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 1
Coordination Chemistry
Hints & Solutions
Explanations:
1) c
In, Ni(CN4)2- oxidation state of Ni is +2 & its valence shell electronic configuration is 3d8 .Since CN- is a strong ligand
,therefore these ligands cause to pair up two unpaired electron ,resulting in vacant 3d orbital .
Hybridization: dsp2
Geometry: Square planar.

In Ni(Cl4)2-, oxidation state of Ni is +2 & its valence shell electronic configuration is 3d8 Since Cl- is a weak ligand ,
no pairing ,none of the 3d orbital is vacant .
Hybridization: sp3
Geometry: tetrahedral

2) c
Oxidation state of Ni is +2 & its valence shell electronic configuration 3d8
For two unpaired electrons geometry is Tetrahedral.

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T
3) b
For term symbol only valence shell is considered.

I N
O
Term symbol 2s+1 Lg/u +/-
S = ½+½ =1 , 2s+1= 3

P
L= 1x(1)+ 1x(-1) = 0 , the term symbol is ∑
When molecular orbital is π , 2s+1= 3 give negative sign to distinguish ∑ terms
g and u are used for molecules which have COS present , u*u =g

A
4) a

HOMO= ϭ* of Cr+2 HOMO= ϭ* of Cr+2

T
+3
LUMO= ϭ* of Co LUMO= π/π* of Ru+3
10
Acceleration =10 Acceleration =102
Inner sphere mechanism is favourable for ϭ→ϭ* transition only.

N
5) d
For a d5 octahedral complex [Mn(H₂ O)6 ]+2 all transitions are Laporte forbidden (orbital forbidden) as
well as spin forbidden. Absorptions associated with doubly forbidden

A
transitions are extremely weak, so it is very lightly coloured.

6) a

U
In the given case ligand in same, so higher the formal oxidation state of the metal , lower will be LMCT.
Mn Oxidation state +7
Cr Oxidation state +6
V Oxidation state +5

Q
So, order is MnO4- < CrO42- < VO43-

7) d
a) Ni+2 = 3d8 , No Jahn - Teller distortion , ideal Oh
b) Mn+2 = 3d5 , No Jahn - Teller distortion , ideal Oh
c) Cr+3= 3d3, No Jahn - Teller distortion , ideal Oh
d) Ti+3= 3d1, shows Jahn - Teller distortion , ideal Oh geometry is not observed

8) b
For 3D

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2S+1 = 3, 2S=2, S=1

S=1, L=2
For term, S, P, D, F
Value of L= 0, 1, 2, 3

T
J can have values from [L+S].....[ L-S]
‫׀‬2-1 ‫׀‬.....‫׀‬2+1‫׀‬
3 2 1

N
Possible J Values are : 3

I
9) b
Charge transfer spectra are possible due to transfer of electron from ligand to metal or from metal to
ligand.

O
In Ceric ammonium nitrate (NH 4)2 [Ce(NO3)6], metal is in a high oxidation state & ligand has
reducing properties undergo ligand to metal charge transfer.So, Intense colour of Ceric ammonium
nitrate, (NH4)2 [Ce(NO3)6] is due to charge transfer from bidentate NO -3 to Ce+4 which has C.N= 12.

P
10) c
Kurnakov test is used to distinguish between cisplatin and transplatin, by using thiourea as a reagent.
Cisplatin+ Aqueous thiourea → deep yellow solution and on crystallisation it gives
yellow needle shape crystal of tetrakis(thiourea) platinum

A
(II) chloride

Transplatin + aqueous thiourea →Colourless solution on crystallisation it gives

T
white needle shape crystal of trans-bis(thiourea)diaammine
platinum (II) chloride

N
11) b

Total isomers = geometrical isomer + ½(optical isomer )

Geometrical isomer = 2 isomers ( trans form + cis form)

A
Optical isomer = 2 isomers ( d –cis-form + l-cis form)
Total isomers= 3

U
12) d
N→ 1s1 2s2 2p3
L=1+ 0 -1= 0
s=3/2

Q
2s+1=2x3/2+1=4
J=(L+S).... (L-S)
=|0+3/2|.... |0-3/2|= 3/2
Therefore, Ground state term = S
Term symbol = 4S3/2

13) c
[Co(NH3)6]3+ highest value of Δ0
Highest energy (v) or lowest value of wavelength is absorbed

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14) b
Number of unpaired electrons = 2.
Thus this complex is tetrahedral. Tetrahedral complexes show only one isomer. Magnetic moment

T
corresponding to two unpaired electrons 2.9 B.M. The hesh values 3.20 due to spin-orbit coupling.

15) b

N
For allowed transition : a)Spin multiplicity should be same or ΔS = 0
Therefore (a) is not allowed as ΔS ≠ 0

I
b) ΔL = 0, ± ,1for allowed transition
Therefore (c) is not allowed as ΔL ≠ 0, ± 1
c) u → g (allowed)

O
g→ g ( not allowed)
Therefore (b) is correct option.

P
16) b
For d3 and d8 , the lowest transition gives the value of Δo

T A
N
A
U
Q
17) b
Substitution nucleophilic unimolecular conjugate base mechanism.

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[CoCl(NH3)5] +2 + OH- →[Co(NH3)4(NH2)Cl] +1 +H2O

_`ab _cde
[Co(NH3)4(NH2)Cl] +1 [Co(NH3) 4(NH2)] +2 + Cl-1

T
[Co(NH3) 4(NH2)] +2 + OH- → [Co(NH3)5OH] +2

N
18) d

I
Explanation

P O
19) c
[Co*(NH3)6]+2→High spin
[Co*(NH3)6]+3 →Low spin
[Ru(NH3)6]+2→ Low spin ;
[Ru*(NH3)6]+3 →Low spin

T A
20) d

N
For Ce+4 ions NO3- behaves as bidentate ligand. Thus C.N. for [Ce(NO 3)6] -2 is 12 and shape

A
corresponding to C.N=12 is icosahedron.

21) c
Ligand Cl- is both ϭ-donor and π donor

U
According to LFT, each ligand is always a ϭ -donor some ligands like: NH 3 which has only one lone
pair of electrons is only ϭ -donor. Some ligands like F-, Cl-, OH- etc. which hence two or more lone pair

Q
of electrons are ϭ as well as π donors. Some ligands like CO, CN -, SH4, bpy, phen, etc. have π* vacant -
orbitals so these are ϭ -donor but π- acceptors.

22) c
Spin-orbit coupling of d-electrons takes place in which t2g orbitals are unsymmetrically filled.

23) d
Nucleophilic attack on olefins under mild conditions

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T
So, it requires activation by coordination to metal.

N
24) b
For Ni+2 ion in free state, the thus having same spin multiplicity as ³F and ³P. In octahedral field, ³F

I
splits into 3A2g , 3T2g and 3T1g terms but 3P does not split but it transforms into 3T1g (P). Therefore orgel
diagram is.

P O
T A
N
Three electronic transitions are 3T2g← 3A2g , 3T1g ←3A2g , 3T1g (P) ←3A2g

A
25) c
f!
We know that number of microstates= h!(f$h)!
For d5, r= 5, l=2 Therefore,

U
n = 2(2l+1)= 2(2x2+1) = 10
ij!
Number of microstates = = 252 = 7×6 q
k!×k!

Q
26) c
For allowed transition :
(a) Spin multiplicity should be same or ΔS = 0
A is not allowed transition as ΔS ≠ 0
(b) ΔL = +/-1 , 0 for allowed transition as ΔL ≠ 0, ± 1
therefore E transition not allowed as ΔL ≠ 0, ± 1
B, C, D are allowed .

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27) a
[Mo2(S₂)6]-2
The structure of [Mo2(S₂)6]-2 cluster is:

T
So, the bridging Sq$q , is two and co-ordination number of Mo is 8.

I N
O
28) c
[Co(H2O)6]+2 → t52g e2g

P
T A
In this electron transition from t52g → e2g , therefore d-d transition.

N
[CoCl4]-2 → t52g e2g

Electron transfer from e to t 2 , therefore d-d transition.

A
29) b

U
Q
Total isomers = geometrical isomer + ½(optical isomer)
Geometrical isomer = 2 isomers (trans form + cis form)
Optical isomer = 2 isomers (d –cis-form + l-cis form)
Total isomers= 3

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30) a

T
I N
O
31) c
Electric dipole allowed transition in d2

P
For electronic transition selection rule, spin multiplicity ∆S=0; ∆l= ±1, ∆J = 0, ±1
3
F→ 3D is allowed transition because ∆S=0, ∆l = -1

32) d
In Be2C3 , Be+ = In tetrahedral voids

T A
N
C3-2 = In FCC arrangement (Lattice point at corner + at each face centre)

A
Therefore, coordination number of Be + = 4
And coordination number of C3-2 = 8

33) a

U
In trigonal bipyramidal complexes, the two ligands lie on z-axis and the three in xy plane somewhere in
between the axes. In xy plane, there are four electrons and on z-axis there is only one electron in 𝑑t u
orbital

Q
q
Electronic Configuration, 𝑑vt q
= 𝑑wt q
< 𝑑vw , =𝑑vq u $w u <𝑑tqu

34) a
Co3O4 is a normal spinel. In normal spinel the Co +2 ions occupy tetrahedral voids and Co +3 ions occupy
octahedral voids. Therefore, spinel structure of Co 3O4 is
(Co+2) t (2CO+3) o O4

35) a
Trans effect of Cl - > NH3
Anti-tumour agent is cis-[Pt(NH 3)2CI]

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The precursor of this complex is [PtCl 4]-2

36) b

T
N
Explanation

I
P O
T A
37) a

N
A
The rate of water exchange in [Cu(H 2O)6] is fastest due to Jahn-Teller distortion. For other three
complexes of 3d-series dipositive metal cation, the rate of water exchange decreases with increase in
effective nuclear charge and decrease in size.

U
Correct order: (i)> (ii)> (iii)> (iv)

38) a

Q
Trans effect Cl- has larger trans effect than NH 3

39) b

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The electronic transition responsible for the colour of the transition metal ions is dπ →dϭ* which is in
according to LFT.

T
I N
P O
A
40) c
The mulliken symbols for the spectroscopic states arising from free ion term F are T₁g +T2g + A2g

T
41) c
Co(II), Zn(II) and Be(II) form tetrahedral complexes with Cl - or OH-.

N
Be(II) has no d-orbitals, therefore it form tetrahedral complexes.
Co(II) and Zn(II) form tetrahedral complexes with halides and OH -.

A
42) a
[CoCl4] 2- +6H2O(blue) ↔ [Co(H2O)6] 2++4Cl-
(blue, tetrahedral) (Light pink, octahedral)

U
43) b
[Bu4N]2 Re2 Cl8

Q
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T
I N
44) d

P O
Among the given ligand CO is most π - acid ligand. Between C2H4 and C2F4 , C2F4 has more tendency
to behave as л-acid ligand due to more electronegative F atoms which holds electron density towards F
atoms and alkene behaves as a better π -аccepting position from metal. NEt 3 has very little behaviour

A
towards л-back bonding. Thus, the order is
NEt3 <C2H4 <C2F4 <CO

T
45) a
VCl64-
Oh = V+2 = d3

(η5-C5H5)2 Cr

N
A
U
Q
[Co(NO2) 6] 3-
Oh = Co3 = d6 → no unpaired electron.
[Ni(EDTA)] 2-
Ni+2 = d8 → square planar → no unpaired electron.
More unpaired electron in VCl64-
So, it contain highest magnetic moment.
𝜇 = 3 3 + 2 = 15 B.M

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46) b
Intensity of C 4A 2g→2E g is lowest, since it is spin forbidden.

47) a

T
As strong field ligand have high crystal field stabilisation energy, according to spec trochemical series of
ligand, the given ligand in order Br- < Cl- < NCS-
Thus, ∆ t of given complexes follow the order: [Co(NCS 4)]2- >[Co(Cl4)]2- > [Co(Br4)]2-

N
48) a

I
Co2+→ t52g e2g → µ = 3.89BM
Cr2+→ t42g e2g → µ = 4.9BM
Mn2+→ t32g e1g→ µ = 4.9 BM

O
2+ 4 2
Fe → t 2g e g→ µ = 4.9BM

49) d

P
For two non-equivalent π-electrons [π 1, π1]

3
ϕ is not possible.

T A
50) c

N
Order of ligand is spectro chemical series

A
SCN- < Cl- < F- < CN-
From above it is clear that CN- will produce highest energy difference, followed by F -, Cl-, SCN-. As
colour of complex is complementary colour of absorbed light.
Thus [Co(CN4)]2- absorbs orange colour radiation which complementary colour is blue therefore colour

U
of [Co(CN4)]2- is blue.

The other combination according to energy are mismatched. Hence, only option (c) is correct.

51) d
2+

Q
Mn → 3d5→ t32g e2g (high spin octahedral)
CFSE in Oh field=(-0.4×3 +0.6×2) =0

Cr+3 →3d3→ t32g e0g (octahedral)

CFSE in octahedral field = -0.4x3∆ 0= -(0.4x3) ∆o = -1.2∆o

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52) b

T
I N
53) c

P O
Pt-S→ dπ-dπ bonding in weaker than that of Pt-P bonding. When Pt-S and Pt-P bond are trans to each
other then Pt-S become weaker therefore in such a situation SCN ligand tends to form bonding through
M atoms of ligand as M do not do not form dπ-pπ bonding. Hence, the most probable structure will be

54) a
Ni2+ is tested by dmg

T A
N
Ni2+ + 2dmg → [Ni(dmg) 2] (Tschygaeff test )
Red
The structure of complex is

A
U
Q
Therefore
Ni-N bonds = 4
Ni-O = 0
Hydrogen bonds = 2

55) a

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NiBr2 reacts with (Et)(Ph2)P at -78°C in CS2 gives red copound 'A' which on standing at room
temperature turns green to give B.
Measured magnetic moments of 'A' is 0.0 BM ( no unpaired electrons)
and 'B' is 3.2 BM ( two unpaired electrons + orbital contribution)

T
For A geometry of Ni 2+ = 3d8 4s0 = hybridisation = dsp2 (square planar)
For B geometry of Ni2+ = 3d8 4s0 = t62g e2g = two unpaired electrons, hybridisation = sp 3 (Tetrahedral)

N
56) a
In [AgL4]2+ and [AgL6]2+ , Ag2+ has d 9 configuration, hence have unpaired electron. Hence

I
paramagnetic.
[AgL4] 3+ , Ag3+ has d8 configuration and dsp2 hybridization (square planar so pairing of electron).
Hence, diamagnetic in nature

O
57) a
[CoL6] 3+ →red colour→ absorbs green radiations

P
[CoL‫׳‬6] 3+ →green colour→ absorbs red radiations.
Energy of green radiations > energy of red radiations, Therefore, L will be stronger ligand than L'. Thus,
L and L' are NH3 and H2O respectively.

58) a

A
[V(H2O)6] 3+ →V3+ → 3d2→t2 egº

T
N
Two transition

A
V1= 3T1g (F) → 3T2g (F) ; V2 =3T1g (F) →3T1g (P)

U
Q
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59) d
For np2 configurations (microstates)

T
I N
O
The configuration (IV) violets the Pauli's Principle, Hence term symbol 3D is not possible.

P
60) a

T A
N
A
U
In the successor complex inert ruthenium bridged to inert chromium.

Q
61) a
(Phen) is an π-acceptor ligands hence there is mixing of donor and acceptor orbital having similar
symmetry this leads to fast transfer of electron leading to enhance rate of reaction.
[Fe(phen) 3] +3
5
↓
0
t 2g e g
[Fe(phen) 3] +2
↓
t 2g e0g
6

π*5ϭ*0 π*6e0g
Electron transfer takes place from π* 6 (Fe+2)→ π*5 (Fe+3)

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Correct answer is (a)

62) a
s and p both form π -bonding with complex and π-bonding capacity of sulphur is greater than

T
phosphorus due to smaller size of d-orbital of sulphur. Hence, in presence of sulphur trans to phosphorus
donor atom phosphorus-metal bond will be weak hence they do not lie trans to each other in the
complex. As nitrogen does not involment in π -bonding with complex hence when nitrogen atom is trans

N
to phosphorus, phosphorus become able to form efficient π -bond with metal hence become stable thats
why P and N are trans to each other

I
63) c

P O
T A
N
A
U
Q
64) a

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Terminal NO=1672 cm¹

Bridging NO=1505 cm

65) d

N=1s 2s 2p
L= +1 0 -1

T
S= 1/2+1/2+1/2=3/2
L=+1+0-1=0

I N
O
66) a

- -
P
A
Trans effect NO 2 > Cl > NH3

67) c

T
N
A
Total isomers = geometrical isomer + ½(optical isomer)

U
Geometrical isomer = 2 isomers (trans form + cis form)
Optical isomer = 2 isomers (d –cis-form + l-cis form)
Total isomers= 3

Q
68) a
Explanation

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T
I N
O
There is spin change during electron transition. Therefore, transition is spin disallowed

69) a
[CoCl(NH3)5]+2 + OH- → [Co(NH3)4(NH2)Cl]+1 +H2O

P
A
[Co(NH3)4(NH2)Cl]+1 → [Co(NH3) 4(NH2)]+2 + Cl-1

[Co(NH3) 4(NH2)]+2 + OH- → [Co(NH3)5OH]+2

T
Base hydrolysis of [CoCl(NH3)5]+2 depends on the concentration of both [CoCl(NH 3)5]+2
and base. In this reaction OH - abstract proton from coordinated NH 3.
The base hydrolysis of [Co(CN)] -3 is independent of base because it has no ionizable proton.

70) c
[Ne] 2p1 3p1

N
A
2s+1=3; 2s=2; s=1

For, D, L=2
J=|L+s|..... |L-s|=|2+1|... |2-1|= 3,2,1

U
Levels for 3D are 3D3 , 3D2 , 3D1

Q
71) a
[MnF6] -3 , Mn+3→3d4 → 𝒕𝟑𝟐𝒈 𝒆𝟏𝒈
(HS)
𝜇= 44+2= 24 = 4.9
S =2 →2s+1 = 2×2+1=5
L=2→D
Ground state term symbol ³D

72) a

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It is first inorganic optically active compound discovered by Werner.

T
I N
O
Number of Co-O bonds = 12
Number of Co-N bonds 12

P
73) a
[CrCl6] -3
Cr 3+ →3d3
𝜇 s = 𝑛(𝑛 + 2) = 3(3 + 2) = 3.87

A
𝜇 L+S = 𝑛 𝑛 + 2 + 𝑙(𝑙 + 1) BM

T
𝜇 L+S = 𝑛 𝑛 + 2 + 𝑙(𝑙 + 1)

N
= 3 3 + 2 + 3(3 + 1) = 15 + 12 = 27 = 5.20 BM

A
74) a
The bonding in phosphine ligands, like that of carbonyls having two components. The primary

U
component is sigma donation of the phosphine lone pain to on empty orbital on the metal. The second
component is back donation from filled metal orbital to an empty orbital on the phosphine ligand. This
empty phosphorous orbital has been described as being either a d-orbital or an antibonding sigma orbital
(ϭ*).

Q
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T
I N
P O
from M(t2g )→ PR3(σ*)

T A
So, in transition metal phosphine (M-PR3) complexes, the back bonding involves donation of electrons

N
75) b
For allowed transition : a)Spin multiplicity should be same or ΔS = 0
Option c and d (incorrect) as ΔS ≠ 0
b) ΔL = ±1 , for allowed transition

A
3S→3P
ΔS = 3-3=0
ΔL= 1-0= 1

U
76) d
ns1 np1
L=1 ≡ 𝑃

Q
S=1 hence, 2S+1=3
For J value, if orbital is less than half filled than
J=|L-S|=|1-1|=0
Hence, 3P0

77) a
Fe(II) protoporphyrin → π →π* transition
[Mn(H₂O) 6]Cl₂ → Mn+2→d5 (high spin) spin forbidden (d-d) transition.

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T
∆S=1. Hence, not allowed.

[Co(H₂O)6]Cl2 →Co+2→ d7 (high spin) (d-d)

I N
P O
∆S= 0. hence allowed

78) c

T A
N
K4[Cr(CN) 6]= Cr+2→ d4 (low spin)
For a compound to show John Teller Distortion e g or t2g set should be electronically degenerate.
(1) Cr+2 → d4 (low spin)

A
U
Electronically degenerate hence show John Teller Distortion.

Q
(2) K4[Fe(CN) 6] = Fe+2 (low spin) = d6 (low spin)

Electronically non-degenerate hence, no Jahn-Teller distrotion

(3) K3[Co(CN)6] = Co+3 → d6 (low spin)

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Same as above hence, no Jahn-Teller Distrotion.

(4) K4[Mn(CN) 6] = Mn+2 (low spin)

T
electronically degenerate

Hence, complex will show Jahn-Teller Distortion.

I N
O
79) a

P
[Fe(Phen) 2 (NCS) 2]
Fe+2 = d6 complex
At high temperature high spin and at low temperature low spin behaviour at 250 K

CFSE = 1.6 Δ0 +1.2 Δ0 =0.44,

T A
N
𝜇 = 𝑛(𝑛 + 2) = 4(4 + 2) = 4.90 at 150 K

A
U
CFSE -0.4 x 6 Δ0 = -2.4∆

Q
𝜇 =0

80) a
Taking the valence shell configuration
Be 2s1 3s1
s=1/2+1/2 =1
Multiplicity =2S+1= 2x1+1=3
L= 0+0= 0 , S term
J= (L+S) = (0+1) = 1
Hence, terms is 3S1

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81) a
[CrO4]2-< [MnO4]2- < [FeO4]2-
All have +6 oxidation state but due to smaller size on going from Cr to Fe, Fe has very high charge

T
density. Hence, it has very high tendency to accept electron. Hence, strongest oxidising agent.

N
82) c
Number of unpaired electrons

I
(A) [CoF6] 3- → d6 (high spin) = t42g e2g 4
(B) [IrCl6] 3- →d6 (low spin) = t62g e0g 0
(C) [Fe(H2O) 6] 2+ →d6 (high spin) = t42g e2g 4

O
Since, A and C has same number of unpaired electron. Hence, they have same magnetic moment. As A
and Care 3d-block metal with weak ligand. Hence, they are high spin while Ir being 5d-metal is low

P
spin. Because 5d has greater splitting power than 3d.

83) a

[Mn (H2O) 6] 2+ = d6 (HS)

T A
N
As all the levels are electronically non-degenerate. Hence, No Jahn-Teller distortion. Therefore, all the

A
Mn-O bond length will be equal.

84) a
[Fe(phen) 3] 2+ → [Fe(phen) 3] 3+ + e-

U
( Red) (Blue)
In presence of oxidising agent like K 2Cr2O7 , [Fe(phen) 3] 2+ changes it colours from red to blue hence,
they are used in redox titration.

Q
85) a
The stability (formation constant for complexation of cryptate complex depends upon)
(1) size of cavity
(2) size of metal cation

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Hence, K+ ion will form most stable complex with cryptand-222.

T
86) c

I N
P O
A
E2 > E1 hence, energy required for transfer of electron from oxygen to Re falls in UV region. Hence,

T
[ReO4] - colourless while in [MnO4] - due to less energy difference it falls in visible region. Hence,
[MnO4] - coloured. Also as both Mn and Fe have +7 oxidation state i.e. they have no d-electron hence,
no d-d transition and colour arises due to LMCT.

N
87) a
[Co(CN) 5Cl] 3- + OH- →[Co(CN)5(OH)] 3- +Cl-
The reaction proceed through dissociative pathway and rate is dependent only concentration of

A
substrates. As substate do not have acidic hydrogen. Hence, it does not undergo S N 1CB mechanism.
[Co(CN) 5Cl] 3- → [Co(CN) 5] 2- + OH- → [Co(CN) 5OH] 3-
(slow)

U
88) a
Explanation

Q
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T
I N
89) c

P O
Tanabe-Sugano are useful in interpretation of spectra of both high spin and low spin complexes of d2-
d8 metal cation.
In Tanabe-Sugano, the energy of excited sate (expressed as E/B) are plotted against ligand field strength
(expressed as (∆0 /B).

A
Zero energy is taken for the lowest term and also two form of same symmetry never cross each other
and they bent for apart from each other due to repulsion.

T
N
A
U
90) b
[CrF6] -3 = d3
Orgel diagram for d3.

Q
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T
I N
ground state= 4F
First excited state = 4P
4
A2g →4T2g (Δ0)
P O
A
v1 = 14900 cm-1 ; v2 = 22700 cm-1 ; v3 = 34400 cm-1

T
Since, 4T1g (P) and 4T1g (F) have no fix energy therefore, they will not provide accurate value of Δ 0.
Thus, energy difference between 4A2g → 4T2g 14900 cm -1 will be correspond to Δ0

91) b

N
For [1s22s2p6 3p1]

A
i
2s+1=2× q + 1 = 2
J=|l+s|..... |l-s|

U
=|1+½|.....|1-½|
= 3/2 1/2
Term symbol 2P3/2 2
P1/2

Q
92) b
3
F→ 3D
Since, for allowed transition (atomic), ∆S=0, ∆L=0,±1
In option a and c spin multiplicity is not same therefore incorrect
In option d , ∆L=2 therefore incorrect.
93) d
[NiIIL6] n+ or n- has shows absorption bands at 8500, 15400, and 26000 cm -1
[NiII Lʹ6] n+ or n- at 10750, 17500 and 28200 cm-1

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as for first complex absorptions bands are at low energy i.e. it has weak splitting therefore, it has weak
ligand and for II complex high energy absorption bands corresponds to strong ligand.Thus, L is weak
and L' is strong ligand.

T
94) b
Number of microstate in 3F is calculated as (2S + 1) (2L+1)
For F, L=3.

N
Hence, (3) (2x3+1) =21

I
95) b
Chelate effect is predominately due to entropy change

∆H nearly same but entropy change is more.

96) b
P O
D6 =
L= ∑ML = 5-3 = 2 = D
S=2 , 2S+1=5
Hence, lowest energy form = 5D

T A
N
97) d
H2 (excited state)

L=0=Σ

A
U
S=1/2+1/2= 1 , 2s+1=3
gxu=u = 3∑.𝒖
For half filled.

Q
98) c
[Cr(bipyridyl)3]+3→ d3 = 4F (ground state term)
As phosphorescence is spin-forbidden transition and also occurs when electron comes from excited to
ground state. Hence, transition 4A2g ← 2Eg is responsible for the phosphorescence.

99) c
For orbital contribution the set should be unsymmetrically filled
[Cu(H2O)6]+2→ t62g e3g →No contribution
[Ni(H2O)6]+2→ t62g e2g →No contribution

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[Co(H2O)6]+2→ t52g e2g → Orbital contribution

[Cr(H2O)6]+2→ t32g e1g → No contribution

T
100) d
In KMnO4 all the electrons are paired. However, its paramagnetic susceptibility of the order of 10 -6 cm3
mol-1 is due to the temperature independent paramagnetism.

N
101) a

I
The complexes having T ground state have orbital contribution to magnetic moment however for
complex having A or E ground state some time µeff is slightly greater than µspin is due to mixing of first
excited state T (having same spin multiplicity to ground state) mixes with A or E due to spin coupling

O
and there is calculated by
𝝀𝜶
µeff = µs 𝟏 −
𝚫

P
A
𝝀𝜶
Hence, higher value of µeff = µs 𝟏 −

T
𝚫

102) a

N
In halogen molecules, the π*→ ϭ*transitions are responsible for their colours as evident from the
following figure

A
U
103) a

Q
The-donor ligands such as Cl -, Br-, I-, N-bonded NCS- etc stabilize the TBP intermediate and favour the
stereochemical change. The trans-forms tendency to isomerise in the order
A = NO2- <Cl- < NCS- <OH

104) d
According to Nephelauxetic series
F- > H2O > NH3 > en > NCS- > Cl CN -
> Br-
The highest value of is for F-

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105) a
The Eg ← A2g transition in the electronic spectrum of [Cr(NH 3)6]+3 occurs nearly at 650 nm.
2 4

106) c

T
[Cr(NH3)6]+3
Ce+4 → 4f0 → No f-f Transition
No unpaired electrons.

N
It is diamagnetic and its colour is due to LMCT. Its C.N. = 10

I
107) c
-4
[FeO4] → Jahn-Teller distorted away from the ideal tetrahedral towards a flatterred structure

O
it is paramagnetic due to unpaired electron D 2d symmetry

P
108) b
[Mn(H2O6)]+2 → H2O is a weak ligand, No pairing occurs.

S=5/2 , 2S+1=6
L=0→ S Term
Ground state term → 6S

Cr+3 =

T A
N
L= 3→F Term
S= 3/2 ; 2S+1=2x3/2+1=4
Ground state term→ 4F

A
Cu+2 = d9
L= ∑ML = 2 →D
S=1/2 , 2S+1=2
Ground state term → 2D

U
109) b
[CoCl(NH3)5] + OH- →[Co(NH3)4(NH2)Cl] +1 +H2O
+2

Q
‡ˆ‰Š ‡‹Œ•
[Co(NH3)4(NH2)Cl] +1 [Co(NH3) 4(NH2)] +2 + Cl-1

[Co(NH3) 4(NH2)] +2 +OH- → [Co(NH3)5OH] +2

110) b
𝑘 𝑘1112𝐾𝑘
= 22 𝑓 = 5×4×10‘ ×2×10’ 20×10k = 2.0×10“
=×1.0

111) a

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Fischer carbene carbon is electrophilic in nature due to strong π- acceptor ligands

112) a

T
The arrangements for [ 1π g ]1 [3ϭu]1configurations are

S= 1, 2S+1=3

I N
O
L=1→ πTerm
Spectroscopic Term = 3π

P
A
L=1→ πTerm
S=0, 2S+1= 1

T
Spectroscopic Term → 1S
Thus one of possible moleculer term symbol is 1π

N
113) a
In CdS, HgS and BiI3 colour is due to LMCT as Cd+2 and Hg+2 has d10 configuration. Hence, no d-d
transition. Also, no MLCT as ligand is not π -acceptor.

A
114) a
Change in CFSE on going for Oh to five coordinate intermediate for ions is as follows.
V+2 (d3) = -2.00

U
Cr+3 (d3) = -2.00
Ni+2 (d8) = -2.00

Q
115) a
NR → Dithiocarbamate
OR → Xanthate
O- → Dithiocarbonate
SR → Thioxanthate

116) b
”•
µeff = µs 1 −
–
i i ij š›
Δ=” “qk
×10
= $—
cm
“qk
=cm-1

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For Cu+2 → Term is 2D , hence, α = 2 , λ =-625 cm -1

q× $“qk דqk qדqk דqk
µeff = 1.73 1 − ›
= 1.73 1 + ›
ij ij
qדqk דqk
1.73 1 + = 1.73{1+ 0.078} = 1.73{1.078} = 1.864

T
ij ›
µeff = 1.864

117) a

N
As the strength of ligand increases energy for d-d transition increases.
Strength of ligand order is F- < ox-2 < en. Option A is correct .

I
All complex have same number of unpaired electron. Hence, all have same spin only magnetic moment.
Option B is correct .
[Cr(ox)3]-3 and [Cr(en) 3]+3 will show optical isomer. As t2g level is electronically non-degenerate.

O
Hence, there will be no Jahn-Teller distortion. Option D is incorrect .

118) a

P
Thus, order for energy absorption is 675 (A) < 615 (B) < 565 (C)
Δ0 increases as the ligand field strength increases H 2O < NH3 < en
Complementary colour of blue → Orange , green →Red, Violet → Yellow
Energy order for absorbed light is yellow > orange > red

A
Thus, A absorbs red hence it is green
B absorbs orange hence it is blue
C absorbs yellow hence it is violet

T
119) d
(A) [TiF6]-3
Ti ⇒ 3d2 4s2

N
Ti+3⇒ 3d1 4s0

A
U
(B) [CrF6] -3

Q
Cr = 3d5 4s1
Cr+3 = 3d3 4s0

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(C) [MnF6]-3
Mn = 3d5 4s2
Mn+3 =3d4

T
I N
O
-3
(D) [CoF6]
Co=3d7 4s2

P
Co-3 =3d6 4s0

T A
N
Hence, A<B<C≈ D

A
120) a
K2CuF6 = 3K [CuF6]-3 oxidation state of Cu+3 = 3d8
+

Thus, Cu+3 (Oh) ,d8

KCuL2 oxidation state of Cu = 1 + x - 4 = 0 => x=+3

U
Cu+3 (d8)

Q
Hence, square planar low spin

121) a
Mechanism of base hydrolysis can be given as
[CoCl(NH3)5] +2 + OH- →[Co(NH3)4(NH2)Cl] +1 +H2O

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_`ab _cde
[Co(NH3)4(NH2)Cl] +1 [Co(NH3) 4(NH2)] +2 + Cl-1
[Co(NH3) 4(NH2)] +2 +OH- → [Co(NH3)5OH] +2

T
122) a

Small P-Pd-P angle , less steric hindrance effective π Pd-SCN - bonding

I N
P O
A
Increase in P-Pd-P angle , increase in steric hindrance . No, effective π bonding from the P atom , the S
atom of SCN- ligand can form π bond but due to steric hindrance SCN - binds through N atom.

T
N
A
P-Pd-P angle , further increase with increase in size of chelate ring and hence steric hindrance increases .
No effective , π bonding from the P atom , the S atom of SCN - ligand can form π bond but steric

U
hindrance favours the Pd- N bonding .

123) b

Q
For d (high spin) there is one spin allowed transition from 5T2g → 5Eg
6

In case of d6 low spin commonly two spin allowed transitions are observed.
1
A1g → 1T1g
1
A1g→ 1T2g
there are additional spin allowed transitions at higher energy but they are marked by allowed transitions.
Hence, are not observed

124) b

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In I3- there is interaction between ϭ* a of I 2 and non-bonding electron of I-. In case propanone and Br 2
there in interaction between ϭ* of Br 2 and non-bonding electron of propanone. Thus, both I 2 and Br2
behave as acid.

125) c
Spin-orbit coupling is larger for the heavier atoms (Inner transition) and very small for lighter atoms.

T
126) c
Co (high spin) → 3d7 4s0
+3

I N
S=1/2+1/2+1/2=3/2
L=4+2-0-1-2
L=3
P O
A
Degeneracy for d-orbital = (2S+1)(2L+1)=(2x3/2+1)(2x3+1)=4×7=28

T
127) b

N
A
U
High value (4.1 B.M.) is due to µspin+ orbital contribution because t 2 is electronically degenerate

CrO4

Q
128)
-2

Cr+6 → 3d0 4s0

O-2 →2s22p6
MoO4-2
Mo+6 → 4d0 5s0
c

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In both Cr+6 and Mo+6 ions, there is no d-electrons, therefore, there is no d-d transition, since in both the
ions. oxidation state is very high, there is LMCT in both cases. The energy gap between 2p 6 (O-2) and
3d0 (Cr+6) is less than that between 2p6 (O-2) and 4d0 (Mo+6). Thus, LMCT energy
in CrO4-2 is less (high λmax) than that of MoO4-2 (low λmax).

129) c

T
S=1/2+1/2=1
2S+1= 2x1+1=3

I N
O
J=|l+s|...|l - s| = |1+0|...|1-0| =1
l=0 → S (term)
3
S1

130) c
Electronic configuration of Cr =3d 4s
Electronic configuration of Cr +2 = 3d4
P
A
Electronic configuration of V +2 =3d3
(A) Because of high nuclear charge of Cr is greater than that of V, Cr has higher. This ionization energy
than V. Hence, Cr+2 is not easier to oxidized than V+2 in gas phase. Thus, option (a) is incorrect.

T
(B) Cr+2 (aq) →[Cr(H2O)6 ] +2 →[Cr(H2O)6]+3 +e-

Less stable More stable

N
A
As less CFSE As more CFSE
V+2 (aq) →[V(H2O)6]+2 →[V(H2O)6]+3 + e-
Thus, V+2 (aq) does not easily oxidized
Thus, Cr+2 (aq) is more powerful reducing agent than V +2 (aq)

U
Q
(C) Cr+2 (aq) is more labile than V +2 (aq). Also, Cr+2 belongs to class1 metals and V+2 belongs to class 3
metals, Thus, the rate of water exchange in Cr +2 (aq)faster than V +2 (aq)

131) d
(I) [Fe(CN)6]-3 + [Co(CN)5]-3 → [(NC)5Fe-CN-Co(CN)5]-6
electron transfer
[Fe(CN)6]-4 + [Co(CN)5(OH2)]-2
(Inner sphere mechanism)

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(II) [Co(bipy)3]+2 + [Co(bipy)3]+3 → [Co(bipy)3]+3 +[Co(bipy)3]+2

(outer sphere mechanism)
H 2O electron transfer
-
(III) [Co(NH3)F]+2 + [Cr(H2O)6]+2 [(H3N)5CoIII-F-CrII(OH2)5]+4

T
H2 O +
[(H3N)5CoII-F-CrIII(OH2)5]+4 [Co (NH3)5(OH)2]+2 + [Cr(OH2)5F]+2
(Inner sphere mechanism)
Marcus equation is applicable only for cross-outer sphere reactions.

N
(B) is a self exchange reaction, its rate of electron transfer can be calculated experimentally.
No need to apply marcus equation.

I
(Reference basic inorganic chemistry by F.Albert Cotton, G Wilkinson and Paul L.Galls) third eddition.
In this question only (d) statement is correct.

O
132) c
For allowed transition : a)Spin multiplicity should be same or ΔS = 0

P
b) ΔL = 0, ± ,1for allowed transition
Therefore (4) is not allowed as ΔL ≠ 0, ± 1
c) u → g (allowed)
g→ g ( not allowed)
Therefore (1, 2) are not allowed

A
[+ → -] → forbidden so, therefore (1, 2) are not allowed
[+ → +] → allowed

T
133) b
NO, I2- , Cu+2 and VO+2 is paramagnetic. Hence, EPR active where as I 2 is diamagnetic and EPR
inactive.

N
134) c
H2 O electron transfer -
[Co(NCS)(NH3)5]+2 +[Fe(H2O)6]+2 [(HN)5Co –SCN-Fe(H2O)5]+4

A
H2 O
[(HN)5Co-SCN-Fe(H2O)5]+4 [Fe(SCN)(H2O)5]+2 +[Co(NH3)5(H2O)]+2
Intermediate
+5H3O+
[Co(NH3)5(H2O)]+2 [Co(H2O)5]+2 +5NH4+

U
[Fe(SCN)(H2O)5] +H2O → [Fe(H2O)6]+3 +SCN-
+2

Intermediate

Q
135) a

136) a

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For strong Jahn-Teller distortion eg orbital must be assymetrical filled.

t62g e1g , t32g e1g , t62g e3g

T
137) a
The correct order of intensity of d-d transitions in the complexes follows order
cis-[M(H2O)4Cl2] > trans-[M(H₂O)4Cl2] > [M(H₂O)6]+2

138) c

I N
P O
T A
N
A react faster than B and B result in a mixture of product

A
139) b
As the oxidation state increases and size of central decreases ligand exchange rate decreases.

U
140) a
Electron transfer reactions by self-exchange electron transfer is fast when HOMO is π* and LUMO is
also π* i.e. electron transfer is from a π*of reductant to the π* of oxidant.
(a) [Ru(NH3)6]+2 + [Ru(NH3)6]+3 → [Ru(NH3)6]+3 + [Ru(NH3)6]+2 [ Reaction is fast]

Q
(π*)6(ϭ*)0 (π*)5(ϭ*)0
6
HOMO=(π*) LUMO=(π*) 5
(b) [Co(NH3)6]+2 +[Co(NH3)6]+3 → [Co(NH3)6]+3 +[Co(NH3)6]+2 [Reaction is slow]
(π*)5(ϭ*)2 (π*)6(ϭ*)0
HOMO=(π*) 5 LUMO=( ϭ*)0
(c) [Cr(H2O)6] + [Cr(H2O)6]+3 → [Cr(H2O)6]+3 + [Cr(H2O)6]+2 [Reaction is slow]
+2

(π*)3(ϭ*)1 (π*)3(ϭ*)0
1
HOMO=( ϭ*) LUMO=( ϭ*)0
(d) [Fe(H2O)6]+2 +[Fe(H2O)6]+3 → [Fe(H2O)6]+3 + [Fe(H2O)6]+2 [Reaction is fast]

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(π*)4(ϭ*)2 (π*)3(ϭ*)0
4
HOMO=(π*) LUMO=( π*) 3
Both reactions (a) and (d) are fast but reaction (a) is much faster than (d) because there is small change
in M-L bond length in reaction (a) i.e. less activation energy is required

141) a
Hg (aq) + X (aq) → [HgX]+ (aq)
+2 -

T
N
The stability constants for [HgX] + (aq) for X= F, Cl , Br follow the order: F < Cl < Br .Because Hg +2 is
soft acid and Br- is soft base.

I
142) c
[Mn(H2O)6]+2 → t2g3 eg2 : High spin complex

O
In this complex, there is neither orbital contribution nor temperature independent paramagnetism (No L-
S coupling) and α =0. Thus, µobserved = µspin
[Co(H2O)6]+3 is a low spin complex.

P
Co+3 → d6 ie. t2g6 eg0

No unpaired electron.

A
Therefore, it is diamagnetic in nature.

T
143) c
Ti →d complex: t2g1 eg0
+3 1

Ti+3 complex exhibit one broad band due to

(i) Vibronic coupling

N
(ii) Jahn-Teller distortion
(iii) Spin-orbit coupling
Co+2 → d7 complex

A
Exhibit three broad bands due to following transitions:
4
T1g →4T2g ; 4T1g → 4A2g ; 4T1g → 4 T1g(P)
•Cr+3 →d3 complex
Exhibit three broad bands due to following transitions:

U
4
A2g →4T2g ; 4A2g → 4T1g(F) ; 4A2g → 4 T1g(P)
•Mn2+ complex→ d5 complex exhibit a series of very weak (spin forbidden, Laporte forbidden and sharp
bands).
•Ni+2 →d8 exhibit three broad bands due to following transitions:

Q
3
A2g → 3T2g ; 3A2g → 3T1g (F); 3A2g → 3 T1g(P)

144) b
trans-[CoLCl(en)2]+ → A (on hydrolysis)
L= NO2-, NCS-, OH- ,Cl-
The tendency to form cis-isomer of the product (A) follows the order:
L= NO2- < Cl- < NCS- < OH-

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145) c

T
N
Ir = 9e-
PPh3= 2e- each

I
CO= 2e-
NO (bent) = 1e- (lets consider)
9e- + 4e- + 2e- + 1e- +1e- -1e- = 16e-

O
Considering NO in bent form gives TVE = 16, thus a square pyramidal structure of complex gains
stability with 16 e-, So we can say NO present in bent mode

P
Ru= 8 e-
PPh3=2 e- each
Cl= 1 e-
NO(bent) = 1 e-

T A
N
NO(linear) = 3 e -
8e- + 4e- + 1e- + 1e- +3e- -1e- = 16e-
Considering one NO in bent form and another in linear gives TVE = 16, thus a square pyramidal

A
structure of complex gains stability with 16 e -, So we can say One NO preset in bent mode and other
in linear mode .

U
Q
Co = 9 e-
AsR3=2 e- each
NCS=1 e-
NO(bent)=1 e-

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9e- + 8e- + 1e- + 1e- -1e- = 18e-

Considering NO in bent form gives TVE = 18, thus an octahedral structure of complex gains stability
with 18e-, So we can say NO present in bent mode

T
Cr=6 e-

I N
O
CN= 1 e- (each)
NO(linear) = 3 e -

P
6e- + 5e- + 3e- + 3e- = 17e-
Considering NO in linear form gives TVE = 17, thus an octahedral structure of complex gains stability
with 18e-, So we can say NO present in linear form (17e - species is considered quite stable as on
putting NO as bent, we were just getting 15e -, which would be too unstable)

A
146) b
An aqueous solution of Fe(III) ion (A) gives a blood-red colour on reaction with KSCN the blood red

T
colour is due to formation of [Fe(SCN)(H 2O)5]+2 (B). The colour may also used for the identification of
Iron (III). This colour is destroyed by the addition of F - ion due to the formation of [FeF6]-3 (C).
NaF
[Fe(H2O)6]+3 + SCN- → [Fe(SCN)(H2O)5]+2 [FeF6]-3

N
(A) (B) (C)
Blood red colour colourles , d-d transition ,laporte
Due to LMCT forbidden ,spin forbidden

A
147) b
In chlorophyll, visible absorption band arise from excitation of electron from the π-HOMO to π*

U
LUMO, thus, has maximum value of molar extinction coefficient value.
[NiCl4]-2 is a tetrahedral comples, thus, p-d mixing will be there, hence, Laporte partially allowed and
spin allowed transition.
In [Cr(H2O)6]+2 , d-d transition will be there. hence, Laporte forbidden and spin allowed transition.

Q
In [Mn(H2O)6]+2 transition is both Laporte and spin forbidden.
So, the order of molar extinction coefficient value is:
Chlorophyll > [NiCl4]-2 > [Cr(H2O)6]+2 > [Mn(H2O)6]+2

148) b
The base hydrolysis of [Co(py) 4Cl2]+ is independent OH- of concentration because there is no protonic
hydrogen in the complex.

149) b

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FeCr2O4 has normal spinel structure thus, Fe+2 occupy tetrahedral site. NiGa2O4 has inverse spinel
structure thus, Ni+2 occupy octahedral site.

T
150) c
cis-[Fe(phen)2 (NCS-N)2] (A) complex at high temperature (300K) exists as high spin with four
unpaired electrons but when temperature is decreased, there is sharp decrease in magnetic moment at

N
174 K and complex becomes low spin. This indicates that at 174K, complex (A) exists as both high spin
and low spin.

I
Thus, at 300K, complex A has four unpaired electrons.
u
µ = u 𝑛(𝑛 + 2) = u 4(6) = 24 = 4.89 BM
Complex [Fe(phen)3]Cl2 (B) at 300K is a low spin complex, thus have t 2g6 eg0 configuration ,hence no

O
unpaired electron.
u u
µ = 𝑛(𝑛 + 2) = 0(0 + 2) = 0 BM

151) c

P
In [IrBr6] oxidation state of Ir is +4 and Ir +4 is low spin. octahedral complex with the electronic
-2

configuration:

T A
There are two charge transfer bands and their origin are ligand→ metal (ϭ →t 2g and ϭ →eg )
as shown in the figure.

N
A
U
Q
Other transitions are of high energy and do not observed.

152)
+2
[*Co(NH3)6] +
High spin
c
[Co(NH3)6]+3 → [*Co(NH3)6]+3 + [Co(NH3)6]+2
low spin
t2g5 eg2 t2g 6 eg0

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Labile Inert
Co- NH3 Co- NH3 Bond length = 193.6pm
Bond length = 211.4pm
The rate of electron transfer for the reaction is very slow (second order rate constant =10 -6 L mol-1s-1)

T
because of following reason :
• Low spin [Co(NH3)6]+3 (configuration t2g 6 eg0) has all the metal -electrons pointing in between the
ligands whereas, high spin [*Co(NH3)6]+2 (configuration t2g5 eg2 ) has two eg electrons pointing directly

N
at the ligands. The electrons present in e g orbitals cause more repulsion with ligands than that of t 2g
electrons. Thus, M-L bond lengths in both complexes are different enough and more activation energy is

I
needed to make them the same in transition state .
Also, no simple addition or removal of an electron can convert these configuration into one another.
Thus, it is necessary to excite the oxidation states before the reaction can occur, as shown below:

O
‹q© to t2g
*Co+2 (t2g5 eg2) → (t2g6 eg1) (t2g5 eg1) → (t2g6 eg0) *Co+3
(electronic transition)
‹q© to t2g

P
Co+3 (t2g6 eg0) → (t2g5 eg1) (t2g6 eg1) → (t2g5 eg2) Co+2
(electronic transition)

153) b

A
Geometrical isomers for complex [RhH (C≡CR)2(PMe3)3] are

T
154) d

N
Solutions of I2, in donor solvents such as pyridine, ethers, ketones, alcohol are brown or yellow due to

A
formation of a charge transfer complex. Acetone or ethanol and similar compounds donate electron
density through a ϭ lone pair to the ϭ* -orbital of iodine.

U
155) b
In the complexes, [Fe(bpy) 3]+2, [Ru(bpy)3]+2 and [Fe(phen)3]+2 , ligands bpy and phen have empty π*
orbitals, thus, band in electronic spectra is due to metal to ligand charge transfer (MLCT). Whereas, the

Q
other complexes i.e. [FeCl4]2- (220 nm), [FeBr4]2- (244 nm), [ReO4]- (227 nm) and [TcO 4]- (286 nm)
show LMCT bands.

156) b
3
d -electronic configuration:

L=2+1+0 = 3 i.e. ‘F’

S= 3 x 1/2 = 3/2
2S+1 = 2 x 3/2 + 1 = 4

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J = less than half filled= L-S= 3-3/2 = 3/2

Thus, ground state term is = 2S+1LJ = 4F3/2

157) c

T
H 2O electron transfer -
[CoIII(NH3)5Cl]+2 + [CrII(OH2)6]+2 [(NH3)5CoIII –Cl–CrII(H2O)5]+4
Inert Labile

N
↓
[(NH3)5CoII –Cl–CrIII(H2O)5]+4

I
Labile Inert
↓
[Co(NH3)5]+2 + [Co(H2O)5Cl]+2
(B)

O
+2 +2
+5H3O+ +2 +
[Co(NH3)5] +H2O → [Co(NH3)5(H2O)] [Co(H2O)6] +5NH4

P
158) d
In [Cr(en)3]+3 , which is an octahedral complex, three spin allowed electronic transitions are
observed.

T A
Trans-[Cr(en)2F2]+ is a tetragonal complex. Therefore, there is splitting of 4T2g , 4T1g, and 4T1g (P) states.

N
4
A2g term does not split. Thus, 6 electronic transitions are observed.

A
U
Q
159) a
The value of magnetic moment will be independent of temperature for [Fe(acac) 3] because this complex
is high spin with electronic configuration and the promotion of electron from t 2g to eg or eg to t2g is spin
forbidden with variation of temperature. Also, the high spin [Fe(acac) 3] has ground state 6A1g and it has
no excited states of the same spin multiplicity as that of the ground state.

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160) b
Solid Thiourea

T
KNO2 in dil . AcOH N2 gas ↑ + SCN- + H2O
(P) ↓ dil FeCl3
[Hg(SCN)4]2- °±`²cdd HgCl2
[Fe(H2O)5(SCN)]2+

N
solution
Colourless (R) Blood red (Q)

161) d
N2 = ϭ 1s ϭ 1s* ϭ22s ϭ22s* π22px = π22py ϭ12pz
+ 2 2

I
O
ϭ12pz = gerade
Ʌ = 0 i.e. Σ

P
S=½
2S+1 = 2 × 1/2 + 1 = 2
As ϭ12pz orbital is symmetric, (+) is used.
Thus, term symbol of N2+, is Ʌ.g/u = 2∑.̧

A
162) c
In the formation of NaCl2 a very large second stage ionization energy is required as Na + already attain
nearest noble gas configuration thus, the calculated heat of formation (∆Hf) will be positive due to high

T
value of I.E2 of Na.
Ca shows +2 as stable oxidation state but it can release only a single electron easily (though it is less
stable than Ca+2). Thus, the calculated heat of formation (∆Hf) will be negative for CaF.

163) Correct option (b)

N
A
Steric hindrance favours dissociative substitution in octahedral complexes, hence statement (1) is correct
Higher charge on metal will not allow dissociation of existing ligand and will not favour acceptance of
electron pair of entering ligands, hence statement (2) is incorrect

U
During dissociative substitution reaction a penta coordinated intermediate is observed, hence statement
(3) is also correct.
Nature of entering ligand does not influence the reaction much, hence statement (4) is incorrect.

Q
164.) Correct option (b)

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165.) Correct option (a)

Oxidation state of metals in 𝑉𝑂»‘$ , 𝐶𝑟𝑂»q$ and 𝑀𝑛𝑂»$ are V(+5), Cr(+6) and Mn(+7) respectively,
Since, 𝜆ÀÁÂÃ ∝ 𝑂𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛 𝑆𝑡𝑎𝑡𝑒 𝑜𝑓 𝑚𝑒𝑡𝑎𝑙
Thus preferred order will be, 𝑉𝑂» < 𝐶𝑟𝑂» < 𝑀𝑛𝑂»$
‘$ q$

As 𝜆ÀÁÂÃ decreases on going down the group,

thus preferred order will be 𝑊𝑂»q$ < 𝑀𝑜𝑂»q$ < 𝐶𝑟𝑂»q$

T
166.) Correct option (b)

I N
Electron transfer between Cr +2(d4 system) and Cr+3(d3 system) takes place via Inner Sphere electron
transfer mechanism, as Cr +2 is Labile complex having bridging ligand (H2O).

P O
electron transfer takes place between HOMO of Cr+2 (eg considered as σ*) to LUMO of Cr+3 (eg
considered as σ*), thus electron transfer is from σ*⟶ σ*. Hence statement A is correct.

A
Statement B is correct as it involves large inner-sphere reorganization energy.
Statement C is incorrect as M–L bond lengths changes while inner-sphere electron transfer mechanism.
Rate of self-exchange electron transfer is always slow than cross-exchange electron transfer mechanism.

167.) Correct option (d)

T
N
A
U
Q
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T
I N
P O
SHORT TRICK:
1.

T A
When point group is C3V then number of IR bands will be N-1, where N is number of CO
ligands

N
2. When point group is C2V then number of IR bands will be N, where N is number of CO
ligands

168.) Correct option (b)

A
U
Ground State term symbol will be
𝑚` = + 2 + 1 + 0 = 3 , thus term will be F

Q
‘
spin multiplicity = 2𝑆 + 1 = 2× + 1 = 4
q
Thus overall ground state term = 4F
Now, according to Orgel diagram for d 3 system

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T
I N
O
169.) Correct option (d)
Point Group of Trigonal bipyramidal geometry is D 3h, as it has C3 principle axis of rotation and 3C2 axes
perpendicular to principle axis, also there is a horizontal plane.

P
The order of energies of d-orbitals for TBP geometry will be 𝒅𝒛𝟐> 𝒅𝒙𝟐−𝒚𝟐 , 𝒅𝒙𝒚 > 𝒅𝒙𝒛, 𝒅𝒚𝒛

T A
N
A
U
Q
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 2
Organometallic Compounds
Hints & Solutions
1. Correct answer: (d)
Oxidation of metal is easier for electron rich systems, so electron rich metals undergo oxidative addition and as reduc-
tion is easier for electron-deficient metal, so it undergoes reductive elimination.

2. Correct answer (c)

This is correct stability order because Ti(CH2Ph)4 has no  -hydrogen .Hence no  -elimination and
compound is stable whereas in Ti(i-Pr)4 has max no of  -hydrogens followed by TiEt4 and TiMe4. So
Ti(i-Pr)4 undergoes fast  -elimination hence least stable.
Ti(i-Pr)4 < TiEt4 < TiMe4 < Ti(CH2Ph)4
3. Correct answer: (b)

Compound Number of electron in outer shell of

central atom

(η5-C5H5)2 Fe 18

(η5-C5H5)2Co 19

(η5-C5H5)2Ru 18

(η5-C5H5)2Co+ 18

5 5 +

Oxidation (loss of electrons) of (  5-C5H5)2, Co to (  5-C5H5)2 Co+ gives an 18

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1
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82

electron compound, (more stable) therefore easy to oxidise.

4. Correct answer: (a)

T
W(CH3)6 having 6 ϭ-bond with metal .

I N
5. Correct answer: (c)
Ni+ 4CO →Ni(CO)4
Fe+5CO→ Fe(CO)5

P O
A
Both Ni and Fe reacts directly with CO to give carbonyl compounds.

T
6. Correct answer: (d)

N
A
U
Electron cluster H2Ru6(CO)18 displays a distorted octahedral metal geometry.

Q
Here each hydride ligand is connected to 3-Ru atoms.

7. Correct answer: (a)

During hydroformylation the intermediate CH 3-CH2-CH2-Co(CO)4 gets transformed to acyl intermediate
CH3CH2CH2 -COCo(CO)3

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8. Correct answer: (a)

Ziegler-Natta catalyst is TiCl4 , Al(C₂H5)3

9. Correct answer is (b).

T
N
M=V, x=6, z=1

I
i.e. [V(CO)6]-1 = 5+2x6+1=18
10. Correct answer is (d).
Because main group element follows octet rule.

O
[Be(η1-C5H5) (η5-C5H5)]

P
2+5+1=8

11. Correct answer is (a)

A
12. Correct answer is (d).
[CpFe(CO)(NO)] 2

T
Step-1: Determine the total valence electron (TVE) = A
A=[5+8+2+3]x2=[18]x2=36

N
Step-2: B=(18n –A) where n number of metal.
B (2x18)-36 =36-36=0

A
No metal-metal bond found.
[CpMo(CO)3]2

U
Step-1: A [5+6+2x3] x2=[17]×2=34
Step-2: B= (18n-A)=2x18-34 = 36-34 = 2

Q
Step-3: B/2 gives the total number of M-M bonds in the complex B =2/2=1
In this complex, the total number of M-M bonds is one

13. Correct answer is (a).

Order of donor ability NMe3 > NH3> pyridine
Order of CO stretching frequency pyridine > NH 3 > NMe3

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14. Correct answer is (a).

T
Option A is Ruthenium(II) carbenoid complexes, also known as Grubb’s Catalysts, they are widely used
for olefin methathesis.

N
15. Correct answer is (b).

I
Compound A does not have any β hydrogen, hence β-hydride elimination is not possible in compound
A, whereas compound B will undergo β-hydride elimination as follows

P O
A
16. Correct answer is (a).
1
H-NMR giving one signal at 5.0ppm indicates presence of η 5-Cp ring, another one signal at 2.5ppm

T
indicates presence of CH 3 group. IR band at 1680cm-1 indicates presence of ketone (C=O) group. Thus
the appropriate structure of molecule.

N
A
U
17. Correct answer is (b).

Q
Ni(CO) Total4 valence electron around Ni 10+ 4x2=18 electron
Substitution reactions at coordinatively saturated tetrahedral complexes with a 18 electron count like
Ni(CO) , or Ni(CO)
4 2(PR3)2 follows a simple first order kinetics.

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Since rate does not depend upon the concentration and nature of the ligand suggesting a dissociative
mechanism.

T
18. Correct answer is (b)
In [WO4] -2 , [MoO4] -2, [ReO4] -2 [CrO4] -2all the metals have same oxidation state but Cr +6 is of

N
smallest size. Therefore it has strongest tendency to attract electrons. Therefore strongest oxidizing

I
agent.

19. Correct answer is (a).

O
Since in product metal Ir is present in the higher oxidation state. So, there is less back bonding to orbital
of CO.

P
T A
N
A
U
Q
Hence, ῡ (CO) product > ῡ (CO) reactant

20. Correct option (b)

Triplet of carbonyl carbon indicates the each CO is attached with chemically equivalent two Rh atoms
that means µ₂-CO complex. Actual structure is

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82

T
21. Corret answer is (b)

I N
O
[Os3(CO) 12]
Step-1: Calculate T.V.E. (total valency electron)

P
8x3 + 2×12 = 48
Step-II: Polyhedral electron count
T.V.E - (nx12) = 48-36=12 n=number of the metal atom

A
Step-III: =P.E.C./2=12/2 =6 = (n+3) =Archano.

T
22. Correct answer is (d).

N
23. Correct answer is (b).

A
U
Because metal carbonyls are stronger bond , to break this bond huge amount of energy are required. But
metal-metal bonds are weaker bond. So, reaction is endothermic and enthalpy predominant and entropy

Q
unfavourable.

24. Correct answer is (d).

[(η5 –C5H5 )RuCl(CO)(PPh3)]
T.V.E = 5+8+1+2+2=18e -
[W(CO)3(SiMe3)(Cl)(NCMe) 2]

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82

T.V.E= 6+ 6+1+1+ 2x2 =18e -

[IrCl3(PPh3)2(AsPh2)]-

T
T.V.E= 9+ 3 +4+1+ 1 =18e -
[Os(N)Br2(PMe3)(NMe2)]-

N
T.V.E= 8+ 5 +2+1+ 1 =17e

I
25. Correct answer is (c)

P O
26. Correct option (a)

T A
N
A
ELECTRON COUNT = 2x5 +M+2 =18
M = 18-12 =6
So, M = Cr, Re+

U
27. Correct answer is (a).

Q
As the π-accepting abilities of phosphine increases v C- O stretching frequency of the complex increases.
So, the order of n-accepting abilities among the given phosphine is:
PF3 > PCl3 > PClPh2 > PMe3
i.e. A>B>C>D.
So, the correct combination for v C- O stretching is:
A→2090

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82

B→ 2040
C→ 1977

T
D→ 1945

N
28. Correct answer is (a)

I
The structure of cluster [Co 3(CH)(CO)9]

So, the number of M-M bond = 3 and bridging ligand=1 CH

P O
A
29. Correct answer is (a)

T
N
A
Since, the molecule is C2 -symmetric. So, two CO's will give two absorption band in IR spectrum.

U
30. Correct answer is (b)

Q
[Rh(CO)2I2]-1 → Hydroformylation.
[Pd(PPh3)4] →Heck coupling (It is a catalyst for Heck coupling)

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207 |Organometallic Compounds
82

T
31. Correct answer is (a).
Step (A) is O.A. because the oxidation state of the metal is increased by two units.

I N
P O
A
Step(B) is transmetallation because the ligand is transferring from one metal to another metal. Step(C) is
reductive elimination because the oxidation state of the metal is increased by two units

T
32. Correct answer is (d)

N
A
(a)[Rh(CO)2I2]- →16e- and a better coordinate for O.A.
-
(b) [Ir(PPh3)2(CO)Cl] →16e species (Vaska's complex) O.A. is possible.

U
(c) [(η2-CpRu(CO)2] →16e- system O.A. is not possible because metal in high oxidation state.
(d) [(η5 -Cp2Ti(Me)Cl] →18e- species as such O.A. is not possible but after the dissociation of ligand

Q
‘CO’, O.A. is possible.
33. Correct answer is (b).

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82

T
I N
18 electron species in excess PPh 3 it becomes 20 electron species but the active catalyst is 16 electron
species. So, in presence of excess PPh 3 the rate of hydroformylation will be decreases.

O
34. Correct answer is (a).
Since SnCl2 will behaves as a carbene and it insert into the M-M bond. So, it is a kind of insertion

P
reaction.

T A
35. Correct answer is (c).

N
A
In Metal-Olefin interaction, the extent of increase in metal → Olefin л-back donation would strengthen
the Metal-Olefin bond which produces a increase in C = C bond length and somewhat single bond

U
character which results a change in hybridisation from sp² to sp³.

Q
36. Correct answer is (c).
[(η7- tropylium)Mo(CO) 3]
In zero oxidation state of Mo, complex have 18 e -1 (stable)

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7 +6+6 -1 = 18
tropylium is a 7e- donor ligand in neutral method and +1 oxidation state

T
oxidation state of Mo = +1+x +0 = +1
x= 0

I N
37. Correct answer is (d)
The above reaction is an example of 1,1-migratory insertion

P O
A
38. Correct Answer (C)

T
Since MeTiCl3 have no electrons for back donation with л-accepting ligands like PMe 3 and CO,
therefore, It reacts in order NMe 3 > PMe3 > CO

N
A
Now, in (CO), Mo(thf), Mo have sufficient e-s and vacant site to react with л-acceptor ligand. Thus, the
order is CO> PMe3 > NMe3

U
Q
39. Correct answer is (c)
Total valency electron 12+18=30 (A)
B = (n×18 - A) = 36-30=6
[(OPh) in bridging donate 3 electron]

Metal-metal bond = B/2 = 6/2=3 Correct answer is (c)

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82

40. Correct answer is (b)

T
A= TVE =60

I N
O
B (n×18) – TVE= 72 – 60= 12

P
metal-metal bond= B/2 =12/2= 6

41. Correct answer is (b)

T A
N
Bond order =
RSFRT
U
=
VFW
U

A= 3.5

U
42. Correct answer is (d)
HCo(CO) 4 , HCo(CO)3PBu3 , HRh(CO)(PPh3)3 . These all are the catalyst for hydroformylation

Q
process.

43. Correct answer is (b)

H3CoRu3(CO) 12 = 3+9+8×3+12×2 = 60 electron

44. Correct answer is (a)

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82

[(H)Co6 (CO) 15] has H encapsulated.

The image shows solid state structure of HCo 6(CO)15,
obtained using neutron diffraction technique. The blue
spheres are Co molecules, white spheres are CO ligands

T
whereas black sphere is H, encapsulated in the crystal.

N
Source: Journal of the Chemical Society Dalton

I
Transactions, Oct. 1999 (DOI: 10.1039/a810025j)

45. Correct answer is (d)

P O
Due to increase in size of Ir, compared to Co, the Metal-Metal bond length also increases, thus the
ability to form bridge carbonyl decreases with increase in M-M bond

T A
No of bridging CO= 3

N No of bridging CO = 0

A
No of Terminal CO= 9 No of terminal CO =12

U
46. Correct answer is (d)
Explanation:

Q
The electrophilic attack of Ph 3C on the given compound, results in removal of one Methyl group from
CDMe2 ligand, thus forming an alkene. Since the reacting species is 18 electron compound, after
reaction, the final product A is also an 18e species.

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82

5+8+4+1 = 18

T
47. Correct answer is (a)

N
CH→4+1=5e
X

I
Co(CO)3→ 9+6=15e CH Co(CO)3
But, CH₂→4+2=6e

O
Ni(CO)2 →10+4=14e not isolobal

P
48. Correct answer is (c)
In case of (c) the chances of conversion of heptacity from η 5→ η3is more due to partial bond fixation.
Others will not undergo change in heptacity, to retain their aromatic properties.

49. Correct answer is (a)

T A
N
A
IR band at 1985 cm-1 indicates terminal CO. Both P atoms are non-equivalent. Each P atom will show
doublet of doublet with (1JPRh and 2Jpp).

U
50. Correct answer is (b)

Q
RT
106. Fe3(CO) 12 [Fe(CO)4] –2
8+8+2=18 electron
[Fe(CO)4] –2 is isoelectronic with Ni(CO)4

51. Correct answer (b)

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82

[(η5-C5H5)(η1-C5H5)Fe(CO)2 ] → [(η5-C5H5)(η5-C5H5)Fe] ( at temp range = 221-298K)

T
52. Correct answer is (c)
Most commonly the metal in the complexes in their low oxidation state with d 8 or d10 configuration
undergo oxidative addition.

53. Correct answer is (c)

Oxidation state of Ni in complex [Ni 2(CO) 6] 2-

I N
2x+0 = -2
P O
A
x=-2/2 , x = -1
M-M bond =1

54. Correct answer is (a)

T
N
A
U
Q
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207 |Organometallic Compounds
82

T
55. Correct option (a)
[Fe3(CO) 15C)]

I N
O
Total valency electron= 8x5+ 15x2+4=74
PEC=TEC- n×12

P
PEC =74-5×12= 74-60=14
PEC/2 =14/2 = 7
7=n+2

A
=5+2=(n+2) Nido where n=no. of metal in electron

T
56. Correct answer is (a)

N
A
U
[η5-C5H5Rh)(C2H4)2] at -20°C shows a typical AA' XX' pattern in the olefinic region due to free
rotation of the ethylene ligand about the metal-olefin bond

R2Si
Q
57. Correct answer is (c)
Co(CO)3 15 electron
6 electron ( not isolobal )
Mn(CO)5 17 electron
CH3 7 electron ( not isolobal )

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82

Fe(CO)4 16 electron
O 6 electron ( isolobal )

T
Mn(CO)5 17 electron
RS 7 electron ( isolobal )

I N
58. Correct answer is (c)
[(ηx-C6H6 )Ru(ηy-C6H6)]
x = 4, y = 6

O
[(η4-C6H6 )Ru(η6-C6H6)]

P
Total electron 4+8+6 =18 electron. (Diamagnetic complex)

59. Correct answer is (b)

A
∆
Ni(CO)4 + PPh3 [Ni(CO)3(PPh3)] + CO
(18 e- )

T
Since Ni(CO) 4 follows 18 electron rule. So, it follow substitution via dissociation mechanism i.e.
Step-1: Ni(CO) 4 →Ni(CO) 3 + CO (slow)

N
(18 e- )
Step-2: Ni(CO) 3 +PPh3 →Ni(CO) 3(PPh3)

A
(16 e- )
So, the rate of reaction depends upon the concentration of Ni(CO) 4 only because this step is slowest

U
step.

Q
60. Correct answer is (b)
H3C-CH= CH2 + CO +H2 → +H3C-CH2-CH2-CHO (butanal)
in presence of Co2(CO) 8 as a catalyst
[ Hydroformylation.]

61. Correct answer is (*), none of the given option is correct .

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62. Correct answer is (b)

T
Co4(CO)12
TVE =36+ 24 = 60

N
PEC=TVE-(nx12)=60-48=12

I
PEC/2=12/2 = 6 = 4+2 (n+2=Nido)

63. Correct answer is (a)

O
Rh(PPh3) 3Cl is a Wilkinson catalyst in hydrogenation step one PPh3 loss due to steric factor and form
Rh (PPh3)2Cl

P
Shape = T-shaped

64. Correct answer is (a)

T A
N
A
U
So, in the product (B) it shows two signals in 1H NMR one for 5H of Cp ring and one for Fe-H
proton with intensity ratio 5: 1.

Q
65. Correct answer is (c)

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207 |Organometallic Compounds
82

16 electron stable complex 18 electron stable complex

[IrCl(CO)(PPh3)2] is a 16 electron complex called as Vaska complex. Only show oxidative addition in
the presence of H2

66. Correct answer is (a)

T
I N
P O
All given options are incorrect except (a) as there is ring current disruption after formation of
complex in [(η6-C6H6)Cr(CO)3] .The shift in δ is attributed to this reason from 7.2 ppm to 4.5 almost .

A
67. Correct answer is (b)
The C2B9H12 is carborane anion.

T
C2B9H12-1 follow wade rule as
C ≡ BH

N
↓ ↓
(4e-) (4e-)

A
C2B9H12-1 ≡ (BH)2B9H12-1 ≡ B2H2B9H12-1 ≡ B11H14-1
Now, B11H14-1 is equivalent to B11H15 neutral borane which follows the formula B nHn-4
which is the general formula of nidoborane.

U
B11H14-1 ≡ B11H15 ≡ BnHn-4 ≡ Nido.

Q
68. Correct answer is (d)
It is a kind of insertion reaction of M-H (metalhydride bond between CO)

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82

69. Correct answer is (a)

Complex (A) HM(CO) 5 =1 + 7+ 10 =18 electron

T
M=Mn [7 electron]
1 + 7+ 10 =18 electron
Complex (B) [(η5-C5H5)M'(CO) 3] 2

I N
[(η5-C5H5)Cr(CO) 3] 2 M'=Cr=6 electron
10+12+12+2 (M-M) bond = 36 electron.

P O
70. Correct option is (c)

T A
[Co(CO)3(NO)] NO in linear form donate (3 electron.)

N
↓ ↓ ↓
9 + (2x3) +3= 18 electron

A
[Ni(η5-Cp) (NO)]
↓ ↓ ↓

U
10 + 5 + 3 = 18 electron
In both complexes NO donating three electron. So, NO is in linear form.

Q
71. Correct option is (a)
[PdCl4]-2+C2H4+H2O CH3CHO+Pd+2HC1+2Cl-
Pd(II) Pd(0)

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82

2CuCl2+1/2 O2+2HCI→2CuCl2 + H2O

T
72. Correct option is (b)
73. Correct option is (a)

I N
O
The refluxing of RhCl3.3H,O with an excess of PPh3, in ethanol gives a complex RhCl(PPh3) 3 is
Wilkinson catalyst and common method for preparation of RhCl(PPh 3) 3 is refluxing of RhCl3.3H2O
with PPh3.Moreover, on counting the total valence electrons, RhCl(PPh 3) 3 = [9+3x2+1] = 16e.{Cl atom

P
cannot be bridging, its contribution is 1}. Wilkinson catalyst is 16e - species.

T A
It is a square planer 16-electron complex. Valence electron counting on rhodium metal centre.
(i) there is no overall charge on complex

N
(ii) there is one anionic ligand (Cl -)
(iii) Rh metal atom must have +1 charge to compensate for the one negatively charged ligand. So,
the oxidation state of Rh is +1.

A
74. Correct option is (a)
β-hydrogen elimination mechanism.

U
Since C-H, σ bond pair electron donate to the metal for this elimination. Therefore, as the donor ability
of the σ electron pair increases rate of β-elimination increases.
In option D, the unit is anti-periplanar and thus β-H elimination not possible.

Q
For β hydride elimination reaction β hydrogen should be closer to metal in option B,C all hydrogen
atoms are far so elimination not possible (sp 2 carbon)
So, more facile β-elimination occur in option (a)

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82

T
Electron donor ability at a bond is C-H (sp³) > C-H (sp 2) >C-H (sp)
So, more facile β-elimination occur in option (a)

I N
75. Correct option is (a)

P O
The reaction follows SN, CB mechanism in which M-Y bond is fully broken before M-X bond begins
to form.
Thus, Id mechanism is the most evidential mechanism.

76. Correct option is (a)

[B12H12] 2- ≡ [BnHn] 2-
Therefore, it is closo structure

T A
77. Correct option is (a)

N
A
SbCl3+3EtMgBr→SbEt3 +3MgBrCl
2SbEt3+SbI3→ [Sb(Et)I2]n +SbEt2I

U
78. Correct option is (c)

Q
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82

Due to this agostic interaction C-H bond becomes weak and hydrogen flanked in between M and C.As
proton come in contact with metal becomes shielded and upfield shift in 1H NMR.

Since v ∝ 𝐾 ,bond strength of C-H bond decreases, in IR spectrum shift to lower wave number.

79. Correct option is (a)

T
N
Suzuki coupling-Palladium catalyzed cross coupling between organoboranic acid and halides.

I
Heck coupling-Palladium catalyzed C-C coupling between aryl halides or vinyl halides and activated
alkenes in the presence of a base.

O
Sonogashira coupling-This coupling terminal alkynes with aryl or vinyl halides is performed with a
palladium catalyst, Cu(I) cocatalyst and amine base.

P
Negeshi coupling-This reaction is the organic reaction of an organohalide with an organic-zinc
compound Pd and Ni catalyst.

A
80. Correct option is (a)
Here, Cp is cyclopentadienyl ligand is one of the most common and popular ligands in organometallic

T
chemistry.

N
It is an anionic ligand that normally coordinates in an η5 mode as a 6 electron donor.

A
Now, 18-electron rule apply on the complexes

U
Q
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207 |Organometallic Compounds
82

T
I N
P O
A
[Mn(η5-Cp)(CO) 3] does not follow 18-electron rule. So, this complex is most deshielded compound
when we are going 3d to 4d and 4d to 5d series in the transition element the shielding effect decrease

T
because of the electron density or the distance between metal to ligand, increases. So, [Fe(η 5-Cp)2] is
more shielded than other.

N
Thus, the compound D is most shielded and compound A is most deshielded.
81. Correct option is (b)
[Ru6(C)(CO)17]

A
TEC =8x6+4+17x2 = 86
PEC= 86 - 6x12 = 14

U
PEC/2= 14/2 = 7
Therefore, 7=6+1=(n+1) closo

Q
[Os5(C)(CO)15]
TEC= 8x5+4 +15x2 = 74
PEC =74-12x5
PEC = 74-60= 14/2 =7= (5+2)=(n+2) .Therefore, nido
[Ru5(C)(CO) 16]
TEC= 8x5+4+16×2

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82

TEC=76
PEC =76-60=16

T
PEC/2=16/2 =8= (5+3)=(n+3) Arachno

N
82. Correct option is (a)

I
For reductive elimination, the eliminating group should be electron releasing group and also the
eliminating product should be neutral.So, only Me group is electron releasing group among all the given
option.

83. Correct option is (C)

P O
T A
N
A
U
All the products are possible but possibility of (4) is least as alkene doesnot undergo reductive
elimination reaction easily as compare to alkane.

Q
84. Correct option is (d)
alkyne can act as a 2 or 4electron donor .
Step-1 (ϭ -bond formed)
L(π)→ M(ϭ)
From filled acetylene π orbitals to empty metal d orbital

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82

Step-2 (π -bond formed)

M(π)→ L(π*)

T
From filled metal d orbital to empty acetylene π* orbitals
Correct option is (d)

I N
85. Correct option is (d)
[W(η5-C5H5)(𝝁-Cl)(CO) 2] 2
TVE(A)= (6+5+3+4)×2=36
P O
A
B = nx18-A = 2×18-36=0
Hence, number of M-M= B/2=0/2 =0

86. Correct option is (b)

T
N
A
U
Q
Example of migratory insertion reaction in which alkyl group insert to CO. A new ligand create acycl a
vaccancy is created which is occupied by new ligand.

87. Correct option is (c)

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207 |Organometallic Compounds
82

T
Hc = central proton
Ha= is anti with respect to Hc

I N
O
Hs= syn with respect to Hc
Ha , Hs , Hc environment are different new intensity ratio 2: 2 :1. When allyl is non-fluxional.

88. Correct option is (b)

C2B5H7 C ≡ BH
P
A
(BH)2 B5H7 ≡B7H9 ≡ (B7H7)-2, (closo)
(BnHn -2)

89. Correct option is (a)

T
N
Structure of Uranocene

A
U
Q
Hence, oxidation state of U=+4
Thus in uranocene U is in +4 oxidation state and have cyclooctatetraenide ligand.

90. Correct option is (a)

-
[V (Co) 6] →[V(CO) 6] ( in presence of H3PO4)
-
[Co(CO)4] → [HCo(CO)4] ( in presence of H3PO4)

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82

91. Correct option is (d)

T
Number of electron involving in metal cluster = T.V.E - 12
T.V.E in Ru(CO) 3 = 8 + 6 = 14 (T.V.E = total valence electron)

N
Hence, number of electron provided for cluster bonding = 14-12=2

I
92. Correct option is (d)

P O
T A
On photolysis of Z first a 16 electron intermediate is formed which is option B, and for final product
allyl attains maximum heptacity therefore η1 allyl is converted η3 allyl which is option D

N
93. Correct option is (a)
Mechanism

A
U
Q
94. Correct option is (a)

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207 |Organometallic Compounds
82

T
I N
-1
Terminal CO=2120-1850 cm
-1
µ2 CO=1850-1750 cm

O
2
In this complex M-M bond order = 1 and two types of CO's terminal as well as -bridging. So,
νco band lies in both range.

95. Correct option is (d)

Explanation:
P
T A
N
A
U
Q
96. Correct option is (c)

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82

Explanation

T
97. Correct option is (d)
B-H= 4e- fragment isolobal fragment should have 14 electron.

I N
O
Cp + Co=5+9=14 e-

P
98. Correct option is (b)
TVE= 9×2 + 8×2 + 2×11 + (4×2)

A
TVE = 18+ 16+ 22+8 = 64 = A
B = (n ×18) –A = (4×18) – 64 = 72-64 =8

T
Number of metal-metal bond = B/2=8/2 = 4

N
99. Correct option is (c)
Structure of CoF2 =

A
U
due to more space requirement for double bond the bond angle ∠F-C-O will be higher that of ∠F-C-F
and also C-O bond order is larger than C-F hence, C-O bond length will be smaller than C-F.

Q
100. Correct option is (b)
As the electron goes to e* 1g (dxz , dyz), orbital of metallocene bond length increases as they are
anologous eg set orbital of an octahedral complex

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207 |Organometallic Compounds
82

T
I N
P O
A
Thus, in Ni(Cp)2 there are highest number of electrons in e* 1g . Hence, it has highest M-C bond

T
length.
Ni(Cp)2 > Co(Cp)2 > Fe(Cp)2

N
101. Correct option is (c)

A
U
Q
Therefore, total protons 8, but in η4-mode COT attached to the four carbon and 4 protons show different
environment at -140°C because fluxonial behaviour slow down and hence , 4 signals will be observed.

102. Correct option is (b)

C2B3H5 = (B-H)2B3H5 = B5H7
Each B-H unit give 2 electron. For cage bonding.

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207 |Organometallic Compounds
82

Hence, 5(B-H)= 5x2= 10 electron. Each hydrogen one electron,

Hence, 2H=2x1= 2 electron

T
Total =12 electrons
C2B4H6 = (BH)2B4H6 =B6H8
6(B-H) 6x2=12e-

I N
2H= 2x1=2e-
Total = 14 electron
B5 H 9

O
5(B-H)=5x2=10

P
4H = 4x1= 4
Total =14 e-

A
103. Correct option is (a)
During fluxional axial ligands are exchanged with equatorial ligand. Hence,

T
N
A
U
Q
104. Correct option is (a)

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207 |Organometallic Compounds
82

T
I N
105. Correct option is (a)

P O
106. Correct option is (c)

T A
N
TVE = 10+12+12=34= A.
B= (n×18) -A

A
B=(2×18)-34 = 36-34=2
Number of metal-metal bond =2/2=1
On heating :

U
TVE 10+12+8 = 30 =A
B=(n×18)-A= 36-30=6

Q
Number of metal-metal bond = B/2=6/2 =3
107. Correct option is (b)

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207 |Organometallic Compounds
82

T
I N
108. Correct option is (c)
T.V.E. = 8 x 2 + 5 x 2 +2 x 2 + 4= 34 = A
B = (nx18)-A=36-34= 2
P O
A
Number of M-M bonds=B/2=2/2=1

T
N
A
3-bridging, 1-M-M bonds.
109. Correct option is (a)

U
When the norbornene is strained molecule because the hybridization is sp 2 when the metal attached with
norbornene back-bonding takes place and due to this back-bonding the hybridization changes to sp 2-sp3
and hence relief to strain

Q
110. Correct option is (b)
Statement I →[Rh(CO)2 I2]-
Converts CH-I and CO into CH3COI
Statement → [Rh(CO)2 I2]- is diamagnetic in nature.
I and II are correct but II is not correct explanation of I.

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82

Correct explanation: Monsanto process occurs via oxidative reaction, migratory insertion and re ductive
elimination reaction for that the starting compound must be square planar.

T
111. Correct option is (a) & (c)
[ReH9]-2 → Tricapped trigonal prismatic

I N
P O
Atoms 1 to 6 are the prism atoms, 7 to 9 are H-atom are equatorial hydrogen.

112. Correct option is (b)

Co(CO)3

T A
N
9+6 =15 (for 18 electron require 3 electron)
P ↔ BH₂
5 3+2 = 5 (for 8 electron require 3 electron)

A
CH ↔ BH2 (for 8 electron require 3 electron)
4+1=5 3+2=5

U
Ni(η5- C5H5) (for 18 electron require 3 electron)
10+5=15

Q
Co(CO)3 ↔ P ↔ CH ↔ Ni(η5- C5H5)

113. Correct option is (b)

[Co(η5- C5H5)B4H8]
Co(η5- C5H5) ↔ BH
14 4

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207 |Organometallic Compounds
82

[BHB4H8] = [B5H5]-4 = [BnHn]-4→nido

[Mn(η2-B3H8)(CO)4]

T
[Mn(CO)4] ↔ [BH2]
7+8=15 5
[ B3H8BH2 ] = [B4H10] = [B4H4]-6 = [BnHn]-6 → Arachno

114. Correct option is (c)

[Rh6C(CO)15]-2

I N
O
TVE = 9x6 + 4 + 15x2 +2 =54+4+2+30 = 90

P
Hence, it has trigonal prism geometry.

115. Correct option is (c)

T A
N
A
U
116. Correct option is (b)
Compound (C) shows four 1H NMR signal

Q
117. Correct option is (b)

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207 |Organometallic Compounds
82

The species having same number of electrons are called isoelectronic.

A =[V(CO)6]=5+12=17e-

T
B =[Cu(η5- C5H5)(CO) ]=11+5+2=18e -
C =[Co(CO)4]-1 =9+8+1=18e-
D=[IrCl(CO)(PPh3)2] = 9+1+2+4=16e-

I N
Therefore B and D are isoelectronic species .
118. Correct option is (c)
Two fragments are isolobal if the number, symmetry properties, approximate energy and shape of their

O
frontier molecular orbitals and the number of electrons in them are similar not identical but similar.
CH3+ = 4+3-1 = 6 ;

P
[Cr(CO)5]=6+10=16
119. Correct option is (a)

A
Na [Mn(CO)5] + CH₂=CH-CH₂-Cl →
Mechanism:

T
N
120. Correct option is (a)

A
U
[B6H6]-2 has 6 + 1 = 7 bonding molecular orbital
[B6H6]-2 = B-H=2x6=12 e-

Q
for 2 negative charge, hence 12e - +2e- =14e-

121. Correct option is (d)

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207 |Organometallic Compounds
82

T
N
[(η5-Cp) Fe (η6-C6H6)]+

122. Correct option is (a)

I
O
In [Fe(S2CNEt2)3] , oxidation state of Fe = +3

P
A
123. Correct option is (a)

T
N
124. Correct option is (b)

A
U
In trigonal prismatic ligand field, energy of 'd' orbital is
2 2
dyz = dxz > dz2> x -y =d dxy

Q
Hence, the most stablized 'd' orbital is dxy

125. Correct option is (c)

Number of valence electron in CH 2 = 6
Hence, fragment having 16 electron will be isolobal to this fragment.
A→ CpCr(CO)2 = 5+6+4=15

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207 |Organometallic Compounds
82

B→CpCu = 5+11=16
C→Ni(CO)2 = 10+4=14

T
D→ Cr(CO)4 = 6+8 = 14
E→Fe(CO)4 = 8+8=16

I N
126. Correct option is (d)
According to reductive elimination reaction mechanism cis-complex can give the product but trans-
complex is not suitable for reaction and does not give reductive elimination product. Since, ligand given

O
in option (d) forms a trans-complex with Pd(II) due to the presence of flexible methylene (-CH 2-)
groups. Therefore, reductive elimination not occured.

P
T A
N
Actually formed but does not give reaction This can give reaction but not formed

A
127. Correct option is (b)
Sn9-4 = 9×4+4=40 , thus it follow 4n+4. Hence, it has nido structure

U
128. Correct option is (b)

Q
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207 |Organometallic Compounds
82

Compound [V(CO)6]- [Cr(CO)6] [Mn(CO)6]+ H3B.CO

ῡco - cm-1 1860 2000 2098 2164

T
[V(CO)6]- < [Cr(CO)6] < [Mn(CO)6]+ < H3B.CO
ῡco streching frequency

N
[V(CO)6]- > [Cr(CO)6] > [Mn(CO)6]+ >H3B.CO

I
C-O bond length

O
129. Correct option is (d)
The insertion of carbon monoxide into a metal carbon bond to form an acyl group is the basis of

P
carbonylation reaction.

T
Intermediate
A
N
130. Correct option is (d)

A
U
Q
Donation of π-electron of the C=C to an empty ϭ orbital of the metal accompanied by back donation
from a filled metal d π orbital into an empty C=C π* orbital
(Synergic bonding ∝ C-C bond length)

131. Correct option is (d)

(A) [{Co(η5-C5H5)}2(C2B6H8)]

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207 |Organometallic Compounds
82

[{Co(η5-C5H5)}2]→18+10=28 is isolobal with (B7H7)

[(BH)7 (BH)2 B6H8]

T
B15H17 → B15H15-2→ closo
(B) [B4C2H8] →[(BH)2B4H8]→B6H10 or B6H6-4 →nido

N
(C) [B10H13 {(Au(PPh3)}]

I
Au(PPh3)→11+2=13 is isolobal with B3H4
[B13H₁7]→ B13H13-4 →nido
(D) [C2B8H10] →(BH)2B8H10 →B10H12 →B10H10-2 → closo

132. Correct option is (b)

P O
[Pd(PPh3)4] and Ni(CO)4 compounds are isoelectronic (follow 18 electron rule) and isotructural in
natural (tetrahedral structure)

A
[Pd(PPh3)4] = 10+8=18e-
[Ni(CO)4] = 10+8=18e -

133. Correct option is (b)

T
N
A
U
Q
134. Correct option is (b)

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 QUANTA POINT
207 |Organometallic Compounds
82

18 e- (A) (18e -) (B) (18e-)

Two signals with three signal with 3:5:15
3:5 intensity ratio intensity ratio

135. Correct option is (d)

T
N
[ReCl8]-2 =2Re+3 (d4 ) + 8Cl-

I
δ -bond: Eclipsed geometry
[Os2 Cl8]-2 has Os+3 d5

O
Bond order =3: staggered

P
T A
136. Correct option is (d)

N
A
In Wacker process, a Co catalyst CuCl 2 which could re-oxidise Pd(0) back to Pd(II)
[PdCl4]-2 +C2H4 +H2O → CH3CHO+ Pd+ 2HCl+2Cl-

U
Pd + 2CuCl2 + 2Cl-→[PdCl4]-2 +2CuCl
2CuCl + ½ O2 + 2HCl →→2CuCl2 + H2O

Q
C2H4+1/2 O2 →CH3CHO

137. Correct option is (b)

As the electronegativity of X in PX 3 increases, π-acceptor tendency increases.
PF3 > P(OPh)3 > PPh3 > PMe3
138. Correct option is (b)

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 QUANTA POINT
207 |Organometallic Compounds
82

In BH3.CO formation CO interact with vacant p-orbital, whereas electron is donated by antibonding

T
N
orbital of CO due to which bond order increases and ν CO increases.

139. Correct option is (b)

I
P O
140. Correct option is (b)
Complex:

T A
N
Mo(PF3)3(CO)3 →2055, 2090
Mo{P(OMe3)3}(CO)3 →1888, 1977

A
Mo(PPh3)3(CO)3 →1835, 1934
Mo(pyridine)3(CO)3→ 1746, 1888

U
π-acceptor tendency of spectator ligand is PF 3 > POMe3 > PPh3 > Pyridine. Therefore, PF 3 reduce more
electron density from the metal in complex to pyridine consequently. As the electron density on metal
decreases, M-C bond strength decreases, C-O bond strength increases. Hence, v CO increases,

Q
141. Correct option is (b)
VCN = [Fe(CN)6]-3 > [Fe(CN)6]-4
Vco=[Cr(CO)6] > [Cr(CO)3(NH3)3]

142. Correct option is (c)

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 QUANTA POINT
207 |Organometallic Compounds
82

[Rh9P(CO)21]-2 → TEC = 9×9+5+2×21+2=130

PEC=130 - 9×12=22

T
PEC/2 = 22/2 =11→ 9+2=(n+2)=nido

N
143. Correct option is (c)

I
Bite angle 85 0
91 0
>120 0

P O 960

A
The linear and branched formylated product is depends upon natural bite angle of biphosphines. As the
natural bite angle increases selectivity for linear product increases.

144. Correct option is (a)

T
N
A
U
Q
145. Correct option is (a)
Ni = 10
Cp= 5e-
Ph2P=3e-
TOTAL = 18e
Therefore, No M-M bonds

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207 |Organometallic Compounds
82

T
146. Correct option is (d)

I N
P O
Electron withdrawing group present on the metal decreases the electron density and hence decreases the
rate of oxidative addition because the rate of oxidative addition is directly proportional to the electron
density on the metal.

T A
N
147. Correct option is (d)
Fe(-1)→ d9 system

A
0
d9 ML3 CH
For d9 –ML3, original co-ordination number will be considered as ML 6.

U
Therefore, [Fe(CO) 2(PPh3)]- having three co-ordination number, missing three from original ML 6 and
similarly for CH, three ligands also missing from original CH 4 . Hence, [Fe(CO)2(PPh3)]- is isolobal
with CH but not with CH2+ (5e-) because two ligands missing from original CH 4.

Q
148. Correct option is (d)
[Ru6C(CO)17]
TEC = 8x6+4+17×2=86
PEC= TEC- n x 12.
PEC= 86- 6x12

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 QUANTA POINT
207 |Organometallic Compounds
82

PEC= 86 - 72=14
PEC/2 = 14/2=7 (n+1) => Closo

T
In the cluster [Ru6C(CO)17]the carbon atom is encapsulated at cavity of cluster and equally interacted
with all Ru centres.

I N
149. Correct option is (c)

P O
T A
N
A
U
150. Correct option is (c)

Q
For reaction A:

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207 |Organometallic Compounds
82

T
For Reaction B:
For reaction C:

I N
P O
151. Correct option is (b)

T A
N
A
U
Two ligands are present on z-axis therefore, d z² -orbital is involved in ϭ bonding. Also three ligands are
present in xy plane, therefore, d x2-y2 and dxy orbitals are involved in ϭ -bonding. Thus the d x2-y2 and
dxy orbitals remain nonbonding.

Q
152. Correct option is (c)

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 QUANTA POINT
207 |Organometallic Compounds
82

T
N
The number of CO bands in fac-[Mo (PPh 3)3(CO)3] =2

I
The number of CO bands in trans-[Mo(PPh 3)2(CO)4]= 1

O
153. Correct option is (b)
In aqueous medium, the most stable vanadium species is hydrated vanadyl ion [VO] +2 i.e

P
[VO(H2O)5]+2

154. Correct option is (d)

A
Cp2Fe

T
10e- +8e- = 18 e-
Number of electron in anti-bonding orbital = 0

N
Cp2Co
10e- +9e- = 19e-
Number of electron in anti-bonding orbital = 1

A
Cp2Ni
- - -
10e +10e = 20e

U
Number of electron in anti-bonding orbital = 2
As the number of electron present in the anti-bonding orbital increases , M-ligand bond becomes weak

Q
and hence, bond length increases. Therefore, the correct order of M-C distance is
Cp2Ni > Cp2Co > Cp2Fe

155. Correct option is (a)

This step is the slowest step and hence rate determining step.

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207 |Organometallic Compounds
82

T
N
156. Correct option is (b)

I
[Fe5(CO)14N]-
TEC= (8x5) + (14×2)+5+1 = 40+28+6 =74

O
PEC =74-(12x5)=14
PEC/2= 14/2 =7 ie.n+2

P
Thus, it is a nido cluster.
[Co6(CO)13N]-
TEC= (9x6) + (13x2)+5+1 = 54+26+6 = 86

A
PEC=86 - (6x12) = 14
PEC/2=14/2 = 7 i.e n+1

T
Thus, it is a closo cluster.

N
157. As per DMG rule , the rate of nucleophilic addition is :

A
U
Q
158. Correct option is (a)

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 QUANTA POINT
207 |Organometallic Compounds
82

Square planar complexes undergo associative pathway. So, ligand substitution process can be better
understood in terms of crystal field activation energy (CFAE). Considering trigonal bipyramid or square
pyramidal geometry in Transition state (T.S.), C.F.A.E. can be calculated.

T
C.F.A.E. (Dq) = C.F.S.E. (Dq) of T.S - C.F.S.E. (Dq) of square planar complex.
The Dq value increases of the heavier congeners and it makes heavier congeners more inert. So rate of

N
substitution will be

I
Ni(II)> Pd(II)> Pt(II)

159. Correct option is (d)

O
The highest rate of substitution of a CO ligand on heating with PPh 3 is easy where slippage of haptacity
is easy.

P
For

T A
slippage is easy because it is not at the cost of aromatic character (η 5 → η3).
But η5 – Cp* , complexes, rate decreases because with respect Cp slippage of haptacity is due to at the

N
cost of aromatic character.

A
160. Correct option is (b)

U
Q
Due to high field strength of Cp*
one unpaired electron
, it forms low spin complexe and having

Cp2*Mn = 2Cp* =10e- and Mn = 7e- =17e-

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207 |Organometallic Compounds
82

12e electrons are in the lower orbitals and remaining five electrons occupies the orbital as follows.

T
Electronic Configuration = e 2g4 a1g1

I N
O
161. Correct option is (c)
Taking 18 valence electron as guide, the products will be predicted.

P
∆
[Mo(N2)2(PMe2Ph)4] [(η6-PhPMe2)Mo(PMe2Ph)3] + N2
18 V.E 18 V.E

[ReCl(N2)(PMe2Ph)4]
∆

T A + N2

N
18 V.E 18 V.E 18 V.E
(Cl as a bridging ligand)

162. Correct option is (c)

A
U
[Fe4C(CO)12]-2
Polyhedron electron count = T.E.C.-12 x n = [4 x 8 + 4 + 24 + 2] -12x4 = 62 – 48 = 14

Q
Hence, x= PEC/2 = 14/2 = 7 = n+3 i.e arachno
T.E.C.= 62
So, it adapts the butterfly structure expected for arachno

163. Correct option is (c)

Mechanism

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207 |Organometallic Compounds
82

T
Protonation of ferrocene with strong acids results intermediate through exo-attack

I N
O
164. Correct option is (a)

P
At +30°C , the compound shows structural fluxionality.

T A
Structural fluxionality

N
So, the two Cp rings display the different bonding modes ϭ(η 1) and π (η5).
At room temperature (30°C) observed doublet due to η 5-Cp and η1-Cp

A
but at -80°C, four peaks observed.
5: 2 : 2 : 1
↓ ↓ ↓ ↓

U
H6-10 H2-3 H4-5 H1

Q
165. Correct option is (d)
The product (A) shows three strong bands at 1986, 1935 and 1601 cm -1.
Three different IR bands suggest, the different CO environment in the complex.

For compound

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 QUANTA POINT
207 |Organometallic Compounds
82

T
three different -C≡O environments are present.
Terminal -C≡O , ῡ-C≡O (terminal) →2120-1850 cm and M-C(=O)-CH 3 ῡ-CO =1700-1600 cm-1

I N
O
compound (b) and compound (c) show two and four different C≡O environments.

166. Correct option (b)

P
In bent mode NO donates one electron to metal centre, thus statement A is incorrect.
IR range for bent NO is 1525 − 1690 𝑐𝑚FW whereas for linear NO it is 1690 − 1900 𝑐𝑚FW. Thus

A
statement B is correct.

T
Electronic configuration for CO is,

Electronic configuration for NO is,

N
Thus statement C is also correct.

167. Correct option (c)

A
Statement A is correct, as in order to form pi bond between metal and carbine, 2 electrons are donated.
Statement B is incorrect, the given carbene is Fischer carbene and it is electrophilic in nature.
Statement C is correct, rotation around the Cr=c(OME)Me double bond has low barrier.

U
168. Correct option (d)
TVE for 𝑅𝑢{ (𝐶𝑂)W~𝐵 F is 86
TVE for 𝑂𝑠{ (𝐶𝑂)WV𝑃 F is 90

Q
TVE for [𝑂𝑠‚ (𝐶𝑂)W{] is 64

Following the below table,

S.No Total Valence Electrons Cluster Framework
1 64 Square
2 86 Octahedral
3 90 Trigonal Prismatic

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207 |Organometallic Compounds
82

169. Correct option (b)

In option (b) both Fe follows 18e rule.
Fe = 8e

T
Cp = 5e
Linear NO = 3
Bridging CO = 2
Total 18e, hence, thermodynamically stable.

170. Correct option (b)

The given reaction is example of Kumada coupling between Pd and Mg

I N
P O
171. Correct option (b)

T A
Carbene whether it is singlet or triplet, they are bent in configuration.
In the presence of +M groups (which is chlorine here), the carbine will be singlet.

N
A
U
Q
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 3
Main Group Elements
Hints & Solutions
1. Correct answer (b):

Stabilisation via back-bonding. Due to innert pair effect stability of +2 oxidation state increases down the group.

2. Correct answer: (a)

Alkali metals in liq. NH3 ,act as source of electrons and are supposed to be a good one-electron reducing agents.


M  (x  y) NH3   M  NH 3  x   e   HN 3  y  .

These solvated electrons can reduce O2 molecule to superoxide ion.

 e   NH 3  y   O 2  O 2  yNH 3

These superoxide ions can combine with solvated metal ion to give alkali metal superoxides.


 M  NH 3  x   O 2  MO 2  xNH 3

3. Correct answer: (a)

Compounds Uses
(A) Na3PO4 Water softener

(B) Ar3PO4 Plasticizers

(C) Et3PO4 Insecticides

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207 |Main Group Elements
82

(D) CaHPO4.2H2O Toothpaste

4. Correct
answer: (a)
B2O3+ 3H2O → 2H3BO3 (orthoboric acid)
N2O5 + 3H2O → 2HNO3 (nitric acid)

T
SO3 + 3H2O → H2SO4 (sulfuric acid)
P4O10 + 6H2O → 2H3PO4 (orthophosphoric acid)

N
5. Correct option (a)

I
Correct answer is (a) closo-{B nHn} species has always -2 charge.

6. Correct answer is (a)

O
BCl→ pπ→-pπ back bonding

P
BCl> BPh3 > BMe3

7. Correct answer is (b)

T A
N
(A) IE, for O and S are 1314 and 1000 kJ mol -1 difference 1314-1000=314
(B) For N and P IE, are 1402 and 1012 kJ mol -1 difference 1402-1012=390
(C) For P and As IE, are 1012 and 947 kJ mol -1 difference 1012-947 = 165 (less 300 kJ )

A
(D) Also for IE, difference is less than kJ mol -1

8. Correct answer is (b)

U
456 789
Na Na+(NH3)x + e-(NH3)y
NH4+ Br- + e-(NH3)y →NH3 + 1/2H2 +yNH3 + Br-

Q
Na+(NH3)x + Br-→ NaBr + xNH3

9. Correct answer is (d)

(SN)x because it is a giant cross linked molecule and have mobile electrons.

10. Correct answer is (a)

Because P-O bond very strong affinity very high not easily break. So, R-O bond break.
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 QUANTA POINT
207 |Main Group Elements
82

11. Correct answer is (c)

The structure of Sodalite cage zeolites is a truncated octahedral (as shown below)

N T
12. Correct answer is (c)

O I
P
s =number of B-H-B bonds = 4

T A
N
t = number of B-B-B = 0
y =number of B-B bonds = 1
x = number of BH2 groups + twice the BH3 groups = 2
Therefore, styx code = 4012

13. Correct option (b)

U A
The Reaction mechanism of typical Bayer’s process is given below
Na2B4O7 +16Na +8H2 +7SiO2 → 4NaBH4 +7Na2SiO3
This is used for synthesis of NaBH 4 from borax

Q
14. Correct answer is (a).
The correct structure of beryllium nitrate contains Be cluster with 5 NO3 units and one O as a part of cluster. (as
shown below)

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 QUANTA POINT
207 |Main Group Elements
82

N T
I
15. Correct answer is (d).
Smaller the internuclear distance between two atoms, stronger will be the bonds. The increasing inter nuclear
distance is as Cl-O < S-O < P-O< Si-O .Therefore strength of pπ-dπ bonding is Cl-O> S-O> P-O >Si-O.

O
16. Correct answer is (c).
NCl3 +4 H2O→NH4OH+ 3HOCl

P
PCl3+ 3H2O →, H3PO3 +3HCl (two different Acids) ,
AsCl3+3H2O → H3AsO3 + 3H2 (two different acids)

17. Correct answer is (b).

A
Alumino silicate is the most used catalyst in oil industry; mostly it is used for the process of Cracking.

18. Correct answer is (a).

N T
19. Correct answer is (d).

U A
Low oxidation state complexes are air sensitive as they easily lose electrons to oxygen, but they are not water
sensitive as they do not bind to a π–donor molecule like H 2O.

20. Correct answer is (d)

Q
PbCl2 and PbSO4 are ionic compounds and insoluble in cold water. Therefore, cannot be used for deposition of
Pb and Pb(Et) is toxic.

21. Correct answer is (b)

Among these elements K is least electronegative and F is most electronegative. Therefore electronegativity
difference is highest for the pair K, F.
22. Correct answer is (b)
C2 B4 H 8
(BH)2B4H8 = B6H10 [ B6H6 ]-4 → nido borane
:;8
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207 |Main Group Elements
82

23. Correct answer is (b).

B(OH)3 +OH- ↔ [B(OH)4 ]- (reversible reaction)
In presence of ethylene glycol, B(OH) 4- is consumed as shown below and boric acid behaves as strong acid.

N T
24. Correct answer is (d)

I
Neso silicates (or Ortho or Island silicates) are the simplest silicates which contain discrete SiO 44- tetrahedral
unit

O
P
A
Soro silicate (or Pyro silicate or disilicate) contain Si 2O76- ions which are formed by joining two tetrahedral
SiO44- which share one oxygen atom at one corner (one oxygen is removed while joining).

N T
Phyllo or two dimensional (2-D) silicates is (Si2O5)n2n- . Each SiO4 tetrahedron shares three oxygen atoms with

A
others and thus by forming two-dimensional sheets.

QU
Tecto or three dimensional (3-D) or Framework silicates is (SiO 2)n . All the oxygen atoms of SiO4 are shared
with other tetrahedra and thus by forming three-dimensional network.

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82

N T
I
25. Correct answer is (d)
As we go down the group in periodic table for sodium family, the number of electrons increases and their

O
attraction towards nucleus increases and simultaneously with addition of new energy shells but increase in
distance is more pronounced as that of increase in e - , So Na loses e-s very easily therefore lowest ionization
energy .

P
In the case of inert gas family, Ne has its complete octet, strongly connected with nucleus e attraction and do
not give e- s to lose easily therefore highest ionization energy.
Thus Na, Ne pair have highest difference in their first ionization energy in given option.

A
26. Correct answer is (a)
Nitrous acid (N₂O) which is commonly known as laughing gas used as a propellent in whipping cream. So, also

T
known as whippits or nangs.

27. Correct answer is (c)

N
The Flame proof fabrics contain urea and phosphoric acid H 2NC(O)NH2.H3PO4

28. Correct answer is (c)

A
(A) N2O3 : HNO2 + HNO2 → N2O3 + H2O
(B) N2O4: HNO3 +HNO2 → N2O4 + H2O

U
29. Correct answer is (a)
As we move from Nb-Ta and Mo-W there is introduction of electron into f-orbital. As the shielding power of f-
orbital is very less. Therefore, as we move from La-Lu in 4f series the size decreases, this is termed as

Q
Lanthanide contraction. This leads to slight increase in size of 5d metal than 4d. Due to this size of d and 5d
metals are nearly similar. Hence Nb-Ta and Mo-W have similar covalent radii.

30. Correct answer is (b)

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82

31. Correct answer is (d)

FeCl3.6H₂O +SOCl2 → FeCl3 (s) + SO2(g) + HCl(g)

N T
32. Correct answer is (c)

I
Large difference between the sizes of Li and Cs. So, it is difficult to get a solid solution of these two metals.

33. Correct answer is (c)

O
P
+ -
ClF3+SbF5 → [ClF2] [SbF6]
SbF5 is a very strong F- acceptor and leads to the formation of ionic compound.

34. Correct answer is (d)

A
Bond order=3 , bond order is directly propotional to bonding energy.
High bond order and HOMO LUMO gap

T
35. Correct answer is (b)
Cesium iodide (CsI) in crystalline form is used as the scintillator for the detection of protons and alpha particles.
Sodium iodide (NaI) containing a small amount of thallium is used as a scintillator for the detection of gamma

N
waves and zinc sulfide (ZnS) is widely used as a detector of alpha particles.
Since in the question, it is asked about radiations (that means gamma rays) thus answer should be NaI

A
36. Correct answer is (a)
H3PO3 is a dibasic and reducing in nature . Thus it should contain two OH groups in the structure.

U
37. Correct answer is (c)
In solid state, aluminum fluorides have 3D network structure unlike Al 3Cl3

Q
38. Correct answer is (c)

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82

N T
The diagram clearly indicates the four centered-two electron interaction (4c-2e). This takes place in Li 4(CH3) 4

I
. The sp3 hybrid orbital is of carbon while the three s-orbitals are of three surrounding lithium atoms.

O
39. Correct answer is (c)
N3P3Cl3F (A) = only 1 isomer

P
T A
N3P3Cl4F (B) = 3 isomer
N3P3Cl3F3(C) = 3 isomer

A N
QU
N3P3Cl2F4 (D) =3 isomer

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207 |Main Group Elements
82

T
N3P3ClF5 (E) = 1 isomer

I N
40. Correct answer is (a)

PO
Relative acidic strength of xenon fluorides follows order XeF 6 > XeO3 > F > XeOF4 > XeF4, XeO2F2 > XeF2.
This order depends upon (i) number of lone pair (ii) number of ‘F’ atoms

A
41. Correct answer is (a)

N T
A
C2B10H12 is show three isomeric derivative which is depend on the the temperature.

42. Correct answer is (d)

U
Styx rule B5H9
(BH)pHq (BH)5H4
S= number of BHB unit ↑ ↑

Q
T= number of BBB unit p q
Y=number of BB unit
X= excess hydrogen attached to B alone.
Hydrogen balance
s+x=q s+x=4 s t y x
orbital balance 2 3 0 2
t+s=p t+s=5 3 2 1 1
Electron balance 4 1 2 0
p+q/2 = s+f+y+x t+y=5-4/2=3
p= f+ y + q/2
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207 |Main Group Elements
221 82

N T
I
43. Correct answer is (d)

PO
The reason is that HNO 3 is better oxidising agent than H2SO4, also acts as dehydrating agent.

A
44. Correct answer is (a)

T
Chromium is extracted from chromite ore:
(I) 4FeCr2O4, +8Na2CO3 +7O2 → 8Na2CrO4 +2Fe2O2 +8CO2
(II) 2Na2CrO4+H2SO4 → Na2SO4 + Na2Cr2O7 + H2O
(III) Na2C2O7+2C → Cr2O7 +Na2CO3 +CO

N
(IV) Cr2O3 +2A1 → Al2O3 + 2Cr

A
45. Correct answer is (b)
The electronegativities of elements are
Ca Al As S

U
1.0 1.5 2.0 2.5

46. Correct answer is (c)

Q
As positive charge increases the size decreases while with increase in negative charge increase the size. This is
due to increase in Zeff, in former case while decrease in Z eff, in later case. Hence, order of size is S 2-> S > S2+ >
S4+

47. Correct answer is (d)

HF exist as H2F2 , and it act as fluoride donar if strong fluoride acceptor is present like SbF 5, AsF5, Therefore,
the reaction will be HF 2 moles = H 2F2
H2F2 (lewis base) + SbF 5 (lewis base) → [H2F] ++ [SbF6] -
SbF5 act as Lewis acids as it has vacant 'd' orbital of suitable energy

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82

48. Correct answer is (c)

All the ions are isoelectronic. Therefore, the size depends upon effective muclear charge.
=
Size of isoelectronic ions ∝ >

F- O2- Na+ Mg2+

Atomic number 9 8 11 12

T
Number of electrons 10 10 10 10
Hence, the order of size will be O 2- > F- > Na+ >Mg2+
Since, atomic number increases.

N
Therefore, z, increases .

I
Therefore, size decreases.

49. Correct answer is (c)

O
The reaction is as follows
Ph2SiCl2 + 2H2O → Ph2Si(OH) 2 +2HCl
1:2 Diphenyl disilanol

P
Diphenyl- (A)
-dichloro silane
Now, (A) undergo condensation polymerisation to yield (B), which is an inorganic silicon, polymer, as follows

T A
50. Correct answer is (a)
Diborane reacts with ammonia as

A N
QU
Here NH3 show unsymmetrical cleavage.
'Y' is actually [A+B].
In 'Y' 'B' part gives quintet and 'A' part gives triplet by 'B' and 'H' coupling.
51. Correct answer is (a)
The crown ether binds metal cation in their cavity. They are selective as they have fixed ring size.

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207 |Main Group Elements
82

Crown ether
Crown-4 Li+
crown-5 Na+
crown-6 K+
crown-7 Rb+

T
crown-8 Cs+
Therefore, 12-crown-4 is best suited for Li + cation. After then as the size increases binding capacity decreases.
52. Correct answer is (a)

N
The reaction of XeF 6 with NaNO3 takes place as

I
XeF6 + NaNO3 → XeOF4+ NaF+ NO2F

53. Correct option is (a)

All the allotropic phosphorous forms changes into white P, discrete units. Which has structure.

54. Correct option is (d)

PO
Pseudo halogen are polyatomic analogous of Halogen whose chemistry resemble with true Halogen common

A
example. CN-, N-3 , SCN-, NCN2-.These anions contain nitrogen atoms.

T
55. Correct option is (c)
;?9?; ==
The average of oxidation states is =
9 9

N
H5P3O10 = +5+3x-20 =0 , 3x =+15 , x=+5
H5P3O7 = +5+3x-14 = 0 ,x=+3
H5P3O8 = +5+ 3x-16=0 , x=+ 11/3
H5P3O9 = +5+3x-18=0 , x= +13/3

56. Correct option is (a)

U A
Due to IPE ns² electron-pair become inactive. In Pb

Q
Therefore, the structure must be

57. Correct option is (a)

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207 |Main Group Elements
82

Acidic strength of Borane depends upon

(i) number of Boron atoms
(ii) decapping
Hence, the correct order of acidity is B 5H9 <B6H10 <B10H14

58. Correct option is (b)

T
The structure of [Si6O18] -12, is

I N
Hence, the number of linked tetrahedrals = 6
The size of ring = 12

59. Correct option is (b)

PO
T A
60. Correct option is (a)

A N
QU
61. Correct option is (a)
ZSM-5 stands for Zeolite Socony Mobil-5, it is an alluminosillicate zeolite belonging to pentasil family of
zeolite. It’s chemical formula is Na nAlnSi96-nO192.16H2O. It is widely used in industries for heterogeneous
catalyst for hydrocarbon isomeriasation.
The mechanism followed for the above reaction is
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207 |Main Group Elements
82

T
62. Correct option is (a)
Structure of P4S3 is

I N
Number of P-S bond=6
Number of P-P bond = 3

63. Correct option is (b)

PO
A
POCl3 → POCl2+ + Cl-
POCl6 + Cl →POCl4-
𝒍5𝒒 𝐏𝐎𝐂𝐥𝟑
(1) Et3N (OPCl2 .NEt3)+ + Cl-

T
POCl6 +Cl →POCl4 ( Cl- concentration is not enhanced)
- -

𝒍5𝒒 𝐏𝐎𝐂𝐥𝟑
(ii) KCl K+ +Cl-

N
The Cl ion produced in this reaction increases the concentration of Cl - and it is not consumed by
-

POCl3
(iii) FeCl3 +OPCl3 →POCl2+ + CeCl4-
(iv) SbCl6 +OPCl3 → POCl2+ + SbCl6-

64. Correct option is (c)

U A
LaI2 exists as La+3 ( 2I- )(e-)
The electron present is responsible for metallic cluster and high electrical conductivity.

65. Correct option is (d)

Q
8C (graphite) + K+ (am)+e- (am) → [K (am)]+ [C8]- (s)
Due to the presence of unpaired electrons in π* band of graphite it is paramagnetic and its electrical
conductance increases. It has eclipsed layer structure

66. Correct option is (a)

CCl4, or C6H6
6S2Cl2 +16NH3 S4N4 +S8 +12NH4Cl
Correct option (a)
67.
B4H10 + NMe3 → Me3NB3H7 + Me3NBH3

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207 |Main Group Elements
82

68. Correct option is (d)

K + graphite →[graphite] - K+
H2SO4 +graphite = [graphite] + HSO4-

69. Correct option is (a)

T
Bi5+3 = 5x5-3 = 22
Hence, (4n+ 2), closo
On addition of 2 electron it become (4n+4), nido

70. Correct option is (c)

NF has two isomers,

I N
71. Correct option is (b)

PO
A
Generally, ionisation energy increases on moving from left to right in a period in periodic table.
• Ionisation energy decreases as we move down in given group
• Ionisation energy will be more for full filled and half filled orbital.

T
72. Correct option is (c)
[PMo12O40]3- is less basic. It is slightly less basic than ClO4-

N
73. Correct option is (a)
The structures of CsCl and CaB 6 are as follows

U A
Q
CaB6 and CsCl both have BCC like structure, the B 6 cluster is present at the body center of Ca lattice.
74. Correct option is (c)
Zn → 3d10 4s2

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207 |Main Group Elements
227 82

Ga→ 4s2 4p1

Ge→ 4s2 4p2
As→ 4s2 4p3
Full filled and half filled orbital have higher ionization energy.
Hence, Ga have lowest first ionisation energy because removal of an electron Ga + achieve stable nobel gas

T
configuration.
75. Correct option is (d)
The above reaction undergoes as follows

N
=FF℃ H4IH45JK LMNOP4MQ5Q
XeF6 +2NF → Na2[XeF8] [XeF6] Perxenate + 2NaF

I
(Z) (A)

76. Correct option is (b)

O
On descending the group, the stability of +3 oxidation state increases and that of +5 oxidation state decreases.
Size usually increases on descending the group (P = 1.10 A 0 and As = 1.21 A0). Thus, AsCl5 is thermally less

P
stable than PCl5 and As is larger than P but less stability of AsCl5 , is not due to larger size of As, instead it is
due inert pair effect.

77. Correct option is (c)

A
Structures of Be2Cl4 (I), B2Cl4 (II) and Ga2Cl4 are

Be2Cl4 = Planar

N T
U
Be2Cl4 = Planar
GaI[GaIIICl4] A
Ga2Cl4 = tetrahedral , No M-M bond

Q
78. Correct option is (a)

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207 |Main Group Elements
82

79. Correct option is (b)

80. Correct option is (c)

N T
Valence electron (N) = P = 2s 2 2p1 =5

O I
P
S=2s2 2p4 = 6 4×5+6×3 = 38
R5SKQ
2c- 2e bond (x) = 9
Un - N Vx + N =U + 38
X= = n= = =7
V U U

81. Correct option is (b)

The correct reaction of B 2H6 with O2 and water are
B2O3+H2O
O2
B2H6
6H2O
2B(OH)3 +H₂

T A
N
82. Correct option is (a)
Magic number →shell model of nucleus
Liquid drop model of nucleus → nuclear fission

A
Actinides →radioactivity
Threshold energy→ Q-value
83. Correct option is (a)

U
[Al2(OH)2 Si4O10] KAl2(OH)2(Si3AlO10]
replaced by 1/4 of Si(IV)
by Al(III)and charge balance by K(I)
Pyrophyllite Muscovite

Q
84. Correct option is (c)

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207 |Main Group Elements
82

85. Correct option is (b)

Poly dimethyl siloxane (PDMS) is :

T
In Siloxanes

N
Me3SiCl : used as terminating agents Me3SiCl + H2O →Me3Si(OH)+HCl
Me2SiCl2, used as chain forming Me 2SiCl2+2H2O→ Me2Si(OH)2 + 2HCl

I
MeSiCl3: used as cross linkers for branching MeSiCl 3+ 3H2O → MeSi(OH)3 + 3HCI

PO
T A
A N
U
86. Correct option is (a)
• Nuclear spin of 10B =3
Nuclear spin of 11B = 3/2

Q
B→H C←H
Electronegitivity: 2.04 2.1 2.5 2.1
This indicates that polarities of B-H and C-H bonds are opposite
•Thermal neutron absorption cross section for 10B=3837 Barn and for 11B=0.005 Barn
•Boron resists attack by boiling conc. aqueous NaOH or fused NaOH upto 500°C.
B+ NaOH (aq) →No reaction
Boron react with fused alkali to give sodium metaborate and H 2.
87. Correct option is (c)
• LiF is sparingly soluble in water but for large anions such as ClO 4- , the Li+ salts are soluble in water.

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 QUANTA POINT
207 |Main Group Elements
82

• Standard reduction potential [E 0] of Li is more negative than that of Na.

Li+ (aq) + e- →Li (s) [E0]red = -3.04
Na+ (aq) +e- →Na(s) [E0]red = -2.71
•Enthalpy of hydration:
Li+ (g) [-520 kJ/mol] > Na+(g)[-406 kJ/mol]

T
88. Correct option is (c)

I N
O
The structure of O2F2 resembles that of H2O2, in its large dihedral angle, which approaches 90°. The reaction of
fluorine with a dil. aqueous solution of NaOH gives OF 2 with sodium fluoride as a side-product.
2F2+ 2NaOH → OF2+ 2NaF + H2O

Oxidation (Reducing agent)

(+1)
H2S + 4O2F2 → SF6 + 2HF + 4O2
(0)

P
A
Reduction (Oxidizing agent)

89. Correct option is (a)

T
In fullerene the juncture bond (C=C) is the donor pi-bond. Hence, its common hapticity will be two
90. Correct option is (c)
• Alkali metal hydrides are saline hydride.

N
• BeH2 has polymeric structure with 3c-2e bonding.

•
•

U A
Bigger metal hydrides are usually interstitial hydrides as H - can be trapped in their bigger voids.
[TcH9]-2 is trigonal tricapped prismatic.

Q
91. Correct option is (a)
(A) The highest oxidation state +8 of group 8 elements is shown readily in oxides like OsO 4 and RuO4 than in
fluorides like RuF8 and OsF8 because these fluorides are unstable due to increased steric hinderance.
(B) Fe can exist in-2 formal oxidation state also in carboxylate like [Fe(CO 4)]-2.
(C) Mn forms Mn(II) compounds easily but Tc and Re rarely form M(II) compounds as indicentis their standard
reduction potentials.
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 QUANTA POINT
207 |Main Group Elements
231 82

Mn+2 (aq)+2e- → Mn(s). E0 = -1.185 V

Negative value of E0 indicates that the reaction Mn to Mn +2 is feasible
Tc+2 (aq) +2e → Tc(s). E 0 =+0.40V
Positive value of E0 indicates that the reaction Tc to Tc +2 is not feasible.

T
92. Correct option is (a)
The structures of dithionite and dithionate are

Dithionite
S2O4-2

I N
O
2x = 8-2
x = +3

P
A
Dithionate
S2O6-2
2x = 12-2

T
x = +5

93. Correct option is (b)

N
•On moving down in a group, the atomic radius generally increases. Even though d-orbital is present in Indium,
its size is greater than that of aluminium as electron is added to 5s orbital which has much higher size than that
of 3s orbital of aluminium. Even after contraction, size of 5s orbital is greater than that of 3s orbital. Due to

A
higher atomic radius of In, its outer electrons experience lesser attraction towards nucleus hence, (IE 1 + IE2 +
IE3) for In is less than that of Al.
•On moving along the period, size decreases thus, effective nclear charge increases and hence I.E. increases.

U
Therefore, IE1 of Co is higher than that of Sc and IE 1 of Se is higher than that of Ga
• Nitrogen has stable half-filled 2s 2 2p3 configuration thus, has higher IE 1 than that of oxygen.

Q
94. Correct option is (d)
Alkane is a hard base react with hard acid. Benzene acts as a soft base reacts with soft acid (Ag +)

95. Correct option is (a)

a.SbF5 + 2HF → [H2F]+ [SbF6]-
b.In the solid state, SbF5 is tetrameric thus, it has octahedral structure.

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207 |Main Group Elements
82

T
c.PF3 acts as a strong π-acceptor ligand towards d-metals.
d.AsCl3 may act as either a Cl - donor or acceptor with an appropriate reagent. Thus, in presence of a chloride
source, AsCl3 can form complexes of type [AsCl 4]-

96. Correct option is (b)

2XeF6 + SiO2 → 2XeOF4+ SiF4

I N
O
quartz (A)
XeOF4+ XeO3 → XeO2F2
(A) (B)

97. Correct option is (a)

The table below defines energies and their proportional interactins
P
A
Type of interaction Strength Energy-distance function
Covalent bond Very strong Complex, but comparatively long range

T
Ionic bond Very strong 1/r, comparatively long range
Ion-dipole Strong 1/r2, short range

N
Dipole-Dipole Moderately strong 1/r3, short range
Ion-induced dipole Weak 1/r4, very short range

A
Dipole-induced-dipole Very weak 1/r6, extremely short range
London dispersion force Very weak 1/r6, extremely short range

U
98. Correct option (c)
Generally for Nitrogen, oxygen and halogen family, electron gain enthalpy of 2 nd period element is less than
that of 3rd period element.

Q
In group 16, O,S,Se and Te. If we apply general trend, that electron gain enthalpy decreases down the group, so
the trend should follow O > S > Se > Te, but as mentioned elements of period 2 are generally have less electron
gain enthalpy, because of their smaller and more compact size, which leads to repulsion between incoming and
existing electrons. Thus oxygen has less electron gain enthalpy than others, so the order becomes S > Se > Te >
O.

99. Correct option (b)

Statement (A) is correct as,
𝐸𝑡 V 𝑂 ∙ 𝐵𝐹9 + 𝑁𝑎𝐵𝐻; ⟶ 𝐵V𝐻b + 𝐸𝑡 V𝑂

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 QUANTA POINT
207 |Main Group Elements
82

Point group of B2H6 is D2h, hence statement (B) is incorrect

Since, , thus statement (C) is correct

T
MOT of B2H6 is given by,

I N
PO
T A
A N
U
Hence, the molecule is Diamagnetic. Statement (D) is correct.

Q
100. Correct option (d)
Reaction (i) and (ii) are possible but reaction (iii) cannot take place.

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 4
Nuclear Chemistry
Hints & Solutions
1. Correct option is (b)
With addition of  particle, atomic mass get increased by 4 and atomic number get increased by 2. With addition of
 particle, atomic number get decreased by value of 1 and with release of  +particle atomic number get decreased
by 1.
Atomic mass of Y = 234+ 4 (due to addition of  ) = 238
Atomic number of Y= 92-1 (due to addition of ²-1) -2 (due to release of  +)
+2 (due to addition of  )
= 91
Thus, resulted nuclei is 91Y238

2. Correct option is (b)

In electron capture process a proton captures an electron from k-shell, and convert into a neutron. In this
process an electron neutrino is also emitted. The reaction is as follows:

Proton electron neutron neutrino

Henuce, the products are neutron and neutrino

3. Correct option is (c)

In neutron activation analysis, the specimen is placed into a suitable irradiation facility and bombarded
with neutrons. This creates artificial radioisotopes of the elements present. Following irradiation, the

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207 |Nuclear Chemistry
241 82

artifical radioisotopes decay with emission of particles or, more importantly gamma rays, which are
characteristic of the elements from which they were emitted.

4. Correct option is (a)

T
The magic numbers of nucleons 2, 8, 20, 28, 50, 82, 126.

N
5. Correct option is (d)

I
The cross-section (σ) can be interpreted as the effective 'target area' that a nucleus interacts with an
incident neutron. Larger the effective area, greater the probability for reaction

O
In reaction 92U235 + 0n1 → 36K94 + 56Ba140 + 20n1 , one neutron react with 92U235 to give two neutron,
which have more tendency to react with other radioactive nuclei. Thus, increases effective area for
reaction.

P
6. Correct option is (c)
2, 8, 20, 28, 50, 82 and 126 are magic number.

7. Correct option is (a)

T A
We have the relation between threshold energy and 'Q' of a reaction, as

KTh = -Q
Ma + M A
MA

N
Here, Ma = mass of moving projectile or bombarding particle
MA = mass of stationary nucleus

A
Also, for endoergic reaction, Q > 0
Therefore, magnitude of threshold energy.

U
Ma + M A Ma + M A
KTh = ⃒-Q⃒ ; >1
MA MA

Q
⃒KTh⃒> ⃒Q⃒

8. Correct option is (b)

In fission of U235 with thermal neutrons
(1) On the average, each fission of a U 235 nucleus produces about 2.5 free neutrons
(2) Each fission produce 200 MeV energy

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207 |Nuclear Chemistry
241 82

(3) Fission always occure in assymmetric fashion, it means number of nuclei undergoing unsymmetrical
fission is maximum.
Hence, correct statement is (1) and (3).

T
9. Correct answer is (d)

N
10. Correct answer is (b)

I
The reaction which involve evolution of γ radiation are called radioactive capture reaction
23
Na + .- n → 24Na + γ

11. Correct answer is (d)

PO
The unstable nuclides like 233U, 235U and 239Pu, undergo fission by thermal neutrons. 232Th is a stable
nuclei, compared to others.
12. Correct answer is (a)

A
24
The kinetic energy of deuteron (d-particle) is very low, hence it cannot excite Mg nuclei.

13. Correct answer is (c)

N T
Particles that are always to emit during positron emission
1
P1 → 0n1 + -. e + ῡ (antineutrino)

A
14. Correct answer is (a)

U
For an element the favourable characteristics both the target and the product in neutron activation is high
neutron cross-section area of the target and long half-life of the product.

Q
15. Correct answer is (a)
.0
In carbon dating , /C undergoes β- ray decay
.0 .0
/C → 1N +β

16. Correct answer is (b)

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207 |Nuclear Chemistry
241 82

(A) 𝟖𝟒Be 2 𝟒𝟐He →

Δm = 2x4.002603 - 8.005300 = -0.000094
There is mass loss. Thus, energy evolve.

T
Therefore, exothermic
𝟖𝟎 𝟒𝟎
𝟑𝟔Kr→2 𝟏𝟖Ar

N
Δm =2×39.96238 - 79.81638 = 0.10838

I
No mass loss, no energy realsed
Therefore, endothermic

O
17. Correct answer is (b)

P
6
-e45 positron)(
.3 .0
.- Ne 3F ;
6
-e95 (β
- particles)
.0 .0
/C 1N ;

T A
A N
Q U
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 5
Inorganic Spectroscopy
Hints & Solutions
1. Correct answer: (b).
Gives the evidence that Cu on is present in tetragonally distorted octahedral field, the unpaired electron resides in the
orbital d x2-y2

2. Correct answer: (c)

SnF4 is ionic, here Sn+4 = 5s0 so no quadrupole splitting.
SnCl4 is covalent, and Sn is sp3 hybridised, So there is s-electron density in the molecule.
Hence quadrupole splitting is possible.
R3SnCl is covalent, and Sn is sp3 so there is s-electron density in the molecule.
Hence quadrupole splitting is possible.
3. Correct answer: (b)
Both Fe(II) TPP and Fe(III)-TPP are square planar (because of tetradentate-planar, porphyrine
type ligand), and both Fe(II) and Fe(III) are dsp2-hybridised, so there is s-electron density,
which is responsible for their quadrupole moment and existence of mossbauer spectra.
So both Fe(II)-TPP and Fe(III)-TPP show increase in s-electron density, but Fe(II) has higher
s-electron density. So Fe(II) has isomer higher shift (0.52 mms-1) than Fe(III) (0.45 mms-1).
4. Correct answer is (b).

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207 |Inorganic Spectroscopy
241 82

At room temperature due to rapid interconversion of axial and equatorial F atoms, all the F will be
19
equivalent. Hence F NMR of PF5 at room temperature will appear as doublet of 5F.

5. Correct answer is (b)

T
𝑉 𝑣
Frequency shift (∆v) =
𝑐

N
Where V =relative velocity of source and observer

I
𝑣 =frequency of emitted radiation
𝟏𝟎8𝟑 𝒎
𝟐. 𝟐× ×𝟑. 𝟒𝟖×𝟏𝟎𝟏𝟖 𝑯𝒛
∆𝒗 = 𝒔 = 𝟐. 𝟓𝟓×𝟏𝟎𝟕 𝑯𝒛 = 𝟐𝟓. 𝟓𝑴𝑯𝒛

O
𝟑×𝟏𝟎𝟖 𝒎/𝒔

P
6. Correct answer is (d)

T A
7. Correct answer is (a)

A N
Q U
Triplet as well as doublet indicate 3 phosphorus atoms in the molecules in two sets
2P = doublet , 1P= triplet
That is possible in mer-[IrCl3(PPh3)3]
fac-[IrCl3(PPh3)3] will give singlet of 3P

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207 |Inorganic Spectroscopy
241 82

trans-[IrCI(Co)(PPh3)2] will give singlet of 2P.

[Ir(PPh3)4]+ will give singlet of 4P.

T
8. Correct answer is (c)
The total numbers of fine and hyperfine EPR lines expected for octahedral high-spin Mn(II), I=5/2
Numbers of fine = No. of unpaired electron in Mn=5

I N
Numbers of hyperfine EPR lines = No. of unpaired electron x (2nI+1)
n= no. of Mn atom = 1 , I= nuclear spin of Mn = 5/2
E

O
Numbers of hyperfine EPR lines = 5 × 2×1× + 1 = 5×6 = 30
F

P
9. Correct answer is (b).
(1)Fe3→High Spin-d5 →Spherical electronic configuration
E F
𝑇FM 𝐸
→ No quadrupole splitting, singlet signal as shown in (B)

A
M

(2)Fe2 →High-Spin- d6→axial electronic configuration

T
O F
𝑇FM M 𝐸 splitting, gives doublet signal as shown in (A)
→quadrupole
E
(iii) Fe3 → Low-Spin- FM
P
M 𝐸𝑇
→ Axial electronic configuration quadrupole splitting,doublet signal as

N
shown in (A)

A
10. Correct answer is (d)

Q U Q
mICH = ± F , mlN =1; mlCu = F ,
R

Multiplicity =(2nnIN+1 )( 2nnICu+1 +1)= (2x4x1+1) (2×1×3/2+1)=9x4=36

11. Correct answer is (d)

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207 |Inorganic Spectroscopy
241 82

ST
Recoil energy =R =
FUV T

ERW T X
= FUV T
𝑒𝑉
ERW T X
= 2.5×10W =

T
QRZ×ZRQ.E

F.E×QRZ×ZRQ.E×QP[
E= = 24.57×10 ReV= 25 keV
ERW

12. Correct answer is (d)

I N
Four H1 are equivalent. Two nitrogen are equivalent.
PO
A
Two fluorine are equivalent. One 2H is separate.

T
Q Q Q Q
Multiplicity= 2×4× F + 1 2×2× F + 1 2×2× F + 1 2×1× F + 1 = 5×3×3×2 = 90

4H1 2N15 2F 1H

13. Correct answer is (a)

A N
If the system has an even number of unpaired electrons then zero field splitting within the ground state
may result in the EPR transitions being undetectable and only one EPR signal is observe . Since Ni(II)
octahedral complex has two unpaired electrons, therefore, number EPR signals is one.

129

U
14. Correct answer is (d)

Q
I, 57Fe , 121 Sb Mössbauer nuclei and they fulfuil all the properties for that 57Co is unstable nuclei
which is used as y-source in the Mössbauer spectro photometer for 57Fe study.

15. Correct answer is (b)

For systems with more than one unpaired electrons s >1/2 the ground state can be split in the absence of
external magnetic field due to local site symmetry-the zero field splitting. For odd electrons systems,

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207 |Inorganic Spectroscopy
241 82

this results in pairs of energy levels known as Kramer's doublets. Since Cr(III) has three unpaired
electrons, therefore number of Kramer's doublets in tetragonally distorted Cr(III) complex in zero field
splitting is 2.

T
16. Correct answer is (a)
SELECTION RULE

N
ΔML= 0, 1 ( for±Zeeman effect)

O I
P
17. Correct answer is (c)

T A
N
ijkkl mn imopVk F.F×QP xy
×npkqokrVs z/i×R.O{×QP |} ~•
𝐷𝑜𝑝𝑝𝑙𝑒𝑟 𝑠ℎ𝑖𝑓𝑡 = =
ijkkl mn tuMvw R×QP} z/i

=2.552x10€ = 25.5 MHz

18. Correct answer is (a)

U A
19
Q
There are two types of F F a , Fb
19
F = F b = doublet due to F a
F = F a = triplet due to F b

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207 |Inorganic Spectroscopy
241 82

T shaped structure.

19. Correct answer is (d)

19

T
The low temperature , (-98°C) F NMR spectrum of SF4 - doublet of triplet

Q
Equatorial F= 2x 2 x F + 1 = 3 , n=2 (axial F)

I N
O
Q
Axial F= 2x 2 x F + 1 = 3 , n=2 (Equatorial F)

P
One C2 axis is present (passes through S and bisect the line joining the two F atoms each) ϭh is absent .
2ϭv present (molecular plane and the plane bisecting the line joining the two Fatoms passing through S).
Symmetry elements E , C2 ,2ϭv

A
Point group symmetry = C2v

T
20. Correct answer is (a)
Fe(II)= 3d 6 4s0 , Fe(III)=3d5 4s0 , Fe(IV)= 3d4 4s0

N
Isomer shift in Mössbauer spectra depend on the s-electron density and d-electron density increase the s-
electron density decrease the isomer shift increase the d-electron density increase the isomer shift.

A
So, so correct order, Fe (II) > Fe (III) >Fe (IV).

U
21. Correct answer is (d)
CD3 (ID= 1)

Q
(2nI+1)= (2x3 x 1 + 1) = 7

22. Correct answer is (b)

Selection rule for EPR , Δms = ±1, Δml = 0.

23. Correct answer is (d)

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207 |Inorganic Spectroscopy
241 82

24. Correct option is (c)

Oxidation of Zn to Zn will be diamagnetic hence EPR inactive.
Fe and S - Inactive.

T
EPR spectroscopy generally used for the species have one or more unpaired electron.
Cu(II) are EPR active because non-paired electron.

I N
25. Correct option is (c)
Mössbauer spectrum of a complex gives information about
(1) Oxidation state and spin state of metal

O
(2) Types of ligands co-ordinate to metal define by quardurpole splitting on the behalf of electronic

P
environment of ligand symmetry.
(3) Also information about geometry of metal

A
26. Correct option is (a)

N T
U A
For vanadium, I= 7/2 . So, 2nI+1= 2(1)(7/2) + 1 = 8
So, in EPR spectrum it has two g values and it has two patterns of 8 lines each.

Q
27. Correct option is (a)
BH3 part of the molecule Ph3P.11BH3
1
H NMR spectrum (2N1I+1) × (2N2I+1) = (2x1x3/2+1)x (2x1x1/2+ 1) = 4x2=8
11
B spectrum (2N1I + 1) × (2N2I+1) = (2x3x1/2+ 1)×(2x1x1/2+ 1) = 4x2 = 8

28. Correct option is (c)

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207 |Inorganic Spectroscopy
241 82

57 57
Fe* can be prepared by electron capture process from radioactive F€CO.

N T
I
29. Correct option is (c)
{•E•Q

O
[XeF5]- = E
= 7 = sp3d3 hybridzation

Shape = Pentagonal Planar

P
T A
as 74% Xe are NMR inactive hence a singlet of five fluorine and due to 26% nuclei a doublet of

N
satellite.

U A
Hence, total number of signal is 3.

Q
30. Correct option is (c)

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207 |Inorganic Spectroscopy
241 82

One C2 axis and one plane of symmetry exist in this molecules,

So, two types of phoshphorous atoms
For aP (2NI+1)= [2x1x1/2+1] = 2 (doublet)
For bP (2NI+1) = (2x2x1/2+1) = 3 (triplet)

31. Correct option is (a)

N T
I
Number of hyperfine line (due to Cu and nitrogen)
(2NICu +1) (2NIN+1)
(2x1x3/2+1) (2×2×1+1)

O
4x5=20.

32. Correct option is (d)

P
Both fluorine in same environment.

T A
N
So, form doublet (2NIF+1)=(2×1×1/2+1) =2

U A
Both are mirror image to each other
but fluorine in different enviornment

Q
(2x2x1/2+1) = 3 triplet
So, total number of line 2+3=5

33. Correct option is (a)

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207 |Inorganic Spectroscopy
241 82

•
•
Since NCS is ambidentate ligand therefore change in co-ordinate mode

N T
I
Change in the spin-state of iron at high temperature

34. Correct option is (b)

O
(R3Ge)2 → 2R3Ge (radical) in R 3Ge (radical)

P
Multiplicity = (2nI + 1) = 2x1x9/2+ 1 = 10 lines
73
Ge [I = 9/2]

A
35. Correct option is (a)

N T
31

31

U A
P {1H} → (2NI+1)=[2×2×1/2+1]=3 (triplet)
P {1H} → (2NI+1) = (2x2x1/2+1)=3 (triplet)

Q
36. Correct option is (c)
H3P. 11BCl3
31
P NMR→(2NIH+1) for 3H=(2x3x1/2+1)=4(quartet)→1:3:3:1
P NMR → (2NIB+1) for B = (2x3/2x1+1)=4(quartet)→1:1:1:1
Intensity ratio: 1:1:1:1:3:3:3:3:313:3:3:1:1:1:1

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207 |Inorganic Spectroscopy
241 82

37. Correct option is (c)

N T
I
In CD3 molecule => I = 1
Number of EPR lines= (2NI+1) = (2x3x1+1) =7

38. Correct option is (c)

PO
mer-[M(PR3)3Cl3]

39. Correct option is (b)

T A
N
Out of 100% molecule of cis-[Pt(PEt 3)2Cl2] , 33.8% [Pt195(PEt3)2Cl2] having doubled satellite in 31P
NMR due to 1JP-Pt coupling and 66.2% [Pt (PEt3)2Cl2] having Singlet signals in 31P NMR due to 1JP-Pt

A
coupling absent.
Overall the 31P NMR signal will be singlet signal with 33.8% doublet satellite as given below.

U
OR
The 31P {1H} NMR spectrum is comprised with satellite peak of a singlet signal.

Q
40. Correct option is (b)
[FeO4]-2

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207 |Inorganic Spectroscopy
241 82

• It is stable in strongly basic medium

• Powerful oxidizing agent
• The isomer shift of its Mossbauer spectrum is more negative compared to that of FeCl 3
41. Correct option is (a)

T
gǁ > g ╧ >g2
the evidence that Cu on is present in tetragonally distorted octahedral field,

I N
PO
A
Ground state tetragonally elongation & unpaired electrons in d x2-y2

42. Correct option is (d)

N T
U A
Both phosphorus are chemically different 2JP-P and 3JP-P and are possible,
Signal for =(2NI* +1)=[2x1×1/2+1]=2→ doublet

Q
Signal for P* = (2NI +1)=(2x1x1/2+1)=2→doublet

43. Correct option is (c)

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207 |Inorganic Spectroscopy
241 82

N T
O I
44. Correct option (a)
P
A
Selection rule for allowed transition is ∆𝑀ƒ = ±1 𝑎𝑛𝑑 t∆𝑀
=0 , thus statement (A) is correct

N T
U A
In tetragonally elongated Cu(II) complex, more electron density is along d z2 orbital hence 𝑔∥ > 𝑔 0
Ground state for tetragonally compressed Cu(II) complexes is d x2-y2 .

Q
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 6
Lanthanides & Actinides
Hints & Solutions
1. Correct answer: (a)
(A) Correct, As 4f-electrons are too well shielded to interact, so they are like inert gas-type ion, like those of alkaline
earth metals, that attracts ligands only by overall electrostatic forces.
(B) Correct, Lanthanides owing to the unavailability of orbitals for bonding, high basicity and rather large size of Ln3+,
form few complexes and mostly with oxygen or oxygen plus nitrogen chelating ligands such as -dietones, hydroxy
acids EDTA etc. So, they rarely show isomerism and also lability of ligands make the isolation of isomers difficult.
(C) Incorrect, C.N. more than 8 are common, due to their larger size and smaller chelating ligand like,
NO3- SO2-4etc.eg. [Ce(NO3)6]2-,C.N=12
(D) Correct, As 4f electrons are well shilded from external fields by the overlying 5s and 5p elec trons.Thus the
magnetic effect of orbital motion is cannot be neglected.
2. Correct answer: (a)
As we move from 2d row transition element (Zr) to 3 row transition element (Hf), size should increase, but due to
lanthanide contraction offset the increase, so Zr and Hf have almost similar size.
3. Correct answer : (d)

64
Gd = [Xe]4f7 5d16s2, Gd+2=[Xe]4f7 5d1 6s°
Removal of electrons takes place from the outermost orbital only.
4. Correct answer : (a)
Uranium fluorides co-precipitate with CaF2
5. Correct answer is (d)
Sm3+due to spin-orbital coupling
6. Correct answer is (a)
Al(OH)3 Amphoteric whereas hydroxides of lanthanoids are all base.

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207 |Lanthanides and Actinides
241 82

7. Correct option (b)

Eu+2 →4f7 →Half-filled→ stable
Yb²+→4f14→ Completely filled → stable

T
8. Correct answer is (d).
Smaller the size of Lu 3+ ion, higher will be the partition coefficient.

9. Correct answer is (d)

I N
Since size of Lu is smallest, therefore Lu(OH) 3 complex most easily formed with NaOH and dissolves.

O
Lu (OH)3 +3OH- → [Lu(OH)6]3-

10. Correct answer is (a)

P
The electronic configuration of Gd +3 and Lu+3 are 4f7 and 4f14, for this ions total angular momentum is

A
zero i.e. there is no orbital contribution. Therefore, calculated and observed values of magnetic moment
are closest for this pair.

11. Correct answer is (a)

N
µobserved = µs + µl
µobserved = µs only if µl =0 T
UA
Q
12. Correct answer is (b)

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 QUANTA POINT
207 |Lanthanides and Actinides
241 82

Ground state term → 6D

2s+1=6
2s=5 => s =5/2 i.e. five unpaired electrons

T
For D, term L=2

I N
PO
13. Correct answer is (b)

T A
N
Sm→ [Xe]4f6 5d0 6s2 , Sm+3 → [Xe]4f5 5d0 6s0

UA
J=|L+S|…|L-S|

Q
=|5+5/2|…. |5-5/2|
= 15/2 5/2
6
H15/2 , 6H5/2
Ground state term= 6H5/2
Eu = [Xe]4f7 5d0 6s2 , Eu= [Xe] 4f6 5d6 6s0

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207 |Lanthanides and Actinides
241 82

L=3+2+1+0-1-2-3

T
0 1 2 3
S P D F

N
J=|L+ S|……|L-S|

I
=|3+3|….. |3-3|
=6 0

O
7
F6 7 F 0
Ground state term 7F0

14. Correct answer is (b)

Sm 4f6 5s0 6s2
P
A
Eu 4f7 5s0 6s2

T
Sm can accept one electron and become half field. So, it is better oxidant.

N
15. Correct answer is (a)
The retention of ion in exchanges column depends upon the size of ion. Smaller the size of cation,
stronger will be its binding ability. In cation exchanger column the aqueous solution of ion is passed

A
where binding ability depends upon hydrated radii.
K+ (aq) < Na+ (aq) < Li+ (aq)

U
Since, size of hydrated ion increases as shown above.
Therefore, binding ability decreases as K + (aq) > Na+ (aq) >Li+ (aq)

Q
Ag+(aq) show polarization effect, hence, has high binding ability.
Correct order : Ag+ > K+ > Na+ > Li+

16. Correct answer is (b)

Dipivaloylmethane, form chelats with lanthanides

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207 |Lanthanides and Actinides
241 82

17. Correct option is (a)

2UO2+ (aq) + 4H+ (aq) → U+4 +UO2+2 (aq) + 2H2O

N T
I
UO2+ disproportionates more easily than UO 2+2 [correct ]
(B)U3O8 is most stable oxide of U. U3O8 is stable at high temperature [correct]

O
(C)[UO2(NO3) 2(H₂ O) 2] co-ordination number = 8 [incorrect]
(D)UO2+2 is linear [O=U=O] +2 [correct]

18. Correct option is (d)

(NH4) 2[Ce(NO3) 6](Z)
P
A
(1) NO-3 behaves as bidentate ligand. Hence, C.N = 12

T
(2) Ce+4 has no unpaired electron hence dimagnetic not paramagnetic.
(3) Ce+4 has higher oxidation state hence behave as oxidising agent.

N
(4) (NH4) 2[Ce(NO3) 6] on reaction with Ph3PO gives [Ce(NO3) 4(Ph3PO)2] having . C.N.=10.
Hence correct statement.
OPPh3 = mono dentate ligand; NO3= bidentate

UA
19. Correct option is (a)
The Eu and Yb donate two electrons in their metallic bonding unlike other lanthanoids which donate
three electrons.

Q
This is due to Eu+2 (4f7) and Yb+2 (4f14) stable configurations
Ln→Ln+3 + 3e-
Eu→ Eu+2 + 2e- (4f7) half filled stable kernel
Yb → Yb+2 +2e- (4f14) full filled stable kernel
Hence, they show abnormally larger sizes than other lanthanoids.
Eu =1.99Å , Yb=1.94 Å

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207 |Lanthanides and Actinides
241 82

20. Correct option is (a)

(a) There is no good agreement between the calculated (µ g = J J +g 1 B.M.) and experimental
+3 +3
magnetic moments for Eu and Sm ions because of low value of spin orbit coupling constant.

T
Therefore, the ground state and the first excited states become equally populated, due to the thermal
motion become equally populated due to thermal motion. Hence, the observed magnetic moment of Eu +3
at room temperature is higher than that calculated from spin-orbit coupling.

N
(b) Lanthanide oxides are predominantly basic in nature.

I
(c) The Sm(II) ion has 4f configuration. Thus, in Sm (II) 4f subshell is not half filled
(d) Since the chemical properties of the tripositive lanthanide ions (due to their similar size) they cannot

O
be separated easily by chemical method. Instead they can be separated by ion exchange chromatography.
21. Correct option is (a)

P
[UO2(NO3)3 ]-1

T A
Co-ordinate number is 8 and geometry is hexagonal bipyramidal.

N
22. Correct option is (d)

A
Lande's splitting factor g is calculated as

g = 1+
J (J+1) +S(S+1)- L(L+1)

U
(J(J+1)

Ce+3 = f1

L=3
S=½
Q
J=|L-S| for orbital less then half filled
J=|3-½|=5/2

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207 |Lanthanides and Actinides
241 82

5/2 (5/2+1) +1/2(1/2+1)- 3(3+1)

g= 1+ (×5/2(5/2+1)

g= 6/7
Pr+3 = f 3

L=3+2 =5

N T
I
S= 1
J=|5-1|=4

O
4 (4+1) +1(1+1)- 5(5+1) 0
g= 1+ (×4(4+1)
=1

23. Correct option is (c)

P
A magic number is a number of nucleons (either protons or neutrons separately ) such that they are

A
arranged into complete shells , within atomic nucleus ,the seven most widely recoginized magic
numbers 2, 8, 20, 28, 50, 82 and 126 are magic number.

24. Correct option is (c)

N T
The calculated and observed magnetic moments of Eu +3 aqua complex are 0 and ~3.5 . The reason is
that with the spin orbital coupling constant is only about 230 cm . This means that the difference in
energy between the ground state and next excited state is small .So most of electrons goes to excited

UA
state and paired .

Q
Hence µ = J J + 1 = 0

25. Correct option is (a)

(a) Lu(III) = [Xe] 4f 14 5d0 6s0 hence diamagnetic
(b) EuI2 has metallic lustre

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207 |Lanthanides and Actinides
241 82

(c) Ce(IV) used as oxidising agent

(d) Tb(III) – f 8 has pink colour

T
26. Correct option is (a)
(A) Due to more expansion of 5f orbital actinoids has more tendency to release electron hence have
more tendency to show oxidation state greater than +3 compared to Lanthanoids

N
(B) Actinoids (III) show either f-d or f-f transition, but no d-d transition

I
(C) UO2+2 and PuO2+2 are stable
(D) All the actinoids have radioactive isotopes

27. Correct option is (b)

Gd+3 ion show isotropic magnetic susceptibility

PO
A
28. Correct option is (a)
Pink → Sm(III)

T
Red → Eu(III)
Green → Tb(III)

N
Blue → Tm(III)

A
29. Correct option is (b)

S=3

Q U
L=3 = F
2S+1=7
J= |L-S| =|3-3|=0
Hence, 7F0
Since, J=0 hence µ should be zero but due to population of higher J level µ >0. But as temperature
decreases population in excited J level decreases hence magnetic moment approaches to calculated value
i.e. zero.

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241 82

30. Correct option is (c)

In hexahydrate of gadolinium (III) chloride, six H₂ O molecules and 2Cl- ions coordinate to the metal
cation resulting in a coordination number of 8.

T
GdCl3.6H2O = [GdCl2(H2O)6]+ Cl-

N
31. Correct option is (d)

I
The configurations and magnetic moment are
M+3 fn µ observed µ calculated

O
Gd+3 4f 7 7.97 7.94
Lu+3 4f 14

P
0 0
Tb+3 4f 8 9.8 9.7
Sm+3 4f 5 1.64 0.85

A
Eu+3 4f 6 3.36 0

• Gd+3 (f7) and Lu+3 (f14) follow spin only formula 5

𝑛(𝑛 + 2) µ=

T
• While for remaining µ(eff) = g 5 J(J + 1) is valid

32. Correct option is (a)

N
Ac shows only +3 oxidation state because it achieve nearest noble gas configuration of Rn.
Lr shows only +3 oxidation state because it achieve fully filled [Rn] 5f 14 configuration.

UA
33. Correct option is (c)
a.Lu+3 = Completely filled f14 configuration thus, no f-f transition.
b. For Tb+3, the main emissions responsible are 5D4 → 7Fn ( n = 6 - 0) with 5D4→ 7F5 the

Q
strongest, whilst for Eu+3 , 5D0 → 7Fn are seen (n= 4-0) with the transitions to 7F0 , 7F1 and 7F2
the most useful
c. Overlapping J levels are observed for Sm +3

34. Correct option (a)

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241 82

The value of 𝜇9:: can be calculated using formula; 𝜇9:: = 𝑔 𝐽(𝐽 + 1)

Where,
𝑆 𝑆 + 1 − 𝐿 𝐿 + 1 + 𝐽(𝐽 + 1)
𝑔=1+
2𝐽(𝐽 + 1)
10
for f configuration

Here, S = 2, L = 6 and J = 8,

N T
I
Solving for 𝑔 will give, 𝑔 = 1.25
Hence 𝜇9:: = 10.6

PO
T A
A N
Q U
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 7
Chemical Bonding
Hints & Solutions

1. Correct answer: (b)

Explanation: Both XeF4 , ICl4- have 2 lone pair of electron. The shape being square plannar with hybridization sp3d2

2. Correct answer: (c)

Explanation:

All three molecules have same hybridization sp3

Bond angles and bond distances are different, shapes are bent, pyramidal and tetrahedral respectively.

3. Correct answer: (b)

Explanation: SO4 -2 is tetrahedral.

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1
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207 |Chemical Bonding

T
IN
4. Correct answer: (a)
Explanation : Taking x-axis as internuclear axis.
N2 = σ21s σ21s* σ22s σ22s* π22py π22pz σ22px
O2+ = σ21s σ21s* σ22s σ22s* π22px π22py σ22px π1*2pz π1*2py

PO
5. Correct answer: (b)
Explanation: I-3 is linear with highest number of lone-pairs ( 9 lone-pairs )
TA
N

6. Correct answer is (a)

A
U
Q

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207 |Chemical Bonding

Number of electrons in antibonding MO of NO = 1

No electron is present in antibonding MO OF CO=0
So, number of antibonding MO is zero .

7. Correct answer is (b)

-

T
(A) N3 → linear, XeF₂, → Linear
+ -
(B) [ClF2] → Bent, [ICl2] → Linear
- 2-
(C) [ICl4] , → square planar, [PtCl4] → square planar

IN
(D) XeO3→ Trigonal pyramidal, SO3→ Trigonal planar

8. Correct option is (c)

9. Correct answer is (d).

PO
Size of d-orbitals decrease with decrease in size of element. The decreasing order of size is
TA
Si > P > S > Cl.
Therefore decreasing order of size of d-orbitals is Si> P > S >Cl.

10. Correct answer is (d).

Number of lone pair of electrons = 9
N
A

11. Correct answer is (d).

Smaller the internuclear distance between two atoms, stronger will be the π bonds. The increasing or
due of inter nuclear distance is Cl-O < S-O <P-O <Si-O Therefore strength of pπ –dπ bonding is Cl-O>
U

S-O>P-O>Si-O

12. Correct answer is (d)

Q

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207 |Chemical Bonding

T
IN
Therefore, order of dipole moment is H 2O > NF3 > NH3

13. Correct answer is (d)

-
CO3 2 : sp²-hybridization (Trigonal planar)
SO3 : sp²-hybridization (Trigonal planar)

PO
XeO3 :sp-hybridization. (Trigonal pyramidal)
NO3 :sp²-hybridization (Trigonal planar)
TA
- -
CO3 2,SO3, and NO3 2, have planar structure.
N

14. Correct answer is (c)

40. When a hydrogen atom is placed in an electric field along the y-axis. The magnetic moment i.e
electron density will he oriented along y-axis and therefore the orbital that mixes most with the ground
state 1s orbital is 2py .
A

15. Correct answer is (d)

Among given compounds NF3 is not hydrolyse easily because, the more electro negative F atom
U

strongly attracts the electrons present in N atom and they are no longer available to get hydrolysed.
BiCl3 is not readily hydrolysed by water to give BiOCl.
BiCl3 +H2O→ BiOCl + 2HCl
Q

But BiOCl redissolve in conc. HCI to produce BiCl, after evaporation. It has quasi molecular structure.
PCl3 is easily hydrolysed by water.

16. Correct answer is (a)

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207 |Chemical Bonding

T
IN
17. Correct answer is (c)
-
More than 8 electrons in the valence shell of P in [PF6]

18. Correct answer is (b)

B2 = σ21s σ21s* σ22s σ22s* π12px π12py

PO
456
B.O. = =1
7
If an electron is added to B 2, then will go bonding to π -orbital.
;56
B.O. becomes= = = 1.5 .
7

19. Correct answer is (b)

Li = 1s2 2s1 2p0
TA
+2
Li 1s1 2s0 2p0 (hydrogen like)
+2
Be = 1s2 2s0 2p0
-
H = 1s2 2s0 2p0
Li has one electron in 2s and no electron in 2p hence the energies of 2s and 2p orbitals will be
different.
N

Li+2 has only one electron in 1s1 hence will have no screening effect
Therefore, 2s and 2p will have same energies.

20. Correct answer is (c)

A

If a homonuclear diatomic molecule is oriented the z-axis, then linear combination of p z orbitals of two
atoms form σ-orbitals.
U

The molecular orbitals formed by linear combination of p x or py orbitals of two atoms is π.

21. Correct answer is (c)

-
Q

+
Number of valence electrons in I 3 central atom are 8 while in I3 are 10 and hence the geometries are
tetrahedral and trigonal bipyramidal.

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207 |Chemical Bonding

T
22. Correct answer is (b)

IN
(I) SCl2 b.p.=2 l. p. =2 Stearic number (S)=4
-
(II) I3 b.p. = 2 l. p. =3 (S)=5
+
(III) I3 b.p. = 2 l. p. =2 (S)=4
-
(IV) ClF2 b.p. = 2 l. p. =2 (S)=4

PO
Shapes of species are
TA
23. Correct answer is (b)
SbPh5 is square pyramidal while PPh5 is trigonal bipyramidal.
This is due to size of central atom. 'Sb' is bigger than 'P', therefore favour square planar while small
sized 'P' favour trigonal bipyramidal
N
A

24. Correct answer is (c)

A maximum five 'd' orbitals can form bonding with each other
U
Q

25. Correct answer is (a)

In the formation of SF6 the following atomic orbitals are involved.

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207 |Chemical Bonding

The 3s, 3p of 's' and 2pz of 'F' are mixed to give ten MO's. Calculations indicate that four of orbitals will
be bonding and four of orbitals will be bonding and four will be antibonding. The remaining two will be
non-bonding. There are 12 electrons to be filled in ten MO's. The first two can enter 1a 1 and the next six
can in it. The remaining four fill the non-bonding pair of orbitals. Thus it gives 1a 2 1t6 e4 gives as
configuration. This gives the molecular diagram of SF 6, as

T
IN
26. Correct answer is (a) & (c)

PO
A δ -bond involves the overlapping of eight lobes by facewise overlapping. This can take place by ‘d’-
orbitals and ‘f’ orbitals. In 'd' orbitals following two possibilities are
TA
Case-I: d x2-y2 + d x2-y2 → δ bond
Case-II: d xy + d xy → δ bond.
N
A

Both cases are reported in many examples like.

Case-I is reported in dimeric copper acetate (II)
-
Case-II is reported in Re2Cl8
U
Q

Hence, options (a) and (c) are correct

27. Correct option is (a)

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207 |Chemical Bonding

The structure of S2O show resonance as

T
Hence, the probable O.S. of 'S' are (0 and +2) from structure 'T' and (-2 and +4) from structure II.

IN
28. Correct option is (b)
+ +
[Br3] = Br. Br2
;>75?
S= 7
= 4 = sp³
Therefore, geometry = tetrahedral.

PO
+
[I5]

geometry = trigonal bipyramidal, sp³d hybridisation)

29. Correct option is (c)

TA
XeF2 ; S = steric number = @AB
B
=5
Therefore, G = Geometry = trigonal bipyramidal (TBP)
N

Hence, the shape linear Xe

A

XeO2F2 s= @AB
B
=5 Geometry =TBP
U
Q

30. Correct option is (a)

The structure of C3O2 (carbon suboxide) is

4σ and 4π

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207 |Chemical Bonding

31. Correct option is (b)

In IF7 and Fe(CO)5 , the rearrangement is so fast that axial and equatorial ligands cannot be
differentiate by spectroscopy). The molecules in which rearrangement leads to configuration which are
chemically equivalent are called fluxional molecule.

T
32. Correct option is (c)
+
The Mo configuration of N2and N2 are

IN
2 2 2 2 2
N2 = σ2s σ2s* π2px π2py σ2pz
𝟖5𝟐
B.O.= =3
𝟐
+ 2 2 2 2 1
N2 = σ2s σ2s* π2px π2py σ2pz
𝟕5𝟐

PO
B.O.= =2.5
𝟐
N₂→ N₂ (Bond order decreases)

33. correct option is (c)

TA
N

3-
Note: The lone pair of [SbCl6] is steriochemically inactive and that of XeF6, is boderline of
stereochemically active and stereochemically inactive condition.
A

34. Correct option is (d)

C2 = valence electron = 12
U

2 2 2 2 4
C2 = σ1s σ1s* σ2s σ2s* π2p
Q

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 QUANTA POINT
207 |Chemical Bonding

T
IN
PO
35. Correct option is (b)
B = σ21s < σ21s* < σ22s < σ22s* < π12px = π12py < σ2px
TA
Centre of symmetry No centre of symmetry

36. Correct option is (b)

N

4>E>?
[TeF5]-1 = =6
7
Number of lone pair = 1
A

Structure is square pyramidal

U
Q

37. Correct option is (c)

The structure of [Al(BH 4)3] is

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207 |Chemical Bonding

T
Thus, number of 3c-2e bond is equal =6

IN
38. Correct option is (c)

PO
Each bond angle is 60°
39. Correct option is (c)
TA
Oxidation state of gold in this complex is 2

40. Correct option is (a)

N

Number of triangular anti-prism are 8 , in icosahedron it is 20 and in tricapped trigonal prism (capped
on square faces) it is 14
A
U

41. Correct option is (a)

Q

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 QUANTA POINT
207 |Chemical Bonding

T
IN
42. Correct option is (a)

PO
;>4×G>? 74
ClO3- = = = 3+1 =4 sp3 (Tetrahedral)
H H

H>4×7 74
TA
Xe= H
= H
=3+1=4→sp3 (Tetrahedral)
N

4>4×G 76
SO3 = = =3→sp2 (Trigonal planar)
H H
A
U

43. Correct option is (d)

4>E>;×G G7
SNF3 = = = 4 = sp3 = Td
H H
H>4×7>;×7 G6
XeO2F2 = = == =4+1= 5=sp3d→TBP
Q

H H

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207 |Chemical Bonding

44. Correct option is (a)

According to Bent's Rule, 'more electro negative element occupy axial position in trigonal bipyramidal
geometry.

45. Correct option is (b)

T
According to Allred-Rochow, electronegativity can be given as
0.3590𝑍NOO
𝑋= + 0.744

IN
r7
where r2 = covalent radius.

46. Correct option is (a)

The correct structure of dinuclear anion [I 2(OH)2O8]-4 with two bridging oxo groups, is as shown below

47. Correct option is (b)

PO
TA
According to MOT
NO→ σ21s < σ21s* < σ22s < σ22s* < π22px = π22py < σ22pz < π1*2pz = π*2py < σ2pz*
10 - 5
Bond order of NO = 2
= 2.5
10 - 4
Bond order of NO+ = =3
2
Hence, as bond order increases v (NO +) increases and NO+ → EPR inactive as no unpaired electron
N

In NO+ HOMO is σ2pz that is close to more electronegative atom (Oxygen).

48. Correct option is (c)

A

The energy difference between π* and σ* is very small and it absorbs at λ max =520 nm. When I2 is
dissolved in a non-donor solvent, there is no effect on energies of π* and σ* of I 2 and it absorbs at λ max
=520 nm. Interaction of solvent donor orbital with the σ* ,I 2 LUMO result in a lower occupied bonding
orbital and a higher uncoupled bonding orbital As a result the π*→ σ* transition for the I 2 donor adduct
U

is shifted higher in a energy and lower wavelength.

Hence, electron donor < weak donor < strong donor
49. Correct option is (d)
Q

(i) The electronegativity of CF 3 is less than NF2

(ii) NH2 group has less electronegative than NF 2
(iii) OH group has less electronegative than NF 2
(iv) CH3 and C2H5 group have almost similar value of electronegativity.
50. Correct option is (c)

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 QUANTA POINT
207 |Chemical Bonding

T
51. Correct option is (c)
According to MOT the LUMO of CN - and O2 respectively are πg and σu

IN
52. Correct option is (a)
As bond order increases, stretching frequency increases.
O2+= 2.5 , O2 = 2, O2- =1.5 O2+2 = 1

PO
53. Correct option is (b)
O2- → σ21s < σ21s* < σ22s < σ22s* < π22px = π22py < σ22pz < π2*2px = π1*2py
O2 → σ21s < σ21s* < σ22s < σ22s* < π22px = π22py < σ22pz < π1*2px = π1*2py
6-3
Bond order of O2- = = 1.5
2
6-2
Bond order of O2 = =2
2
Bond order of O2 is more than O2- thus, bond length of O2- is more than O2.
TA
• The superoxide ion O2- is able to abstract proton from weak acids. It reacts with a proton or
proton donor to form HO2
O2- +HX → HO2 + X-
• The superoxide ion O2- is a stronger oxidising agent than O2
• O2- does not possess dipole moment thus, it is IR inactive.
N

54. Correct option is (d)

The MO diagram of benzene is
A
U

Thus both HOMO and LUMO are doubly degenerate.

Q

55. Correct option is (a)

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 QUANTA POINT
207 |Chemical Bonding

T
IN
56. Correct option is (a)

PO
The bond order can be calculated by molecular orbital theory
Molecule Bond Order
+
NO 3
O2+ 2.5
N2+ 2.5
+
C2 1.5
NO = σ 1s < σ 1s* < σ 2s < σ 2s* < π22px = π22py < σ22pz
+ 2 2 2 2
TA
O2+ = σ21s < σ21s* < σ22s < σ22s* < π22px = π22py < σ22pz < π1*2pz = π1*2py
N2+ = σ21s < σ21s* < σ22s < σ22s* < π22px = π22py < σ12pz
C2+ = σ21s < σ21s* < σ22s < σ22s* < π22px = π12py
8-2
Bond order of NO+ = =3
2
8- 3
Bond order of O2+ = = 2.5
2
N

7- 2
Bond order of N2+ = 2
= 2.5
5- 2
Bond order of C2+ = 2
= 1.5
A

57. Correct option is (d)

According to VSEPR theory as the size of central atom increases bond angle decreases. Hence, Bond
U

angle of NF3 > SbCl3 ,SbF3

Now, in between SbCl3 and SbF3 . 'F' is more electronegative and pull the bond pair towards itself due
to which bond angle FSbF decreases. The experimental bond angles are
Q

58. Correct option is (c)

•VSEPR theory is applicable for main group elements not for transition metal elements. Hence [PtCl 4]2-
can't be explained.

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207 |Chemical Bonding

•Also VSEPR theory can not explain the structure of molecules which have stereochemically inactive
lone pair. In [TeCl6]-2 there is one such lone pair. It is perfectly octahedral and hence can't be described
by VSEPR theory.
•PF3 is having lone pair and is trigonal pyramidal according to VSEPR theory. And SF 6 is perfectly
octahedral having no lone pair on 'S'.

T
59. Correct option is (b)
In B2 and C2 , s-p mixing takes place thus, energy of 2σg is greater than 1πu whereas there is no s-p

IN
mixing takes place in O2, thus, energy of 2σg, is less than that of 1πu

60. Correct option is (c)

SO32-
Valence electrons = 6

PO
6–2–2=2
↓ ↓ ↓
1σ 2σ [one
1π 2O- lone
1O pair]
Hybridisation=1+2+1 = 4 i.e. sp 3
TA
Shape = Trigonal pyramidal
BrF4-
Valence electrons = 7
7 – 3 = 4 + F-
N

↓ ↓ ↓
3σ [Two [One
3F lone coordinate
A

Pair] bond]
Hybridisation = 3 + 2 + 1 = 6 i.e. sp 3d2
U

Shape = Square planar

Q

CO32-
Valence electrons = 4
4-2-2=0
↓ ↓
1σ 2σ
1π 2O-

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207 |Chemical Bonding

1O
Hybridisation = 1 + 2 = 3 i.e. sp²

Shape = Trigonal planar

T
61. Correct option is (a)
Allred-Rochow electronegativity (χAR):

IN
χAR = (3590 z*/r2)+ 0.744
where, r = covalent radius (in pm), z* =effective nuclear charge

62. Correct option is (c)

Firstly draw the molecular orbitals. Then add electrons and count the number of bonding and anti

PO
bonding electrons.
The bond order of a bond is half the difference between the number of bonding and antibonding
electrons.
Bond order = 1/2 [Bonding-Anti-bonding]
The C-C sigma bonds.
Each C-C σ bond is a localised. It has 2 bonding electrons and zero non-bonding electrons.
σ Bond order = ½ (B-A) = ½ (2-0) = 1
TA
The C-C π bond.
Benzene has 6 molecular π -orbitals of these, three are bonding and three are anti-bonding. The six π -
electrons go into the three bonding orbitals.
π Bond order= ½ (B-A) = ½ (6-0) = 3
This is the π bond order for 6 C-C bonds for one C-C π bond, Bond order = 3/6 =0.5
For a single C-C bond in Benzene, the total Bond Order σ + π = 1+ 0.5 =1.5
N

63. Correct option (c)

Applying VSEPR theory we can easily find out structures of the molecules
A

𝑩𝒓𝑭𝟑 has 3 bond pairs and 2 lone pairs, hence it’s geometry is TBP but structure is T-shaped
𝑭𝑪𝒍O𝟐 has 3 bond pairs and 1 lone pair, hence its geometry is Tetrahedral but structure is pyramidal.
[𝑿𝒆𝑭𝟓]− has 5 bond pair and 2 lone pairs, hence its geometry is Pentagonal bipyramidal but structure is
U

pentagonal plannar.
[𝑪𝒍𝑭𝟒]− has 4 bond pairs and 2 lone pairs, hence its geometry is Octahedral but structure is square
plannar.
𝑿𝒆𝑶𝟑 has 3 bond pairs and 1 lone pair, hence its geometry is Tetrahedral but structure is pyramidal.
Q

64. Correct option (a)

The molecular structure are as follows

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207 |Chemical Bonding

T
IN
65. Correct option (a)
Electronic configuration of Hg = 5d 10 6s2

PO
For Hg+ = 5d10 6s1
In order to form [Hg2]2+ there will be one sigma bond between two Hg + atoms.
TA
N
A
U
Q

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 8
Acids and Bases
Hints & Solutions
1. Correct answer is (b).

Higher the charge and smaller size of the central metal cation increases the acidic strength of hydrated complex be-

cause it polarizes O-H band of H2O easily.

In [Sc(H2O)6]+3 , Sc is in +3 oxidation state and has smallest size.

Therefore, in size of depositive ions increase in the order

[Sc(H2O)6]+3 > [Ni(H2O) 6]+2 > [Mn(H2O)6]+2 > [Na(H2O)6]+

2. Correct answer is (b).

nH2O+ Cl-  [Cl(H2O)n]-

If negative end of O-H dipole approaches the Cl- ion, then there will be repulsion.

ion dipole interaction positive and of OH dipole approaches the Cl- ion and form Cl(H2O)n]-

Not stabilized. Thus H2O does not behave as a base 6H2O+Mg+2  [Mg(H2O)6]+2

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207 |Acids & Bases

In this reaction Mg+2 behave as lewis acid and H 2O behave as a ligand or lewis base.

3. Correct answer is (b).

4. Correct answer is (c)

CH3COOH+C5H5N : → CH3COO- + C5H5NH+ (solvo cation)

T
CH3COOH+H2SO4 →CH3COOH2+ + HSO4- (solvent anion)
HClO4+H2SO4 →ClO4-+H3SO4+ (solvent cation)→ [weak acid]
SbF5+2HF→ [SbF6]+H2F+ →[strong acid]

IN
5. Correct answer is (c)
HClO4 behave as an acid in H2SO4 ,because HClO4 contain higher dissociation constant than that of
H2SO4.

PO
HClO4, pKa, value -9
H2SO4 , pKa value -3,
HNO3 , pKa value -1,
CH3COOH , pKa value 4.7.
pKa value of HClO4 > pKa value of H2SO4
TA
6. Correct answer is (d)
For aqua ion complex , acidity is more when (i) small size
(ii) greater charge.

7. Correct option is (b)

(I) 2[Fe(CN)6]3- +H2O2+ OH- → 2[Fe(CN)6] 4- + 2H2O +O2
N

(alkaline medium) Reduction

(II) 2[Fe(CN) 6] 4- +2H+ +H2O2 → 2[Fe(CN)6] 3- + 2H2O
(acidic medium) Oxidation
(III) 2MnO4 +6H +5H2O2 → 2Mn2+ +8H2O+5O2
- +
A

(acidic medium) Reduction

8. Correct option is (a)

U

In reaction (i)Water acting as an oxidant oxidizing Ca to Ca +2 getting itself reduced to H₂.

In reaction (ii) Water act as Lewis acid accepting elecron from Cl - which act as a ligand.
In reaction (iii) Water act as Lewis base donating electron to Mg +2 .
Q

In reaction (iv) Water acting as an redutant reducing F to F -.

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207 |Acids & Bases

i) H₂O + Cl-1 = [Cl(H₂O)n] -1

Where, Cl = Base, H₂O = Acid
iii) 6H₂O +Mg+2 → octahedral complex shown below

T
IN
9. Correct option is (c)

PO
TA
Separation of XeF4 from a mixture involves preferential complexation of XeF 2 and XeF6 and XeF4 is
then removed in vacuum
N

10. Correct option is (b)

N2O4
(A) NOCl +Sn [NO]++ Cl- ([NO]+ is not majore product )
(B) NOCl+ AgNO3 → AgCl + N2O4 (Neutralization reaction)
A

(C) NOCl +BrF3→ [NO]+ + BrF4-

(D) NOCl+ SbCl5 → [NO]+ + SbCl6-
U

11. Correct option is (a)

KF +BrF3 → K+ + BrF4-
SnF4 +2BrF3 → 2[BF]+ +[SnF6]-2
Q

SbF5 +BrF3 → BrF2+ + [SbF6]-

This only KF increases the concentration of BrF 4- in BrF3.

12. Correct option is (c)

Due to more acidity of HCl it will undergo more ionization. Hence, concentration of Cl - will be
maximum.

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207 |Acids & Bases

13. Correct option is (d)

Cl2 → solvolysis and disproportionation of Cl 2 in NH3
Cl2 +2NH3 →NH2Cl + NH4+ + Cl-
S8 → undergoes disproportionation in liquid NH3
5S8 +16NH3 → 4SN- +4 S𝟔(𝟐 + 12NH4+
CH3COOH acts as strong acid in NH 3

T
CH3COOH+NH3 → CH3COO- +NH4+
Molecules that do not behave as acid in water, may behave as weak acids in NH 3
H2NCONH2 +NH3 → NH4+ + NH2CONH-

IN
14. Correct option is (d)
AsF5 + 2HF → [AsF6]- + [H2F]+
PF5 + 2HF →[PF6]- + [H2F]+

PO
BF3 + 2HF → [BF4]- +[H2F]+
BrF3+ HF →[BrF2]+ + [HF2]-
BrF3 acts as base as it donate F - in HF

15. Correct option is (d)

SbF5 + Br → [BrF2]+ + [SbF6]- →Lewis base behaviour of BrF 3
[BrF2][SbF6] + Ag[BrF4]→ Ag[SbF6] + 2BrF3→Neutralization
TA
KF + BrF3 →K+ + [BrF4]- → Lewis acid behaviour of BrF 3
2BrF3 →[BrF2]+ +[BrF4]- → self-ionization

16. Correct option is (d)

A → Cl2 + 2H2O → HOCl + H3O+ + Cl-
B → Cl2 + 2NH3 → NH4Cl+ NH4+ +Cl-
N

Above both reactions are example of solvolysis as well as disproportionation.

17. Correct option is (b)

MnO4- + e- →MnO4-2 (By Na in liq. NH3)
A

Me3CH →Me3C+ (By super acids, only super acids attack C-H bond)
Ag + Au →Ag[AuF4]
H3PO4 +H+→P(OH)4+
U

(This reaction occurs in H 2SO4 because in H2SO4 solvent, H3PO4 acts as a base)

18. Correct option is (b)

Q

SbF5 is strongest acid and PH3 is strongest base.

19. Correct option is (a)

IO3- (aq) + 5I-(aq) + 6H+ (aq) → 3I2(aq) + 3H2O(l)

20. Correct option is (a)

•When aqueous solution of AgNO3 is added to an aqueous solution of KCl, white ppt of AgCl is formed.

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207 |Acids & Bases

KCl+AgNO3 →AgCl + KNO3

White ppt
But in liquid NH3, the direction of the reaction is reversed.
AgCl + KNO3 → KCl+ AgNO3
• NH4Br + KNH2 → KBr + 2NH3
This reaction is neutralization reaction in liquid NH 3

T
Ammonia solutions of alkali metals and alkaline earth metals are strong reducing agents.
Fe(CO)5 +2e- → [Fe(CO)4]-2 + CO

IN
21. Correct option is (c)
2BrF3 + SnF4 →(BrF2)2[SnF6]
Species formed in reaction are BrF 2+ and [SnF6]-2
AuF3 + BrF3 → BrF2+[AuF4]-

PO
Species formed in reaction are BrF 2+ and [AuF4]-

22. Correct option is (d)

This can be explained with the help of HSAB principle.
•Be+2 is hard acid hence favour hard base F -
•Also La+3 is hard acid, thus favour hard base CO 3-2 . Therefore, process B and D are not feasible.
gives
La2(CO3)3 + Bi2S3 La2S3 + Bi2(CO3)3
TA
HA HB ← HA SB
gives
BeF2 +HgI2 BeI2 + HgF2
HA HB ← HA SB

23. Correct option is (d)

HOSO2F + HF → [H2F]+ + [SO3F]-
N

Acid

CH3CO2H+2HF → [CH3C(OH)2]+ + [HF2]-

A

Base

LiF + HF → Li+ [HF2]-

U

(Base)

H2O + HF → H3O+ + F-
(base)
Q

24. Correct option (d)

In first reaction, Xe is acting as electron donor to become [Xe] +, hence as a base.
In second reaction XeF 4 is accepting electron to become [XeF 4]-, hence it is an acid.

25. Correct option (a)

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207 |Acids & Bases

Lewis acidity of silicon halides depends on electronegativity of halide groups

𝑙𝑒𝑤𝑖𝑠 𝑎𝑐𝑖𝑑𝑖𝑡𝑦 L𝑜𝑓
∝ 𝐸𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑒𝑔𝑎𝑡𝑖𝑣𝑖𝑡𝑦
𝑆𝑖𝑋 𝑜𝑓 𝑋
since, electronegativity order is F > Cl > Br > I , thus correct order of lewis acidity is 𝑺𝒊𝑰𝟒 < 𝑺𝒊𝑩r𝟒 <
𝑺𝒊𝑪l𝟒 < 𝑺𝒊𝑭𝟒. Hence Statement (i) is correct.
In statement (ii) SnCl2 is given, which is a Hypovalent compound, having incomplete octet and hence
will behave as Lewis Acid.

T
Aluminosilicates have general formula AlM xSiOy since there is NO H+ ion present thus there is no
chance of Brönsted acidity.

IN
PO
TA
N
A
U
Q

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 9
Bioinorganic Chemistry
Hints & Solutions

1. Correct Option (b)

Vitamin B12 molecule is built-around a Corrin ring containing cobalt (III) atom.

2. Correct answer: (b)

Carboxypeptidase enzyme contains Zn+² ion and it cleaves (hydrolyses) the carboxy terminal amino
acid from a peptide chain.

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207 |Bio-inorganic Chemistry

T
IN
3. Correct answer is (b)

PO
TA
4. Correct answer is (c).
Camptothecin, an quinolone alkaloid, is used as a chemotherapeutic agent in the treatment of leukemia
N
A

5. Correct answer is (d)

U

N₂+ 8H+ +8e- +16 ATP → 2NH3 +H2 +16ADP+16Pi

6. Correct answer is (c).

Q

EPR studies show that,Mn2+ can replace Mg2+ in nucleic acid processing enzymes

7. Correct answer is (d).

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 QUANTA POINT
207 |Bio-inorganic Chemistry

T
8. Correct answer is (a).

IN
Hemoglobin

PO
TA
9. Correct answer is (a).
N
A

10. Correct answer is (c).

U

NAD+←Biological reductant
↓
Flovoprotein
Q

↓
cyt b→ cyt bf → PC

11. Correct answer is (a).

Fe= Hb & Mb cytochromes
Mo= nitrogen fixation
Cu= hemocyanin

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 QUANTA POINT
207 |Bio-inorganic Chemistry

Zn= metalloezymes

12. Correct answer is (b)

Because zinc is a Lewis acid and hence,

T
So, correct option is (b)

IN
However, oxidase are enzyme that catalyse the reduction of O 2→ H2O or H2O2 .
O₂(g) + 4e- +8H+ (inside) →2H2O(l) + 4H+ (outside)

13. Correct answer is (b)

Free heme (i.e. without globular protein chain) it foms 𝜇 -oxodimer) i.e.

PO
µ-oxo-dimer (hematin)

which is unable to bind O2

14. Correct answer is (d)

TA
The coordination geometry of copper (II) in the type I copper protein plastocyanin is distorted
tetrahedral
N
A

15. Correct answer is (a)

U

Nitrogenase enzyme cofactor contains Fe, Mo also known as Iron-molebdenum cofactor.

Q

16. Correct answer is (b)

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 QUANTA POINT
207 |Bio-inorganic Chemistry

Hemerythrin, one iron centre is penta coordinated and other is hexacoordinated and iron exist at
peractive site found in marine invertebrates.

17. Correct answer is (c)

Wilson's disease is caused by excess accumulation of Cu in the body. Thus the reason being low level of
copper-storage protein, ceruloplasmin.

18. Correct answer is (d)

Prolonged use of ZnSO4, for the cure of Zn deficiency, reduces the amount of copper, iron and calcium
levels in body.

19. Correct answer is (b)

l-DOPA, also known as levodopa and l-3,4-dihydroxyphenylalanine, it crosses the protective blood-
brain barrier, whereas dopamine itself cannot. Thus, l-DOPA is used to
increase dopamine concentrations in the treatment of Parkinson's disease and dopamine-responsive
dystonia.

20. Correct answer is (a)

Catalase is a tetramer of four polypeptide chains covering 500 amino acids.
It works as H2O2+ Fe (III)-E → H₂O+O=Fe (IV) - E
H₂O₂+O= Fe(IV) – E+ → H₂O + Fe(III)-E + O₂
The colour arises as Fe(III) changes into Fe(IV).

21. Correct answer is (b)

The chemical reaction involved is shown below:
N2 +8H+ +8e- +16 ATP → 2NH3 +H2 +16ADP+16Pi

22. Correct answer is (c)

Ozone is a diamagnetic gas which is of dark blue coloured due to absorption of red light.
(λ=557 and 602 nm)

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 QUANTA POINT
207 |Bio-inorganic Chemistry

Ozone depletion discovered by J.C. Farman over Halley Bay in Antarctica.

Ozone also show strong absorption in λ =255 UV which is good for earth, it act as a green house ,
sunlight can come in but it can not go out .
'UV-b' is most dangerous, would damage the DNA of all living beings.
Ozone protects earth by keeping it warm .

T
23. Correct answer is (d)
Molybdoenzymes containing Molybdenum as the central metal, since it exists in two stable oxidation

IN
states (IV) and (VI), thus it can transfer oxygen atom to substrate as well as it can abstract oxygen atom
from the substrate.

24. Correct answer is (a)

The movement of iron atom and imidazole side chain of histidine toward the porphyrin plane results in

PO
breaking of some of the salt bridges. The breaking of these salt bridges reduces the strain in hemoglobin
molecule. Therefore, the oxyform of hemoglobin is called relaxed state (i.e., R state). The T form of
deoxyhemoglobin discourages the addition of first dioxygen molecule.
The bonding of one dioxygen molecule to a subunit of hemoglobin reduces the steric hindrance in the
other subunits (due to breaking of salt bridges) and therefore encourages the third as well as fourth
subunits. This is called cooperative mechanism
TA
25. Correct answer is (a)
Total number of π-electrons in microcyclic rings of heme, coenzyme B 12 and chlorophyll is
Heme=11 π electrons in microcyclic ring
Coenzyme B12= 5 π electrons in microcyclic ring
Chlorophyll= 10 π electrons in microcyclic ring
Check-out below images.
N
A
U
Q

Chlorophyll, 10 π electrons in
HEME, 11 π electrons in microcyclic ring
microcyclic ring

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207 |Bio-inorganic Chemistry

T
Vitamin B12, 5 π electrons in
microcyclic ring

IN
PO
26. Correct option (b)
TA
27. Correct answer is (d)
In 1956, in Japan minamata disater had been broken out in coastal area. This is a neurological syndrome
N

caused by mercury pollution. The Hg +2 get converted into MeHg+ by carbonic biomethylation. Which
form strong bonding with thiol(-SH) group of protein having cysteine amino acid. Hence, A, B and C
are correct.
A

28. Correct answer is (a)

Myoglobin is pH independent .
U
Q

Lungs (gills) Hb+ 4O2 → (HbO2) 4

Tissues Hb(O2) 4 +4Mb → 4MbO2 + Hb

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 QUANTA POINT
207 |Bio-inorganic Chemistry

pH dependent shown by hemoglobin is known as Bohr effect (binds one H + for every dioxygen
molecules)

29. Correct answer is (a)

Oxyhemocyanin stables as oxygen carrier.
Carbonic anhydrase

T
Carbonic anhydrase converts CO 2 to H2CO3
Cytochrome P450 oxidizes alkene to epoxide.

IN
Carboxy peptidase A catalyzes the hydrolysis of C-terminal peptide bond.

30. Correct option is (a)

PO
The carbonic anhydrase enzyme that catalyst the rapid interconversion of carbon-dioxide and water to
bicarbonate and protons (and vice versa).
TA
CO2+H2O→H2CO3 (in tissue high CO2 concentration)
HCO3- + H+→H2CO3→→CO2 + H2O (in lungs and nephronse of kidney)
Hydration occur in blood at high pH values.
Dehydration occur in lungs at low pH values.
Carboxypeptidase A is a pancreatic exopeptidase that hydrolise peptide bond of C terminal.
N
A

Where, Rʹ =Arg, Lys, and Ornithine

31. Correct answer is (a)
U
Q

Deoxy . Hb Oxy Hb
Fe+2 HS Fe+2 LS

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 QUANTA POINT
207 |Bio-inorganic Chemistry

t2g4 eg2 t2g6 eg0

Fe is above the plane which Fe is fitted well inside the plane thus
tends to increase the Fe-N distance . reducing Fe-N bond distance.

32. Correct option is (a)

Oxy-hemocyanin are proteins that transport oxygen throughout the bodies of some invertebrate animals.

T
These metalloprotein contain two copper atoms that reversibly bind a single oxygen molecule (O₂).
The total of six coordinated imidazole units of histidine present in the active site of oxy-hemocyanine.

IN
33. Correct option is (a)

PO
Myoglobin is found in tissue and store the oxygen in tissue transported by Haemoglobin ,it contain
high-spin five coordinate Fe(II), reacts readily & reversibly with O 2 to produce a low-spin Fe(II)-O2
TA
complex [ storage of O 2]
Cytochrome P450 haem containing monooxygenases, catalyses the insertion of oxygen in substrate ,
oxidation of 5-exoposition of camphor, oxidation of alkene etc.
N

34. Correct option is (b).

A

In deoxyhaemocyanin Cu is in Cu(I) state i.e. have d 10s0 configuration therefore it colourless and
diamagnetic. Diamagnetism is due absence of unpaired electrons and colourless is due to no d-d
transition as all the orbitals are filled.
U
Q

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 QUANTA POINT
207 |Bio-inorganic Chemistry

35. Correct option is (d).

O2 in free state, 𝜈()( = 1580 cm-1 when O2 bound to hemoglobin, it makes strong coordinate bond with
Fe of hemoglobin and O-O bond strength decreases slightly, so in oxy-hemoglobin, 𝜈()( = 1100 cm-1.

36. Correct option is (a).

T
Hemoglobin - O2 trasnport & iron
Cytochrome b- Electron carrier & iron
Vitamin B12- Group transfer reactions & cobalt

IN
Hemocyanin - O2 transport & copper

37. Correct option is (a)

Absence of globin chain following reaction is occur
PFeII + O2 →PFeII-O2 + FeIIP → P-FeIII-O-O-FeIII-P

PO
234 (66) III
2PFeIV =O PFe -O-FeIII-P
reversible
(Haematin)

38. Correct option is (c)

Pt- complex used as anticancer drug
Au-complex used as anti arthritis agent
TA
Gd-complex used in MRI as contrast agent due to their strong paramagnetic behaviour
Li-complex used in Maniac depression

39. Correct option is (a)

Structure of m-porphyrine complex can be shown as
N
A
U

Here, (A) represents = five membered ring

(B) represents = six membered ring.
Q

Thus, these are four 5-membered ring and four-6-membered ring.

40. Correct option is (a)

cis-platin modifies the DNA structure by binding to N-7 nitrogen atom of guanine base.

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 QUANTA POINT
207 |Bio-inorganic Chemistry

T
IN
41. Correct option is (a)
In carbonic anhydrase OH group first attack on CO 2 and then CO2 interact with Zn.

PO
TA
N

Here, step (2) shows attack of OH group with CO 2, the product formed after step (3) shows later
interaction of CO2 with Zn metal.
A

42. Correct option is (a)

U
Q

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 QUANTA POINT
207 |Bio-inorganic Chemistry

T
IN
Number of inorganic sulfur (sulfide) which do not belong to protein chain in ruberdoxin, 2-ferredoxin
and 4- ferredoxin are 0, 2, 4 respectively.

PO
43. Correct option is (b)
Co-enzyme B12 catalyses dehydration, 1, 2-carbon shift reaction in organic substrates and conversion of
ribonucleotide to deoxyribonucleotide.

44. Correct option is (c)

Metallothionines → Cystein rich protein
Plastocyanin →Electron Transfer
TA
Ferritin→ Iron storage
Chemotherapy→ Carboplatin

45. Correct option is (b)

Heme A → Iron porphyrin →Colour due to π-π* water splitting enzyme contains bridged Mn 4 cluster
N
A

[Cr(H2O)]+2 → t32g 1
g → Tetragonal
e elongation

46. Correct option is (a)

U

In oxyhemerythrin ῡO-O = 850 cm-1

In oxyhemoglobin ῡO-O = 1100 cm-1
Q

47. Correct option is (a).

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T
IN
48. Correct option is (b)
Metallothioneins are cystein rich, low molecular weight protein. Due to soft sulfur centre they prefer to
bind.

49. Correct option is (a)

PO
Both deoxyhemerythrin and deoxy hemocyanin are O 2 transport protein in biological system. Both
contain two metal ion at active site and they bind only O 2 per active site.

50. Correct option is (c)

Cytochrome-c shows redox reaction and it is an essential component of electron transport chain.
whereas it is carriers of one electron and does not bind oxygen
TA
51. Correct option is (c)
In oxyhemerythrin, both the Fe are present as Fe(III) and there is presence of hydrogen bonding and
dioxygen bind to only one Fe.

52. Correct option is (d)

Cubane like ferredoxin is Fe4S4 . It has four inorganic sulfide which can be removed by treatment with
N

acid.
H+
Fe4S4 Fe4+8 + 4H2S
A

53. Correct option is (d)

The Cu ion is essential that can not be replaced by other metal atom while retaining activity. On the
other hand, the Zn+2 ion can be replaced by other divalent metals atom such as Co or Cd with retention
U

of most of the activity.

54. Correct option is (d)

Q

(1) In oxygenation of hemocyanin each Cu atom is oxidized by one.

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(II) It becomes intense blue from colourless due to LMCT (O 2-2 to Cu+2)
(III) O2 is reduced to O2-2 because each Cu is oxidized by one.
(IV) The O2-2 binds to two Cu atoms in the µ-ղ2 : ղ2 manner.

55. Correct option is (a)

T
IN
Trans effect of Cl - > NH3
In blood it stays in equilibrium with cis-[Pt(NH3)2Cl(H2O)]+

PO
In DNA stand, cis-platin binds to two adjacent guanin bases (Not to cytosine bases)

56. Correct option is (a)

TA
N
A

57. Correct option is (a)

Oxymyoglobin → O2- →1105 cm-1
U

Oxyhemocyanin → ղ2 : ղ2O2-2 →803 cm-1

Oxyhemerythrin → HO2- → 844 cm-1
Q

58. Correct option is (c)

Siderophores/siderochromes are small, high-affinity iron-chelating compounds secreted by micro
organisms such as bacteria and fungi and serving to transport iron across all membranes.

59. Correct option is (d)

(P) Dichlorodifluoro methane →(iv) Ozone layer depletion
(Q) Sulfadiazine→ (iii)Antibacterial

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(R) Cortisone→ (i)Anti-inflammatery

(S) Hexachlorobenzene→ (ii)Insecticidal

60. Correct option is (c)

Cytochrome P-450 is a membrane bound metalloenzyme. The function of most cytochrome P-450
enzyme is to catalyze the oxidation of organic substrate. In the active site of cytochrome P-450, iron is

T
in +3 oxidation state and it is in octahedral geometry whereas the basal plane is composed of four N
atoms from the porphyrin ring, fifth position is occupied by a cysteine moiety and sixth position is

IN
occupied by H2O molecule.

61. Correct option is (d)

PO
Coenzyme Vit-B12 was the first organometallic compound discovered in living systems. This coenzyme
catalyses 1, 2-rearrangement.
TA
•Coenzyme B12 readily accepts a methyl group or hydroxyl methyl group (bound to Co) that can be
transferred to add a carbon to a substrate
N
A

•Coenzyme B12 reduces -CH(OH) group to –CH 2 group

62. Correct option is (b)

U

•Both oxymyoglobin and cytochrome P450 contain dianion of protoporphyrin-IX.

•Oxymyoglobin has fifth ligand bonded to metal centre from protein hackbone but in cytochrome P 450
one S-atom of cysteine is coordinated instead of histidine from protein backbone.
Q

•Both contain single active site [Fe (III)]

63. Correct option is (a)

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T
Procaine is a local anesthetic drug of aminoester group. It is used primarily to reduce the pain of
intramuscular injection of penicillin.

IN
Warfarin is used as an anticoagulant. It is commonly used to treat blood clots such as deep vein

PO
thrombosis and pulmonary embolism and to prevent stroke in people who have atrial fibrillation values
heart diseases as artificial heat value.
TA
Cefalexin, also spelled cephalexin, is an antibiotic that can treat a number of bacterial infections. It kills
gram-positive and same gram-negative bacteria by dissrupting the growth of the bacterial cell wall.
Cefalexin is a beta-lactam antibiotic within the class of first-generation cephalosposins.
N

64. Correct option is (b)

In oxymyoglobin, Fe+3 present in low spin. Thus, have configuration t 2g5 eg0 i.e one unpaired electron.
[Fe(ox)3]3-
Fe+3 = 3d5
A
U

(B) [Fe(CN)6]-3
Fe+3 → 3d5
Q

(C) [NiCl4]2-
Ni+2 = d8 = t2g4 eg4
2 unpaired electron

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(D) [Cu(NH3)4]2+
Cu+2 = t2g5 eg4
1 unpaired electron

65. Correct option is (a)

(A) Ni present in coenzyme F 450 (III) which catalyzes the release of methane (Y) in the final step of

T
methanogenesis.
(B) Zn present in carbonic anhydrase (I) which catalyses the hydration of CO 2 into H2CO3 (Z).

IN
(C) Mo present in Xanthine oxidase (II) which catalyzes the oxidation of Xanthine to uric acid (X).

66. Correct option is (d)

PO
It is an orally active antitumor agent. Its action seems to be similar to that of Cisplatin, but with the
added feature that its ligands protect it from reaction in digestive system and allow it to be absorbed into
TA
blood stream.
•Glutathione (GHS) is capable of preventing damage to important cellular components caused by
reactive oxygen species.
N

has promising anticancer activity as it binds to GSH and when followed by oxidation, promotes binding
A

to guanine in DNA.
U
Q

shows anti-metastatic action as instead of binding with DNA, it interacts with actin type proteins on cell
surface or with collagens of extra-cellular matrix, which leads to reduced mobility of invasive cancer
cells,

67. Correct option is (a)

The molecular orbital diagram for binding of O 2 to myoglobin is

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T
IN
PO
this is responsible for the formation of ϭ bond and the orbitals involved for its formation are π* of O 2
and dz2 of Fe(II)

68. Correct option is (d)

In the catalytic cycle of cytochrome P 450, peroxo complex [(porphyrin)Fe III(OOH)] undergoes
protonation which leads to removal of one oxide ion as water via heterolytic O-O cleavage to form
oxyferryl complex with one electron having been oxidized from π -HOMO of porphyrin ring leaving it
TA
as a radical cation i.e. [(porphyrin)+●FeIV(O)]

69. Correct option (c)

Zeolite is used for capturing CO 2,
Indium tin oxide (ITO) is a form of perovskite used in solar cells.
LiCoO2, Lithium cobalt oxide is a dark blue or bluish-gray crystalline solid, and is commonly used in
N

the positive electrodes of lithium-ion batteries

Pt alloy is used in fuel cells. Pt is used as the catalyst for both the hydrogen oxidation reaction (HOR)
occurring at the anode and the oxygen reduction reaction (ORR) at the cathode.
A

70. Correct option (a)

Biological function of Hemerythrin and Hemocyanin is O 2 transport.
U

Cytochrome P450 and Tyrosinase are Oxygenase

Rieske Protein and Azurin are used for electron transfer.

71. Correct option (a)

Q

In 3-iron ferredoxins, the number of sulfide bridges is 3 and cysteinyl ligands are also 3

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IN
72. Correct option (d)
Rubredoxin consist of Fe+2 centre with Tetrahedral geometry, hence statement (A) is correct.

PO
Reduced form of iron is paramagnetic in nature, statement (B) incorrect.
Due to presence of asymmetric electrons in eg orbitals, Jahn-Teller distortion is observed. Thus
statement (C) is correct.
Rubredoxins are [1Fe–4S] clusters, hence statement (D) is incorrect.
TA
N
A
U
Q

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Analytical Chemistry
Hints & Solutions
1. Correct option is (c)
In inductively coupled plasma atomic emission spectroscopy, the plasma gas flows in a helical pattern (i.e. induction
coil) which provides stability and helps to late thermally the outside quartz tube.
2. Correct option is (a)
In thermometric titration, the determinant of the degree to which a reaction will proceed to completion is
the free energy change, which must be favourable. Other condition to obtain best result in thermometric
titration are
• The reaction should be accompanied by sufficient heat change.
• Heat of dilution should be negligible
• Reaction should be a simple one step changed
• Transfer on heat between the titration vessels and its surrounding should be avoided.
3. Correct option is (c)
• The hollow cathode lamp is an excellent, having highest sensitivity, bright line source for most of the elements
determinable by atomic absorption.
• The most advanced and widely used high sensitivity sampling technique for atomic absorption is the graphite
furnace. Detection limit for the graphite furnace fall in the ng/L range for most elements. The sample is
atomised in a very short period of time, concentrating the available atoms in the heated cell and resulting in the
observed increased sensitivity.
4. Correct option is (c)
(a) In spectrofluorimetry the wavelength of incident light can range from 200 nm to 900 nm.
(b) Intensity and colour of the fluorescence of many substance depends upon the pH of solutions.
(c) Since, presence of O2 decreases the fluorescence, thus oxygen is eradicated from the solution.
(d) In flourimetry absorbance of analyte solution is generally kept near to 0.05.

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1
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82

5. Correct option is (a)

• In conductometric titration the end point of titration is determined by means of conductivity
measurements. For example, via conductance/resistance vs volume of alkali plot.
• Amperometric titration refers to a class of titrations in which the equivalence point is determined
through measurement of the electric current produced by the titration reaction.
• Differential pulse polarography is an electrochemical technique where the cell current is

T
measured as a function of time and as a function the potential between the indicator and reference
electrodes.

IN
6. Correct option is (b)
H3PO4 is used in the estimation of Fe(II) with K 2Cr2O7 using diphenylamine sulphonate as indictor to
reduce the electrode potential for the Fe +3 →Fe+2 reaction by stabilising the ferric ion.

PO
7. Correct option is (d)
•Copper (Cu), Silver (Ag) and Gold (Au) are called currency metal (present in native form).
Amperometric titration is the one of the economic technique for estimation of these metals.
• It is a class of titration in which the equivalence point is determine through measurement of electric
current produced by the titration reaction.
• Amperometric titration sensitivity is always higher than than those of spectrophotometeric titrations.
•Amperometric titration does not generally require an indicator.
TA
•Amperometric titration does not require inert atmosphere.

8. Correct option is (a)

Thermometric titration is the method in which a titrant is added stepwise to a vessel containing another
reactant. The enthalpy change on heat of reaction causes a temperature change which when plotted
versus volume of titrant is used to detect the end point.
N

(i) Electron capture detector is a device for detecting atoms and molecules in a gas and is used in atoms
and molecules in a gas and is used in Gas-liquid chromatography.
(ii) The abnormal peak which appears in polographic titration can be supposed by addition of Gelatin.
(iii)In spectrofluorimetry laser may used as source.
A

9. Correct option is (a)

A commonly used measure of the separating efficiency of a column is height equivalent theoretically
U

plate (HETP). It can be determined by van Deemter equation.

HETP depends upon
• Mean carrier gas velocity
Q

• Temperature of the column

• Packing of the column
HETP does not depends upon particle size

10. Correct option is (b)

Electron diffraction is used to get the bond parameters of gaseous samples

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11. Correct option is (c)

(a) Oxalic acid versus potassium permanganate:
End-point is colorless → pink purple (λ max = 525 nm)
(b) Iron (II) versus 1, 10-phenanthroline:
End-point is colorless → Reddish-orange (λ max =512 nm)
(d) Nickel (II) versus Dimethylglyoxime:

T
End-point is colorless Red (λmax = 445 nm)
(c) Cobalt (II) versus Eriochrome Black-T:

IN
End-point is Blue-green → green
(pH=8) (λmax =660 nm) (λmax =600 nm)
Free EBT → Co(II) + EBT complex
Since, color change at end-point is not significant for option(c) which is requirement of the
spectrophotometric titration. Therefore, color monitoring method is not suitable in this case.

PO
12. Correct option is (d)
The peak area of differential thermal analysis is proportional to
(i)mass of the sample
(ii) heat of decompositional phase change

13. Correct option is (b)

TA
Phosphorescence has been observed form a wide variety of compounds and is differentiated from
fluorescence by long lived emission of light after extinction of the excitation source i.e. it done after
fluorescence, if parsists.
Phosphorescence increases when heavy atoms like iodine silver and lead etc. are added.
Phosphorescence increases, when analyte used become immobile.
Hence, both (A) and (B) are correct.
N

14. Correct option is (b)

Correct statement are
•Area of different thermal analysis peak is proportional to amount of sample
•In the thermo gravimetric analysis area of curve is proportional to mass loss
A

•In thermo gravimetric analysis two metal ion simultaneously determine.

15. Correct option is (d)

U

Primary analytical method is isotopic dilution mass spectrometry (not using a reference).

16. Correct option is (c)

Q

Decomposition temperature of CaCO 3 in thermogravimetric analysis will be highest in dynamic

atomosphere due to the presence of 1:1 mixture of O 2 and CO.

17. Correct option is (a)

Coulometry is based on Faraday's law of electrolysis

18. Correct option is (a)

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Inductively coupled plasma atomic spectroscopy (ICP-AES) is an analytic technique used for detection
for trace metals and it is better than AAS for simultaneous determination of metal ions. Hence, option
(d) is correct.
In Atomic Absorption Spectroscopy mercury lamp is not suitable source but hollow cathode lamp (HCI)
are the most common radiation source in Atomic Absorption Spectroscopy and atomizers most
commonly used are flame and electro thermal (graphite). Solid sample is used in determination.

T
19. Correct option is (a)

IN
Thermometric titration is the method in which a titrant is added stepwise to a vessel containing another
reactant. The enthalpy change on heat of reaction causes a temperature change which when plotted
versus volume of titrant is used to detect the end point.
(1) Electron capture detector is a device for detecting atoms and molecules in a gas and is used in atoms
and molecules in a gas and is used in Gas-liquid chromatography.

PO
(2) The abnormal peak which appears in polographic titration can be supposed by addition of Gelatin.
(3)In spectrofluorimetry laser may used as source
20. Correct option is (d)
The residual current in case of DCP is non-faradic current which should be minimum to get the accurate
result. This problem of non-faradic current is overcome by use of DPP in which non-faradic current is
less than DCP. That is why DPP is more sensitive than DCP.
Though the polarograph is different in both cases but it has nothing to do with sensitivity.
TA
21. Correct option is (a)
Increase of intensity of light used increases fluorescence as the fluorescence life-time increases. Molar
absorptivity increases absorbance which further enhances fluorescence.

22. Correct answer (a)

N

For ICP-OES and ICP_MS argon is most suitable gas to generate plasma.
A number of gases cane be used to produce plasma, like Ar, Ne, N 2, O2, H2 , air and mixture of gases.
The physical properties of the gases play a decisive role in this regard. Such important properties are
ionization and dissociation energy, thermal conductivity, atomic weight and chemical reactivity.
A

Argon belongs to the group of inert gases. It means that it does not react with the material during
production of plasma. Its atomic weight - the highest among all plasma gases and it generates high
kinetic energy of the plasma beam. Due to its low ionization potential argon is excellently suitable for
U

generating the plasma beam. However, argon has a low thermal conductivity and a low thermal capacity
which limits its application is some specific areas only.
Q

23. Correct answer is (c)

Gel permeation chromatography is a size exclusion chromatography , that separates analytes on the
basis of size. So, the size difference in fatty acids and low molecular weight peptides is greater so they
can be separated by using gel permeation chromatography.

24. Correct answer is (d)

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In thermogravimetric analysis (TGA) use of dynamic innert atmosphere is decrease with respect to
temperature.

25. Correct answer is (a)

Statements A, B and C are correct.

T
26. Correct answer is (b)
Chemical reactions between analyte and matrix that prevent the atomization of the analyte. One
common one is that Sulfate or phosphates anions will form non-volatile salts with Fe +3 , so its signal

IN
decreases. Can be treated in two ways
1. Releasing agents can add to metal to prevent formation of interference complexes. example EDTA or
8-hydroxyquinoline.

PO
27. Correct answer: (d)
(a) O2 must be removed as it give its own polarogram, due to following reactions,
O2 + 2H+ + 2e- = H2O ; O2 + 4H+ + 4e- → 2H2O
(b) Dropping mercury electrode is the working electrode
(c) Id ∝ C
(d) Residual current need not to be made zero.
TA
28. Correct answer is (c)
N
A
U
Q

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