INORGANIC CHEMISTRY

1. PERIODIC TABLE & PERIODICITY IN PROPERTIES

1.1 (C) (II) The d-block elements have general electronic configuration [noble] (n 1) d1 10 ns0
2
. It is configuration of copper which belongs to d-block and group number 11th.
(IV) This is the configuration of F (electronegativityk = 4.0) which belongs to p-block and
group number 17th.
1.2 (D) As 'q' is noble gas, p, r and s having atomic number Z-1, Z+1 and Z+2 should belong to
halogen, alkali metal and alkaline earth metal reapectively.
As halogen has one electron less than stable noble gas configuration it has greater tendency
to accept an additional electron forming anion. Alkaline earth metal having valence shell
configuration ns2 exists in +2 oxidation state.
1.3 (D) (1) Mg2+, Na+ and F are isoelectronic and thus follows the order 12Mg2+ < 11Na+ < 9F.
Al belongs to third preiod and has no charge so it is largest.
Na+ = 102 pm; Mg2+ = 72 pm; AI = 143 pm, F = 133 pm.
(2) K+ = has more number of shells than Mg2+ and AI3+ and Mg2+ are isoelectronic buit Al3+
has higher nuclear charge so Al3+ < Mg2+. Mg2+ and Li+ has diagonal relationship. But due to
+2 charge in Mg2+, the Mg2+ is smaller than Li+. Hence Al3+ is the smallest one.
K+ = 1.38 A, Li2+ = 0.76 A, Mg2+ = 0.72 A and Al3+ = 0.535 A.
(3) As the number of electrons ar3e lost, the attraction between valence shell electrons and
nucleus increases. As a consequence of this the elecrtons are pulled closer to the nucleus
leading to the contraction in size of ions.
(4) Across the period the nuclear charge increases and thus the size of atoms dec4eases.
Mg = 160 pm; Al = 143 pm; Si = 118; P = 110 pm.
1.4 (C) (1) Down the group size increases and ther3e fore, ionization energies decrease . Hence the
order is correct.
(2) Cation is smaller biut anion is bigger than its parent atom. As charge on cation increases
the ionic radius decreases. Similarly as charge on anion increases the ionic radius increases.
1
IE Hence the ordrer is correct.
atomic / ionic radius

1.5 (C) O+ = 2s2 2p3half filled configuration has extra stability & F+ = 2s22p4 partially filled less stable
thus IE2 of O > F. As nuclear charge increases the IE2 increases. So IE2 of N> C.
1.6 (D) Due to small size of F atom, the electron-electron repulsions in compact 2-p sub shell are
large and hence the incoming electon is not acepted with the same ease as is the case with
CI (less electone - electron repulsions)
1.7 (C) (i) Across th4e period size decreases as electrons are added in the same shell and njuclear
charge increases by one unit for addition of each successive element.
In contrary, the ionization energy increases as size of atom decreases and nuclear chargve
increases.
(ii) Electron affinity kvalues of halogens are exothermic (negative) and that of noble gases
are endothemic (positive)
(iii) IE1 of phosphorus is greater than that of sulphur on account of stable half filled electron
configuration; P = 1060 kJ mol1 and S = 1005 kJ mol1
 (iv) Isoelectronic series of ion; all have the xenon electron configuration.
1
Ionic radius = nuclear charge
Atomic number : Te = 52; I = 53; Cs = 55; Ba = 56.
1.8 (B) (A), (C) and (D) are correct statements
(B) First decreases from B to Al and then increases marginally owing to discrepancies in
atomic size of the element.
1.9 (A) As non-metallic character of element attached to exygen atom increases, the differ ence
between the electronegativity values of element and oxygen decreases and the acid
character of oxides increases and vice-versa.
1.10 (D) (A) As electronegativity increases the non-metallic character increases as tendency to form
anion increases.
(B) It is based on their SRP values. (Oxidising power may be cumulative effect lof hydration
energies, electronegativities, bond dissociation energies and electron gain enthalpies)
(C) C = 121 ; Si = 135; P = 60; N = + 31 (all values are in KJ/mole). It depends on
various factors lide size of atom, nuclear charge, partially filled, half filled and completely filled
electronic configurations.
1.11 (B) Oxidaton state eletronegativity.
Electronegativity increases with increase in oxidation state; so the difference in electronegativity
decreases (between element and oxygen) and acidic charcter increases.
1.12 (A,B,C,D)
Species having same number of electrons are called isoelectronic specis.
1.13 (C,D)Generally the electron affinity values of 3rd period elements are higher than the elements of
2nd period of the same group because of less interelectronic repulsions. Atomic size, nuclear
charge and electrons configurations also affect the electrons configurations also affect the
electron affinity.
Electron gain enthalpies in kJ mol1 are :
C = 121; Si = - 134; P = 74; N = O; o= 142; jF = 328
1.14 (B,D)(B) Addition of second electron to O is opposed by electrostatic repulsion due to same
charge. Hence energy klis given for the addition of IInd electron.
(D) Ar has staable electronic confiugration (ns2 np6). Hence energy has to be given to add
an extra electron to form Ar
1.15 (A,B,C,D)
(A) As screening effect increases, effective nuclear charge decreases thus valence shell
elecrton is loosely bound. Hence I.E decreases.
(B) Be and Mg has ns2 configuration (stable configuration).
(C) Due to lanthanide contraction.
(D) rrmetallic > r covalent (covalent bond formation involves the overlapping of orbitals).
1.16 (A,B,C,D)
(A) Oxygen atom is smaller as compared to sulphur; so in oxygen there is more inter-
electronic repulsion than that of sulphur.
(B) Charge increases so size decrease and numbere of electrons per proton also decreases;
so valence shell electron graduallyub becomes more tightly held by the nucleus.
(C) As = valance shell elecrton configuration is ns2np3 (half filled staable configuration). Se=
valence shell electron configuration is ns2np4 (partially filled less stable configuration).
As = 0.947 MJ/mole; Se = 0.941 MJ/mole.
 (D) Down the group atomic size increases. Fluorine experiences more inter electronic repulsion
than that of chlorine; so fluorine has less electron affinity than that of chlorin.
1.17 (A)
1.18 (A)
1.19 (C) Be has completely filled stable 2s2 orbital and thus Be has higher ionisation energy than B.
2s orbital has less energy than orbitall.
1.20 (D) Statement-1 is false. Electrons configuration 16S 2+ =1s 22s 2 2p 63s 23p 2 and 15P 2+ =
1s22s22p63s23p1. Sulphur has higher nuclear charge and smaller size than that of phosphorus
so IE3 of S > P. IE3 (P) = 2, 912; (S) = 3, 361 KJmol1.
Statement-2 is true statement.
1.21 (A) Both statements are true and State4ment-2 is the true explanation of the Statement-1. kThe
magnitude of and elements electron affinity depends on the elements valence shell electrons
configuration.
18 5 2
25Mn = [Ar] 3d 4s configuration,
18 5 2
25Cr = [Ar] 3d 4s configuration
18 6 2
25Fe = [Ar] 3d 4s configuration

1.22 (A) Statement-1 is True, Statement-2 is Trur; Statement-2 is a correct exp;anation for Statement-1.
1.23 (A) High electronegativity and small size, has only oxidation state.
1.24 (A) S1 : Metal comprises more than 78% of all kinown elements.
S2 : Selenium is not a semi-metal.
S3 : As ionization energies decrease the metallic charcter increases.
S4 : Down the group the lattice and hydration energies decreases but the chanbge in lattice
energy is more as compared to hydration energy.
1.25 (B) S3 : The size of the osoelectronic species is not effected by electron-electron inter action in
the jouter orbitals but is effected bgu the nuclear chartge.
S1, S2 and S4 are correct statements.
1.26 (A) S1 : Long form of periodic table does not help at all in predicting the oxidation state4 of
elements, additional information regarding the number of unpaired electrons is also required.
S2 : rmetallic > rrcovalent Metallic bond is weaker than covalent bond and in covalent bond
formation some part of the combining orbitals become common due ton overrlapping.
S3 : This is correct order of electron affinity values.
S4 : is correct statement as argon has completely filled outer shell adfnd in the formation of
Se2 there is electrostatic repulsions between Se anion and incoming electron (due to same
charge).
1.27 (D) S1, In case of Rb second electron has to be removed from a stable noble gas electrons
configuration I.e. ns2np6.
S2, It is correct statement.
S3, It is correct statement.
S4, Electrons configuratio of Cu+,[Ar]18 3d10 4s0 and K+,[Ar]18 4s0. So in case of K+, the
electron is to be removed from inert gas configuration and there fore, IE2 of K > Cu.
1.28 (C) S1 : Na2O2 < MgO<ZnO <P4O10 : as non-metallic character increases the acidic charcter
increases. MgO, Na2O are basic, ZnO ampoteric and P4O10 acidic.
S2 : Na<Si>AI<Mg: Mg has higher than Na due to small size and higher nuclear charge. Mg
has higher than AI because of ns2 configuration (has extra stability and high electron
phenetration power of s-sublhell electrons) and Si has higher than AI because of higher
nuclear charge and small size. IE1 : Na = 496, AI = 577, Mg = 737 and Si = 786 kJ/mole
 S3 : There is more interelectronic repulsion in 2p-subshell of fluorine than chlorine (3p). So
extra electron will be added easily in 3-sukbshell of chlorine as compared to 2p-subshell of
fluorine. Down the group electron affinity values gernerally decreases with increasing atomic
number due to increase in atomic size, So CI > F>Br.
S4 : Isoelectronic serees of ion; all hve the xenon configuration.
1
Ionic radius = nuclear charge

Atomic number : Te = 52; I = 53; Cs = 55; Ba = 56.

1.29 (D) As ionisation energy decreases electropositive charcter increases and thus the tendency to
form cation increases. Therefore, metallic charcter increases.
1.30 (B) As ionisation energies decrease fown the group ht ereducing charcter increases and as
across the periond, ionisation energies increases, so reducting charcter, decreases.
1.31 (D) As electronegativity difference between element and oxygen decreases th4e acidic charcter
of oxides increases. The electronegativity also increases with increasing oxidiation states. In
geniral, as non-metallic character increases across the period, the acidic charcter of their
oxides increases.
1
1.32 (A) Ionic size a nuclear charge

1.33 (C) Both (A) and (B) are correct statements.

1.34 (A) Covalent bond formation involves the overlapping of atomic orbitals and in doing this some
part of the orbitals becomes common. So rcovalent < rmetallic
1.35 (D) Value correspondes to Noble gas . Hence, T is inert toward chemical reactivity.
1.36 (B) metal having lown IE1 and higher IE2 corresponds ot alkali metal. Hence, Q is most reactive
metal (easily forms cation).
1.37 (A) Non-metal having higher negative value of electron gain enthalpy corresponds to halogen.
Hence R is more reactive non-metal (easily forms anion)
1.38 (A) In a periond the IE increases due to decrease in atomic size & increase in nuclear charge.
But IE1 of Mg is greater than AI due to more penetration power of s-sub shell electrons and
stable 3s2 configuration (completely filled s-orbital)
1.39 (D) All statements are correct.
1.40 (D) Orbitals beatint lower value of n will be more closer to the nucleus and thus electrons will
experiences greater attraction from nucleus and so its removal will be diffecult not easier.
1
1.41 (C) Heg kJmol = 349; F = 328; S = 200; O = 141

1.42 (D) (A) As theyi have high ionisation energies and low electron affinities.
(B) They have intermediate values of elwctroneghativity.
(C) The electropositi9ve character is inversely propertional to the ionisation enirgy, which
increase accross the period and decreases down the group.
1.43 (B) The element with olow oxidation state has low electronegativbity value. Thus the difference
of accross the period and decreases down the group.
1.44 (A) Atomic radius decreases, the negative value of electron gain enthaply increases (as attraction
for extra electron increases).
1.45 (A -q); (B - p, t); (C - s); (D - r)
 (A) inert gases exist as monoatomic molecule. They have highest IE1 and IE2 and positive electron
gainenthalpies.
(B) Alkali metal IE1 is low because of bigger size of atom and IE2 is high due to noble gas
configuration. As it has low IE1, it can lose one electron easily and thus more electropositive. So
it acts as strong reducing agents and their oxides are basic in nature. Thery have low negative
value of Heg because of large size.
(C) IE1 and IE2 both high and negative vbalue of electron gain enthaopy is very high because of
high nuclearcharge and small size of atoms, so it has a greater tendency to accept an additional
electron. So it (F) acts as a strong oxidising agent.
(D) As it has less negative value for Heg then (C) thus ith will be least reactive non metal (I).
1.46 (A - p,r); (B - r); (c - q,s,t); (D - q,s)
(A) Nitrogen has less favourble electron affinity because of stable half filled electron configuration,
ns2np3 Nitrogen has higher first ionisation energy because of stable half filled electron configuration,
ns2np3.
Across the period, atomic size decreases; elecrtons are added in the same valence shell but for
addition of each sucessive element the nucleat charge increases by one unit positiv charge (i.e.
proton)
Electronegativity of nitrogen (3.0) is greater than than that of carbon (2.5) on acount of small
atomic size.
C = ns2 np2; N = ns2np3
(B) eg H; Se = 195 kJmol 1; Br = 325 kJmol1
1 1
IE1; Se = 941 kJmol ; Br = 1142 kJmol
Covbalent radius /pm; Se = 117; Br = 114
Electronegativity; Se = 2.48; Br = 3.0
Se = [Noble gas] ns2np4; Br = [Noble gas] ns2np5.
(C) eg H; K =48kJ mol1; Mg= O (stable configuration ns2)
1 1
IE1; K = 419 kJ mol ; Mg = 373 kJ mol
Metallic radius/pm K = 227; Mg = 160
Electronegativity ; K = 0.8; Mg = 1.2
K = [Noble gas] ns1; Mg = [Noble gas] ns2
(D) EgH; F = 328 kJ mol1 (More interelectronic repusions on account of small size)
CI = 349 kJ mol1
1 1
IE1; F = 1680 kJmol ; CI = 1256 kJmol
Covalent radius./pm; F = 64; CI = 99
Electronegativity ; F = 4.0; CI = 3.2
Have same number of valence electrons because both belong to same group i.e. halogen.
1.47 (Ar) ; (Bq,r); (Cs) ; (Dp,s)
(A) For isoelectronic species, the kionic size decreases with increase in nuclear charge. Hydration
charge on anion and heavier hydrated ions move slowly. Number of atomic shells increases,
inonic size increases.
(B) heavier hydrated ions move slowly. Number of atomic shells increases, ionic size increases.
(C) correct order; as CI has less inter electronic repulsions than F due to bigger size of 3p-
subshell.
(D) Oxidation state increases, the electronegativity increases. For isoelectronic species
ionisationenergy and electron affinity increases with increasing nuclear charge.
1.48 Last electron enters in d-subshell so it belongs to d-block elements.
For d-block elements group number
= no of electrons in (n 1) d subshell + number of electrons in valence shell (i.e. ns)
= 7 + 2 = 9.
1.49 First gas which contains d-electron is Kr.
1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6
Total number of d-electrons = 10
Total number of p-electrons = 6 + 6 + 6 = 18
Total number of s-electrons = 2 + 2 + 2 + 2 = 8
Defference in total number of p- and s - electrons = 18 8 = 10
So inert gas is 36Kr.
1.50 There is jump in ionization energy from second to third one. Alkaline earth metals have the electron
configuration [noble gas]ns2; third electron is to be removed from the electron configuration [noble
gas] which will requir3e very high energy. These data are of beryllium.
1.51 In M4+ ion total number of electrons = 20
1s2 2s2 2p6 3s2 3p6 3d2
Electronic configuration =
2 8 10
Number of electrons in metal = number of protons = 4 + 20 = 24
1.52 Acidic charcter of oxides increases as non-metallic character of the element that is combined with
oxygen increases.
The ionisation energy is the measure of metallic and non -metallic character.
As ionisation energy of element decreases the metallic charcter increases and non-metallic character
increasing non-metallic character.

+4 +5 +6 +7
CO2 N2O5 SO3 CI2O7
th th th th
14 group 15 group 16 group 17 group

increasing acidic character

 INORGANIC CHEMISTRY

2. CHEMICAL BONDING

2.1 (B) As anion is same, the covalent character in ionic compound will depend upon the size and
charge on the cation. According to fajans rule, pbO (most ionic) = pb2+, Mn2O7 (most
covalent) =Mn+7
2.2 (B) NO2+ Number of electron pairs =2
Number of bond pairs = 2
Number of Ione pair = 0
So, the species is linear with sp hybridisation.
+
O=N=O
sp

NO3 Number of electron pairs = 3

Number of bonbd pairs = 3
Number of Ione pair 0
So, the species is trigonal planar with sp2 hybridisation.
+ O
O N sp2
O
NH4+ Number of electron pairs = 4
Number of bonbd pairs = 4
Number of Ione pair 0
So, the species is tetrahedral with sp3 hybridisation.
H +

N sp3
H H
H

2.3 (D) Hyvbridisation is calculated by steric number rule.

Steric no. = no. of atoms attached to central atom + no. of lone pairs present on central
atom.
Steric no. for IO4 = 4 + 0 = 4 sp3; Steric no. for ICI4 = 4 + 2 = 6 sp3d2;
+ 3
Steric no. for IF4 = 4 + 1 = 5 sp d; Steric no. for SO3 = 3 + 0 = 3 sp2;
Steric no. for SO42 = 4 + 0 = 4 sp3; Steric no. for SO32 = 3 + 1 = 4 sp3;
+ 3
Steric no. for PCI4 = 4 + 0 = 4 sp ; Steric no. for BF4 = 4 + 0 = 4 sp3;
3
Steric no. for XeO3 = 3 + 1 = 4 sp ; Steric no. for XeO4 = 4 + 0 = 4 sp3;
3 2
Steric no. for XeF4 = 4 + 2 = 6 sp d ; Steric no. for CIO4 = 4 + 0 = 4 sp3;
I
2.4 (B)
I +
[:N=N=N:] O=N=O
sp I sp
(linear) sp3d (linear)
(linear)

2.5 (A) BF3 (sp2) + F BF4 (sp3).

2.6 (D) F
2
B sp N sp3
F F F F
F
Trigonal planar Trigonal pyramidal

2.7 (D) F F
O F
I S
O F
F F
3 3
sp d sp d
see-saw see-saw
F
2.8 (C) According to VSEPR theory
Number of wlectron pairs = 5
Number of bond pairs = 2 Xe
Number of lone pairs = 3
Hence structure is linear F
hybridization = sp3d

O
F + F
F F
F
Xe
I Br F
(A) F F (B) (D)
F
F F

In XeOF4, In lF4+, In BrF3,

2.9 (A) The hydrogen atoms are in a vertical plane with the axial fluorine atoms.
F
F
H
170
97.5
C= S

H F
F

Hydrogen atoms lie in the CSF2 axial plane. We know that the p bond involvintg a p-orbital
on the carbon atom must lie in the equatorial plane of the molecule. And the resulting
repulsion between the p electrons and the electron pair bonding the equatorial fluorine atoms
is dramatic; The Feq Feq angle has been reduced to 97.5.
2.10 (D) (A) NO2+ = 7 + 16 1 = 22; CO2 = 6 + 16 = 22.
So isoelectronic (both have 22 electrons in valence shells)
+
O=N=O, O=C=O, both are linear so isostructural.
sp sp

(B) NO3 = 7 + 24 + 1 = 32; BF3 = 5 + 27 = 32.

So isoelectronic and are isosturctural as both have trigonal planar structures.
 sp2 F
O sp2
O N B
O F F
(C) NH3 = 7 + 3 = 10 CH3 = 6 + 3 + 1 = 10
So isoelectronic.

N sp3 C sp3
H H H H
H H

Both are pyramidal so isostructural.

2.11 (D) F
89 F
104 due to lp bp repulsions
S 177

F
F
Remaining molecules/ions have symetrical structures; so have all bonds equal.

2.12 (D) S
O O
S (B) O
(A) (S2O32) S S O (S2O42)
O O
O

O O O O O

(C) O S S O (S2O52) (D) S S

O O
O
O O
O O

In structure os S2O72there is one SOS bond but no SS bond.

2.13 (A) C O = 1.43 ; C = O 1.23 ; C O 1.09
CO = C O; partial triple bond character ; bond length is inter mediate of C = O and C O
bonds CO2 = O = C= O; double bond length

CO32= C partial double bobnd charcter; intermediate of C= O and CO.

O O

H
CH 3OH = H C OH single bond length.
H
 1s2 1 s2 2 s2 2 s2 2p2 y 2p2z 2p x
2.14 (D) (A),(B) M.O. for C2 = , teo molecular orbitals
HOMO LUMO

are involved in bonding .

(C) It is isoelectronic with N2 and has one sigma and two pie-bonds.
(D) In both, all electrons are paired so diamagnetic.

2.15 (B) (a) N2 = 1s2 1s2 2s2 *2s2 2p2x = 2p2y 2p 2z

10 4
B.O. = = 3; n = 0 (D)
2
N2+ = 1s2 1s2 2s2 2s2 2p x 2 2p y 2 2pz1

94
B.O. = = 2.5; n = 1 (P)
2
(b) O2+ = 1s2 1s2 2s2 2s2 2p z 2 2p x 2 2p y 2 2p x1 2p y0

10 5
B.O. = = 2.3; n = 1 (P)
2
O22+ = 1s2 1s2 2s2 2s2 2p z 2 2p x 2 2p y 2 2p x0 2p y 0

10 4
B.O. = = 3; n = 0 (D)
2
(c) B2 = 1s2 1s2 2s2 2s2 2p x 2 2p y1

64
B.O. = = 1; n = 2 (P)
2
10 4
B2+ =
2
5 4
B.O. = = 1/2 ; n = 1 (P)
2
(d) NO = 1s2 1s2 2s2 2s2 2p z2 2p x 2 2p y 2 2p x1 2p y1

10 6
B.O. = = 1.0 ; n = 2 (P)
2
NO = 1s2 1s2 2s2 2s2 2p z 2 2p x 2 2p y 2 2p x1 2p y0

10 5
B.O. = = 2.5; n = 1 (P)
2
2.16 (D) = q d
1.2 1018 = q 108 cm
1.2 10 18
q= = 1.2 1010
10 8

q 1.2 10 10
% charge = = 100 = 25%
e 4.8 10 10
2.17 (A) (i) In CH4 and CCI4 being tetrahedral(symmetrical molecules), bond dipoles cancel other
resulting in zero diple moment.
(ii) As electronegativity difference between two bonded atoms increases, the bond polariaty
increases resulting into the increase in dipole moment.
2.18 (D) (A) In (CH3)3 SiOH, because of pd dilocalisation between silicon and oxygen, (CH3)3SiO
becomes stable.
(B) Si having larger size is unable to form multiple bonding like C in CO and thus SiO is
unstable.
(C) Due to resonance.
Cl Cl Cl

C=O C=O CO
Cl Cl Cl

2.19 (B) Strengtyh of H-bonds on following factors.

(i) Electronegativity of element covalently bonded to hydrogen atom.
(ii) Size of electronegative element.
(iii) Ease of donation of lone pair of electrons by electronegativbe element.
2.20 (C) Number of polatisable electrons strength of vander waals force boiling point.
boiling point CHCI3 = 61C and CCI4 = 73C.
2.21 (A,B,C,D)
F +
+
F F CI F
CI
F
Br
(A) (B) Sn CI (C) F CI F (D) I
F F
CI F
F CI F
octahedral trigonal bipyramidal linear see-saw

2.22 (A,C) F

Xe
(A)
F
(B) Oxygen can not exceed it convalence as it does not have vacant d-orbital.
10 4
(C) NO+ ; Bond order = = 3
2
NO ; Bond order = 10 5 = 2.5
Bond order bond strength.
+ +
O O
(D)
O O O O

2.23 (A,B,D)
Steric number of CIF3 = 3 + 2 = 5 ; Steric number of CIF3O = 4 + 1 = 5 ;
Steric number of CIF3O2 = 5 + 0 = 5 ; Steric number of CIF2O+ = 3 + 1 = 4 ;

Steric number of CIF4O = 5 + 1 = 6 ; Steric number of XeOF4 = 5 + 1 = 6 ;
Son answer are A, B, D as steric number are same for these molecules & thus their
hybridisations are also same in each pair.
2.24 (A,B,D)
(A) According to VSEPR theory as electonegativity of central atom decreases, bond angle
decreases So bond angle of H2O > H2S > H2Se > H2Te
(B) C2H2 > C2H4 > CH4 > NH3. In Nh3 there is bp-ip repulaion so bond angle decreases to
107from 109.5.
sp sp2 sp3 sp3
180 120 109 107
(C) SF6 < NH3 < H2O < OF2 is this case bond angle of NH3 is highest because Ip - Ip
repulsion is absent in it.
(D) CIO2 > H2O > H2S > SF6
F
CI O S F F
> > > S
O O H H H H F F
F
2 3 3 3 2
sp sp sp sp d
(~117)
~ (104.5) (92) (90)

Note : It is supposed that in H2S the hybrid orbitals donot participate in bonding but pure p-
atomic orbtals participate in bonding.
2.25 (B, C)
Bond order :
(A) O2 = (10 7)/2 = 1.5, O2 = (10 6)/2 =2
(B) N2 = (10 4)/2 = 3, N2+ = (9 4)/2 = 2.5
(C) NO+ = (10 4)/2 = 3, NO = (10 6)/2 = 2
(D) CO = (10 4)/2 = 3, O22+ = (10 4)/2 = 3

10 4 94
2.26 (A,C) (A) N2 = = 3.0; N2+ = = 2.5
2 2
10 4 10 5
(C) N2 = = 3.0; N2 = = 2.5
2 2
2.27 (B,C)
Polarity depend on net dipole moment. If diple moment = 0 it is nonpolar.
F F
Xe XeF4 = 0 non polar
(A)
F F

(B)
F Xe XeF6 o polar
F F
F
F

O
F F
Xe XeOF4 o polar
(C)
F F
 F
F

(D) Xe F
XeF 5 = 0 non polar
F
F
2.28 (A,C,D)
Hydrogen bonding is possible in CH3NH2, CH3COOH, CCI3CH(OH)2
H H O
Cl
O HO
CH3 N H N CH3 ; CH3 C C CH3 ; Cl C C H
OH O
H H Cl H O

2.29 (A) Transition metal ions have pseudo inert gas configuration which have higher polarising power
due to poor shielding of d-electrons. Alkali metal and alkaline earth metal ions have less
polarising power due to inert gas configuration (more shielding effect of s-and p-electrons to
d-electrons).
2.30 (C) S-1 : It is correct statement because all three p-orbitals are involved in sp3 hybridisation and
thus non p-orbital is left for side wise overlapping.
S-2 : XeO3 is sp3 hybridise and Xe form three double bonds through p-d overlapping.

p -d
Xe
O
O O

F
2.31 (A) 87-40'
P
1.698 Cl F 1.598
Q
87-40'
F

due to p p repulsion

2.32 (C) H 112

F
+2 +
F N = Nsp N N N
sp2 F 1.24 1.13

(i) Bond angle 112 due to p bp repulsion

(ii) Smaller bond length 1.13 A due to the atraction betwen the opposite poles.
2.33 (B) Both S-1 and S-2 are true statements but are different and different and reason is not true
explanation of assertion. High electrinegativity of atoms attached to carbon atom indirectly
results into the contraction of the size of p-orbitals. As carbon atomic size is smaller and
thus it has effective overlapping.

+
2.34 (A) C2H5 O C2H5+ HCl C2H5 O C2H5Cl

H
Diethyl oxonium chloride
(stable oxonium salt)
2.35 (A) Number of electrons NO+ = 7 + 8 1 = 14
Number of electrons CN = 6 + 7 + 1 = 14
10 4
Bond order = =3
2
Both are diamagnetic.
2.36 (B) Within the Ca2+ / SO42 layers the ions are held together by strong electrovalent bonds. But
theseseparated Ca2+ / SO42 layers linked by reativbe weak Hbond. The weaker Hbonds
link SO42 ions in the intermediate region. Consequently, the gypsum can be readily cleaved
and stretched along the layer of water molecules.
Anhydride has a completelyionic structure involving only Ca2+ and SO42 ions.
2.37 (C) S1: OF2 < 109.5 and OBr2 > 109.5
OF2 : Fluorine being more electronegative attracts the bond pairs of electrons towards itself
and thus ther is more Ip-Ip repulsion decreasing the bond angle.
OBr2 : The bond pairs are close to more electronegative oxygen atom and thus there is
repulsion between bp-bp increasing the bond angle. The bulkier Br atoms also create steric
repulsion which also increase the bond angle.
S2 : Anion of maleic acid (cis-form) gets stabilised through intramolecular hydrogen bonding
after giving one protons as given in following structure. In fumaric acid (trans-form) no such
intramolecular H-bonding is possible.
O

CH2CO
H
CH2CO

O
3
S3 : All have sp hybridisation and one lone pair of electrons.

F F
F F
(A) Sb and S
F F
F F
2.38 (A) both see-saw shaped.

(B)
Se
Cl O
Cl

O
F
3 2
(C) F I F steric no. = 6; sp d

F F
F
F
F O

Xe O
(D) S O and

O
F F
F
2.39 (C) H H O
N
S1 : NN ; S2 : H H; S3 : CH3C
H H O Cl
H sp3

2.40 (B) S1 : KHF2, FH --- F ; H 212kJ mol1 involves resonance HF --- H H F H .

HF, FH --- F ; H 28.6 kJmol1

S2 : CH3CI > CH3F ; due to large charge separtion in CH3CI as compared to
that in CH3F.
CH3F ; = 1.85 D, CH3CI; = 1.87 D
S3 : In sp2 hybrid orbitals charcter is 33.3% and p charcter is 66.6%
H H H
S4 : B B
H H H
Terminal BH bond are covalent while bridging BH bonds are three cenbtre-two electron
bonds.
2.41 (A) As size of cation decreases and charge on cation increases, the polarisation increases
according to fajans rule. Hence the covalent character increases.
2.42 (C) As size of cation increases and charge on cation decreases, the polarisation decreases
according to Fajans rule. Thus the ionic charcter increases. So SnO with +2 oxidation state
will be most ionic.
2.43 (D) Agl shows highest polarisation due3to following two factors (A) Ag+ has pseudo inert gas
configuration (B) I is biggest anion.
2.44 (C) Bond angle is less than 10928 because of Ip-Ip repulasion as bond pairs are more cllose
to fluorine atoms.

S
F F
sp3
(B) Bond angle is close to 120 because of sp2 hybridisation.

N=N
H sp2 H

(C) KrF4 has square planar shape.

F F
90

Kr
F F
3 2
sp d
(D) Bond angle is less than 120 because of repjulaion between double bond and lone pair.
-electrons of double bond create more repulsion than single congalent bond.

N
O Cl
sp2
 + + +
F F

2.45 (B) (i) Xe F (ii) S (iii) C

F F F F
F F

sp3d sp3 sp2

(T-shape) (trigonal pyramidal) (trigonal planar)

F
87-40'
P
1.698 Cl F 1.598
2.46 (D) (A)
Q
87-40'
F

due to p p repulsion
F
89 F
104 due to lp bp repulsions
(B) S 177

F
F
Adjacent bonds, thereby distoring the structure as donded oxygen atom require more space
than a single bonding pair and repel.

Cl Cl
(C) I 90
Cl Cl

(D) Bond angle in OBr2 is more than OCI2 due to Ip - Ip repulasion and steric hindrance of
bulkier Br.

Br Br
> 1110
3
sp

1
2.47 (D) (A) Bond order bond length

Bond order O2+ = 2.5, O2 = 2 O2 = 1.5.

so correct order of bond length is O2 > O2 > O2+.
22
(B) Bond order for He2 = = 0. So He2 does not exist.
2
(C) In all these molecules all electrons are paired in molecular orbitals. So they are all
diamagnetic.
(D) F2MOT configuration :
1s2 1s2 2s2 2s2 2pz2 2p y2 2pz2 2py 2 2p z2 2pz2
2.48 (A) O2 O2 O22 O2+
Bond Order 2 1.5 1 2.5
2.49 (B) Species N2 N2+ O2 O2+
Bond Order 3 2.5 2 2.5

S
2.50 (B) H 97 H
R

R = 22SH 2 2SH cos 97

R = 2 SH 1 0.12

R =
1.5
R = D
2 0.94

1.5 10 9 1.6 10 19
(SH)Cal = 10
10 30
3
(SH)Cal = 3 0.15 1.6 10 D
1.5 1
So % Ionic charcter = 100 = 16 %
2 0.94 0.15 16 3

H Cl

C C
2.51 (D)
Cl
Cl Cl H H H
H3C C Cl Cl
Cl
I II III
I = 3 CCI cos 70.5 + CH3 = 1.5 + 0.4 = 1.9 D
II = 3 CCI cos 70.5 CH = 1.5 0.4 = 1.1 D
III = 3 CH cos 70.5 + CCI = 1.9 D

CH3
2 cos 60 C O
2.52 (A) CH3

CH3 2.5 D
net = 2.5 + CH3 = 2.5 + 0.4 = 2.9 D.
2.53 (C) Bond polarity of a diatomic molecule is because of the difference in electronegativities of the
two atoms.

2.54 (C) (A)

N N
H H F F
H F
 So NH3 has higher dipolemoment than NF3.

CH3CH2 Cl
(B) C=C
Cl CH3
It has some dipole moment due to unsymmetrical molecule.
Cl

(C) Cl C Cl
Cl
It does not have dipole moment due to symmetrical molecule.

(D) S
O O
It has some dipole moment due to unsymmetrical milecule.
2.55 (B) Cyclohexane (C6H12) and carbontetrachloride (CCI4) both are non-polar compounds so there
exist London dispersion force betwen the constituent molecules.
2.56 (A p, q, r, s); (B - p, q, r, s) ; (C - q, r)
(B) Ca2+/ SO42 are held together by electrostatic force of attraction i.e., ionic bond but alternate
layers by H bonds with water molecules
2.57 (A - p, q, r, s); (B - p, q, s); (C - p, s); (D - p, q, r, s)

S 3
(A) sp (trigonal pyramidal)
F F1
O

(B) F F
I 3 2
F F1
sp d (square pyramidal)
O

F1
O
(C) O Xe sp3d (trigonal bi-pyramidal)
O
F

S
(D) HO O1 sp3 (tetrahedrall)
O 1
O
H
2.58 (A p, q, r, s); (B - p, q, r, t) ; (C - q, s); (D - r)

F
F
Kr 90 N
S N Me
(A) (B) F (C) (D) Me
F F F F
O Me
< 10928' < 120 < 10928'
sp3(bent) < 10928 sp2 (bent) sp3 (trigonal pyramidal)
3 2
sp d (square planar)
2.59 (A - p, q, r, s); (B - p, r, s); (C - p, r, s); (D - q)
(A) sp3 hybridisation, empty orbital participate in hybridisation; there are two types of bonds,
covalent and 2e 3c bonds (banana bond).
H H H
B B
H H H
3
(B) sp bybridisation, empty orbital participate in hybridisation; ther are two types of bonds covalent
and coordinate bonds.
Cl pm Cl
22
1 Cl
Al Al
pm
6
20 Cl
Cl Cl
3
(C) sp bybridisation, empty orbital (two) participate in hybridisation; ther are two types of bonds
covalent and coordinate bonds.

pm
0 Cl Cl
22
98.2
Be 82 Be 263pm Be

Cl Cl
Solid state
(D) sp3 bybridisation, because of involvement of lone pair of electrons in p-d delocalisation
between N and empty d-orbital of silicon. Only convalent bonds.

CH3 CH3
CH3 CH3
Si Si
N
CH3 CH3
Si
H3C CH3
CH3

2.60 (A - p, r); (B - r); (C - q, s); (D - p, q, r, s)

(A) CIF5, BrF4+, IF6; all have same oxidation state (+5)

F + F
F
F F F F

Cl Br I

F F F F F
F F F
(square pyramidal) (see-saw) (distorted octahedral)
 All have one lone pair of electrons each ; but different shapes; 0 so polar,
(B) CIF3, BrF2+, ICI4; all have same oxidation state (+3)
F
+ Cl Cl
CI F Br

F
F
Cl Cl
F
= 0 (polar) = 0 (polar) = 0 (non-polar)
(T - shaped) (bent) (square planar)

(C) XeF2 = +2 ; lCl2 = +1 ; l 3 = +1 ; F Xe F ; Cl I Cl ; I I I

All have three lone pairs each and same shape but different oxidatrion state. In all = 0; so non
- polar
(D) CIOF3, CcIF4+, IO2F2 ; All have same oxidation number (+5)
F F + F
F F O

CI CI I

O F O
F F F
see - saw see - saw see - saw
In all = 0, so all polar)
2.61 (A - p, q, r, s); (B - p, q, r, s); (C - p, q, r, t); (D - p, r, t)
84
(A) C2 bond order = = 2
2
All electrons are paird so diamagnetic.
Undrgoes oxidation as well as reduction.
Mixing of 2s and 2p orbitals takes place.

10 4
(B) N2 bond order = = 3
2
All electrons are paird so diamagnetic.
Undrgoes oxidation as well as reduction.
Mixing of 2s and 2p orbitals takes place.

10 8
(C) O22 bond order = = 1
2
All electrons are paird so diamagnetic.
Undrgoes oxidation as well as reduction.
Mixing of 2s and 2p orbitals does not takes place.

10 8
(D) F2 bond order = = 1
2
All electrons are paird so diamagnetic.
Undrgoes reduction only.
Mixing of 2s and 2p orbitals does not takes place.
2.62 (A s); (B - p, r, t) ; (C - q, r, t); (D - r, t)
H
Cl O F F
Cl C C H 120
(A) (B) H H H H
Cl O F F
H
Chloral hydrate Hydrogen fluoride
H H

H H H H
B

B H H B
H H

H H H H

H H H H
B B

H B
H H H

H H
Boric acid
In the solid state, the B(OH)3 units are hydrogen bonded together in toe two dimensional sheets
with almost hyxahonal symmetry. The layered are quite a large distance apart (3.18 A).
HO O HO O
S2+ S2+
HO O HO O
Sulphuric acid
Note : HF, H3BO3 and H2SO4 have low volatility i.e. high boiling points due to intermoleclar
hydrogen bonding.

2.63 HO O
P
O O
O O
P P
OH O OH

O

O N
2.64
O
2.65 NOHSO4 exists as NO+ and HSO4; NO+ is dirivative of oxygen and isoelectronic with O22+. Bond
order is 1/2 (10 4) = 3.
 H H

O
H H H O O
2+
O Cu :O O S

2.66 H H H O O
O

H H

2.67 Ncal. = 4.8 1010 e.s.u. 108cm

= 4.8 1018 esu cm
= 4.8 D.
1.2
% ionic charcter = 100 = 25%
4.8
% co-valent charcter = 75%

3
filled sp orbital
H H H

2.68
B B sp3
H
H H
3
vacant sp orbital

No of vacant sp3 hybrid orbitals participaticipating in the formation of banana bnonds are 2.
 INORGANIC CHEMISTRY

3. COORDINATION COMPOUNDS

H3C CH3
O O CC
O=CO
C C N N
(1) (2) (3)
3.1 (B) H3C C CH3 O=CO
H O O
H
3.2 (C) (A) [Pt(en)(SCN)2 (NH3)2]0 ; it is not ion
(B) [Pt(en)(SCN)2 (NH3)2]2+ ; it should not be platinate
(C) correct name
(D) [Pt(en)2(SCN)2(NH3)2]2+ ; its co-ordination number = 8
3.3 (A) Na2[Cr(edta)].
3.4 (C) Oxidation state of iron in [F2e(CO0)2(NO+)2] = x + 2(0) + 2 = 0; x = 2
So EAN = 28 = 8 = 36
Oxidation state of cobalt in Co2(CO)8 = 2x + 8 (0) = or x = 0
So EAN = 27 + 1 + 8 = 36.
3.5 (A) (a) Ni is in +2 oxidation state with electron configuration [Ar]18 3d8 4s0, so
28

3d 4s 4p 4d
[Ni (NH3)6]2+
sp3d2 hybridisation

Number of unpaired electrons = 2

(b) 24Cr is in +3 oxidation state with electron state with electron configuration [Ar]18 3d3 4s0;
so
3d 4s 4p
[Cr (NH 3) 6] 3+
d2sp3 hybridisation

Number of unpaired electrons remains three, whether ligand is strong field or weak field
ligand when electron configuration is 3d3.
(c) 27Co is in +3 oxidation state with electron configuration[Ar]18 3d6 4s0 ,so
3d 4s 4p
[Co (NH3)6]3+
d2sp3 hybridisation

All electrons are paired, so complex ion is diamagnetic.

(d) 30Zn is in +2 oxidation state with electron configuration [Ar]18 3d10 4s0, so
3d 4s 4p 4d
2+
[Zn (NH3)6]
sp3d2 hybridisation
3.6 (B) (A) [Cr (H2O)6]2+ is high spin complex with four unpaired electrons.
[Cr(CN)6]4 is low spin complex with two unpaired electrons.
3d 4s 4p
3+
(B) [V (NH3)6]
d2sp3 hybridisation

3d 4s 4p
(C) [Co (CN6 )]4
d2sp3 hybridisation 5s (or 4d)

3d 4s 4p
(D) [Mn3 (NO)3 (CO)]
sp3 hybridisation

3.7 (A) (P) Fe3+, n = 5; (Q) Co3+, n = 4

(R) V3+, n = 2 ; (S) Ti3+, n = 1
n = no. of unpaired electrons.

3d 4s 4p
[Ni Cl2(PPh3)2]
3.8 (B)
sp3 hybridisation

3d 4s 4p
[Ni (HDMG)2]
dsp2 hybridisation

3d 4s 4p
[Ni (CO)4]
sp3 hybridisation

3d 4s 4p

3.9 (C) [Co(ox)3]3 , 3d6

d2sp3 hybridisation
All electrons are paired, so diamagnetic.
3d 4s 4p

[Co(NH3)6]3+, 3d6

d2sp3 hybridisation
All electrons are paired, so diamagnetic.
3d 4s 4p 4d

Fis a weak ligand [CoF6]3, 3d6

sp3 d2 hybridisation

It contains four unpaired electrons, so it is paramagnetic.

3.10 (D) Ni(CO)4sp3 (Co strong field ligand) ; [A+3gF4]dsp2 (4d18 electron configuration)
[Zn(CN)4]2sp3 (3d10 electron configuration) ; [PtCI4]2dsp2 (5d8 electron configuration)
[RhCI(PPh3)3]dsp2 (4d8 electron configuration)
all complexes are diamagnetic in nature which show decrease in their weights in magnetic field.
 3d 4s 4p 4d
I +
[Fe(H2O)5NO]
3.11 (C)
sp3d2 hybridisation

Number of unpaired electrons = 3 ; So, = 3(2 3) = 3.87 B. M.

Brown colour is due to charge transfer from ligand to metal.
3.12 (D) (A) 22Ti4+ E.C = 3d 4scolourless
+ 10
(B) 29Cu E.C = 3d 4s colourless
3+
(C) 24Cr E.C = 3d3 4s coloured (most likely)
3+
(D) 23V E.C = 3d2 4s coloured (most likely)
hc
3.13 (A) corresponds to the wave length of the visible light and =
The order of ability to produce d-orbital spliting of various loigands;
CO > CN > NO2 > en > NH3 > H2O > OH > F > CI > Br > I
strong field weak field
ligands ligands
(larger ) (smaller )

Br Cl Cl Cl
Cl Br Cl Br
en Co3+ en Co3+ en Co 3+ en Co 3+
3.14 (C) Cl Br Br Cl
Br Br Br Br
3.15 (A) It shown geometrical, ionisation and linkage isomers.
NO2 NO2 cis-trans.
NO2 ONO cis-trans.
ONO ONO cis-trans.
NO2 NO3 cis-trans.
ONO NO cis-trans.
------------------------------------
Total number of isomers = 10.
3.16 (A) (A) has three symmetrical bidentate lignds, which lack plane of symmetry.
(B) and (C) has square planar geometry and has plane of symmetur. (D) has one of the
plane of symmetur. So (B), (C) and (D) will not show chirality.
3.17 (C) (A) [Co (NH3)3 (NO3)3] shows fac - mer isomerism but does not show optical isomerism.
(B) [Co(ox)3]3 does not show fac - mer isomerism but shows optical isomerism.

N N N N N N N N

(C) O Co3+ O O Co3+ O N Co3+ O O Co3+ N

O N N O O O O O

mer one pair of enantiomers fac one pair of nantiomers

3.18 (A,B,D)
CO32 and NO3 1 or 2 donor oxygen atoms
C2O422 donor oxygen atoms.
CH3C N 1 donor nitrogen atom.
3.19 (A,B,C)
A, B and C are correctly matched.
(D) tetrahedral, CO stronger ligand so pairing of electrons occurs.

3d 4s 4p
Fe2=
sp3 hybridisation

3.20 (A, B)
(A) 25Mn3+[Ar]18 3d4 4s0
3d 4s 4p

[Mn(CN6)]3 : two unpaired electrons.

d2sp3 hybridisation
(B)24Cr3+[Ar]18 3d3 4s0
3d 4s 4p

[Cr(NH3)6]3+ three unpaired electrons.

d2sp3 hybridisation
(C) 26 Fe2+[Ar]18 3d6 4s0
3d 4s 4p

[Fe(CN)6]4 : all electrons are paired.

d2sp3 hybridisation
(D) 27 Co3+[Ar]183d6 4s0
3d 4s 4p

[Co(cN)6]3 : all electrons are paired.

d2sp3 hybridisation

3.21 (A,C, D)
Option (A) is correct according to IUPAC nomenclature.
Ni is in +1 oxidation state and CN is strong field lighand. So,

3d 4s 4p

[Cr(NO+)(NH3)(CN)4]2
d2sp3 hybridisation

One electron is unpaired in 3d subshell, so magnetic moment = 1(1 2) = 3 B.M.

It can exist in two geometrical isomers as given below.
+
NO CN

NC CN NC NH 3
Co Co
+
NC CN NC NO

NH3 CN
trans- cis-
 SCN
SCN
en Co exist in only one form.
3.22 (A) SCN
SCN
3.23 (A)

3 3
ox ox N N N N

O Co3+ O O Co3+ O
(A) ox Cr Cr ox
Cl Cl
O N N O
Cl Cl
mer one pair of enantiomers
+ +
3+ 3+ en
en en en
Cl Cl
en Co Co
(B) en Co Co
Cl Cl
en en
en en

(C) [Pt CI(dien)]CI , [Ni CI2 (PPh3)2] complex is square planar whereas [Ni CI2 (PPh3)2] is tetrahedral.
(D) [Co (NO3)3 (NH3)3] has plane of symmetry but cis- [Pt (en)2 CI2] CI2 shows optical isomerism.
3.24 (D) Cr3+ having 3d3 configuration always have 3 unparied electrons with strong field as well as
wead field ligands.
3d 4s 4p

[Cr(NH3)4BrCl] =
2 3
d sp hybridisation
3.25 (B) As metal ion charge increases the ligands are drawn closer to the metal ion because of its
increased charge density. As the ligands move closer, they cause greater splitting of tghe d-
orbital, there by producing a large value.
3.26 (C) [Ni (en)3]CI2 is parmagentic withtwo unpaired wlectrons and has octahedral geometry with
sp3d2 hybrdisation and as nd orbital participate in hybridisation it is outer orbital complex. As
all ligands are os same type, the complex is termed as homoleptic.
3.27 (A)

O H O

CH3 C = N N = C CH3
+2
S1 : Ni ; so it exist in only one form.
3.28 (D) H3C C = N N = C CH3

H O O
rosy red ppt
I I

Co3+ Co3+
S2 : Br Br
OH2 H2O
Cl Cl
3.29 (A)
eg

3.30 (B)
+3
S1 : [ Mn Cl6 ]3 : Mn

t2g

eg

[ FeF6 ]3 : Fe+3

t2g

eg

3+
[ CoF6]3 : Co

t2g

S2 : V.B.T. does not give andy interpretation about the relative thermodynbamic stabilities of
various complexes. This is one of the limitation of V.B.T.S3 is correct statement.
3.31 (A) S1 : Has plane of symmetry, ther3efore, does not show optical isomerism.
S2 and S3 are correct statements.
3.32 (D) S1, S2 and S3 are correct statements.
S4 : It is an example of only hydrate isomerism not ionisation isomerism because such
isomerism occurs owing to exchange of ions between coordination and ionisation spheres.
3.33 (C) S1 : [CoF6]3 is paramagnetic with 5unpaired electrons but [Co(ox)3]3 is diamagnetic as all
electrons are paired.
S2 : It exists as [Co(NH3)3CI3]
S3 : It kjis correct statement.
S4 : [Fe(+I)(H2O)5NO+]S]O42
3.34 (C) S1 : PentaamminethiocyanatoNchromium (III) tetrachlorozincate (II).
or
Pentaammineisothiocyanatochromiume (III) tetrachlorozincate (II).
S2 : In CoSO4, the oxidation state of Co is +2 i.e. [Ar]18 3d7 4s0 electrons configuration. It has
two unpaired electrons so it is parmangetic and coloured.
S3 : [Co(NH3)4(No2)2]NO3
[Co(NH3)4(NO2)(NO3)]NO2 io nisation isomerism
[Co(NH3)4(NO2)2]NO3
[Co(NH3)4(NO2)(ONO)]NO3 Iinkage isomerism
 This complex has cis- and trans isomers.
Total isomers = 10.
S4 : The bond length CO in CO itself is 1.128, while the bond length in [Fe(CCO)5] molecules
are 1.15A on account of synergic interaction between Fe and Co.
3.35 (D) It is homogenious catalyst for hydrogenation of alkenes.

NH3 Br
H3N Br NH3
H3N

Co Co
3.36 (D)

H3N Br H3N NH3

NH3 Br
cis trans
It shows geometrical isomerism but not optical isomerism due to the presence of at least
one plane of symmetry.
[Co(NH3)4Br2]NO2 and [Co(NH3)4BrNO2]Br are ionisation isomers and later complexreacts
withAgNO3 solution to give pale yellow ppt. [Co(NH3)4BrNO2]Br and [Co(NH3)4BrONO]Br are
linkage isomers.

Cl 2+
CH2NH2 IV NH2 CH2
3.37 (C)
Pt

CH2NH2 NH2 CH2

Cl

Trans-form is optically inctive as it is achiral.

3.38 (D) As it suffer lose in weight with H2SO4, ionization sphere spther3e contains H2O molecle. As
complex also give white ppt. with AgNO3, the ionisation sphere should contain CI ion. So
formula may be [CoBrCI(en)2]CI.H2O.
3.39 (C) SCN is weak field ligand
eg

3d6
no. of unpaired electrons = 4 ; = 3(3 2) = 4.9 B.M.
t2g

3.40 (A) Only one CI ion is of free ion from complex so 1 mole of complex will generate precipitate
of half mole of Pb2+ + 2CI PbCI2. (white).
3.41 (B) (X) = [Co(SCN4)]2 ; (Y) = [Co(d,g)2].
3.42 (A) X = [Co(SCcN)4]2 , cobalt is in +2 oxidation state and SCN is weak field ligand. So,

3d 4s 4p

[Co(SCN)4]2 : (tetrahedral)
3
sp hybridisation

[Ni(dmg)2] : Nickel is in +2 oxidation state and dmg is chelation ligand. So,

 5d 6s 6p

[Ni(dmg)2] : (square planar)

2
dsp hybridisation

3.43 (C) X = [Co(SCN)4]2 , cobalt is in +2 oxidation state and SCN is weak field ligand. So,

3d 4s 4p

[Co(SCN)4]2 : (tetrahedral)
3
sp hybridisation
[Ni(dmg)2] : Nckel is in +2 oxidationstate and dmg is chelating ligand. So,
5d 6s 6p

[Ni(dmg)2] : (square planar)

2
dsp hybridisation
[Ni(dmg)2] shows intra moelcular H-bondign as shown below.
Reactions involved :
Co2+ (aq) + 4SCN (aq) [Co(SCN)4]2 (aq.) blue colour complex.

O HO

2+
CH3 C=N OH CH3 C = N N = C CH3
Ni (aq) + 2 NH4OH 2+
Ni red precipitate
CH3 C=N OH H3C C = N N = C CH3

OH O

hc (6.626 10 34 J.s) (3.0 108 m / s)

3.44 (B) = hv = = 3.65 1019 J/ion
544 10 9 m
= (3.65 1019 J/ion) (6.02 1023 ions/ mole)
21.97310 4
= kJ mol1 = 219.73 kJ mol1.
1000
3.45 (C) As it absorbs blue colour light ( = 455 nm), the colour of the complex must be orange.
3.46 (C) (i) 78Pt(II)has 5d8 configuration, all electrons are paired; so diamagnetic.
(ii) 27Co2+ has 3d7 configuration ; SCN is weak field ligand. So the complex is paramagnentic
with three unpaired electrons.
(iii) 29Cu2+ has 3d9 configuration; complex is paramagnetic with one unpaired electron.
(iv) 80Hg2+ has 5d10 condigukration ; all electrons are paired so diamagnentic.
3.47 (B) Donation of electrons from a filled d-orbital of metal into the vacant antibonding bonding
orbital of CO decreases the bonbd order three to two and half or slightly more thus increasing
the bond length between CO.
1
Bond order Bondlength

3.48 (C) Ni (CO)4 sp3 diamagnetic

Fe (CO)5 dsp3 diamagnetic
V (CO)6 dsp3 paramagnetic
Cr(CcO)6 dsp3 diamagnetic
 3d 4s 4p
3.49 (B) V = 23

3d 4s 4p

[V(CO)6]
d2sp3 hybridisation

3.50 (A r, q, r); (B p, r); (C p, q, r); (D p, q, s, t)

(A) Acetyl acetonato (CH3COCHCOCH3)
O O
C C
H3C C CH3
H
(B) Oxalato (C2O42)
O O
C C
O O
(C) Dimethylglyoximato (HONCC(CH3)C(CH3)NO)
H3C CH3
C C
N N
O O
H
(D) NItrito (NO2)
It may Ink to central metal ion either through nitrigen or oxygen; so it is ambidentate ligand.

N
O O

3.51 (A p, r, s); (B p, q, r, s, t); (C p, q, r); (D p, q, r)

(A) It has tetrahedral geometry; so it does not show gemometrical isomerism. but it has chiral
atom and therefore, have a pair of enantiomers. Oxidation state of cobalt in the complex is +3 and
the compound is beteroleptic (having differe3nt types of ligands) and neutral.

I I

Co3+ Co3+

Br Cl OH2 H2O
Cl Br

(B) Oxidation staat3e of cobalt in the complex is +3 and the compound is homoleptic (having
same type of ligands) and neutral.

N N N N N N N N

(C) O Co3+ O O Co3+ O N Co3+ O O Co3+ N

O N N O O O O O

mer one pair of enantiomers fac one pair of enatiomers

 (C) Oxidation state of cobalt in the complex is +3 and the compound is heteroleptic (having
different types of ligands).
[Co (NH3)2CI2(en)]NO3 (aq) [Co (NH3)2CI2(en)]+ (aq) + NO3(ap)
+ +
+ + Cl NH3
Br NH3
Cl Cl
NH3 Cl en en
Co Co
en Co en Co NH3 NH3
NH3 Cl
NH3 Cl
Cl NH3

(D) Oxidation state of cobalt in the complex is +3 and the compound is beteroleptic (having
different types of ligands).
K3[CoCI2(C2O4)2] (aq) 3K+ (aq)+ [CoCI2 (C2O4)21]3 (aq)

3 3 3
ox ox Ol
O O
O O O O
O O 3+
3+ 3+ ox Co ox
ox Co Co ox
O O
O Cl Cl O
Cl
Cl Cl
trans

cis-one pair of enantiomers

3.52 (A p, s); (B r); (C p, q, s); (D p, s, t)
III III
(A) [ Co (NH3)5CI] CI2. H2O and [ Co (NH3)5H2O] CI| hydrate isomerism. In later form all (i.e.six)
secondary valences of metal are satisfied by neutral molecules.
III III
(B) [ Co (NH3)5Br]SO4 and [ Co (NH3)5SO4]Brionisation isomerism.
(C) [Cr (H2O)6]CI3, [Cr (H2O)5 CCI] CI2. H2O and [Cr (H2O)4 CfI2] CI.2H2O hydrate isomerism. In
first form secondary valences (i.e.six) of the metal are satisfied by only neutral molecules.
Cr(III) has 3 unpaired elecrons whether the ligand is weak or strong field. B.M. = 3(3 2) = 3.87 B.M.
(D) [Cr (H2O)6]NO2 and [Cr(H2O)5 (NO2)]NO2. H2O lindage isomerism.
In first form secondary valences (i.e. six) of the metal are satisfied by only neutral molecules. In
the complex the Cr is in +1 oxidation state with electron configuration [Ar]183d5s.
3.53 (A p, r); (B q, r); (C p, r); (D p, s).
(A), (B)3d6 configuration, d2sp3 hybridisation.
This arrangement has a very large3 CFSE. Most of the ligands are strong enough to cause spin
pairing. Such complexes are diamegnetic. The one exception is [CoF6]3 which is a high spin
complex and is paramegnetic.
(C) NO2 strong field ligand, so compels for pairing of electron and thus it is diamagnetic with d2sp3
hybridisation.
(D) Paramagnetic with sp3d2 hgybridisation
3.54 (A p); (B q); (C p, r); (D r).
(A) dsp2 hybridisation; Au is in +3 oxidation state and complex is diamagnetic. (5d8 configuration)
(B) sp3 hytbridisatyion; Cu is in +1 omidation staste and complex is diamagnetic. CN is strong
field ligand but no empty d-orbitalis available for dsp2 hybridisation.
(C)sp3d2 hybridisation; Co is in +2 oxidation state and complex is paramagnetic with one unpaired
electron.
(D)sp3d2 hybridisation with Fe in +1 oxidation state and paramagnetic with three unparied wlecrons.
 3d 4s 4p 4d

[Fe(H2O)5 NO]2+ :
sp3d2 hybridisation

3.55 (A p, q, r); (B q, r, s); (C p, q, r, s); (D p, q).

III III
(A) [ Co (en)2NH3CI]2+ SO42 and [ Co (en)2NH3SO4]+CI ionisation isomerism.
2+
NH3 2+
en 2+
en
NH3
3+ NH3
en Co en Co3+
Co3+
Cl
Cl
en

en
Cl
cis
Note : trans-form has a centre of symmetry and several planes of symmetry, butthe cis-form has
neither.
(B) Has total 10-isomeric forms including linkage (NO2 - ambidentate ligand), ionisation (exchange
of No2 Compound is optically inctive as cis- and trans-).
(C) Exchange of NO2and CIgives rise to ionisation isomerism.
Linkage through either Oand Ngives rise to linkage isomerism.
N + + N en
en
NO2
N O2N N
3+ 3+
Co Co
*N NO2 O2N N*
pn
pn
N** **N
mirror plane
cis
N + + N en
en
NO2
N O2N N
3+
Co3+ Co
**N NO2 O2N N**
pn pn
N* *N
mirror plane
cis
+ +
NO2 NO2
*
N N **
N N
3+ 3+
ph Co en ph Co en
**
N *
N
N N

NO2 NO2
trans trans
Thus exists in two trans - and two cis-isomers and each of cis-isomer show optical isomerism.
 1 2 3
CH2 CH CH3 (1, 2-diaminopropane(pn))
H2N NH2

y O y O
gl gl
N N N N
gly

gly
3+ 3+
Co Co

(D) O O N O
gly gly
N O
cis trans

Both cis- and trans - isomers have each a pair of optical isomers because of absence of any one
of symmetry elements.

3.56 AIF3 + KF K3 [AIF6]

Electronic configuration of AI is [Ne]10 3s2 3p1.
EAN for K3[AIF6] = 13 3 + 2 6 = 22.
3.57 The oxidation state of Cr is+1 in the complex [Cr(NO+)(NH3)(CN)4]2 and thus the valence shill
electron configuration would be [Ar]18 3d54s0. As the CN and NH3 ae strong fields ligands, they
compel for paring of electrons so
eg

2 5 no. of unpaired electrons = 1

[Cr(NO)(CN)4(NH3)] =3d

t2g

3.58 Complex ion is [Fe (H2O)5 SCN]2+ ; it has coordination umber six.
3.59 [Pt (NH3)2(SCN)2] cis and trans isimers = 2.
[Pt (NH3)2(NCS)(SCN)] cis and trans i9somers = 2.
[Pt (NH3)2(NCS)2] cis and trans isomers = 2.
The complex is square planar; so it does not have a pair of enantiomer on account of the presence
of plane of symmetry.
3.60 Net stabilization energy of Fe2+ with CN
ligands t2g2,2,2 eg0,0 = 2.4 0 + 2P =m (2.4 25000 + 2 15000)cm1
= 30000 cm1
Net stabilisation energy of Fe2+ ions with H2O ligands t2g 2,1,1
eg 1,1 = 0.4 0
= 4000 cm1
So required difference = 26000 cm1 = 26 105 m1
= 610 343108 2610561023103kJ/mole
= 2808101kJ/mole = 281kJ/mole = 280.8 kJ/mol

0.625
3.61 Co = = 0.625 ; = 1
0.625
53.125 3.125
NH3 = = 3.125 ; =5
17 0.625
 10 0.625
O= =0.625 ; = 1
16 0.625
Hence the complex is Co2(NH3)10O2 and the cations are
A : [(NH3)5 CoOOCo(NH3)5]6+
B : [(NH3)5 CoOOCo(NH3)5]5+
1 4+
C : [(NH3)5 Co O O Co(NH3)5]
2
3.62 Complex Cr(NH3)4 CIBr has two isomers. Since co-ordination numbjer of Cr is six and thus two
forms may be
+ AgBr
AgNO3
[Cr(NH3)4CI2]Br [Cr(NH3)4CI2]+ +NO3 yellow ppt, soluble partially in
conc. NH3 i.e., [Ag(NH3)2]Br
+ AgCI
AgNO3
[Cr(NH3)4Br.CI]CI [Cr(NH3)4CIBr] +NO3 white
+ ppt soluble
in dil. NH3 i.e., [Ag(NH3)2CI]
NH3is strong field logand so,
3d 4s 4p

[Cr(NH3)4CL2]/[Cr(NH3)4Br4CI] :
d2 sp3 hybridisation
Hybridisation of Cr in (A) and (B) is d2 sp3 having 3 unpaired electrons(3d3)
For d3 configuration, the magnetic moment is alway 3.87 with weak field or strong field liagnd.
Magnetic moment = [n(n 2)] B. M. = [3(3 2)] = 3.87 B.M.
 INORGANIC CHEMISTRY

4. METALLURGY

4.1 (B) (A) Calamine = ZaCO3, Sidereite= FeCO3 (B) Argentite = Ag2 Sand Cuprite = Cu2O
(C) Zinc blende = ZnS, Pyrites = FeS2 (D) Malachite = CuCO3 Cu(OH)|, Azurite =2CuCO3
Cu(OH)2
4.2 (A) Argentite Ag2S; Cuprite Cu2O; Sidirite Feco3; jCarnallite KCI. MgCI2.6H2O
4.3 (D) (A),(B) and (C) stat4ements are correct.

4.4 (B) ZnS+4NCN Na2[Zn(CN)4](soluble compolex)+Na2S.

4.5 (C) This process is si,ply calcination.
4.6 (B) PbS reduces PbO to Pb and SO2 is liberaated. This is called as self reduction.
4.7 (A) I = In manufacture os steel, II + Self reductio of Cu2O to Cu O to Cu vby CuS.
Re duction
4.8 (C) Fe2O3+ 3CO 2Fe =3CO2; impurities are removed by oxidation as given below..
oxidation
2Mn + O2 oxidation
2MnO ; Si + O2 SiO2: MnO + SiO2 MnSiO3(slag)
4.9 (B) Copper pyrites contain Fe and Cu. Iron oxide is removed during smelting, FeSiO3.
FeO+SiO2 FeSiO3
4.10 (B) Most of the impurity of iron sulphide is removed during smelting, 2FeS +3O2 2F3eO
2FeO + 2SO2
FeO + SiO2 FeSiO3 (3)
4.11 (B) PbS + 2PbO 3Pb + SO2 (self reduction)
SnO2 + C Sn + CO (carbon-reduction)
SnO2 + 2CO Sn + 2CO2
4.12 (D) (A) Cassiterite contains iron and manganese tungstate, called as Wol- framite.
They have magnetic properties.
(B) Purified ore that contains 70% SnO2 iscalled black tin.
SnO2 + 2C Sn+ 2CO (carbon reduction)
(C) Roasting is done at moderate tempe in presence of air in reverberatory furnace. Then
air supply is stopped and temperature is increased to melt the mass when self-
reduction takes place.
(D) At 500 - 800K (lower timperature range in the upper part of blast furnace)
3Fe2O3 + CO
2Fe3O4 + CO2

Fe3O4 + CO
3Fe + 4CO2

Fe2O3+ CO
2FeO + CO2
At 900 - 1500K (higher timperature range in the lower part of blast furnace:
C + CO2
2CO ; FeO + CO
Fe + CO2
4.13 (A) From saltsof magnesium, magnesium can not be extacted by other chemical methods as
magnesium itself acts as a reducing agent and Mg obained at cathode during electrolysis of
its salt solution, reacts with water forming Mg (OH)2.

MgCl2 Mg2+ + 2Cl ; At cathode Mg2+ + 2e Mg ; At anode 2Cl Cl2 +2e

4.14 (C) White bauxite containing the impurity ofsilica only is removed by heating with coke in
atmosphere of nitrogen.

Al2 O3 + 3C + N2
2AlN + 3CO

SiO2 + 2C Si + 2CO ; AlN + H2O
Al(OH)3 +NH3; 2Al(OH)3 AI2O3 + H2O

4.15 (B) (A) Molten mixture of alumina and cryolite

(B) 2PbS + 3O2
2Pb + 2SO2 (self reduction)

PbS + 2PbO
3Pb + SO 2 (Self reduction)

PbO + C
Pb + CO (carbon reduction)

(C) SnO2 + C
Sn + CO (carbon reduction
(D) siderite = FeCO3 ; cassiterite = SnO2 and argentite = Ag2S.
4.16 (A) Cyanide processAg; Self reductionCu; Electrolytic reductionAI, Carbon reduction Sn.
4.17 (A,B,C)
(A) Self reduction takes place in Bessemer converter.
(B) Slag formation and reduction of haemalite to iron take place in blast furnance at different
temperatures.
(C) Cr2 O3 + AL AL O3 + 2Cr.
This is called sluminothermic process.
(D) Tin is Obtained by carbon reduction of SnO2 (cassiterite ore)
4.18 (A,B)
Cu2S+2Cu2O 6Cu + SO2
PbS + 2PbO 2Pb + SO2
HgS + 2HgO 3 Hg +SO2
4.19 (C,D)
(C) It occurs in fusion zone at higher tempt. with Fe2O3 which escapes reduction zone.
(D)It occurs in slag formation zone.
4.20 (A,B)
(C) Magnesite (MgCO3) is ore of magnesium.
(D) Tin is extracted by carbon reduction. SnO2 + 2C
Sn + 2CO
(A) and (B) are correct statements.
4.21 (A,B,C)
(A) True statement
(B) CaO + SiO2 CaSiO3 (slag); (C) PbO + SiO2
PbSiO3

CaO Converts the PbSiO3 to PbO, PbSiO3 + CaO

PbO + CaSiO3
4.22 (B) CaF2 - Ionic compound lonises to give ions & thus increases the number of ions in the
electrolyte and as impurity decreases the melting point of AI2O3.
4.23 (B,C,D)
(A) FeSiO3

(B) CaCO3 CaO + CO2.

CaO + SiO2
CaSiO3.
These reactions take place in slag formatin zone at temperature 1275 K.
(C) True statement.
(D) Infusible matter + Flux = Fusible matter (slag).
4.24 (A,B,C,D)
Selenium, tellurium, silver, gold and platinum are the metals present in anode mud. This is
because these are less reactive than copper.
4.25 (A) Randomness increases on changing the phase from soilid to liqid or from liquid to gas.
2
4.26 (A) O
Au(S) Au+(aq.)

Au+ + 2CN- (aq.)

[Au (CN)2]-soluble complex.

4.27 (C) 2CuFeS2 + O2

Cu2S + 2FeS + SO2;

2FeS + 3O2
2FeO + 2SO2

FeO + SiO2
FeSiO3; thus remove the impurity of iron oxide.

4.28 (A) Cast iron contains 3% carbon.

4.29 (A) Upper most layer of pure molten aluminium, middle layer of molten fluorides of Na+, Ba+2 and
Al +3 and lower layer of Molten impure aluminium have different densities.
4.30 (C) S-1 : It lowers the fusion temperature of MgCi2 and provide conductivity to the electrolyte.
S-2 : MgCi2. 6H2O is calcined in a stream of dry HCI gas to have anhydrous MgCI2. In
absence of dry HCI, It forms MgOCI2 (MgO. MgCI2) because of hydrolysis.
4.31 (A) S1 : In Upper part at lower temperature reduction of Fe2 O3 takes place by carbon monoxide
but unreduced FeO is reduced by carbon at higher temperature in lower part of blast furnace.
S2 : Sphalerite = ZnS
S3 : True statement.
S4 : Evolution of SO2 Produces blister like apprearance on the surface of solidfied copper.
4.32 (A) S1 : Cu2O, Fe2 O3 . 3H2 O, ZnO ; S2 : MgCO3, KCI, MgCI2. 6H2O
S3 : Cu2S, 3CuCO3. Cu(OH)2 ; S4 : Both contain aluminium

4.33 (B) (A) Cr2 O3 + 2AIO3

Ai2O3 + 2Cr. + 2Cr..

[Au(CN2]- + Zn = [Au (CN)2]-+2Au.

(B) Au + 2CN - + H2O + O2
(C) True statement.
2
O
(D) Ag2 S + 4NaCN 2Na [Ag (CN2] + Na2 S

2Na [Ag (CN)2] + Zn

Na2 [Zn (Cn4] + 2AG
4.34 (A) Reaction occurs during roasting in reverberatory furnace at moderate temperature in presence
of air.
4.35 (A) O2 oxidases silver to silver (I) ion which then produces soluble complex with CN-ions.
2Ag + 4 NaCN + O2 + H2O 2Na [Ag (CN)2] +2 NaOH.

2Na[Ag (CN2] + Zn
Na2 [Zn (CN)4] + Ag

4.36 (A) Red bauxite contains the impurities of iron oxides, titanium oxide and silica which are removed
by Baeyers and Halls processes. The Serpecks method is used when bauxite contain only
the impurity of silica.
4.37 (A) At about 10000 C, lines cross and thus at this temperature zinc and carbon have equal
affinity for oxygen.
4.38 (B) This wil be above a temperature when two curves intersect that is > 10000 C.
4.39 (D) All statements are true.
4.40 (A)

4.41 (D) Au [Au+] which then form complex with CN-.

2[Au(CN2] + Zn 2Au + [An (CN)4]2-. Zinc acts both as complexing and reducing reagent.
4.42 (C) The process which involves the dissolution of ore into a suitable reagent and then extraction
of metal from the solution by more eletropositive element is called hydrometallurgy.
4.43 (A) [X] = CuCO3 Cu (OH)2 or 2CuCO3. Cu(OH)2 ; [Y] = Cu2 S or CuFeS2
4.44 (D) It is sulphide ore (Cu2 S or CuFeS2) & is called as chalcopyrites or chalcocites ; S2- gives
yellow precipitate of CdS with CdCO3.
4.45 (C) G1 = SO2 ; sulphur can increase & decrease its oxidation state.
4.46 (A) CuCO3 + 2HCI CuCI2 + CO2 + H2O ; CuCI2 + 2KI CUl2 +2KCI2 2CuI2 Cu2I2 (P) + I2
4.47 (A - r) ; (B - q) ; (C - s) ; (D -p)
(A) Limonite is Fe2 O3 and cuprite is Cu2O.
(B) Calamine is ZnCO3 and Cerussite is PbCO3.
(C) Pyragyrite is Ag3 SbS3 and Zinc blende is ZnS.
(D) Anglesite is PbSO4 and Langbeinite is K2Mg2 (SO4)3.
4.48 (A - q, s) ; (B - p); (C- r, s); (D - r, s, t)
(A) Fe2 O3 ; calcination; At lower part of furance reduction of unreduced FeO by carbon at higher
temperature and in upper part of furnace reduction by CO at lower temperature.
(B) CuFeS2; FeSiO3 formation mainly occurs during roasting (now a day) / smelting and left FeO
reacts with SiO2 in Bessemer converter.
(C) KCI, MgCI2. 6H2O calcination in presence of dry HCI to remove 6 water molecules. Mg
extraction by electrolytic reduction from molten mixture of anhydrous MgCI2 + CaCI2.
leaching
(D) Al2 O3 (S) + 2NaOH (aq) + 3H2O (I) 2Na [AI (OH)4] (aq)
1275K
AI2 O3; 2AI (OH)3
Calcination
AI2 O3 + 3H2O; Extration of AI from purified AI2 O3by electrolytic
reduction.
4.49 (A -p); (B - p); (C -q); (D -s)
(A) Gold dissolves in NaCN solution forming a soluble complex leaving behind impurities is called
leaching process. Hence the extraction of gold is called hydrometallurgy.
(B) Insoluble copper pyrites dissolves in H2SO4 forming soluble CuSO4 is called leaching. Hence
the extraction of copper is called hydrometallurgy
 (C Reduction of Fe3 O4 by CO in blast furnace is smelting.
(D) Heating Mgin dry HCI gas to convert into anhydrous MgCI2 is calcination.
4.50 (A - q) ; (B - s); (C -r) ; (D -p)
Silver involves formation of soluble complex with dilute NaCN solution in presence of air followed
by precipitation with zinc.
Lead involves roasting (of PbS) followed by self reduction.
Iron involves calcination (of Fe2 O3) followed by reduction with carbon monoxide.
Magnesium involves calcination (of MgCI2. 6H2 Oin presence of dry HCI gas) followed by fused salt
electrolysis.
4.51 Cryolite is 3NaF.AIF3 or Na3[AIF6]. It gives that coordination number of aluminium is six. It can
expand its covalency by using empty d-orbitals.
4.52 Carnallite is KCI.MgCI2. 6H2O.
4.53 At 500-800 K (lower temperature range in the blast furnace)
3Fe2O3 + CO
2Fe3 O4 + CO2

Fe3 O4 + CO
3Fe + 4 CO2

Fe2 O3 + CO
2FeO + CO2
At 900-1500 K (higher temperature range in the blast furnace) :
C + CO2
2CO ; FeO + CO
Fe + CO2

4.54 2HgS + 3O2

2HgO + 2SO2 ; 2HgO + HgS
2Hg + SO2

Cu2 S + 3O2
3Cu2O + 2SO2 ; 2Cu2O+Cu2S
6Cu +SO2

2PbS + 3O2
2PbO + 2SO2 ; 2PbO + PbS
3Pb + SO2

4.55 Copper pyrites (CuFeS2) contains copper and iron.

 INORGANIC CHEMISTRY

5. S-BLOCK ELEMENTS AND COMPOUNDS

5.1 (B) (A), (C) and (D) decreases down the group but (B) increases down the group with increasing
metallic character.

5.2 (C) (A) 4LiNO3 2Li2 O 4NO 2 O 2

2NaNO3 2NaNO2 O2 (similar decomposition with the itrates of K, Rb and Cs)

(B) Only LICl is deliquescent and crystallises as a hydrate LiCl.2H2O
(C) 2M 2H2O 2M 2OH H2 (M an alkali metal)
(D) Halides of Li are covalent in nature.
5.3 (C) When sodium and potassium react with water, the heat evolved causes them to melt, giving a
larger area of contact with water, lithium on the other hand, does not melt under these condition
and thus reacts more slowly.
Li Na K
Melting point (C) 180 98 64.

5.4 (C) M (x y)NH3 [M(NH3 )x ] [e(NH3 )y ]

Solutions are deep blue coloured due to the absorption of light in visible region by solvated
electrons. It is paramagnetic due to the presence of the unpaired electrons.
5.5 (A) Basic strength of the oxides increases in the order Li2O < Na2O < K2O < Rb2O < Cs2O. The
increase in basic strength is due to the decrease in I.E. and increase in electropositive character.
The melting points of the halides decrease in the order NaF > NaCl > NaBr > NaI, as the size of
the halide ion increases. The decrease in melting point is due to increase the covalent character
with increase in the size of anion according to Fazans rule.

5.6 (C) NH3 CO2 H2O NH4HCO 3

NaCl NH4HCO3 NaHCO3 NH4 Cl

150 C
2NaHCO3
Na2CO3 CO 2 H2O

2NH4 Cl Ca(OH)2 2NH3 H2O CaCl2 (by product)

1
5.7 (B) (2) KO2 2H2 O KOH H2O2 O2
2

(3) 4KO2 2CO 2 2K 2CO3 3O2

5.8 (D) NaNO2 (sodium nitrite) acts both as oxidising agent and reducing agent because the nitrogen
atom in it is in + 3 oxidation state (+ 3 intermediate oxidation state for nitrogen)
Oxidising property : 2NaNO 2 2KI 2H2SO 4 NaSO 4 K 2 SO 4 2NO 2H2O I2

Reducing property : NaNO 2 H2O 2 NaNO3 H2O.

5.9 (C) 2M(NO3 )2 2MO 4NO2 O2 (M Be, Mg, Ca, Sr, Ba)
5.10 (C) (1) The solubility increases down the group because the change in latice energy is more as
compared to hydration energy. Thermal stability and the basic character both increase down the
group as metallic character increases.
(2) It is correct statement.
(3) Beryllium and aluminium and diagonally related. Chlorides of both are covalent in nature and
thus are soluble in organic solvents. Chlorides of both are electron deficient and thus act as
strong Lewis acids.

5.11 (B) 3Mg N2 Mg3N2 ;

Mg3N2 6H2O 3Mg(OH)3 2NH3

(X) (Y)
CuSO 4 4NH3 [Cu(NH3 )4 ]SO 4 (blue colour)
5.12 (A,B,C)
(A) This is because the heat from the flame excites the outermost orbital electron to a higher
energy level. When the excited electron comes back to the ground state, there is emission of
radiation in the visible rgeion as given below :
Metal Li Na K Rb Cs
Violet/
Colour Crimson Yellow Lilac Red Blue
red violet
(B) Down the group the change in lattice energy is more than that of hydration energy.
(C) Because of low ioniation energy and melting point.
(D) Reducing nature increases down the group as their stability decreases down the group
CsH > RbH > KH > NaH > LiH.
5.13 (A,B,C,D)
All statements are correct.
5.14 (A,B,C)
Charge on cation
(D) Hydration energy
Size of cation
(A), (B) and (C) are correct statements.
5.15 (A,B,C)
(A) Li+ and Mg2+ have higher polarising power and thus attract more nmber of water molecules.
(B) Li is least reactive because of its highest ionisation energy on account of smaller size.
(C) It is one of the uses of liquid sodium. It has low melting point.
(D) LiI is the most covalent due to smaller cation and bigger anion. (According to Fajans rule)
5.16 (A,B,D)
M (x y)NH3 [M(NH3 )x ] [e(NH3 )y ] . Blue colour of the solution is due to ammoniated
electrons and good conductor of electricity because of both ammoniated cations and ammoniated
electrons.
O 2 e O2 ; O 2 2e O 22 (change of oxidation states from 0 to 1).
5.17 (A,B,C)
(A) 2MnO 4 (pink) 16H 5O22 2Mn2 8H2O 5O2 .
450 C
(B) Na2O 2 O 2
300 atm
2NaO 2 (O 2 contains one unpaired electron in * MO)
400 C
(C) 2Na2O Na2O 2 2Na.
(D) gives only H2O2.
5.18 (A,B,C)
(A) P4 3NaOH 3H2 O PH3 3NaH2PO 2

(B) 4S 6NaOH Na2S 2O3 2Na2S 3H2 O

(C) 3Cl2 6NaOH 5NaCl NaClO3 3H2O

(D) 2B 6NaOH 2Na3BO3 3H2

5.19 (A) Statement-1 and Statement-2 are correct statements and statement-2 is the correct explanation
of statement-1.
5.20 (A) Beryllium and aluminium have diagonal relationship.

5.21 (B) S1 : M (x y)NH3 [M(NH3 )x ] [e(NH3 )y ]

S2 : Above 3M concentration, the solutions are no longer blue but are bronze/copper-bronze
coloured with a metallic luster due to formation of metal ion clusters.
5.22 (B) (i) Bigger cation stabilises bigger anions and vice-versa.
(ii) Alkali metal carbonates and their bicarbonates stabilities depend on their metallic character.
Stability of carbonates and bicarbonates Metallic character of their i.e. electropositive character.
5.23 (A) Potassium and caesium have low ionisation energies and, therefore, their valence shell electrons
can be easily eject out by the energy of light.
5.24 (A) S1 : In concentrated solution unpaired electrons pair up together and become dimagnetic S2 and
S3 are correct statements.
S4 : Be(OH)2 2OH [Be(OH)4 ]2 beryllate ion

Be(OH)2 2HCl 2H2O [Be(OH2 )4 ]Cl2

5.25 (B) S1 : Na /Hg H2O NaOH H2 Hg

S2 : Potassium is more reactive than sodium than sodium due to its more negative value of
reduction potential.
S3 : True statements.
S4 : Alkaline earth metal salts have more number of water molecules as compared to those of
alkalii metal salts, because of higher nuclear charge and smaller ionic radius.
5.26 (C) S1 : True statement-salt of weak base and strong acid.
S2 : As we move down the group from Li to Cs the strength of metallic bonding decreases as size
of atom increases. Due to this there occurs a decrease in close packing of atoms in crystal lattice
from Li to Cs and thus the softness increases from top to bottom.
S3 : It is hemihydrate of CaSO4(2CaSO4.H2O).
S4 : KHCO3 is soluble in water and cannot be precipitated like NaHCO3.
5.27 (C) The thermal stabilities of carbonate increase donw the group due to increase in metallic character
i.e. electropositive character. Further bigger cation stabilise bigger anion through crystal lattice
energy effects.
5.28 (C) Down the group the change in lattice energy is more than that of hydration energy.

5.29 (A) NaCl (conc.) Na Cl

H2O H OH

At cathode : AH 2e H2

At anode : 2C Cl2 2e
 Na OH NaOH

5.30 (D) Here solvated electrons acts as a reducing agent.

5.31 (C) 4KO2 3CO 2 2K 2CO3 3O2

5.32 (D) (A) M2O H2 O 2MOH

1
(B) M2O H2O 2MOH O2
2

(C) 2MO 2 2H2O 2MOH H2 O2 O2

5.33 (D) Dilute solution of Na metal in liquid ammonia is deep blue coloured and highly conducting and
paramagnetic in nagure because of solvated cations and solvated electrons.
M (x y)NH3 [M(NH3 )x ] [e(NH3 )y ]

5.34 (B) Na2CO3 N2O3 2NaNO2 CO2

(A)
5.35 (C) O2 is paramagnetic as it contains two unpaired electrons in antibonding 2px and 2py orbitals.

5.36 (D) NH4NO 2 N2 2H2O
(D)
Reactions involved :
500C
2NaNO3 2NaNO2 O2
(A) (B)
800C
4NaNO3 2Na2 O 5O2 2N2
(C) (B) (D)
5.37 (A p,q); (B q); (C r); (D s)
(A) Down the group the decrease in latice energy is more as compared to that of hydration energy with
increase in size of cations. So the solubility order is correct. Similarly the thermal stability of the oxo-
salts increases with increase in metallic character. So the thermal stability order is correct.
(B) The correct order of solubility is MgSO4 > CaSO4 > SrSO4 as in this case decrease in hydration
energy is more as compared to that of lattice energy.
The order of thermal stability is correct, as down the group metallic character increases and thus the
thermal stability of oxo-salts increases.
(C) Down the group strength of metallic bond decreases. Due to this there occurs a decrease in close
packing of atoms in crystal lattice from Li to Cs and thus softness increase down the grup.
1
(D) Hydration energy
Size of atom
So Be > Mg > Ca is correct order.
5.38 (A p,q,r); (B p,q,r); (C p,r); (D p,q,s)
(A) NaSO 4 C CaCO3 Na 2CO3 (sp2 ) CaSO 4 (sp3 ) (White)

(B) NaCl NH4 .HCO3 NaHCO3 (sp2 ) (White) NH4Cl(sp3 )

(C) Na2CO3 Ca(OH)2 CaCO3 (sp2 ) (White) NaOH

(D) 2KOH 4NO 2KNO2 (sp2 ) N2O H2O(sp3 )

 If 4KOH 6NO 4KNO2 N2 2H2 O

5.39 (A r); (B s); (C p); (D q,t)

(A) 3Ca(OH)2 2Cl2 Ca(OCl)2 .Ca(OH)2 .CaCl2 .2H2O (bleaching powder).
Ca(OCl)2 is constituent of bleaching powder.
1
(B) CaSO4 . H2O is called as Plaster of Paris.
2
(C) KO2 absorbs CO2 and gives O2 gas according to the following reactions, so used as air purifier in
submarine.
3
2KO2 CO2 K 2CO3 O2 ; 2KO2 2H2O 2KOH H2O2 O2
2
(D) Calcium oxide i.e. quick lime is used for the removal of temporary hardness of water.
CaO H2O Ca(OH)2 ; Ca(OH)2 Ca(HCO3 )2 2CaCO3 2H2O

Ca(OH)2 Na2CO3 CaCO3 2NaOH (causticising process).

5.40 (A r,s); (B r); (C p); (D q)

(A) & (B)
NH3 H2O CO 2 NH4HCO 3

NH4HCO3 H2O NH4 OH H2CO3

250 C
2NaHCO3
Na2CO3 H2 O CO 2

NH4HCO3 NaCl NaHCO3 NH4 Cl

CaO H2O Ca(OH)2

Ca(OH)2 2NH4Cl CaCl2 2NH3 2H2O

2NH4 Cl Ca(OH)2 2NH3 2H2O CaCl2

(C) The solutions of Na2CO3 and NaHCO3 in water are alkaline in nature and thus turn the litmus paper
blue.
(D) The commercial name of sodium peroxide is oxone which is used for the manufacture of oxygen
gas.
1
Na2O2 H2O 2NaOH O2
2

1
5.41 Na O2 Na2O; Na2O O2 Na2O2
2
It exists as 2Na+ and O22 . So oxidation state of O is 1.
5.42 All alkaline earth metal nitrates decompose to form metal oxide, NO2 and O2.
2M(NO3 )2 2MO 2NO2 O2 (M = Be, Mg, Ca, Sr or Ba)

5.43 The temperature of decomposition of these sulphates increases as the electropositive character of
the metal increases down the group. For example,
Compound : BeSO4 MgSO4 CaSO4 SrSO4
Temp. of decomposition : 773 K 1168 K 1422 K 1644 K
effloresces
5.44 Na2 CO3 .10H2O
9H2O
Na2CO3 .H2O (monohydrate)
 INORGANIC CHEMISTRY

6. p-BLOCK ELEMENTS AND COMPOUNDS

6.1 (D) (A) AlCl3 3H2O Al(OH)3 3HCl (fumes)

(B) It exists as dimer in non-polar solvents like benzene and in vapour state below 350C.
(C) 4Al2O3 3S 2Cl2 9Cl2 8AlCl3 6SO2
So all options are correct.
6.2 (D) It forms a stable cyclic complex with polyhydroxy compounds like cis-glycerol, cathechol, etc. This
helps in the release of H+ as H3O+ and, therefore, boric acid acts as a strong acid and hence can
be titrated with sodium hydroxide using phenolphthalein.
6.3 (C) (A) It is a wak monobasic acid soluble in water and in aqueous solution in boron atom completes
its octet by accepting OH from water molecules :
B(OH)3 2H2O [B(OH)4 ] H3 O
(B) Only Tl3+ acts as an oxidising agent on account of inert pair effect.
(C) In the solid state, the B(OH) 3 units are hydrogen bonded together into two dimensional
sheets with almost hexagonal symmetry.

(D) B(OEt)3 imparts green colour to the burner flame.

6.4 (C) HCN 2H2O HCOOH(X) 2NH3 ; HCOOH CO[Y] H2O
(C) Only K4(Fe(CN)6] gives CO with conc. H2SO4 according to the following reaction.
K 4 [Fe(CN)6 ] 6H2SO 4 (conc.) 6H2O 2K 2SO 4 FeSO 4 3(NH4 )2 SO 4 6CO
(A) MMalonic acid gives C3O2; (D) Action of conc. HNO3 on charcoal gives (CO2. (B) C3O2 gives
CO2.

6.5 (A) O Si O
R n
 FeCrO
6.6 (A) CO(g) H2 (g) H2O(g)
673K
4
2H2 (g) CO 2 (g)

6.7 (D) (A) This is due to the inert pair effect in the heavier p-block elements.
(B) 3HNO2 HNO3 H2 O 2NO
(C) This is due to the presence of completely filld d and l or f orbitals in heavier elements.
Covalent raidus l pm; N = 70, P = 110, As = 120, Bi = 150.

6.8 (B) (A) 2NaN3 2Na 3N2 ; (B) (NH4 )2 SO 4 2NH3 H2SO 4 ;

(C) NH4NO2 N2 2H2O.

(D) (NH4 )2 Cr2O7 N2 Cr2O3 4H2O.

6.9 (D) 2Cu 6HNO3 2Cu(NO3 )2 NO NO2 3H2O

20C
NO NO2 N2O3 (blue); (A) 2HNO2 N2O3 H2 O

(B) N2 O3 2KOH 2KNO 2 H2O

(C) 2HNO3 As2O3 2H2O NO NO2 2H3 AsO4

250K
N2 O3

All options are correct.

6.10 (D) (A) 2N2 O 2N2 O 2 .
It produces one third oxygen by volume of total gas produced while air has one fifth volume of
oxygen.
PO
(B) 2HNO3 2 5
H2O N2O5
(C) White phosphorus most reactive and black phosphorus is almost inert.
(D) White phosphorus turns to red phosphorus on heating in the atmosphere of CO2 or coal gas
at 573 K.
So (A), (B), (C) are correct and (D) is correct.
O

P diabasic as contains two replaceble protons.

6.11 (A)
HO OH
H reducing hydrogen.

Oxidation state of P is + 3 can be decrease to 3 and increase to + 5. Hence it can act as both
reducing as well as oxidising agent.

14
6.12 (C) 3Ca3 (PO 4 )2 CaF2 H3PO 4 10Ca(H2PO 4 )2 2HF (Triple sup er phosphate).

6.13 (A) NH4 CIO 4 HNO3 HClO 4 NH4NO3

2NH4NO3 2N2 O 4H2O

platinum/Rhodium catalyst
6.14 (A) 4NH3 (g) 5O2 (g)
850C, 5 atmosphere
4NO(g)

cool to
4NO(g) O2 (from air) 2NO2 (g)
25 C

H2 O NO2 O2 HNO3 NO.


6.15 (C) KCNO (NH4 )2 SO 4 NH4 CNO NH2 CONH2

6.16 (C) (1) NH3 has higherboiling point than AsH3 and PH3 on account H-bonding. SbH3 has highest
boiling point on account of highest molecular weight.
(2) As the size of element increases, the strength of MH bond decreases and thus tability
decreases.
(3) Basicity decreases down the group. (Drago rule).
(4) HEH angle () : NH3 = 107.8; PH3 = 93.6, AsH3 = 91.8; SbH3 = 91.3.

O O O OH
O O O O
S P

(A) O O (B) O S S O (C) O O (D)
O S O O S O
6.17 (A) O O O O
S S O O P P O O
O O HO OH
O O

O O
+6 0 0 +6
6.18 (A) O S S S S O

O O

O2 (air)
6.19 (A) 2-ethylanthrqiniol H2O2 oxidised product.
H2 / Pd

6.20 (D) H2 O2 H HO2 ; H2O2 2H O22

2NaOH H2O 2 Na2O2 2H2O.

6.21 (A) (A) SO2 2H2O H2SO 4 2H. Hence bleaching is through reducing (temporary) and

Cl2 H2O 2HCl [O] bleaching is through oxidation (permanent).

So (A) is correct and (B), (C) and (D) are incorrect.
6.22 (B) H2SO4 is stronger oxidising agent and Hl is stronger reducing agent. So H2SO4 oxidises to Hl to
I2 and is itself reduced to SO2.
NaI H2SO 4 NaHSO 4 Hl

Hl H2 SO 4 I 2 SO2 2H2O

6.23 (A) 2MnO 4 16H 2Cl 2Mn 2 Cl2 8H2O

O O O
|| || ||
6.24 (A) (A) P P P
H OH H OH OH OH OH
H OH

S
(B) O || O
O

(C) SO32 contains one lone pair of electrons on sulphur atom.

 F F
F F F F
(D) Xe Xe Xe
F F F F
F F
6.25 (D) It is used because it has very low solubility in blood.
6.26 (B,C,D)
Compound [X] is Na2B4O7.
(A) two boron atoms are sp2 while other two boron atoms are sp3 hydridised.
(B) product is sodium peroxoborate which is used as brighter in soaps.
(C) H3BO3 is formed wich with HF gives HBF4.
(D) Green bead in oxidising as well as in reducing flame in cold.
6.27 (A,B) (A) (B) Correct statements.
(C) Graphite sp2 hybridisation bond length 1.42 , diamond sp3 hybridisation bond length 1.54 .
(D) Diamond more dense (3.51 g/ml) than graphite (2.25 g/ml)
6.28 (A,D) (A) As number of reducing hydrogen increases, the reducing character also increases. In H3PO4
there is no reducing hydrogen so it should be least reducing.
(B) + 1 < + 2 < + 3 < + 5
(C) Down the group the availability of lone pair of electrons decreases as they are present in
more concentrated s-orbital.
(D) As down the group bond energy decreases, the removal of H becomes easier.

6.29 (A) (A) 2H3 5O2 2NO 3H2 O

(B) Due to the formation of NO2 according to following reaction
3HNO3 HNO2 2NO2 H2O O 2 .

(C) H2 S O H2O S

(D) N2 O3 H2O 2HNO2

6.30 (C) 2Na2 S(sq) 3SO2 (g) S Na2S 2O3 (aq)

6.31 (A,B,C,D)
(A) H2 S2 O8 H2SO5 (caros acid) H2SO 4

(B) 2KClO3 3H2SO 4 2KHSO 4 2ClO 2 HClO 4 H2O

(C) 2Na2S2O3 I 2 Na2 S4O 6 2NaI

(D) 2KIO3 5SO2 4H2O I 2 3H2SO 4 2KHSO 4

I 2 SO2 2H2O 2HI H2SO 4

6.32 (A,B)
(A) Two hydroxl groups lie in different plane (have open book like structure)
(B) It turns blue litmus red because of acidic character which is then bleached by bleaching
action of H2O3.

O
O O
S (D) HO O O OH
6.33 (B,D) (B) O O OH S S
O
H O O
 boiling
6.34 (A,C) (A) Na2 SO3 S
OH or H O
Na2S2O3
2

(B) S2O32 formed in presence of acid precipitates sulphur and liberates SO2 gas according to
the following reaction.

S2O32 H S (white) SO2 H2O

disproportionation

heating
(C) 2Na2S 3 3O 2
air
2Na2S 2O3 2S
Zn
(D) 2HSO3 SO 2 S2O 42 SO32 H2O

6.35 (B,C) (A) 2FeBr2 3Cl2 2FeCl3 2Br2

1
(B) SO2 H2O O2 H2 SO4 2HCl
2

(C) Al2S3 6H2O 2Al(OH)3 3H2S

(D) 4KMnO 4 2H2O 4MnO 2 4KOH 3O 2

4NH3 3O2 2N2 6H2O

6.36 (B,C) Cl2 and SO3 being stronger oxidising agent, oxidise Br to Br2 gas
2Br Cl2 Br2 2Cl

SO3 SO2 [O]

2Br 2H [O] Br2 H2O

2Br SO3 2H Br2 H2O SO2

HI being reducing agent and I2 being weak oxidising agent (comes after bromine) dont liberate
bromine from Br.

6.37 (B,D) (B) ClO 4 IO4 BrO4 according to their reduction potential.
(D) HOCl > HOBr > HOI. As electronegativity of halogens increases the acidic character increases.
GIven (B) and (D) are correct order.
6.38 (A,B,C,D)
XeF4 O 2F2 XeF6 [X] O2

(A) XeF6 H2O XeOF4 2HF

(B) XeF6 turns to yellow liquid on melting where as XeF2 and XeF4 turn white.
(C) 2XeF6 SiO2 2XeOF4 SiF4

(D) XeO3 2XeF6 3XeOF4

6.39 (C) Orthoboric acid acts as lewis-acid in water not as proton donar because it completes its octet by
accepting OH from water.
OH OH

B O H B + H+
HO OH H HO OH OH
6.40 (A) Statement-1 is True, Statement-2 is True, Statemen-2 is a correct explanation for Statement-1.
For example
SiCl4 4H2O H4 SiO 4 or Si(OH)4 (ortho silicic acid) 4HCl

6.41 (A) Na2 Al2Si2O8 .xH2O Ca2 CaAl2Si2O 8 .xH2O 2Na

Na2 Al2Si2O8 .xH2O Mg2 MgAl2Si2O8 .xH2O 2Na

6.42 (C) S1 : Pb2+ is more stable because of inert pair effect. I being larger has the tendency to lose the
electron easily.
S2 : Smaller and highly electronegative elementsl like F can stabilize the higher oxidation state
not I.

6.43 (A) P4O10 12NH3 6H2O 4(NH4 )3 PO 4 .

6.44 (D) 2NaOH 2NO2 NaNO2 NaNO3 H2O

6.45 (C) S1 : Conjugate base of HNO3, the NO3 is more stable (charge dispersion on three oxygen

atoms) than conjugate base of HNO2, the NO2 (charge dispersion on two oxygen atoms).
S2 : There are three nitrogen to oxygen bonds in HNO3 and two in HNO2.
6.46 (A) Filling of 10 electrons in 3d-subshell enances the effective nuclear charge on account of the
pooer sheilding and thus the electrons are held more tightly. This is the reason why selenium is
reluctant to attain the highest oxidation state of (VI).
6.47 (D) Kept in plastic or wax-lined glass containers containing urea or phosphoric acid, because traces
of alkali metal ions and metal ions from the glass and the metal surface respectively can catalyse
the explosive decomposition of H2O2.

6.48 (B) S1 : 2H2O SO2 SO24 4H 2e (increase in [H+] will shift the equilibrium in backward
direction)

SO2 4OH SO42 2H2O 2e (incease in [OH ] will shift the equilibrium in forward
direction)
moisture
S2 : 2H2S SO 2 2H2O 3S

6.49 (A) Inertness of SF6 is due to the presence of sterically protected sulphur atom which does not allow
thermodynamicall favourable reactions like hydrolysis to take place.

6.50 (A) Fe 2HCl FeCl2 H2

Liberation of hydrogen prevents the formation of ferric chloride.
6.51 (D) X-Y is polar due to difference in their electronegativities where as X-X bond is non-polar. In X-Y, X
is bigger halogen so X-Y bond length is bigger and thus weaker as compared to X-X bond.

6.52 (B) XeF6 H2O XeOF4 2HF

2XeF6 SiO 2 (from glass) XeOF4 SiF4

6.53 (C) S1, S2 and S3 are correct statements.

S4 : GeO2 is acidic while SnO2 is amphoteric in nature.
6.54 (A) S1 : N2H4 is formed in aqueous dilute solution in presence of glue or gelatin and in concentrated
solution yields N2.
 S2 : PH3 solution in water explodes forming red phosphorus and H2.

S3 : Ba(N3 )2 Ba 3N2
S4 :

Oxidation state
Name Formula of Characteristic bonds and
phosphorus their number
One POH
Hypophosphorus H3PO2 +1 Two PH
One P=O
Two POH
Orthophosphorus H3PO3 +3 One PH
One P=O
Two POH
Pyrophosphorus H4P2O5 +3 Two PH
Two P=O
Four POH
Hypophosphoric H4P2O6 +4 Two P=O
One PO
NH ( )
6.55 (A) 3N2O 4Na NH3
3
NaN3 3NaOH 2N2

(NH4 )2 Cr2O7 N2 4H2O Cr2O3 (green)

CaCN2 3H2 O CaCO3 2NH3

Cu2 2NH3 [Cu(NH3 )4 ]2 (deep blue)

6.56 (B) S1 : Metaphosphoric is prepared by heating phosphorus acid and Br2 in a sealed tube, and
S2 : I 2 O3 I 4 O9
S3 : -Sulphur is stable above 369K.

6.57 (D) S1 : Se2Cl2 SeCl4 3Se (disproportionation)

S2 : 2PbO2 2H2SO 4 2PbSO 4 2H2O O 2

S3 : Fe3 2S2O32 [Fe(S2O3 )2 ] ;

Fe3 [Fe(S2 O3 )2 ] (pink or violet) 2Fe 2 S 4O 62 (colourless)

S4 : PbS2O3 H2O PbS (black) H2SO 4

6.58 (C) S1 and S2 are correct statements.

S3 : 2XeF2 (s) H2 O( ) 2Xe(g) 2HF(aq) O2 (g)

6XeF4 12H2O 4Xe XeO3 24HF 3O2 Complete hydrolysis

XeF6 3H2O XeO3 6HF

S4 : XeF2 PF5 [XeF] [PF6 ]

XeF4 SbF5 [XeF3 ] [SbF6 ]

XeF6 MF M [XeF7 ]
M = Na, K, Rb or Cs.
 covalent bond
H
H 33 H
1.
.1
9 B B sp3
1
6.59 (D) H H H

3c - 2e bond

6.60 (B) 4BF3 12H2O 4H3BO3 12HF

12HF 3H3BO3 3H 3[BF4 ] 9H2O
4BF3 3H2O H3BO3 3H 3[BF4 ]

B sp3
F F
F

2p 2p
F
6.61 (D) B F
F

There is 2p 2p bonding.
Ether
4BF3 (A) 3LiAlH4 2B 2H6 (P) 3LiAlF4 ; B2H6 3O2 B2O3 3H2O Heat
Molecular weight of compound (P) = 21.76 + 6 = 27.76.
6
% of H in compound (P) i.e., B2H6 = 100 21.72
27.76

B2H6 NH3 B3N3H6 (inorganic benzene) H2 .

6.62 (D) (A) and (B) statements are the correct explanation of the question.

6.63 (C) Sheet silicate, the two dimensional is called phyllo-silicate. When SiO44 units three corners, the

structure formed is an infinite two dimensional sheet of empirical formula (Si2O5 )n2n .
6.64 (B) (A) True statement.
(B) SiO bonds are stronger than the CO bonds. There is donation of electrons from oxygen to
empty d-orbital of silicon giving rise to pd bonding.
(C) The anion skelton is penetrated by channels, giving a honey comb-like structure. These
channels are large enough to allow them to exchange certain ions. They can also absorb or lose
water and other small molecules without the structure breaking down. Natrolite Na2[Al2Si3O10]2H2O
is a natural ion exchange.

6.65 (C) H2 O 2NO 2 HNO3 HNO2

6.66 (B) (A) N2 O3 2KOH 2KNO 2 H2 O.

(B) H2 O 2NO 2 HNO2 (reducing agent) HNO3 (oxidising agent)

(C) Neutral to litmus as neutral oxide
(D) In the liquid state, N2O4 tends to ionise

2NO2 N2O4 NO NO3

6.67 (D) (A) NN bond length (1.75 ) is longer than usual NN single bond length which is believed to be
due to + charge and lone pair of electrons on N atoms which causes repulsion.
O O
N N

O O

N N
(B) O O O O
132C

(C) N N
sp
O and the structure suggests that it will have some dipole moment.

6.68 (D) Following reactions are responsible for the depletion of ozone layer
O3 h O O 2 ; Cl O3 ClO O 2 ; ClO O Cl O 2

6.69 (D) (A) and (B) are correct statements.

2500C queching
(C) True, O 2 2O; O O2 O3 .
(D) Its (i.e., ozone) advantage over chlorine is that it avoids the upleasent smell and taste of
chlorine.
6.70 (D) (A) Red light.
(B) Oxides of nitrogen and the halogen can damage the O3 layer.
(C) I4O3 is formed.
(D) 2KOH 5O3 2KO3 5O 2 H2O

6.71 (C) IO 4 2I H2O IO3 I 2 2OH

IO3 5I 6H 3I 2 3H2O

6.72 (D) (A) Disproportionation is slow at the ordinary temperature for OCl, it is fast for OBr and very
fast for OI.
(B) E for the 1/2 F2 | F electrode = + 2.9 V.
(C) HI is stronger acid than HBr because of its low bond dissociation enthalpy.
(D) Because of low bond dissociation energy and high hydration energy of F2, F2 acts as strong
oxidising agent and oxidising power decrease down the group. E 1/2 F2 | F = + 2.9 V.
6.73 (D) (I) HCl because of high bond enthalpy of it.
(II) 2KCIO3 I 2 2KIO3 Cl2 .
(III) Correct order, F because of high electron density on account of small size easily donate the
electron pair, is strongest base.
(IV) It is used as bleaching as well as sterilising agent (as it acts strong oxidising agent).

6.74 (A) 2K 2MnF6 4SbF5 4K[SbF6 ] 2MnF3 F2 .

Xe
6.75 (D) (A) (B) S8 24XeF2 24Xe 8SF6 (S sp3 d2 )
sp3d
F

(C) XeF2 SbF5 [XeF] [SbF6 ]

6.76 (D) (B) test of ozone (not given by H2O2)
500 800
(C) 2BaO O 2 (air) 2BaO2 ; 2BaO 2 BaO O 2
(A) O3 forms I4O9 with dry iodine (incorrect statement)
6.77 (B) (A) F2 gives O2 gas (C) H2O2 in acidic medium form CrO5, not O3
(B) KI 3O3 KIO3 3O2

KI 4O3 KIO 4 4O 2
H
XeF2
2
Xe 2HF
(A) (B) (C)
H2
XeF2 H2O
Xe HF O 2
(B) (C) (D)

3O2 2O3 ; 5O3 2KOH 2KO3 (orange solid) 5O2 H2O

(D) (E)
Electrolysis
HF KF KHF2 (molten) F2
(C) (G)
6.78 (Ap); (Bp,q); (Cp,r); (Dp,r)
(A) B2O3 3H2O 2H3BO3 (B) B2H6 6H2O 2H3BO3 6H2

(C) B3N3H6 9H2O 3B(OH)3 3NH3 2H2 (D) BCl3 3H2O B(OH)2 3HCl.
6.79 (Aq,r); (Bq,s); (Cp,r); (Dp,r)

O
sp3
P
ionisable proton
H OH
(A) H3PO2;
H
Hypophosphorus acid

(B) H3BO3; B(OH)3 2H2 O [B(OH)4 ] H2O .

Monobasic Lewis acid as it completes its octet by accepting OH from water.
OH
sp2
B
OH OH

Orthoboric acid

O O
sp3
P P ionisable
HO OH proton
(C) H4P2O6 :
OH OH

Hypophosphoric acid

O O
sp3
S S ionisable
HO OH proton
(D) H2S2O5 : O

Pyrosulphurous acid
6.80 (Ap,q,s); (Bp,q,s); (Cr,s); (Dq,s)
Hydrolysis
(A) (NH4 )2 S2O8 H2O 2NH4HSO 4 H2O 2
Alkaline hydrolysis
(B) 2NaBO 2 H2O 2 6H2O
Na[(OH)2 B2 (OO)2 (OH)2 ] 6H2O
disproportionation
(C) 2Na2SO3 Na2S Na2SO 4

(D) 2-Ethylanthraqunol air(O2 ) 2-Ethylanthraquinone H2O2

6.81 (Ap,q); (Bp,q,r,s); (Cp,q); (Dq)

Zn
S2 3 O42 SO32 (trigonal pyramidal) H2O
(A) 2HSO3 SO2

S2O42 and SO32 both and as reducing agents.

(B) Na2Cr2O7 C Cr2 3 O3 Na2CO3 (trigonal planar) CO
CO acts as a reducing agent and in the purification of nickel metal (Monds process)
(C) P4 6Cl2 (g) 12H2O 4H3P 3 O3 12HCl
H3PO3 acts as a reducing agent.
(D) H2 SO 4 HI I 2 SO2 2H2O
SO2 acts as reducing agent.
6.82 (Aq,r,s); (Bp,r); (Cp,r); (Dp,r,s)
Disproportionation
(A) 3HNO2 HNO3 2NO H2O
One of the product is paramagnetic (NO) and colourless gas, one of the products gives brown
ring test.
Comproportionation
(B) NH4 Cl (aq) NaNO2 (aq) N2 (g) 2H2O NaCl (aq).
One of the products is diamagnetic and colourless gas. Laboratory method of preparation.
(C) 6HN3 4Li 4LiN3 2NH3 2N2
One of the products is diamagnetic and colourless gas.
(D) Mg 2HNO3 (cold dilute) Mg2 (NO3 )2 H2
One of the products gives brown ring test, one of the products is diamagnetic and colourless
gas.
6.83 (Ap); (Br,s); (Cq,t); (Dp,t)
(A) 3Sn 4HNO3 (concentrated) (x 2)H2O 4NO 3SnO 2 .xH2O (metastrannic acid)
(vogel)

(B) 4Sn 10H NO3 (dilute) 4Sn2 NH4 3H2 O (vogel)

(C) Ag 2HNO 3 (concentrated) AgNO3 NO2 H2O

(D) 3Ag 2HNO3 (dilute) 3AgNO3 NO 2H2O

6.84 (Ap,q,r,s); (Bp,q,r,s); (Cp,q,r,s); (Dq,s,t)
Hydrolysis
(A) XeF2 2H2O
2Xe 4HF O2

XeF2 2HCl Xe 2HF Cl2

as oxidising agent
 Addition reaction
[XeF] [PF6 ]
XeF2 PF5
F

Xe

F
Hydrolysis
(B) 6XeF4 12H2O
Disproportionation
4Xe 2XeO3 24HF 3O2

XeF4 2Hg Xe 2HgF2

as oxidising agent
Addition reaction
[XeF3 ] [SbF6 ]
XeF4 SbF5

F F
Xe
F F

Hydrolysis
(C) XeF6 3H2O XeO3 2HF

XeF6 3H2 6HF Xe

as oxidising agent
Addition reaction
CsF XeF6
CsXeF7
Addition reaction
[XeF6 ] [PtF6 ]
XeF6 PtF6

F
F F
Xe

F F
F

(D) XeO3 OH HXeO4

2HXeO 4 2OH XeO 64 Xe O2 2H2O

XeO3 6H 6e Xe 3H2O (E 2.10 V)

acts as oxidising agent.

Xe
O O
O

1.1 3c
H 9 H - 2e H
e B 1.3 B ~122
-2 3 97
6.85 H 2c
H H
1.77
 O

O

O O
6.86
O O

O O O

6.87 6CaO + P4O10 2Ca3(PO4) 2

6[40+16] [314+1610] Calcium phosphate
= 336 = 284
According to above reaction,
284 g of P4O10 are completely reacted with 336 g of CaO.
336 852
852 g of P4O10 will react with g of CaO
284
336 852
Hence, required weight of CaO = 1008 g.
284
6.88 Hypophosphorus acid is H3PO2 which has following structure.
O

P
H OH
H

6.89 Ca3P2 6H2O 3Ca(OH)2 2PH3

4 0 6
6.90 6 XeF4 12H2O 4 Xe 2 XeO3 24HF 3O2
 INORGANIC CHEMISTRY

7. d-BLOCK ELEMENTS AND COMPOUNDS

7.1 (D) (A) Higher the number of unpaired electrons higher will be the strength of metallic bonds. Hence
transition elements have higher enthalpies of atomization.
(B) In Cr the second electrons has to be removed from stable half filled electron configuration i.e.
3d5. In Cu the second electron has to be removed from stable completely filled electron
configuration i.e. 3d10.
(C) The sum of IE1 and IE2 of Ni is less than that of Pt whereas the sum of IE1, IE2, IE3 and IE4 are
reversed.
(D) Occurs in the middle, e.g., manganese has + 7 oxidation state.
7.2 (C) Cr2+ is reducing as its configuration changes from d4 and d3, the latter having a half-filled t2g
level. On the other hand, the change from Mn3+ to Mn2+ results in the half-filled (d5) configuration
which has extra stability.

7.3 (D) VOSO4 VO2 SO24 ; ax( 2) 2 4.

7.4 (A) [MO4]2; Mn is in + 6 oxidation state. Electronic configuration is [Ar]183d14s0. As it contains one
unpaired electron it is paramagnetic and green coloured because of d-d transition in visible
region. [TiCl6]2, [VO4]3 and CrO2Cl2 are diamagnetic as all electrons are paired.
7.5 (A) (I) VCl3; 23V3+; [Ar]18 3d2 = 2 unpaired electrons.
(II) VO2+; V4+; [Ar]18 3d2 = 1 unpaired electrons.
(III) [VO4]3; V5+; [Ar]18 3d0 = no unpaied electrons.
(IV) [V(H2O)6]2+; V2+; [Ar]18 3d3 = 3 unpaired electrons.
7.6 (A) This is due to the increasing stability of the lower species to which they are reduced.

7.7 (D) (A) MnO4 7; [Ar]18 3d5 4s2 7. (B) Cr2O72 6; [Ar]18 3d5 4s1 6.

(C) VO34 5; [Ar]18 3d3 4s2 5. (D) FeO24 6; [Ar]18 3d6 4s2 8.

300 C
7.8 (D) True statement, 2FeCl3
(FeCl3 )2 (g)

7.9 (B) (B) 2Fe 3Cl2 2FeCl3 (anhydrous); (A), (C), (D) do not give anhydrous FeCl3 but hydrated
FeCl3.
7.10 (A)

OCH3
FeCI3.6H2O + CH C CH3 FeCI3 + 12CH3OH + 6CH3COOH3
7.11 (A)
OCH3

7.12 (B) 2CuSO 4 4Kl 2K 2SO 4 Cu2 I 2 I 2

2Na2 S2O3 I 2 Na 2S4O 6 2NaI; CuI2 is not formed according to following reaction.

2CuI 2 (unstable) Cu2 I 2 I 2 .

7.13 (D) (A) AgNO3 PH3 Ag HNO3 H3PO3
Organic tissue (proteins)
(B) AgNO3 Ag (black)

(C) Ag 2KCN [Ag(CN)2 ]

7.14 (C) CO2 H2O H2CO3 2H CO42 ; CrO24 2H Cr2 O72 (orange red) H2 O

VI VI
Fusion H H / H O
7.15 (D) 4FeCr2O4 8Na2 CO3 7O2
Na2 Cr O4
HO
Na2 Cr2 O7
2 2

2

VI
HO
Cr O(O2 )2 (deep blue violet)
2
O2 H2O Cr 3 .

Na2 Cr2O7 H2O 4 2CrO3 (chronic anhydride) Na2SO 4 H2 O.

7.16 (D) 2Mn 2 5S 2O82 8H2 O 2MnO 4 10SO 42 16H

7.17 (A) 2KMnO 4 3H2SO 4 2KHSO 4 (MnO3 )2 SO 4 2H2 O

(MnO3 )2 SO 4 H2O Mn2 O7 H2 SO 4

Mn2O7 2MnO 2 3O2

7.18 (A) 2KMnO 4 KBr H2O KBrO3 3KOH 2MnO 2

7.19 (A,C,D)
(A) As metal ions generally contain one or more unpaired electrons in them and hence their
complexes are generally paramagnetic.
(B) Because of having larger number of unpaired electrons in their atoms, they have stronger
inter atomic interaction and hence stronger bonding between the atoms.
(C) May be attributed to the presence of unpaired electrons (d-d transition in most of the
compounds)
(D) This activity is ascribed to their ability to adopt multiple oxidation state and to form complexes.
7.20 (C) (A) VCl3; 23V3+; [Ar]18 3d2 = 2 unpaired electrons.
(B) VO2+; V4+; [Ar]18 3d2 = 1 unpaired electron.
(C) [VO4]3; V5+; [Ar]18 3d0 = no unpaired electron.
(D) [V(H2O)6]2+; V2+; [Ar]18 3d3 = 3 unpaired electrons.
7.21 (A,B)

H
(A) Na2CrO4 Na2Cr2O7 (orange colour)

H
(B) MnO24 MnO4 MnO2 , in neutral or acidic medium
(C) False-In acidic medium no colour change.
OH
(D) MnO4 e MnO42 , in strong alkaline medium changes to green.

7.22 (A,B) Fuse with KOH in presence of air or oxidising agents like KNO3, KClO3 etc.
2MnO2 4KOH O2 2K 2MnO 4 2H2O
electrolytic oxidation
MnO24 MnO 4 e

7.23 (A,B) (A) In making negative/positive of photographic film.

(B) In fixing of photographic film by removing unreduced AgBr as soluble complex.
7.24 (A,B,C)
(A) Brass contains 60-80% Cu and 40-20% Zn.
(B) Gun metal contains 87% Cu, 3% Zn and 10% Sn.
(C) Solder metal contains 67% Sn and 33% Pb.
(D) Bronze contains 75-90% Cu and 25-10% Sn.
7.25 (A,B,D)

3CuCl2 .2H2O CuO Cu2Cl2 2HCl Cl2 H2O;
(C) only Cl2 is liberated is wrong as evident from chemical equation.
7.26 (B) (A) In both compounds central metal has + 6 oxidation state.
(B) Solution dichromate is Na2Cr2O7.2H2O, so it can not be weighed correctly for the preparation
of standard solution.
3
(C) 2K 2Cr2 O7 2K 2CrO4 Cr2O3 (green) O2
2

(D) 4KMnO 4 4KOH 4K 2MnO 4 (green) 2H2O O 2

7.27 (D) (D) CuO 2HCl CuCl2 H2O; Cu2Cl2 is not formed.

(A) 2CuSO 4 2NaCl 2H2O SO2 Cu2 Cl2 Na2SO 4 2H2SO 4

(B) Cu HCl [O] CuCl2 H2 O; CuCl2 Cu Cu2Cl2

(C) CuSO 4 2HCl CuCl2 H2SO 4 ; CuCl2 Cu Cu2Cl2

7.28 (A,B,C,D)
(A) KMnO 4 Cu2O KOH 2Cu(OH)2 K 2MnO 4 .

(B) 2MnO2 2K 2CO3 O 2 (fromKNO3 ) 2K 2MnO 4 2CO 2 .

(C) HCHO 2KMnO2 2KOH 2K 2MnO 4 H2O HCOOH.

(D) 4KMnO 4 4KOH 4K 2MnO 4 2H2O O2 .

7.29 (D) The electrons are removed from outer most shell i.e. 4s2.
7.30 (B) Mn3+ = [Ar]18 3d4, Cr3+ = [Ar]18 3d3, V3+ = [Ar]18 3d2, Ti3+ = [Ar]18 3d1
and Cr3+ is most stable due to greater CFSE of t32g configuration.

7.31 (A,C) It is because of required change from d5 (half filled) to d4 (partially filled) in case of Mn.
Eo Cr3+/Cr2+ = 0.41 V
Eo Mn3+/Mn2+ = + 1.57 V
7.32 (C) Cupric ion produces blue colour in solution due to the presence of unpaired electron (d-d transition)
while cuprous ion does not have unpaired electron.

7.33 (A) Ag2O C6H12O 6 2Ag C6H12O7

6 6
7.34 (C) 2Cr O24 2H Cr2 O72 H2O
(yellow) (orange)
There is no change in oxidation state. So the explanation is wrong.
7.35 (B) S1 : It is because Mn2+ has 3d5 configuration which has extra stability.
S2 : Note titanium but Copper, because with + 1 oxidation state an extra stable configuration, 3d10
results.
 S3 : Note stable as it undergoes disproportionation 2Cu (aq) Cu2 (aq) Cu(s). The Eo
value for this is favourable.
7.36 (A) S1 : Due to strong interatomic forces. S2 : Hydrochloric acid is oxidised to chlorine.
OH
S3 : MnO4 e MnO24 S4 : 2KMnO 4 5H2 2KOH 2MnO H2 O.

7.37 (B) Both V+ 4([Ar]18 d1 rs0) and Cu2+ ([Ar]18 d9 4s0) have one unpaired electron in the d-orbital and
thus exhibit same colour.
7.38 (C) = 1.73 i.e. one unpaired electron, Ti (E.C.) = [Ar]18 3d2, 4s2, so it will lose three electrons to
have one unpaired electron and thus the oxidation state of titanium is + 3.
7.39 (D) (A) Has five unpaired electrons in 3d-sub shell. (B) is a obvious fact (C) number of unpaired
electrons first increases to five and then pairing begins so number of unpaired electrons
decreases.
7.40 (C) (A) There are three complete rows, 3d, 4d and 5d series and one incomplete 6d series.
(B) Cu2S is chalcocyte or copper glance and Ag2S is argentite.
(C) Siderite is FeCO3 i.e. carbonate ore.
3Fe2 O3 CO 2Fe3O 4 CO 2 500-800 K.

Fe3 O 4 CO 3FeO CO2 500-800 K.

FeO CO Fe CO 2 900-1500 K.

FeO C Fe CO above 1500 K.

(D) As the involvement of greater number of (n 1)d electrons in addition to ns electrons results
into strong interatomic bonding.

3d 4s 4p

7.41 (C) (I) 28 Cr( IV) 3d8 4s2 ; [Cr(CO)4 ]4

sp3 hybridisation
CO is strong field ligand so complex is diamagnetic and tetrahedral.

3d 4s 4p

(II) 28 Ni( II) 3d8 ; [Ni(DMGH)2 ]

2
dsp hybridisation

DMGH is a chelating ligand so complex is diamagnetic and square planar.

5d 6s 6p

(III) 78 Pt( II) 5d8 ; [PtHBr(PEt 3 )2 ]

2
dsp hybridisation

5d8 configuration has greater CFSE so complex is diamagnetic and square planar.

4d 5s 5p

(IV) 47 Ag( I) 4d10 ; [Ag(SCN)4 ]3

sp3 hybridisation

No empty d-orbital is available for dsp2 hybridisation and SCN is weak field ligand so complex is
tetrahedral and diamagnetic.
 5d 6s 5p

(V) 79 Au( III) 5d8 ; [AuBr4 ]

2
dsp hybridisation

5d8 configuration has greater CFSE so complex is diamagnetic and square palanar.

7.42 (B) (A) The correct order is VO2 Cr2O72 MnO4 and this is attributed to the increasing stability of
the lower species to which they are reduced.
(B) According to crystal field theory, the colour of the complex is due to d-d transition of the
electrons. In the absence of ligand, crystal field splitting does not occur and hence TiCl3 becomes
colourless.
(C) Copper pyrites is CuFeS2. It has iron sulphide as impurity which is removed as slag, FeSiO3
in blast furnace during smelting.
2CuFeS2 2O2 Cu2S 2FeS SO2

2FeS 3O2 3FeO 2SO2

FeO SiO2 FeSiO3 (slag)

(D) In both complexes, for the square planar shape (because of 5d8 configuration) the hybridisation
is dsp2. Hence the unpaired electron in 5d-orbital pair up to make one d-orbital empty for dsp2
hybridisation. Thus there is no unpaired electron in [PtCl4]2 and [Pt(CN)4]2 complexes.

7.43 (D) (A) 2MnO 4 2NH3 2MnO2 N2 2OH 2H2 O

(B) MnO4 is pink coloured and colour is due to charge transfer..

(C) MnO4 is in highest oxidation state i.e. +VII and hence can not be oxidised.
Fusion [e ]
MnO24
(D) MnO2 OH O2 (air) MnO4

7.44 (C) (A) MnSO 4 II; (B) MnO24 VI; (C) MnO4 VII

7.45 (D) (III) MnO24 [Ar]18 3d1 paramagnetic and tetrahedral

(VI) MnO4 [Ar]18 3d3 diamagnetic and tetrahedral

3MnO24 4H 2MnO 4 MnO 2 2H2O

Solution of passage :
MnSO 4 (A) 2KNO3 K 2CO3 K 2MnO 4 (B) 2KNO2 2CO 2 K 2SO 4

H
MnO24 e
MnO4 (C)

Mn2 2OH Mn(OH)2 ; Mn(OH)2 Br2 2NaOH MnO2 (D) 2NaBr 2H2O

MnO2 4HNO3 2Mn(NO3 )2 2H2O O2

Mn(NO3 )2 5PbO2 6HNO3 2HMnO 4 (E) 5Pb(NO3 )2 2H2O

SO24 Ba2 BaSO 4 (white) (F).

A = MnSO4, B = K2MnO4, C = KMnO4, D = MnO2, E = HMnO4, F = BaSO4.
7.46 (A p,q,s); (B r,t); (C p,q); (D p,t)
0 V 1 O

(A) 5AgNO3 (aq) 3 I 2 (excess) 3H2O HiO3 5Ag I 5HNO3

N
It is disproportionation and redox reaction. NO3 has planar structure. O 2
O
sp
(B) 2CrO24 H Cr2O72 H2O.
2
O O O

O Cr Cr O

3
O sp O

Cr2O72 has dimeric bridged tetrahedral metal ion.

The colour is due to charge transfer spectrum.

(C) NO2 is being oxidised and MnO4 being reduced according to the following reaction.

O
N
O 2
O
sp

So it is redox reaction, 2MnO 4 5NO2 6H 2Mn2 5NO3 3H2O.

(D) Fe2+ is being oxidised and NO3 being reduced according to the following reaction. So it is

redox reaction, 3Fe2 2NO3 4H NO 3Fe3 2H2O.

Fe2 NO 5H2O [Fe(H2O)5 NO]2 (brown ring)

The colour is due to charge transfer spectrum.
7.47 (A q,r,s); (B p,q,r); (C p,q,s); (D q,r)

(A) 2FeSO 4 Fe2O3 SO3 SO3

(B) 2Mn2 5S2O82 8H2O 2MnO 4 10SO 42 16H ; MnO 4 is coloured due to charge transfer..

(C) Na2Cr2O7 H2SO 4 2CrO3 (bright orange) Na2SO 4 H2O; CrO3 is strongly acidic and
coloured due to charge transfer
(D) N2H4 2CuSO 4 Cu N2 2H2SO 4

7.48 (A q,r,s); (B p,q,r); (C p,q,s); (D q,r)

(A) 3MnO24 4H MnO2 2MnO 4 2H2O

(B) 2Cu (aq) Cu(s) Cu2 (aq)

(C) Cr2O72 6H 4Cl 2CrO2Cl2 (deep red) 3H2O

(D) Fe2 (SO 4 )3 2I 2FeSO 4 SO 42 I 2 (violet or purple)

7.49 (A t); (B s); (C p); (D r)

(A) HO HO + 2AgBr(s) O= =O + 2HBr + 2Ag (black silver particles)

Hydroquinone acts as developer

 (B) BaCl2 K 2Cr2O7 3H2SO 4 K 2SO 4 2CrO2 Cl2 2BaSO 4 3H2O

(C) FeSO 4 K 3 [Fe(CN)6 ] KFeII [FeIII (CN)6 ] K 2 SO 4

(D) Cu(OH)2 2NH4OH (NH4 )2 SO 4 [Cu(NH3 )4 ] SO 4 4H2O

(E) Co(NO3 )2 ZnO CoZnO 2 or CoO.ZnO

7.50 4FeCr2O 4 16NaOH 7O 2 8Na2CrO 4 2Fe2O3 8H2O.

Let the oxidation state of Cr in CrO24 is x.

So x + 4( 2) = 2 or x=6

eg

7.51 Cr 3+; 3d 3 n=3

t2g

7.52 n(n 2) 3.9 BM or n 3; n number of unpaired electron

2
O O O
7.53
O Cr Cr O

3
O sp O

Six CrO bonds are equivalent due to resonance and two bridged CrO bonds are equivalent (no
resonance).

7.54 Cr2 O72 14H 6e 2Cr 3 7H2O.

2I I 2 2e 3
Cr2O72 14H 6 I 2Cr 3 3I 2 7 H2O

Molecular w.t.
So eq. wt. =
6
7.55 (C) (A) is TiCl 4 as it has no unpaired electron and is liquid at room temperature on account of
covalent character because of high polarising power of Ti4+. TiCl4 being covalent gets hydrolysed
forming TiO2(H2O)2 and HCl (B) which fumes in air.
In [Ti(H2O)6]C]3 complex Ti(III) has one unpaired electron (3d1) which gives violet l purple colour
due to d-d transition.
Hydrolysis
TiCI4 TiCI3 [Ti(H2O6)CI3
H2O
(A) purple or violet
Colour less (B)
moist air

TiO2(H2O)2 + HCI (white fumes)

 INORGANIC CHEMISTRY

8. QUALITATIVE ANALYSIS

8.1 (B) Na2 S Na2 [Fe(CN)5 NO] Na 4 [Fe(CN)5 NOS] (purple colouration)
Sodium thio nitroprusside

8.2 (A) SO23 Zn 8H H2S 3Zn2 3H2O

Pb2 S 2 PbS (black)

8.3 (A) Sulphite gives SO2 with H2SO4 which turns acidified K2Cr2O7 green according to following reaction
K 2Cr2O7 H2SO 4 3SO 2 K 2SO 4 Cr2 (SO 4 )3 (green) H2O. H 2 S also gives green
cloured solution with acidified K2Cr2O7 solution but a slightly coloured precipitate of sulphur is
also obtained. The H2S gas has rotten egg smell.

8.4 (D) NH4 OH NH3 H2O
(A) NH3, alkaline in nature turns red litmus blue;
NH3 HCl NH4 Cl (white fumes)

(B) 2HgNO3 2NH3 Hg(NH

2 )NO3 Hg

NH4NO3 ;
black

CuSO 4 4NH3 [Cu(NH3 )4 ]SO 4 (int ense blue)

(C) 2K 2 (Hgt 4 ) NH3 3KOH HgOHgNH2 I (brown) 7KI 2H2O

8.5 (D) Pb2 OH Pb(OH) (white); Pb2 CO23 PbCO3 (white)

Pb2 2Cl PbCl2 (white); Pb2 (aq) SO24 PbSO 4 (white)

8.6 (B) CuSO 4 H2S CuS (black) H2SO 4

CuS 2HNO 3 Cu(NO3 )2 (blue solution) NO S H2 O

2Cu2 4 I Cu2 I 2 (white) I 2 (colour of solution is yellow/brown)

8.7 (D) (B) Cu2 2NH4OH [Cu(NH3 )4 ]2 (deep blue) 4H2O

Bi3 3NH4OH Bi(OH)3 (white) 3NH4

(C) Cu2 [Fe(CN)8 ]4 Cu2 [Fe(CN)6 ] (chocolate brown)

Bi3 [Fe(CN)6 ]4 no change observed.

8.8 (D) (A) (B) (C) can be precipated by HCl as well as H2S as their insoluble chlorides and sulphides
respectively.
(D) Sn2 2HCl SnCl2 (soluble) 2H . It can be precipitated only by H2S as its insoluble
sulphide (brown).
8.9 (C) 2CuS 8CN 2[Cu(CN)4 ]3 S 22 .

[O]
8.10 (A) MnO 4 /H [O] : Fe2
Fe3 [Fe(CN)6 ]4 Fe4 [Fe(CN)6 ]3

8.11 (B) Fe3 3NH3 3H2O Fe(OH)3 (reddish brown) 3NH4

Cu2 4NH3 [Cu(NH3 )4 ]2 deep blue solution.

Zn2 4NH3 [Zn(NH3 )4 ]2 colourless solution.

8.12 (C) Cr(OH)3 OH [Cr(OH)4 ]

2[Cr(OH)4 ] 2OH 3H2O2 2CrO24 (yellow colour solution) 8H2O

Fe(OH)3 remains as brown precipitate.
8.13 (B) On adding HCl the equilibrium will shift in backward direction.

8.14 (A) 2Br Cl2 Br2 (reddish brown) 2Cl ; SO24 BaCl2 BaSO 4 (white) 2Cl

Mg2 2NaOH Mg(OH)2 (white) 2Na

Suspension of Mg(OH)2 in water is used as ant-acid and sodium gives golden yellow colour
flame.

8.15 (B) 2Cl MnO 2 H2 SO 4 2H Mn2 SO24 2H2O Cl2 (yellowish green)

NH4 OH NH3 H2O

Hg

NH3 2K 2HgI 4 3KOH O NH2 I (brown) 7KI 2H2 O

Hg

Fe3 5H2O SCN [Fe(H2O)5 (SCN)]2 (deep red colouration)

HCl NaOH
8.16 (D) Mn2 H2S MnS (buff/light pink coloured)
MnCl2
[O]
MnO2 (Brown/black)

fusion
MnO2 2KNO3 Na2CO3
Na2MnO 4 (green compound) KNO 2 2NaOH CO2

8.17 (D) Fe2 [Fe(CN)6 ]4 K 2Fe [Fe(CN)6 ] [white] (in absence of air)

Fe3 [Fe(CN)6 ]4 Fe4 [Fe(CN)6 ]3 (prussian blue precipitate or solution)

Zn2 [Fe(CN)6 ]4 (excess) K 2 Zn3 [Fe(CN)6 ]2 [bluish white]

Ca2 [Fe(CN)6 ]4 K 2Ca[Fe(CN)6 ] [white]

Cu 2K [Fe(CN)6 ]4 Cu2 [Fe(CN)6 ] [chocolate brown]

8.18 (B) Fe4 [Fe(CN)6 ]3 2OH 4Fe(OH)3 3[Fe(CN)6 ]4 .

8.19 (B,C,D)
cold
(A) 2HCO3 Mg2 Mg(HCO3 )2 (soluble) MgCO3 MgCO3 CO2 2H2O
 (B) Ca(HCO3 )2 2NH3 (NH4 )2 CO3 CaCO3
(C) True statement

(D) CO23 2Hg2 3H2O Hg4 O3CO3 (reddish brown) 6H

basic mercury (II) carbonate

8.20 (A,B,C)
(A) S2 Ag Ag2S; Ag2 S HNO3 AgNO3 S NO H2 O

(B) S2 Cd2 CdS (yellow)

II II
(C) S2 Na2 [Fe(CN)5 NO ] Na4 [Fe(CN)5 NOS]

(D) [Pb(OH)4 ]2 H2S PbS (black) 2OH 2H2O

8.21 (B,C,D)
(B) Red colour compound of unknown composition is formed when moist SO2 is brought in contact
with Zn[Fe(CN)5NO] (salmon colour) paste in water. No colour change with CO2.
(C) 5SO2 2IO3 4H2O I 2 5SO 42 8H ;

I 2 starch blue colour.

No colour change observed with CO2.
(D) 3SO2 Cr2O72 2H 2Cr 3 (green solution) 3SO 42 H2O.
No colour change observed with CO2.

8.22 (C,D) 2I Cl2 I 2 (purple/violet); 2I Br2 I 2 (purple/violet).

8.23 (A,B,C,D)
(A) It is deep red colouration due to the formation of Fe(SCN)3.
(B) In presence of moisture following reaction will occur : CrO 2Cl2 H2O H2CrO 4 HCl; So
test is carried out only in dry test tube.
(C) White precipitate of PbSO4 is formed and hence brown ring is not visible.
(D) Gives yellow precipitate of CdS.
8.24 (A,C,D)
(A) [Al(OH)4 ] NH4 Al(OH)3 (white) NH3 H2O

(B) Pb2 (aq) 2Br (aq) PbBr2 (white)

(C) BiI3 (black precipitate) H2O BiOI (orange)

(D) Ca2 2K [Fe(CN)6 ]4 K 2Ca[Fe(CN)6 ] (white)

8.25 (A,B,D)
(C) is incorrect as with KI, Cu2+ salts form a white precipitate of Cu2I2 and I2 gas is liberated.
8.26 (A,B,D)
(A) Bi3 3NH4 OH Bi(OH)3 (white) 3N4

(B) Pb2 2NH4OH Pb(OH)2 (white) 2NH4

(C) Due to common ion effect of NH4 , the OH ion concentration is not excess enough to
precipitate Mg2+ as Mg(OH)2 because of its high solubility product.
 (D) Fe3 3NH4 OH Fe(OH)3 (reddish brown) 3NH4

(E) Cu2 4NH3 [Cu(NH3 )4 ]2

In presence of ammonium salts, precipitation does not occur at all, but blue colour solution is
formed right away.
8.27 (A,B,C,D)
HCl
(A) Fe3 3C6 H5N(NO)ONH4 Fe[C6 H5 N(NO)O]3 (reddish-brown) 3NH4
Ammonium salt of nitrosophenl hydroxyl amine.
(B) AsO34 Mg2 NH4 MgNH4 AsO 4 (white crystalline)

(C) Bi3 C9 H7 ON(5%) H 4I C9 H7 ON.HbiI 4 (red)

8-hydroxyquinoline 8-hydroxyquinoline-tetraiodobismuthate
(D) Hg2 Co2 4SCN Co[Hg(SCN)4 ] (deep blue cryssstalline)

8.28 (A,B,C,D)
(A) CaSO 4 (NH4 )2 SO 4 (NH4 )2 [Ca(SO 4 )2 ] (soluble)
(B) BaCrO4 is insoluble in dilute acetic acid and thus gets precipitated with K2CrO4 (low Ksp in
K2CrO4 solution in acetic acid).
(C) Cr(OH)3 is soluble in NaOH and Br2 water forming sodium chromate while Fe(OH)3 is insoluble.
(D) [Cu(CN)4]3 is more stable than [Cd(CN)4]2 gives yellow precipitate with H2S.

8.29 (B) S1 : Ba(OH)2 CO 2 BaCO3 (white) H2O; BaCO3 H2O CO2 Ba(HCO3 )2 .

S2 : CO23 Ag Ag2CO3 (white)

boiled
Ag2CO3
Ag2O (yellow/brown) CO2

8.30 (B) PbI2 2I [PbI4 ]2 soluble complex.

Reaction is reversible and shifts in backward direction on dilution with water.

8.31 (A) BiCl3 H2O BiO Cl (white) 2HCl

8.32 (A) due to common ion effect the concentrations of OH ions is just sufficient to precipitate the
cations of IIIrd group as their hydrolysis. (As they have low Ksp values).
8.33 (D) Ksp of ZnS is large and thus is completely precipitated only in presence of ammonium hydroxide.

8.34 (A) Zn3 (PO 4 )2 12NH3 3[Zn(NH3 )4 ]2 2PO34 .

8.35 (B) Ksp of SrCrO4 and CaCrO4 are much higher than BaCrO4. Addition of acetic acid lowers the
concentration of CrO24 . Hence BaCrO4 is precipitated only because its Ksp value is lower..
8.36 (B) In presence of ammonium salts the reaction proceeds in backward direction forming ammonia
gas.
8.37 (A)
8.38 (A) MgSO4 on reaction with Na2HPO4 in presence of NH4OH gives white precipitate of Mg(NH4)PO4.
MgSO 4 Na2HPO 4 NH4 OH Mg(NH4 )PO3 Na2 SO 4 H2O.

8.39 (B) S1 : SO23 Ba2 BaSO3 (white); CO23 Ba2 BaCO3 (white)
 S2 : Ag2 SO3 H 2Ag SO 2 H2O

S3 : 2Cu2 5I CuI I3 (I2 I )

I3 2S2O32 3I S 4O 62

S4 : 2Cu(SCN)2 SO2 2H2O 2Cu(SCN) (white) 2SCN SO 42

8.40 (D) S1 : 2Br Cl2 Br2 (orange red colour in water) 2Cl
S2 : True statement.
S3 : NO3 4Zn 7OH 6H2O NH3 4[Zn(OH)4 ]2

8.41 (C) S1 : H2 O K 2HgI4 2CuSO 4 SO 2 Cu2 [HgI4 ] (scarlet/red) K 2SO 4 2H2SO 4

S2 : CuSO 4 2NaOH Cu(OH)2 (blue) Na2SO 4

2Cu(OH)2 CH2OH(CHOH)4 CHO Cu2O (red) H2O CH2OH(CHOH)4 COOH

moist
S3 : Cu2Cl2
Air
CuCl2 .3Cu(OH)2 (dark green material)

8.42 (C) S1 : In aqueous medium of sodium sulphide, both Cu3+ and Zn2+ will precipitate as their sulphides.
Concentration of S2+ ions provided by the ionization of Na2S in aqueous solution is sufficient to
precipitate both the ions.
S2 : Ca2+ and Mg2+ will not precipitate as Ksp of their hydroxides are very high.
Bi3 3(OH ) Bi(OH)3 (white)

Al3 3OH Al(OH)3 (white)

S3 : 2Cl MnO 2 H2SO 4 2H Mn2 SO 42 2H2 O Cl2 (yellowish green)

Hg

S4 : 3KOH NH3 2K 2 [HgI 4 ] O NH2 I (Brown) 7KI 2H O

2

Hg

8.43 (C) S1 : SrCrO4 is appreciable soluble in water.

S2 : White precipitate of K(NH4)Ca[Fe(CN)6]

S3 : Mg2 2NH3 2H2O Mg(OH)2 2NH4

S4 : HgS S2 [HgS2 ]2 (soluble complex)

3HgS 6HCl 2HNO3 3HgCl2 3S 2NO 4H2O

8.44 (B) S1 : CrO2Cl2 reacts with water forming H2CrO4 and thus prevents the evolution of deep red
vapour.
CrO 2Cl2 2H2O H2 CrO 4 2HCl

S2 : Ba2 SO 24 BaSO 4 (brown ring is not clearly visible)

S3 : (CH3 COO)3 Fe H2O Fe(OH)2 (CH3COO) (Brownish red) 2CH3 COOH

S4 : NO 2 3I 4CH3 COOH I3 2NO 4CH3 COO 2H2O

I2 starch white starch paste turns blue

8.45 (B) SO23 2H SO 2 H2 O

SO2 Ca(OH)2 CaSO3 (white) H2O

Cr2O72 2H 3SO 2 Cr 3 3SO 24 H2O

8.46 (C) 2KBr 2H2SO 4 Br2 SO2 SO24 2K H2O

2I Br2 2Br I 2

I 2 starch blue colour complex.

8.47 (D) (A) 3I Cl2 I3 2Cl ; I3 8Cl2 9H2O 3IO3 16Cl 18H

(B) 3NO3 8Al 5OH 18H2O 3NH3 8[Al(OH)4 ]

(C) SO24 3Hg2 2H2O HgSO 4 .2HgO (yellow) 4H

(D) 6CH3 COO 3Fe3 2HgO [Fe3 (OH)2 (CH3COO)6 ]2 2H

[Fe3 (OH)2 (CH3 COO)6 ] 4H2O 3Fe(OH)2 CH3COO (brownish red) 3CH3COOH H

8.48 (A) Both Bi3+ and Cd2+ will be precipitated as Bi2S3 (black) and CdS (yellow) by H2S as both have low
values of Ksp than Al3+, Zn2+ and Ni2+ (as sulphides).
8.49 (C) 2M HCl is group reagent for group Ist cations. PbCl2 and Hg2Cl2 will get precipitates, as their
solubility products (Ksp) are less than that of other radicals.

8.50 (B) Fe3 3NH4 OH Fe(OH)3 (reddish brown) 3NH4

Cu2 4NH3 [Cu(NH3 )4 ]2 (blue colour soluble complex)

Zn2 4NH3 [Zn(NH3 )4 ]2 (colourless soluble complex)

8.51 (B) (A) [Al(OH)4 ] NH4 Al(OH)3 (white) NH3 H2O

On addition of ammonium chloride solution of [Al(OH) 4] soluble complex, the hydroxyl ion
concentration is reduced owing to the formation of the weak base ammonia, which can be readily
removed as ammonia gas by heating. Thus, white precipitate of Al(OH)3 is obtained.
(B) Pb2 (aq) 2Br (aq) PbBr2 (white)

(C) BiI3 (black precipitate) H2O BiOI (orange)

(D) Ca2 2K [Fe(CN)6 ]4 K 2Ca[Fe(CN)6 ] (white)

8.52 (B) (A) Hg2 2I HgI 2 (red/scarlet)

HgI 2 2I [HgI 4 ]2 (soluble complex)

(B) Hg22 2I Hg2 I 2 (green)

Hg2 I 2 2I [HgI 4 ]2 Hg (black)

(C) Bi3 3 I BiI 3 (black)

BiI3 I [BiI 4 ] (orange colour soluble complex)

(D) 2Cu2 5 I 2CuI (white) I 3

8.53 (D)
(A) Zn(OH)2 dissolves in both NaOH and NH3 forming [Zn(OH)4]2 and [Zn(NH3)7] respectively.
(B) Cd(OH)2 dissolves in ammonia but does not dissolves in NaOH.
(C) Cu(OH)2 NH3 [Cu(NH3 )4 ]2 soluble complex butit does not dissolve in NaOH.

(D) Al(OH)3 OH [Al(OH)4 ] soluble complex but does not dissolve in NH3.

8.54 (B) As complete precipitation of Fe(OH)2 (Ksp very high) does not take place in presence of NH4Cl so
it is oxidised to Fe3+ by HNO3 and Fe(OH)3 has lower Ksp which is completely separated as
reddish brown ppt.
8.55 (D) (A) As Ksp of hydroxides of Al3+, Fe3+ and Cr3+ are low and NH4Cl suppresses the ionisation of
NH4OH because of common ion effect.
(B) (NH4 )2 SO 4 Ba2 BaSO 4 (white) 2NH4 .
(C) True statement.

8.56 (C) 2K 2 (HgI 4 ) NH3 3KOH HgOHgNH2 I 7Kl 2H2 O

8.57 (C) Fe2 K 3 [Fe(CN)6 ] FeII3 [FeIII (CN)6 ]2 3K

8.58 (D) All are black and gives gas with dil. H2SO4.
S2 2H H2S

5 4 2 0
8.59 (D) (C) 2H N O3 H2 O 2 N O2 [O]; (B) H2 S [O] H2O S

8.60 (D) (A) SO24 (CH3 COO)2 Pb PbSO 4 2CH3COO

(B) 2CuSO 4 4KI 2K 2SO 4 Cu2 I 2 I 2

(C) CuSO4 .5H2O

2H O
CuSO4 .3H2O
2

8.61 (A) Cu(NO3 )2 Zn Zn(NO3 )2 Cu (reddish brown)

AgS, FeS, CuS, or PbS H2SO 4 FeSO 4 H2S

(A) (B)

H2 S 2HNO3 2NO 2 2H2O S

(C) (D)

CuSO 4 BaCl2 CuCl2 BaSO 4 (white)

(E)

CuSO 4 H2S CuS (black) H2SO 4

(F)

3CuS 8HNO3 3Cu2 6NO3 3S 2NO 4H2O

Cu2 4NH3 [Cu(NH3 )4 ]2 (blue colour soluble complex)

(G)

Cu2 [Fe(CN)6 ]4 Cu2 [Fe(CN6 )] (chocolate brown).

8.62 (D) As bottle 2 + bottle 3 gives colourless odourless gas, it may be carbon dioxide. Generally
carbonates are decomposed by acids giving CO2 gas. It suggests bottle 2 and 3 contain sodium
carbonate and HCl.
Bottle 3 + 4 gives blue precipitate which confirms the Cu2+ in either of bottles. CuSO4, CuCl2 and
Cu(NO3)2 are soluble and CuCO3 is soluble in water as evident from the reaction.
Cu2 CO23 CuCO3 (blue). Thus blue precipitate must be of copper carbonate.
Hence, bottle 4 is CuSO4, 3 is Na2CO3, 2 is HCl (from above) and 1 is Pb(NO3)2 as it gives white
precipitate of PbCl2 with bottle (2).
Note : PbNO3, Na2CO3 and HCl solutions are colourless but CuSO4 is blue colour solution.

8.63 (A) (A) 2Cu2 4I Cu2I2 (white) I2

(B) 2Cu2 [Fe(CN)5 ]4 Cu2 [Fe(CN)6 ] (chocolate brown)

(C) Pb2 4OH [Pb(OH)4 ]2 (colourless soluble complex);

Cu2 2OH Cu(OH)2 (blue).

(D) Pb2 4Cl [PbCl4 ]2 (colourless soluble complex).

8.64 (D) Bottle 4 is CuSO4 and that gives deep blue colouration with excess of ammonia solution.
Cu2 (aq) 4NH3 (aq) [Cu(NH3 )4 ]2 (intensive deep blue colour) (aq)

8.65 (D) Pb2 CO23 PbCO3 (white)

Pb2 2Cl PbCl2 (white)

Pb2 SO24 PbSO 4 (white)

8.66 (A p,q,r,s), (B p,q), (C p,q,r), (D q,r,s)

(A) Ag2CO3(white), Ag2SO3(white), Ag2S(black), AgNO2(white)
(B) BaCO23 (white), BaSO3(white), BaS (soluble), Ba(NO2)2 (soluble)
(C) PbCO3(white), PbSO3(white), PbS(black), Pb(NO2)2(soluble)
(D) No reaction,decolourises pink colour of KMnO4 and PbSO4(white), decolourises pink colour of
KMnO4 and PbSO4(white), decolourises pink colour of KMnO4.
8.67 (A p,r), (B q,r,s), (C p,q,r,s), (D p,q,r)
(A) Pb(CN)2white, not soluble in excess of reagent AgCNwhite, soluble in excess of reagent Hg +
Excess
Hg(CN)2black, not soluble in excess reagent. Cu(CN)2 yellow K 3 [Cu(CN)4 ] soluble.
Excess
(B) Pb(OH)2 white Na2 [Pb(OH)4 ] soluble.
Ag2Obrown, Hg2Oblack, Cu(OH)2blue
Excess
(C) PbI2 yellow [PbI4 ]2 soluble complex only with concentrated solution of KI (4M).
Excess
AgI yellow
No reaction
Excess
[HgI4 ] Hg black.
Hg2I2 Green

CuI white I3 White ppt in brown coloured solution.

(D) PbCrO4 yellow

Ag2CrO4 (brick red/brownish red)
Hg2CrO4 red (with hot solution of K2CrO4)
In cold, brown precipitate is obtained.
8.68 (A s), (B r), (C q), (D p)
(A) Cu2 2SCN Cu(SCN)2 (black)

2Cu(SCN)2 2CuSCN (white) (SCN)2

H
(B) Hot Bi3 (aq) C6H3 (OH)3 Bi(C6H3 O3 ) (yellow) 3H

(C) 2Ag (aq) AsO34 (aq) Ag3 AsO 4 (brownish-red)

(D) Mn2 (aq) 2OH (aq) Mn(OH)2 (white)

Mn(OH)2 O2 2MnO(OH)2 (brown)

8.69 (A t), (B r), (C p,s), (D p,q), (D p,q), (E p,r,s)

(A) Fe3 Fe(OH)3 (reddish brown)

Cu2 [Cu(NH3 )4 ]2 deepblue solution; Zn2 [Zn(NH3 )4 ]2 colourless solublecomplex

(B) dissolve in 50% HNO3 forming soluble nitrates
(C) Pb2 2KI PbI 2 (yellow) 2K ; Pb2 K 2 CrO 4 PbCrO 4 (yellow) 2K

(D) Bi3 3KI BiI3 (black) 3K

BiCl3 3Na2 SnO 2 6NaOH 2Bi (black) 3Na2SnO3 6NaCl 3H2 O

(E) [Ag(NH3 )2 ]Cl KI AgI (yellow) 2NH3 KCl

[Ag(NH3 )2 ]Cl 2HNO3 AgCl (white) 2NH4NO3

[Ag(NH3 )2 ]Cl K 2CrO 4 Ag2 CrO 4 (brick red) 4NH3 2KCl

8.70 (A p,r), (B p), (C p,s), (D q,s)

(A) 2Bi3 3H2S Bi2S3 Black 6H

Bi3 3I BiI3 Black

(B) Cu2 H2S CuS Black 2H

Cu2 2SCN Cu(SCN)2 Black

Which on standing slowly changes to white
2Cu(SCN)2 2Cu(SCN) white (SCN)2
Cu2I2 is white precipitate and Cu2[Fe(CN)6] brown precipitate.
(C) Zn2 H2S ZnS white 2H

2K 2[Fe(CN)6 ]4 3Zn2 K 2 Zn3 [Fe(CN)6 ]2 white

ZnI 2 soluble

(D) 4Ag [Fe(CN)6 ]4 Ag4 [Fe(CN)6 ] white

Ag SCN AgSCN white

Ag2S black; AgI yellow
8.71 (A p,q,s), (B s), (C p,s), (D r,s)
(A) Fe(OH)2 green; PbSO4 white
 (B) Bi2S3 black
(C) Ni(OH)2 green; NiS-black
(D) (NH4)3[Co(NO2)6] yellow; CoS black.
8.72 (A p,q,r), (B r,s), (C p,q), (D p,s)
(A) Zn(OH)2 4KCN K 2 [Zn(CN)4 ] 2KOH
colourless soluble complex
Zn(OH)2 4NH3 [Zn(NH3 )4 ](OH)2
colourless soluble complex
Zn(OH)2 2NaOH Na2 [Zn(OH)4 ]
colourless soluble complex
(B) It is slightly soluble in cold
Cr(OH)3 6NH3 [Cr(NH3 )6 ]3 (pink or violet soluble complex) + 3OH

Cr(OH)3 OH [Cr(OH)4 ]
green soluble complex
2Cr(OH)3 3Na2O2 2Na2CrO 4 2NaOH 2H2O
yellow solution
(C) AgCl 2NH3 [Ag(NH3 )2 ]Cl

AgCl 2CN [Ag(CN)2 ] Cl

r, s NO

(D) 2CuS 8CN 2[Cu(CN)4 ]3 S 22 colourless soluble complex (Redox reaction).

HO
CuS Na2O 2
2
CuSO 4 NaOH

CuS H2O CuSO 4 soluble compound

NH OH
8.73 Ni2 2dmg
4
[Ni(dmg)2 ] (bright red).

O HO

CH3 C = N N = C CH3
+2
Ni
H3C C = N N = C CH3 Ans. 2

OH O
rosy red ppt
8.74 Here NO is NO+; so in [Fe(H2O)5NO+]2+, the oxidation state of iron is + 1.

O O
(2) Cr (1)
8.75 O || O Ans. 2
O

8.76 Pb2 2Cl PbCl2 (white); Hg22 2Cl Hg2Cl2 (white)

Ksp of chlorides of Pb2+ and Hg22 is low as compared to Ksp of Hg2+ and Cd2+. Chloride ion concentration

provided by dilute HCl is just enough to exceed the Ksp of PbCl2 and Hg2Cl2. Thus Pb2+ and Hg22 are
precipirated as their chlorides. Ans. 2
8.77 Hg2 Co(SCN)2 Co[Hg(SCN)4 ] (deep blue)
Ans. 4

8.78 SO23 H2SO 4 SO24 SO2 H2O; K 2Cr2O7 H2SO 4 3SO2 Cr2 (SO 4 )3 (green) ( gjk ) +
K2SO4 + H2O
NO3 H2 SO 4 HSO 4 HNO3 ; 4HNO3 2H2O O 2 4NO2

Cu 4HNO3 Cu(NO3 )2 2H2O 2NO2 ; Ag HCl AgCl (white) (lQsn) + H+

AgCl 2NH4 OH [Ag(NH3 )2 ]Cl; [Ag(NH3 )2 ]Cl HNO3 AgCl 2NH4NO3

[Ag(NH3 )2 ]Cl KI AgI 2NH3 KCl; Zn2 H2S ZnS (white) (lQsn) + 2H+

3Zn2 2K 2[Fe(CN)6 ]4 K 2 Zn3 [Fe(CN)6 ]2 .

Ans. Ag+, Zn2+ and SO23 and NO3 .

8.79 [A] = K+ and I, [B] = Hg2+ and Cl
As black sulphide is only soluble in aquaregia and further it gives greyish black ppt with SnCl2 the one
of the cation may be Hg2+. As salt mixture give lilac colour in flame, the other cation is K+.
2KI Cl2 2KCl I 2 CCl4 (violet colour)

KI AgNO3 AgI (bright yellow) KNO3 .