2

2 D

Galaxy School
D
Marks:25 Subject:12th-Che D Date:29/10/18
2
Chapter:4 2 coordination compound Time:01H:00M
1 D
[A] Answer the following Qustions. [Each carries 2 marks]
7) [08]
D
1. Mention the basic requirements for the formation of complex compounds.
X
22. Explain the following words :
2 This is demo ans.
(1) Mixed Ligand complex compounds.
2 (2) Unicentred complex compounds.
(3) Polycentred complex compounds.
2
3. Write limitations of valence bond theory.
2 Explain the application of complexes in biological systems and photography.
2 4.
2
1
2
8)
2[B] Answer the following Qustions. [Each carries 3 marks] [09]
2
25. Explain geometrical structure and magnetic properties in complex ion [NiCl 4 ] 2– by
X
2
2 hybridization.
2
2 This is demo ans.
2 6. Explain the hybridization and gemetrical structure of MnO–4 complex ion.
2
7. Explain crystal field splitting in tetrahedral complexes.
1
2
2[C] Answer the following Qustions. [Each carries 4 marks]
9)
2 [08]
28. What is meant by Ligand ? Explain its classification giving illustrations.
2
X
2
2 9. Explain crystal field splitting in octahedral complexes and write the limitations of crystal field
2 This is demo ans.
2 theory.
2
D = D
2
2
2 D
2
2
2
2
2
2
2
2
2
2

2
2

2
2
2 a b
2
2
2
2
2
2
2
m
2
2
2
< Ankur Sir -- 9620262924 >
2
2
 Answer Key
Marks:25 Subject:12th-Che Date:29/10/18
Chapter:4 2 coordination compound Time:01H:00M

Section [ A ] : 2 Marks Questions

No Ans Chap Sec Que PageNo BookType

1 - Chap 4 (Part 2) A 6 Kumar

RA
2 - Chap 4 (Part 2) A 8 Kumar
3 - Chap 4 (Part 2) A 24 Kumar
4 - Chap 4 (Part 2) A 29 Kumar

ND
Section [ B ] : 3 Marks Questions

KE
No Ans Chap Sec Que PageNo BookType
5 - Chap 4 (Part 2) A 15 Kumar
6 - Chap 4 (Part 2) A 20 Kumar

N
7 - Chap 4 (Part 2) A HA 27 Kumar

Section [ C ] : 4 Marks Questions

No Ans Chap Sec Que PageNo BookType

AS

8 - Chap 4 (Part 2) A 4 Kumar

9 - Chap 4 (Part 2) A 26 Kumar
AK
PR
AR
M
KU

Kumar Prakashan Kendra Welcome To Future M:91-7359 662200

 Paper Solution
Marks:25 Subject:12th-Che Date:29/10/18
Chapter:4 2 coordination compound Time:01H:00M
1 2
[A] Answer the following Qustions. [Each carries 2 marks]
7) [08]
221. Mention the basic requirements for the formation of complex compounds.
X
2 Some basic requirements are necessary for formation of complex compound. The capacity of
2
22 This is demo
transition ans. metal ions of formation of complex compounds is more than that of other
element
2 elements.

RA
22 Basic requirements :
(i) The ligand must have electron pair which can be easily donated.
22
2 (ii) There must be vacant orbitals in the metal ion to receive electron pairs.

ND
(iii) The metal ions should have the symmetry of vacant orbitals same as the symmetry of orbitals
2
v of ligand having electron pairs. Hence, co-ordinate covalent bond can be formed by
overlapping of orbitals having electron pair in ligand.
2
2 These basic requirements are satisfied by metal ions and so complex salts are easily formed.

KE
v Even then it is not necessary that each transition element easily forms complex compounds
2
2 similar.[Co(NH
2
2 There is change in capacity of formation of complex compounds according to different oxidation

N
states of metal ions.
[Co(NH
22 In addition, there is difference in the stability of the compounds that are formed.
HA
v
2. Explain the following words :
22 (1) Mixed Ligand complex compounds.
(2) Unicentred complex compounds.
v Polycentred complex compounds.
(3)
AS

22 (1) Mixed Ligand complex compounds :

2 It is not necessary that any metal ion form only one type complex salt of with ligand. Sometimes
2 different types of ligands form complex compounds with metal ion. This type of complex
AK

2 compounds are called mixed ligand complex compounds.

2 In the complex [Cr(NH3)4(CN)2]NO3, four ammonia molecules and two cyanide ions, total six
unidentate ligands are combined. If ligand is of only one type, the complex salts are called
2 simple complex compounds.
PR

(2) Unicentred complex compounds :

2 If only one metal ion is present in any complex compound, then it is called unicentred complex
compound, e.g. K[MnO4]
AR

2 (3) Polycentred complex compounds :

2 If more than one metal ions are present in the complex compound then it is called polycentred complex
compound. e.g. K2[Cr2O7].
23. Write limitations of valence bond theory.
M

2 When co-ordination compounds are formed, the valence bond theory is mostly applied for
KU

magnetic nature and structural formation. It has following limitations :

2 (i) It consists of some assumptions.
(ii) It cannot interpret the magnitute of the magnetic information.
(iii) It is not able to explain the colours of co-ordination compounds.
(iv) It cannot interprete magnitude of thermodynamics and kinetic stability of co-ordination
compounds.
(v) It does not make exact prediction regarding the tetrahedral and square planar structures of
four co-ordination number complexes.
(vi) It cannot distinguish the weak and strong ligands.

Kumar Prakashan Kendra Welcome To Future M:91-7359 662200

 // Page:2 //
4. Explain the application of complexes in biological systems and photography.
2 In Biological systems : Co-ordination compounds are very important in biological systems.
2 The dye matter chlorophyll formed by magnesium is responsible for photosynthesis.
22 Iron containing co-ordination compound haemoglobin dye-matter conducts O2 and so red
2 colour of blood is observed.
22 Cobalt contains co-ordination conpound vitamin B12 or cyanocobalamine which is antimatter of
petnicious anemia.

RA
22 The other compounds which are substances having biological importance are in enzyme formed
by formation of compound with metal viz. carboxypeptidase and carbonic anhydrade (catalysts
2

ND
of biological system-Enzymes).
2 In Photography : Film is stabilized by washing with solution of hypo in white and black
photography which is soluble in non-decomposable AgBr whose formation takes place from

KE
2 complex ion [Ag(S2O3)2]3–
1
[B] Answer the following Qustions. [Each carries 3 marks]
8) [09]

5. Explain geometrical structure and magnetic properties in complex ion [NiCl 4 ] 2– by

X

N
hybridization.
2 This is demo ans.
HA
2 [Ni(CN)4]2– complex ion : In tetrachlorido nickelate (II) complex ion, Ni2+ metal ion is combined
with four weak Cl– ligands.
2
2 As CN– strong ligand comes nearer to the metal ion because it possesses more attraction, while
AS

weak Cl– ligand does not come near to metal ion because it possesses less attraction.
22
2 Hence, the 3d-orbital of Ni2+ ion is not capable of forming co-ordinate covalent bond with four
Cl– weak ligand.
AK

22
22 Hence, the rearrangement of electrons in 3d-orbitals if Ni2+ metal ion is not required.
3
22 a part in bhybridization and form sp hybrid orbitals
Here, one 4s, and three 3d-orbitals take
PR

22 having same energy, which is arranged at the angle of 109°28' tetrahedrally in which the four
electron pairs coming from four weaka Cl– ligandb are arranged.
2
22
AR

2
22
2
2
M

2
2
KU

2
2
3
Unpaired electrons n = 2 sp hybridization
Hence, m = 2.83 BM
2 Hybridization : [Ni(Cl)4]–2 complex ion has sp3 type of hybridization and its geometrical structure
becomes tetrahedral.
2 As there are two unpaired electrons in two 3d-orbitals, the theoretical value of its magnetic
moment becomes 2.83 BM and the value of experimental magnetic moment is 2.90 BM. So it
becomes paramagnetic.
Kumar Prakashan Kendra
m Welcome To Future M:91-7359 662200
2 becomes tetrahedral. D
D D
2
22 As there are two unpaired electrons in two 3d-orbitals, the theoretical value of its magnetic
D
moment becomes 2.83 BM and the // Page:3
value //
of experimental magnetic moment is 2.90 BM. So it
2 becomes paramagnetic.
6. Explain the hybridization and gemetrical structure of MnO–4 complex ion.
2
2
2 [MnO4]– complex ion : In tetraoxomanganate (VII) complex, four O2– weak ligands are combined
2 with Mn7+ metal ion, so it possesses tetrahedral structure.
2
22 The electronic configuration of Mn metal and Mn7+ metal ion are [Ar]3d 5 4s2 and [Ar]3d 0
respectively.

RA
22 Here 3d and 4s-orbitals are vacant. In Mn7+ metal ion, one 4s and three 3d-orbitals overlap and
D
d3s type hybridization occurs.
22 D
In d3s Dhybridisation, four hybrid orbitals having same energy are arranged on the four corners
2
D

ND
of tetrahedral.
D
22 Four electron pairs of exygen ions from co-ordination covalent bonds in hybrid orbitals.
D D
D

KE
2 D
2 D

N
2
HA
2
2
3
2 d s hybridization
AS

2
2 Hybridization :
2
2 In [MnO4]– complex ion there is d3s hybridization.
2
AK

22 Magnetic properties : The co-ordinate bolds formed by O2– weak ligand electrons undergo d-
2 d transition in d-orbital so that even though there is no unpaired electrons in Mn+7 of Mn–4 it
gives coloured ion.
2
PR

7. Explain crystal field splitting in tetrahedral complexes.

2 In the formation of tetrahedral structure, the splitting of d-orbitals is in opposite nature to
octahedral complexes.
AR

22 Like octahedral, if tetrahedral complex possesses equal distance between, metal, ligand, metal-
4
2 ligand, then Dt = D0 .
9
2 Hence if the Dt value of At is not sufficiently high, pairing of electrons does not occur.
M

D = D
2 Hence low spin is observed in less propotiors.
2 D
KU

22

22

2
Kumar Prakashan Kendra Welcome To Future M:91-7359 662200
 // Page:4 //
2 The splitting of d-orbitals in tetrahedral structure is shown in the figure.

Energy

RA
ND
d-orbitals Average energy of Splitting of d-orbitals
free ion the d-orbitals in in tetrahedral
spherical crystal field crystal field
d-orbital splitting in a tetrahedral crystal field

KE
1
[C] Answer the following Qustions. [Each carries 4 marks]
9) [08]
8. What is meant by Ligand ? Explain its classification giving illustrations.
X
2 Ligand : “The lignad has negative electric change or is a neutral molecule”. The classification of

N
2 This is demo
ligands ans.
is made of basis of the number of electron pair donating atoms.
2
HA
Classification of Ligands : It is made on the basis of the number of electron pair donating
atoms.
Ligand
2
AS

2
Unidentate ligand Didentate ligand
2
2
AK

Didentate Tridentage Hexadentate

2 Ligand Ligand Ligand
2
2 Generally the ligand has a negative electric change or is a neutral molecule.
PR

(1) Unidentate ligand :

2
2 If only one atom of ligand of negative ion or neutral molecule donates one atom to metal ion
by giving one electron pair and form one co-ordinate covalent bond, then it is called unidentate
ligand.
AR

22 E.g. : H2O, NH CO
2 Negative ions like Cl–, CN–, F–
22
M

In [Cr(NH3)6]Cl3 complex compound, nitrogen atom of each ammonia combine by giving one
electron pair to chromium metal ion, it is called unidentate ligand.
2
KU

In [Cr(H2O),]C13 complex compounds each molecule of water co-ordinates with chromium

2 metal ion by giving one electron pair, so it is unidentate ligand.
22 The atom present in negative ion or neutral molecule gives electron pair to metal-ion which is
2 called the co-ordinate site of ligand and it is shown as M ¬ L, where M is metal ion and L is
ligand.
2 Unidentate ligand :
.. ..
H2 O :, :NH3, :CO, CH 3 N H 2 , C2H5N (Py)
22 Unidentate Negative ion ligand :
2 ¬ –), O2–, S2–, N3–.
OH– , F–, Cl–, Br–, I–, CN–, NH2–, NO3–, NO2–, CH3COO– (ACO
Unidentate Positive ion ligand : +NO, +NO2
2 (2)
Kumar Didentate ligand
. . Prakashan :
Kendra Welcome To Future M:91-7359 662200
2 H The
O 3
ligand which can 2
donate two electron pairs and forms two co-ordinate covalent bonds, is
 H2 O :, :NH3, :CO, CH 3 N H 2 , C2H5N (Py)
Unidentate Negative ion ligand :
OH– , F–, Cl–, Br–, I–, CN–, NH2–, NO3//
–, NO –
Page:5 // – – 2– 2– 3–
2 , CH3COO (ACO ), O , S , N .
Unidentate Positive ion ligand : +NO, +NO2
(2) Didentate ligand :
2 The ligand which can donate two electron pairs and forms two co-ordinate covalent bonds, is
called didentate ligand.
2 In this type of ligand two atoms combine with metal ion by giving two electron pairs and form
two co-ordinate covalent bonds.
2 Thus, only one ligand satisfies two secondary valencies of metal ion viz. In ethane 1-2 diamine

RA
(ethylene diamine-en), its one molecule forms two co-ordinate covalent bonds by giving two
electron pairs on two nitrogen atoms, to metal ion.
2 In oxalate (OX)2– negative ion, two electron pairs on two oxygen atoms are given to metal-ion
and two co-ordinate covalent bonds are formed.

ND
OR

KE
Ethane 1, 2-diamine Oxalate
[Pt(en)2]2+

N
OR HA
[Cu(XO)2]2–
AS

OR
AK

(3) Tridentage ligand :

2 The ligand in which there are three co-ordination sites is called tridentate ligand. In this type of
ligand, three atoms form three co-ordinate covalent bonds by giving three electron pairs.
PR

2 Thus only one ligand satisfies three secondary valencies of metal ion viz. Propane 1-2-3 triamine
(Propylene triamine-ptn) one neutral molecule form three co-ordinate covalent bonds by giving
three electron pairs on its three nitrogen atoms. Similary, PO 34 - is a negative ion tridentale ligand.
CH2 – CH – CH2
AR

| | |
:NH2 :NH2 :NH2 (ptn)
M

2 Tridentage ligand : PO43–, ASO43–

E.g. :
KU

Propane 1, 2, 3 - triamine Phosphate

(propylene triamine (ptn))

Kumar Prakashan Kendra Welcome To Future M:91-7359 662200

 // Page:6 //

(4) Hexadentate ligand :

RA
2 The ligand in which there are six co-ordination sites is called hexadentate ligand.
2 Six atoms of this type of ligand give six electron pairs to metal ion and form six co-ordinate

ND
covalent bonds.
2 Thus, only one ligand satisfies six secondary valencies of metal ion viz. In ethylene diamine
tetraacetate (EDTA), four oxygen atoms and two nitrogen atoms give four electron pairs and two

KE
electron pairs respectively to metal ion and form six co-ordinate covalent bonds.
2 E.g. [M EDTA]+n

N
HA
AS
AK
PR

2 Multidentate ligand : Generally, the ligand in which two or more co-ordination sites are there
AR

or the ligand in which two or more atoms donate electron pairs to metal ion and form co-
ordinate covalent bond, is called multidentate ligand.
Some ligands and their types are shown in table.
M
KU

Unidentate
Neutral
ligand
Unidentate
Negative
ion ligand
Unidentate
Positive
ion ligand
Didentate
Neutral
ligand
Kumar Prakashan Kendra Welcome To Future M:91-7359 662200
Didentate
22
Multidentate ligand : Generally, the ligand in which two or more co-ordination sites are there
or the ligand in which two or more atoms donate electron pairs to metal ion and form co-
22 // Page:7ligand.
ordinate covalent bond, is called multidentate //
Some ligands and their types are shown in table.
22

2 Unidentate
Neutral
ligand
2 Unidentate
Negative
2

RA
ion ligand
Unidentate
Positive
ion ligand

ND
Didentate
Neutral
ligand

KE
Didentate
Negative
ion ligand
Tridentate

N
Neutral
ligand
HA
Tridentate
Negative
ion ligand
AS

Hexadentate
Negative
ion ligand
AK

ion

9. Explain crystal field splitting in octahedral complexes and write the limitations of crystal field
theory.
PR

2 In octahedral complex, there are six ligands around the metal atom or ion.
2 Here there is repulsion between electrons of d-orbital and electrons of ligand (or between
2 negative ions).
AR

22 dx2_ y2 and dz2 orbitals arranged on this axis experience more repulsion with ligand and will be
raised in energy, while there is less repulsion between dxy, dyz, dxz orbitals arranged between
2 the axes, with ligand.
2
M

Hence, their average energy of spherical crystal field decreases.

2 As the degeneracy of these orbits is removed, it results into three orbitals having lower energy
2
KU

t2g and higher energy possessing eg orbitals.

2 This type of phenomenon is called crystal field splitting.
2 The splitting of energy of orbitals observed in octahedral complex is shown by D0. Thus, in eg
3 2
D0 and there will be D 0 decrease in energy of three t2g orbitals.
orbitals there will be increase by
5 5
2 The splitting of crystal field (D0) depends on electric charge of metal ion and ligand. Some
ligands produce strong field, so that the splitting of orbitals is more in proportion.
2 While certain ligands produce weak field so that the splitting of orbitals is less in proportion.
Generally, the series of ligands on the basis of increase in strength of fields by ligands, can be
shown as below :
I– < Br– < SCN– < CI– < S–2 < F– < C2 O42 < H2 O < NCS– < EDTA < NH 3 etc.
2 The
Kumar above series Kendra
Prakashan is called spectrochemical
Welcome series.
To Future M:91-7359 662200
2 If in the metal ion, there are 1, 2 or 3 electrons in d-orbitals, then their arrangement will be in
2 While certain ligands produce weak field so that the splitting of orbitals is less in proportion.
Generally, the series of ligands on the basis of increase in strength of fields by ligands, can be
// Page:8 //
shown as below :
I– < Br– < SCN– < CI– < S–2 < F– < C2 O42 < H2 O < NCS– < EDTA < NH 3 etc.
2 The above series is called spectrochemical series.
2 If in the metal ion, there are 1, 2 or 3 electrons in d-orbitals, then their arrangement will be in
t2g orbitals having low energy, according to Hund’s rule. But if there are 4 electrons(d4) in the
d-orbitals then there are two possibilities as follows :
(i) The fourth electron will be arranged by pairing with any one electron present in t2g orbitals.
(ii) The fourth electron will be arranged in eg orbital neglecting giving energy for pairing.
2 Which of the above two possibilities can be possible depends on the splitting of crystal field (D0)

RA
and on reactive magnitude energy of pairing; p.
(a) If D0 < p then the fourth electron will be arranged in eg orbital so that electronic structure
will be t2g 3 eg1. For the ligands producing weak field, D0 < p and form complexes having

ND
higher spins.
(b) If D0 > p then the fourth electron will be arranged in t2g orbital so that the electronic
structure will be t2g4 e.g. for ligands producing strong field D0 > p and for complexes having
low spins.

KE
2 Experimental findings suggest that for complexes having d4 to d7 electronic configuration the
ligands having stronger field give more stability than complexes having weak field.
Limitations of crystal Field Theory :

N
2 The magnetic properties, colour and the formation of structures of complex compounds can be
successfully explained by crystal field model.
HA
2 The effect of many diversities is observed in change of ligand and the ionic bonds.
2 The position of anionic ligand is observed at the lower end in the spectro chemical series.
AS

2 The limitation of CFT led to the development of field of study of molecular orbital theory.
AK
PR

2
AR

D = D
2 D
2
M
KU

Kumar Prakashan Kendra Welcome To Future M:91-7359 662200