 3+
1) 6,8 2) 6,5 3) 8,6 4) 7,7 9. Which of the following are not coloured ?
LEVEL-II (C.W) - KEY 1) CuSO4 .5 H 2O 2) FeSO4 .7 H 2O
1) 1 2) 3 3) 2 4) 2 5) 1 6) 3 7) 1 3) NiSO4 .7 H 2O 4) ZnSO4 .7 H 2O
8) 3 9) 1 10) 3 11) 3 12) 2 13) 1 14) 1 MAGNETIC PROPERTIES
15) 4 16) 4 17) 2 18) 3 19) 1 20) 3 21) 2 10. Identify the order in which the spin only
22) 3 23) 1 magnetic moment (in BM) increases for the
following four ions (Eamcet - 2011)
I) Fe +2 II) Ti +2 III) Cu +2 IV) V +2
LEVEL-II (H.W) 1) I, II, IV, III 2) IV, I, II, III
3) III, IV, I, II 4) III, II, IV, I
IONIZATION ENERGIES OF 3d SERIES 11. Which one of the following sets correctly
1. Which of the following is ionic in nature? represents the increase in the paramagnetic
property of the ions (E 2009)
1) CuF2 2) CuCl2 3) CuBr2 4) CuI 2 + + + +
1) Cu > V > Cr > Mn
2 2 2 2
2. Metal-Metal bodning is more frequent in 4d
or 5d series than in 3d series due to 2) Cu +2 < Cr +2 < V +2 < Mn +2
1) Their greater enthalpy of atomisation 3) Cu +2 < V +2 < Cr +2 < Mn +2
2) Large size of the orbitals which participate 4) V +2 < Cu +2 < Cr +2 < Mn +2
in bonding
POTASSIUM PERMANGANATE
3) their ability to involve both ns and ( n − 1) d 12. The electrolysis of potassium manganate
orbitals in bond formation solution gives
4) The comparable size of 4d and 5d sereis 1) MnO2+KOH 2) KOH+H2
elements 3) KOH+O 2
4) KMnO4+KOH
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13. Baeyer’s regent is 22. Which of the following statements is false
1) KMnO4+H2SO4 2) KMnO4+KOH 1. An acidified solution of K2Cr2O7 liberates
3) K2Cr2O7+H2SO4 4) K2Cr2O7+KOH iodine from potassium iodide
14. In dilute alkaline medium, the equivalent 2. In acidic solution, dichromate ions are
mass of KMnO4 is converted to chromate ions
3. Ammonium dichromate on heating under
M M
1. (52.66) 2. (31.60) goes endothermic decomposition to give Cr2O3
3 5
4. Potassium dichromate is used as a titrant for
M Fe2+ ions
3. (26.33) 4. M(158.00)
6
15. The reaction LEVEL-II (H.W) - KEY
2 MnO42− + Cl2 → 2 MnO4− + 2Cl − takes place in 1) 1 2) 1 3) 2 4) 3 5) 2 6) 3 7) 3
1. Basic medium 2. Acidic medium 8) 4 9) 4 10) 4 11) 3 12) 4 13) 2 14) 1
[Link] medium 4. Both a and b 15) 1 16) 2 17) 1 18) 3 19) 1 20) 3 21) 3
16. Potassium manganate is formed when :
22) 2
1. Cl2 is passed into an aqueous solutions of
KMnO4 LEVEL-III
2. MnO2 is fused with KOH in air
MAGNETIC PROPERTIES
3. formaldehyde reacts with KMnO4 in presence 1. The atomic number of the element having
of strong alkali. magnetic moment equal to 1.7 BM in its + 2
4. KMnO4 reacts with concentrated H 2 SO4 oxidation state is
1) 29 2) 25 3) 24 4) 30
17. The reaction, MnO4− + e− → MnO42− takes place in: 2. Atomic number of a transition metal is 25
1) basic medium then its magnetic moment in its + 3 oxidation
2) acidic medium 3) neutral medium state is
4) both acidic and basic medium 1) 1.73 BM 2) 2.84 BM 3) 4.9 BM 4) 5.9 BM
3. Find the correct statement
POTASSIUM DICHROMATE (K2Cr2O7)
18. Ammonium dichromate on heating i) Magnetic moment Mn 2+ ion is 35
decomposes with spark. This reaction is ii) Ti 4+ is exhibit purple color
called iii) 1 Bohr Magneton=9.273 x 10 −24 J. Tesla −1
1. Aphosphorescence 2. Incandescence
iv) Secondary valency of transition metal ion
3. Chemical volcano 4. None of these
is equal to its co-ordination number
19. When acidified solution of K2Cr2O7 is shaken
1) Only i is correct 2) Only ii is correct
with aqueous solution of FeSO4, then
3) i,iii,iv are correct 4) All are correct
1. Cr2 O72 − ion is reduced to Cr3+ ions
ORBITAL SPLITTING
2− 2− 4. In the presence of strong eletrical field, the
2. Cr2 O ion is converted to Cr O
7 4
ions
following set of orbitals are not degenerate
3. Cr2 O72 − ion is oxidised to Cr
1) 3d xy and 3d z2 2) 3dxy and 3dyz
2−
4. Cr2 O ion is oxidised to CrO3
7
3) 3dxy, 3dyz and 3dzx 4) 3d x 2 − y2 and 3d z2
20. One of the products formed when K2Cr2O7
reacts with conc. H2SO4 in cold is GENERAL
1. Cr2(SO4)3 2. Cr2O3 3.CrO3 4. CrO4Cl2 5. Which transition metal is known as stratagic
21. The oxidation state of Cr in K2Cr2O7 is or Wonder metal?
1. +5 2.+3 3.+6 4. +7 1) Tungsten 2) Platinum 3) Iron 4) Titanium
 TRANSITION ELEMENTS JEE-MAIN-SR-CHEM-VOL-II
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6. Four successive members of the first row 15. The oxioanion which contains all equivalent
transition elements are listed below with their M-O bond is
atomic numbers. Which one of them is
expected to have highest third ionization I) CrO4−2 II) MnO4− III) Cr2O7−2
enthalpy? 1) III only 2) I,II,III 3) I,II 4) I only
1) Vanadium (Z = 23) 2) Chromium (Z = 24) 16. In context with the transition elements, which
3) Manganese (Z = 25) 4) Iron (Z = 26) of the following statements is incorrect?
7. Many transition metals form interstitial [AIE-2009]
compounds. The characteristics of these
interstitial compounds are 1) In addition to the normal oxidation states,
I) They have low melting points the zero oxidation state is also shown by these
II) They are very hard elements in complexes
III) They retain metallic conductivity 2) In the highest oxidation states, the transition
IV) They are chemically more reactive than metal show basic character and form cationic
the pure metals. complexes
1) II, III only correct 2) I, III only correct 3) In the highest oxidation states of the first five
3) II, IV only correct 4) IV only correct transition elements (Sc to Mn), all the 4s and
8. Which of the following oxides are acidic in 3d electrons are used for bonding
nature?
4) Once d 5 configuration is exceeded, the
1) V2O5 2) MnO 3) Cr2O3 4) MnO2
tendency to involve all the 3d electrons in
9. The magnetic moment of an ion is close to bonding decreases.
36 × 10 −24 Joule /Tesla. The number of 17. Iron exhibits +2 and +3 oxidation states
unpaired electrons of the ion are which of the following statements about iron
1) 4 2) 2 3) 1 4) 3 is incorrect? [AIE-2012]
10. In Nesslers reagent, the active ion is
1) Ferrous compounds are relatively more ionic
1) Hg + 2) Hg 2+ 3) Hg 22− 4) HgI 42− than the corresponding Ferric compounds
11. Na2CrO4 on treatment with lead acetate gives 2) Ferrous compounds are less volatile than the
a precipitate. This dried precipitate is used corresponding ferric compounds
as a pigment for road signs and markings . 3) Ferrous compounds are more easily
The solid is known as hydrolysed than the corresponding ferric
1) White lead 2) Chrome green compounds
3) Chrome yellow 4) Red lead 4) Ferrous oxide is more basic in nature than
12. Gold dissolves in aqua-regia forming
the ferric oxide.
1) Auric chloride 2) Aurous chloride
3) Chloroauric acid 4) Aurous nitrate 18. The non transition metal present in German
13. Which of the following sulphides is yellow in silver is
colour? 1) Cu 2) Zn 3) Ni 4) Pb
1) ZnS 2) NiS 3) CdS 4) MgS 19. Transition metal present in the alloy Gun
14. Which of the following are correct about metal is
Zn, Cd , Hg 1) Ni 2) Zn 3) Sn 4) Cu
I) They exhibit high enthalpy of atomisation 20. Which one of the following does not contain
as the d-subshell is full zinc ?
II) Zn, Cd do not show variable oxidation 1) Brass 2) German silver
states, Hg can show +1,+2 states 3) Bronze 4) Bell metal
III)compounds of Zn, Cd , Hg are 21. Which of the following is a constituent of
paramagnetic lithopone
IV) They are soft metals 1) ZnSO4 2) ZnS 3) ZnCl2 4) ZnO
1) I,II,III 2) I,III 3) II,IV 4) IV only
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22. When H 2 S is passed through HgCl2 , we get 30. Four successive members of the first row
transition elements are listed below with
1) HgS 2) HgS + Hg 2 S atomic numbers. which one of them is
3) Hg 2 S + Hg 4) Hg 2 S expected to have the highest EM0 +3 / M +2 value?
23. Which of the following factors may be (Jee mains 2013)
regarded as the main cause for lanthanoid
contraction ? 1) Cr ( Z = 24 ) 2) Mn ( Z = 25)
1) poor shielding of one of 4f electrons by 3) Fe ( Z = 26 ) 4) Co ( Z = 27 )
another in the subshell
2) effective shielding of one of 4f electrons by LEVEL-III - KEY
another in the subshell
1) 1 2) 3 3) 3 4) 1 5) 4 6) 3 7) 1
3) poor shielding of 5d electrons by 4f electrons
4) poor shielding of 4f electrons by 5d electron 8) 1 9) 4 10) 4 11) 3 12) 3 13) 3 14) 3
24. Calomel on reaction with NH 4OH gives 15) 3 16) 2 17) 3 18) 2 19) 4 20) 4 21) 2
1) HgNH 2Cl 2) NH 2 − Hg − Hg − Cl 22) 1 23) 1 24) 1 25) 2 26) 4 27) 3 28) 3
29) 4 30) 4
3) Hg 2O 4) HgO
25. The correct order of E M2+/M values with LEVEL-III - HINTS
negative sign for the four successive elements 1. µ = 1.7 BM means it contains 1 unpaired
Cr, Mn, Fe and Co is (AIEEE-2010) electron.
1) Cr > Mn > Fe > Co 2) Mn > Cr > Fe > Co 2. Atomic number = 25, Electronic configuration
3) Cr > Fe > Mn > Co 4) Fe > Mn > Cr > Co is 3d 54s 2. In +3 state contains 4 unpaired
26. Which of the following arrangements does
not represent the correct order of the electrons, so µ = 4.9 .
property stated against it ?(jee main-2013) 3. Ti +4 has unpaired d electrons.
1) Ni 2 + < Co 2 + < Fe 2 + < Mn 2 + ionic size 4. In d orbitals the splitting is
2) Co3+ < Fe3+ < Cr 3+ < Sc 3+ stability in a) dxy , dyz , dzx - degenerate orbitals
aqueous solution b) d x2 − y 2 , d z 2 degenerate orbitals
3) Sc < Ti < Cr < Mn number of oxidation
states 6. Mn +2 has d 5 configuration.
4) V 2 + < Cr 2 + < Mn 2 + < Fe 2 + paramagnetic 8. Oxides with highest oxidation state is acidic.
behavior 9. µ = 36 ×10−24 J / T 1BM = 9.273 × 10−24 J / T
27. Percentage of Cu is minimum in 36 ×10−24
1) Brass 2) Bronze no. of unpaired electrons = .
9.273 ×10−24
3) Duralumin 4) Gun mental
28. The number of moles of KMnO4 that will be 11. Na2CrO4 + Pb (CH 3COO )2 →
needed to react completely with one mole of 2CH 3 COONa + PbCrO4
ferrour oxalate Fe (C2O4 ) in acidic solution PbCrO4 is known as chrome yellow.
is 12. HNO3 + 3HCl → 2 H 2O + NOCl + 2 [Cl ]
1) 1 2) 2/5 3) 3/5 4) 4/5
29. Potassium manganate can be converted into Au + 3 [Cl ] → AuCl3
potassium permanganate by oxidation
i) with chlorine ii) with ozone AuCl3 + HCl → HAuCl4
iii) electrolytically 21. ZnS and BaSO4 mixture is called lithopone
The correct statements is / are: 30. ECr0 +3 / Cr +2 = −0.41V ; EMn
0
+3
/ Mn+2
= +1.57V
1) i only 2) ii only 3) iii only 4)i,ii,iii 0
EFe +3
/ Fe+2
= +0.77V ; 0
ECo +3
/ Co+2
= +1.97V