CONTENT

CHEMISTRY
CLASS : XI

Preface Page No.

1. Periodic Table & Periodicity

Exercise 01 - 05

2. Chemical Bonding
Exercise 06 - 44

3. LIQUID & Gaseous state

Exercise 45 - 62

4. Chemical Equilibrium
Exercise 63 - 83

5. Ionic Equilibrium
Exercise 84 - 117

6. Equivalent Concept & Titration

Exercise 118 - 134

7. Hydrocarbons
Exercise 135 - 154

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 PERIODIC TABLE & PERIODICITY
EXERCISE # 1
PART - I
A-8. (i) Alkali metal, potassium forms K+ (number of electrons = 18) which is isoelectronic with P3– (number of
electrons = 18)  Q.
(ii) Transition element, chromium show maximum oxidation state of +6 in Cr2O72– and CrO42– and they are
coloured  S.
(iii) Noble gas, Kr has largest atomic radius because radius is expressed as vander Waal's radius and there
is interelectronic repulsions due to completely filled outer most shell. Inert gas has highest first ionisation
energy in the respective period because of stable valence shell electron configuration  T.
(iv) Element (Z = 13), aluminium has intermediate value of electronegativity and therefore its oxide is amphoteric
in nature  R.

A-10. d-block has 10 colums.

A-12. Electron configuration is [Ar]18 3d10 4s2 4p3 . As last electron enters in p-subshell it is p-block element and
thus its group number is equal to 10 + 5 = 15. As principal quantum number of valence shell is 4, so it is 4th
period element.
B-3. Zn – 1s2 , 2s2 2p6 , 3s2 3p6 , 3d10, 4s2
30
 = 0.35 × 1 + 18 × 0.85 + 10 × 1 = 25.65
 Zeff = 30 – 25.65 = 4.35
B-8. Due to 4f-orbital electrons (poor shielding effect) there is increase in effective nuclear charge which leads to
the contraction of the size of atoms. This is called lanthanide contraction.
C-2. (A) Al3+, Mg2+, Na+ and F– are isoelectronic and thus follows the order 13Al3+ < 12Mg2+ < 11Na+ < 9F–. Al belongs
to third period and has no charge so it is largest. Na+ = 102 pm; Mg2+ = 72 pm ; Al = 143 pm, F– = 133 pm.
(B) Isoelectronic series of ions; all have the xenon electron configuration.
1
Ionic radius  nuclear ch arg e

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

(D) Across the period the nuclear charge increases and thus the size of atoms decreases. Mg = 160 pm ; Al
= 143 pm ; Si = 118 ; P = 110 pm.
C-8. D2 = T2 = P2
(The ionisation potential of isotopes of an elements will be same)
D-1. Be and N has 1s2 2s2 and 1s2 2s2 2p3 stable configurations respectively. So addition of extra electron is
difficult in their valence shell. The atomic size of C is smaller than B and also C has higher nuclear
charge; so addition of electron will be easier in C than B.
D-7. (A) IE (I) of N is more than O due to stable half filled electronic configuration of valence shell.
(B) is true as electron affinity of O (–141 kJ mol–1 ) is less than sulphur and selenium due to its exceptionally
small to atomic size.
(C) Electronegativity on Mulliken's scale is 2.8 larger than electronegativity on Pauling scale.
(D) The ionic radius decreases as mor electrons are ionized off. Cr6+ = 44 pm, Cr3+ = 61.5 pm.
D-8. All are isoelectronic species so with increasing effective nuclear charge.
(i) size decreases (as r = 1/nuclear charge).
(ii) Ionisation energy increases (as it depends on the magnitude of nuclear charge).
(iii) electron affinity increases (as it depends on the magnitude of nuclear charge).
E-1. X, Y and Z are phosphorus, aluminium and sodium respectively because of the following reasons.
(A) the P4O10 when dissolve in water forms acid H3PO4 which turns blue litmus red.
(B) the Al2O3 is amphoteric in the nature so reacts with both strong acids as well as with strong alkalies
forming salts.

RESONANCE Periodic Table - 1

 (C) the Na2O when dissolves in water forms an aqueous solution which is strongly alkaline in nature.
All these elements belong to third period. So across the period the size decreases and electronegativity
increases.
E-4. Both react with acid as well as base forming salts.
SnO + H2SO4  SnSO4 + H2O ; SnO + 2NaOH  Na2SnO2 + H2O.
ZnO + H2SO4  ZnSO4 + H2O ; ZnO + 2NaOH  Na2ZnO2 + H2O.

E-6. As En (difference in electronegativities between element and oxygen) decreases, the acidic character
increases.
So, SiO2 < CO2 < N2O5 < SO3 .

PART - II

1. (A) 1s2 2s2 2p6 3s2 3p6 3d6 4s2

 for 3d electron = 0.35 × 5 + 1.0 × 18 = 19.75
so Zeff = 26 – 19.75 = 6.25
(B) 1s2 2s2 2p6 3s2 3p6 3d6 4s2
 for 4s electron = 0.35 × 1 + 0.85 × 14 + 1.0 × 10 = 22.25
so Zeff = 26 – 22.25 = 3.75
(C) 1s2 2s2 2p6 3s2 3p6 3d6 4s2
 for 2s electron = 0.35 × 1 + 0.85 × 2 = 2.05
so Zeff = 26 – 2.05 = 23.95
(D) 1s2 2s2 2p6 3s2 3p6 3d6 4s2
 for 2p electron = 0.35 × 7 + 0.85 × 2 = 4.15
so Zeff = 26 – 4.15 = 21.85
So outer most shell 4s electrons experience maximum shielding effect. Therefore 4s electron feels minimum
attraction force from nucleus.
2. Fe = 1s2 2s2 2p6 3s2 3p6 3d6 4s2
S = 0.3
Z* = 26 – 0.3 = 25.7
3. Na = 1s2 2s2 2p6 3s1
6. Orbitals bearing lower value of n will be more closer to the nucleus and thus electrons will experience greater
attraction from nucleus and so its removal will be difficult not easier.
7. Z = 19 = K ; Z = 17 = C ; Z = 30 = Zn ; Z = 20 = Ca ; Z = 51 = Sb
(A) K has larger atomic volume. It has lower density than the Na and Rb.
(B) Cl (Z = 17) has less inter electronic repulsions than F (Z = 9) due to bigger size of 3p-subshell.
(C) 30Zn = [Ar]18 3d10 4s2 ; so no unpaired electron and because of completely filled configuration there is
inter electronic repulsion. So electron cloud expands and so, Zn(Z = 30) has higher atomic radius than
Cu(Z = 29). ZnO is amphoteric in nature.
(D) 20Ca = [Ar]18 4s2 ; so no unpaired electron and across the period size decreases, so Ca is bigger than
Cu.
(E) Z = 51 which is Sb. The Sb is metalloid because it is able to form Sb3+ (as metals form) and Sb3– (as
nonmetals form).

EXERCISE # 2
13. IP is always endothermic , First EA is normally exothermic and Second EA is always endothermic

EXERCISE # 3
1. Co is neutral towards litmus. SnO2 and ZnO are amphoteric as they form salts and water with acids and
bases. SiO2 is acidic as it forms salts with bases. SiO2 + 2NaOH  Na2SiO3 + H2O.

2. IE2 of Na > Mg as in Na second electron is to be removed from stable inert gas configuration i.e.,1s22s22p6.

3. For alkaline earth metal hydroxides down the group the change in lattice energy is more as compared to
change in hydration energy with increasing atomic radii. So down the group with increasing atomic
number, the solubility of their hydroxides increase.

RESONANCE Periodic Table - 2

4. Negative electron gain enthalpy of F is less than Cl. This is due to the fact that when an electron is added to
F, the added electron goes to the smaller n = 2 energy level and experiences significant repulsion from the
other electrons present in this level. In Cl, the electron goes to the larger n = 3 energy level and consequently
occupies a larger region of space leading to much less electron-electron repulsion.

5. Larger the charge on the ion smaller will be the size of ion for the same element. For P3+, there are 15 protons
for 12 electrons while for P5+, there are 15 protons for 10 electrons. Thus in P5+ the valence electrons are
more strongly attracted by the nucleus than those of P3+. As a result, there is a larger contraction in the size
of P5+ than that of P3+. Hence P3+ is bigger than P5+.

6. All are isoelectronic species having 10 electrons in each species but different nuclear charge and thus ionic
1
radius  Nuclear ch arg e .
So correct order is 9F– < 8O2– < 7N3–.
7. As non-metallic character of element attached to oxygen atom increases, the difference between the
electronegativity values of element and oxygen decreases and the acid character of oxides increases and
vice-versa.

8. Be has completely filled stable 2s2 orbital and thus Be has higher ionisation energy than B. 2s orbital has
less energy than 2p orbital.

9. Down the group the effective nuclear charge remains almost constant. But down the group with increasing
atomic number the number of atomic orbits increases and there by atomic size increases. As a result, the
distance of valence shell electron from nucleus increases and attraction between them decreases and
therefore ionization energy decreases.
10. As the metallic character decreases, the basic character decreases and acidic character increases. In other
words if electronegativities difference between elements and oxygen decreases the acidic character increases.
CaO is most basic, CuO is weakly basic, H2O is neutral and CO2 is acidic.
11. 3
Li– - 1s2 2s2 completely filled stable configuration, so more stable.
4
Be– - 1s2 2s2 2p1
5
B– - 1s2 2s2 2p2
6
C– - 1s2 2s2 2p3 half filled stable configuration, so more stable.
As Be– has less nuclear charge than B–, so it will have lower ionisation energy than B–.

12. According to their positions in the periods, these values are in the order.
Yb+3 < Pm+3 < Ce+3 < La+3
At. Nos. 70 61 58 57
Ionic radii (pm) 86 98 103 106
This is due to lanthanide contraction.
13. According to modified modern periodic law, the properties of elements are periodic functions of their atomic
numbers.
14. ZnO is an amphoteric oxide and dissolves readily in acids forming corresponding zinc salts and alkalies
forming zincates.
ZnO + H2SO4  ZnSO4 + H2O zinc sulphate
ZnO + 2NaOH  Na2ZnO2 + H2O sodium zincate
15. Number of electrons in N3– = 7 + 3 = 10.
Number of electrons in F– = 9 + 1 = 10
Number of electrons in Na+ = 11 – 1 = 10.
16. Ammonia is a Lewis base, accepting proton to form ammonium ion as it has tendency to donate an electron
pair.

RESONANCE Periodic Table - 3

17. The basic nature of oxides can be predicted on the basis of the factors given below.
(i) If electronegativity difference between element and oxygen is less than 1.4, the oxide is generally
acidic and if this difference is more than 1.4, the oxide is generally basic.
(ii) The basic character increases with increasing metallic character down the groups and decreases
across the period.
(iii) For the same element the basic character of their oxides increases with decreasing oxidation state.
7 6 4 3 2
Hence the correct of increasing Bronsted basicity order is Cl2 O7 < SO3 < CO2 < B2O3 < BaO

18. Isoelectronic species are those which have same number of electrons but different number of protons (i.e.
nuclear charge).
19
K+ = 19 – 1 = 18; 20Ca2+ = 20 – 2 = 18
21
Sc3+ = 21 – 3 = 18; 17Cl– = 17 + 1 = 18
Thus all these ions have 18 electrons in them.
 nucleus charge 
19. O 2 has the highest value of ionic radii as this can be explained on the basis of z/e  no. of electrons  .
 
When z/e ratio increases, the size decreases and when z/e ratio decreases the size increases.
20. With decrease in size from Al to S the basic nature of oxides decreases and acidic nature increases.
3 4 3 4
Al 2O3 < SiO2 < P2O3 < S O2
AI2O3 is amphoteric. SiO2 is slightly acidic whereas P2O3 and SO2 are the anhydrides of the acids H3PO3 and
H2SO3.
21. CaO - basic, CO2 and SiO2 - acidic, SnO2 - amphoteric, as it reacts with both acids and bases.
SnO2 + 4HCI  SnCI4 + 2H2O SnO2 + 2NaOH  Na2SnO3 + H2O
22. Nitrogen has half filled stable configuration, ns2np3. So, ionization enthalpy of nitrogen is greater than
oxygen. Across the period with increasing effective nuclear charge and decreasing atomic size the ionization
energies increases but down the group decreases due to increasing atomic radii. So, the correct of increasing
the first ionization enthalpy is B < P < C < O < N. (Ionisation energy in kJ mol–1 B = 801 ; P = 1011 ;
C = 1086 ; O = 1314 ; N = 1402).
23. Number of electrons in SO32– = 16 + 8 × 3 + 2 = 42
Number of electrons in CO32– = 6 + 8 × 3 + 1 = 32
Number of electrons in NO3– = 7 + 8 × 3 + 1 = 32
These are not isoelectronic species as number of electrons are not same.
24. Element : B S P F
I.E.(kJ mol–1) : 801 1000 1011 1681
In general as we move from left to right in a period, the ionization enthalpy increases with increasing atomic
number. The ionization enthalpy decreases as we move down a group. P (1s2, 2s2, 3s2 3p3) has a stable half
filled electronic configuration than S (1s2, 2s2, 2p6, 3s2, 3p4). For this reason, ionization enthalpy of P is
higher than S.
25. K+ = 19 – 1 = 18 e– CI– = 17 + 1 = 18 e–
2+
Ca = 20 – 2 = 18 e –
Sc3+ = 21 – 3 = 18 e–
Thus all the species are isoelectronic.
26. All have same number of electron i.e. 14.
NO+ = 7 + 8 – 1 - 14 ; C22– = 2 × 6 + 2 =14
CN– = 6 + 7 + 1 = 14 ; N2 = 7 + 7 = 14.
27. Down the group ionic radii increases with increasing atomic number because of the increase in the number
of atomic shells but across the period the ionic radii decreases due to increase in effective nuclear charge as
electrons are added in the same shell. Li+ and Mg2+ are diagonally related but Mg2+ having higher charge is
smaller than Li+, so correct order is Na+ > Li+ > Mg2+ > Be2+.
Be2+ = 0.31 Å
Mg2+ = 0.72 Å
Li+ = 0.76 Å
Na+ = 1.02 Å

RESONANCE Periodic Table - 4

28 In hydrides of 15th group elements the basic strength decreases down the group and the correct order is,
SbH3 < AsH3 < PH3 < NH3
29. O2–, F–, Na+, Mg and Al3+ have same number of electrons (i.e. 10 electrons) but different nuclear charges
and, therefore, they are isoelectronic species.
1
For isoelectronic species ionic radii  nuclear ch arg e .

So, correct order of ionic radii is 8O2– > 9F– > 11Na+ > 12Mg2+ > 13Al3+.

30. Order of ionic radii Ca2+ < K+ < Cl– < S2–
in isoelectronic species as Z/e increases size decreases.

SOLUTION OF ADVANCED LEVEL PROBLEM

1. As magnetic moment = n(n  2) = 1.73 ; So, n=1

Since atom has only one unpaired electron hence it must be 29Cu [29Cu = [Ar]18 3d10 4s1].
Hence element below it in periodic table has atomic number 29 + 18 = 47.
17. (i) N has half filled stable electronic configuration which is reluctant to accept an additional electron.
Therefore, nitrogen has less negative value of electron gain enthalpy than oxygen.
(ii) Because of interelectronic repulsion in compact small fluorine atom (2p-subshell), the addition of extra
electron is difficult as compared to chlorine (3p-subshell). So fluorine has less negative electron gain
enthalpy than chlorine.
18. M = 2.1 F=4
xA – xB = (4 – 2.1) = 1.9
% ionic character = 16(1.9) + 3.5 (1.9)2 = 43.03%
So, % covalent character = 100–43.03  57%.

RESONANCE Periodic Table - 5

 CHEMICAL BONDING
Chemical Bonding Part-1
EXERCISE # 1
PART - I
A-9. Here xz = 3 – 1 = 2 > 1.7  XZ is ionic
yz = 2 – 1 = 1 < 1.7  YZ is covalent.


 H 
 | 
A-16*. (A) H — N — H Cl– (B) K+C  N–
 | 
 H 

(C) (D) Na+O–H

B-3. Fluorine has no vacant d–orbital in its valence shell.

B-12. N atom in NO2+ is sp hybridised while in NO2– and NO3–, it is sp2 hybridised.
Bond order = 2

 2 1
Bond order = = 1.5
2

  2  1 1
Bond order = = 1.33
3

1
Bond order  Bond length

So, bond length order is NO3  NO2  NO2 .

1
B-13. Bond length  Bond order

Bond order of CO = 3 (as isoelectronic with N2)

No. of bonds in all possible sides
Bond order = No. of resonating structures
4
Bond order of CO2 = =2
2
4
Bond order of CO32– = = 1.33
3
So, order of bond length of C – O is CO < CO2 < CO32–
B-14. (i) Negative charge should be at more electronegative atom.
(ii) Less formal charge provides more stability.

RESONANCE Chemical Bonding # 6

B-15. P : CH3 – C  N
Q : H -- N = C = O
O

R : CH 3 C NH 2 .

B-16. Bond energy  Bond order

Species Bond order
CO 3
CO2 2
CO32– 1.33

B-17. (D) Position of atoms are different.

(E) Has unpaired electrons and this is not possible since the molecule is diamagnetic.

B-18. ; there is positive charge on two adjacent nitrogen atoms. This leads to repulsion and thus

increases the energy of the molecule.

C-1.

x>y=z

C-2.

D-1. (A) (B)

(C) (D) Zero overlap

D-3*. (b) If X-axis is internuclear axis, then it will result in  bond.

(c) It will result in  bond.
(d) It shows zero overlap with no bond formation.
D-6. Since  bond is weaker than  bond the stated value of bond energies are wrong.
2 2
D-7 Structure of C34– is ( C  C  C )

D-8. CaC2 exists as Ca2+ and C22– .

RESONANCE Chemical Bonding # 7

D-9. 19 and 4.

D-13*. C*  1s2 2s1 2p3 4 unpaired electron  4 bonds

B*  1s2 2s1 2p2 3 unpaired electron  3 bonds
I*  5s2 5p4 5d1 3 unpaired electron  3 bonds
P*  3s2 3p3 3 unpaired electron  3 bonds
* represent excited state
E-3. Hybridization does not take place without s-orbital

E- 7.

E-9. SnCl2 – sp2

XeF4 – sp3d2
3– – sp3d
NCl3 – sp3
HgCl2 – sp

E-11. (a) Electronic configuration of boron in ground state is 1s22s22p1.

BCl3 :

(b) Electronic configuration of nitrogen in ground state is 1s22s22p3.

NH3 :

(c) Electronic configuration of phosphorus in ground state is 1s22s22p63s23p3.

PCl3 :

(d) Electronic configuration of boron in ground state is 1s22s2.

BeF2 :

E-12.
steric No. = 2
 Hybridisation sp.

RESONANCE Chemical Bonding # 8

E-15. E-17.


F-5. (i) (ii) [N  N  N] 2
sp

(iii) PCl5 (s) exists as [PCl4]+ and [PCl6]– ,

(iv) I2Cl6() [ICl2]+ + [ICl4]–

self ionisation

F-6. see-saw

F-7. (A) BF3 (sp2) + F–  BF 4– (sp3). (B) NH3 (sp3) + H+  NH4+ (sp3)
(C) 2 SO2 (sp2) + O2  2 SO3 (sp2) (D) H2O (sp3) + H+  H3O+ (sp3)

F-9. The hybridization & shape of ClO3 is sp3 & pyramidal but hybridization & shape of NO 3 is sp2 & trigonal
planar.
O F
O¯
O¯
Xe
Xe
F-11.* (A) (B)
O¯ O¯
F
O
Perxenate ion [XeO6]
4- XeF2 (Linear)
O
F
F
F

(C) Xe (D) O Xe

F F O
F
XeOF4 (one l.p.) XeO2F2(one l.p.)

RESONANCE Chemical Bonding # 9

F-14. The cation should be
[H – C  N – Xe – F]+
Hybridisations sp sp sp3d

F-19. , sp but bent structure due to LP-BP repulsion.

G-2. (A)

(B) Bond angle is 180º because of sp hybridisation of nitrogen.

(C)

(D)

G-4. Generally lone pair causes more distortion than a double bond so
equitorial in SOF4 > equitorial in SF4

OCF2 :

due to low bond pair bond pair repulsion because of flourine & large repulsion due to double bond.

SF4 axial FSF < 180° due to lone pair.

Similar orbitals on hybridisation can not decrease their energy due to energy conservation law

G-6*. (A) Due to the presence of lone pair bond angle decreases.

CH3
|
B
(B) H C CH3
3
2
sp hyb.
(C) NH4Cl is an ionic compound and ‘N’ is in sp3 hybridisation.
(D) S8 molecule has 16 electron parirs left behind after the bonding.
G-7. As the electronegativity of central atom increases the bond angle increases due to repulsion between bond
pair and bond pair as bond pairs are more close to the central atom.

RESONANCE Chemical Bonding # 10

G-9. H2S– No hybridisation bond angle  93º
NH3 – Pyramidal 104.5º
CH4 – Tetrahedral 109º28'
BF3 – Triaganalplaner 120º
G-11. P4 bond angle = 60°
PH3 bond angle  90° (Drago's rule)
H2O bond angle = 104.5°
G-13. (a) According to VSEPR as electonegativity of central atom decreases, bond angle decreases. So bond
angle of H2O > H2S > H2 Se > H2Te
(b) C2H2 > C2H4 > CH4 > NH3 with bond pair- lone pair repulsion
sp sp2 sp3 sp3
(c) SF6 < NH3 < H2O < OF2 in this case bond angle of NH3 is highest because lp - lp repulsion is absent
in. it.
(d) ClO2 > H2O > H2S > SF6
ClO2 bond angle is highest due to its sp2 hybridisation, rest all are sp3 or sp3d2 hybridised more repulsion in
double bond electrons.
Cl.
: : : : :
O O
> > > SF6 (Octahedral)
O O H H S S

G-14.

G-15. S1 : SnCl2 ; bonding takes place in ground state.

Due to lp-bp repulsion bond angle slightly decrease from 120º.

S2 :

S3 : due to bp-lp repulsions

RESONANCE Chemical Bonding # 11

 F
H F
C=S
G-16. H F
F
Hydrogen atoms are in a vertical plane with axial fluorine atoms, -bond involving a p-orbital of carbon atom
must lie in equatorial plane of the molecule.
Six atoms, i.e. 2 H-atoms, C,S. and both axial F-atoms lie in one plane.

G-18*. B and C  Drago's rule, ICl3

G-24. XeF6 +6 As the oxidation no. increases, size of central atom decreases
XeF4 +4
XeF2 +2
G-28. Due to small size of nitrogen, the lp–lp repulsion is more than that in P. Hence statement B is correct
G-29. Oxidation no. of N in N2O5 is + 5
Anhydride of HOCl is Cl2O.
The bond length decreases with increase in difference of electronegativity.

PART - II

1.

Cl-atom is in sp3d hybridisation state. Hence geometry is trigonal bi-pyramidal which is similar to 3–
2. Number of electrons pairs = 6 ; number of bond pairs = 5 ; number of lone pairs =1. According to VSEPR
theory geometry of the molecule is square bipyramidal. As all positions are equivalent the lone pair of
electrons can occupy any position in octahedral geometry as given below.

3.  sp3d2

(A)  sp3d (B)  sp3d2 (C)  sp3

RESONANCE Chemical Bonding # 12

4.

Valence shell electron configuration of Cl, 3s2 3p5

To obtain effective p – d overlap the size of the d orbital must be similar to size of the p orbital. Hence in
chlorine, p – d bonding is so strong that no polymerization of oxoanions occurs.
5. (A) With hydrogen sulphur does not undergo sp3d2 hybridisation because of larger difference in energies
between s, p and d-orbitals. Sulphur show +6 oxidation state with highly electronegative elements like O and F.
(B) As fluorine is smaller and more electronegative than oxygen.
(C) I– being stronger reducing agent reduces Fe3+ to Fe2+.

7. (A) ; (B) ;

(C) ; (D) ;

EXERCISE # 2

–
F F
F
6. XeF4 XeF5– Xe F

F
F

+
F
|
F2SeO2 XeF3+ Xe – F
|
F

F
F Xe F
XeOF4 ClOF3
F O

RESONANCE Chemical Bonding # 13

 –
Cl Cl

ICl4– I SCl2 S
Cl Cl
Cl Cl

OSF4

8. (i) =4 (ii) =4 (iii) = 3 (iv) =5

20. As the s character in hybrid orbital decrease, size of hybrid orbital increases.

EXERCISE # 3
1. NO2+ Number of electron pairs = 2
Number of bond pairs = 2
Number of lone pair = 0
So, the species is linear with sp hybridisation.

O N O
sp

NO3– Number of electron pairs = 3

Number of bond pairs = 3
Number of lone pair = 0
So, the species is trigonal planar with sp2 hybridisation.

 sp2

NH4+ Number of electron pairs = 4

Number of bond pairs = 4
Number of lone pair = 0
So, the species is tetrahedral with sp3 hybridisation.

 sp3

2. According to VSEPR theory

F F
F F F
S C Xe
F F F F F
F F
p = 1 p = 0 p = 2
sp3 d-hybridisation sp3-hybridisation sp3d2-hybridisation
see-saw shape tetrahedral shape square planar shape

RESONANCE Chemical Bonding # 14

3. According to VSEPR theory
XeF2
Number of electron pairs = 5,
Number of bond pairs = 2, (linear)
So, Number of lone pairs = 3
Thus XeF2 is linear with 3 lone pairs occupying
3 equatorial positions of trigonal bipyramidal so as to minimize the repulsions.
XeF4
Number of electron pairs = 6,
Number of bond pairs = 4, (square planar)
So, Number of lone pairs = 2
Thus XeF4 is linear with 2 lone pairs occupying
2 axial positions of octahedral pyramidal so as to minimize the repulsions.

XeO2F2
Number of electron pairs (including super electron pairs) = 5,
Number of bond pairs = 4, (see-saw)
So, Number of lone pairs = 1
Thus XeO2F2 is see-saw with 1 lone pairs occupying
one equatorial position and two double bonds occupying other
two equatorial positions of trigonal bipyramidal so as to minimize the repulsions.

Cl
Cl
4. P — Cl steric number = 5, so sp3d hybridisation;
Cl
Cl

Cl

B steric number = 3, so sp2 hybridisation;

Cl Cl
:

N steric number = 4, so sp3 hybridisation;

H H
H
[PtCl4]2– is 5d8 configuration so square planar i.e. dsp2.

5.

6. 

7.

RESONANCE Chemical Bonding # 15

8. Number of electrons in NO3– = 7 + 3 × 8 + 1 = 32.
Number of electrons in CO32– = 6 + 3 × 8 + 2 = 32.
So both are isoelectronic.
NO3– steric number = 3 ; CO32– steric number = 3.

trigonal planar trigonal planar

As both have same shapes they are also isostructural (same hybridisation and no lone pair of electrons).

9. In

From left to right.

Note : Hybrid orbitals always form -bonds due to overlapping on their axis.
10. There are 5 electron pairs and all are bonds pairs in PCl5 . So to have the minimum repulsions between bond
pairs it acquires trigonal bipyramidal shape. In BrF5, there are 6 electrons pairs out of which one lone pair and
rest all are bond pairs. So to have the minimum repulsions between bond pairs and lone pairs it acquires
square pyramidal shape.

PCl5 (trigonal bipyramidal), BrF5 (square pyramidal)

11.

12. (A) The sulphur is in sp2 hybridisation but due to lp-bp repulsion the bond angle decreases to 119.5º.
(B) The oxygen is in sp3 hybridisation but due to lp-lp repulsion the bond angle decreases to 104.5º.
(C) It is believed that pure p atomic orbitals participate in bonding and due to lp-lp repulsion the bond angle
decreases to 92.5º.
(D) The nitrogen is in sp3 hybridisation but due to lp-bp repulsion the bond angle decreases to 107º.
SO2 OH2 SH2 NH3
o o o
Bond angle : 119.5 104.5 92.5 107o

13. (A) CF4 is tetrahedral where as SF4 is see-saw shaped.

(B) , O = C = O both linear according to VSEPR.

(C) BF3 is trigonal planar and PCl3 is pyramidal.

(D) PF5 is trigonal bipyramidal and IF5 is square pyramidal.
14. According to VSEPR theory,
total number of electron pairs = 6.
total number of bond pairs = 5.
so total number of lone pair = 1.
There is one Xe—O double bond. The -electrons of double bond create more F F
repulsion than single covalent bond. To minimize the repulsions the lone pair and Xe
F F
Xe—O double bond are trans to each other in octahedral geometry.
sp d
3 2
O

RESONANCE Chemical Bonding # 16

15. According to VSEPR theory two lone pairs out of six electron pairs are
trans to each other to have minimum repulsion. The shape of XeF4 is
square planar and geometry is octahedral with sp3d2 hybridisation. The
molecule looks like :

In OSF4, there are five electron pairs and all are bond pairs. So geometry is trigonal bipyramidal. As double
bond creates more repulsion than singles bond, the double bond acquires one of equatorial position of
trigonal bipyramidal to have minimum repulsions.
The structure looks like:

16.

Maximum 12 bond angles are of 90º.

17. The correct order of bond angle (smallest first) is
H2S < NH3 < SiH4 < BF3
92.6o < 107o < 109o28’ < 120o

18. (A) (B) (C) (D)

sp3 sp 2 sp3 sp 2 sp 3 sp sp 3 sp 2
19. (A) CH3  CO  CH3 (B) CH3  C OOH (C) CH3  C  N; (D) CH3  CO NH2
Acetone Acetic acid Acetonitrile Acetamide

RESONANCE Chemical Bonding # 17

20. According to VSEPR theory
The number of electron pairs around I = 5
The number of bond pairs around I = 2
The number of lone pairs around I = 3
To have minimum repulsions among lone pair and bond pairs, the lone pairs acquire
the three equatorial positions of trigonal bipyramidal as given in the structure,
ClO3–, XeF4 and SF4 have 1, 2 and 1 lone pair of electrons respectively.
21. According to VSEPR theory

F F
F F F
S C Xe
F F F F F
F F
p = 1 p = 0 p = 2
sp3 d-hybridisation sp3-hybridisation sp3d2-hybridisation
see-saw shape tetrahedral shape square planar shape

2
 1 
22. Calcium carbide is ionic carbide having [: C  C :] 2– Ca2+ : C 2 C :
 

23. Due to small size of B, it is very difficult to remove the electrons from boron to form ionic bond as it will require
very high energy. On the other hand, due to its very small size having high polarising power causes greater
polarisation and eventually significant covalent character according to Fajan's rule.
24. The spatial arrangement of six electron clouds (five bond pairs and one
lone pair) round the central Br-atom is octahedral. Due to the presence of
one lone pair of electrons in the axial hybrid orbital, the shape of BrF5 gets
distorted and becomes square pyramidal. Basal F-atoms are slightly
displaced upwards from the base of the square pyramid.
Br – F(b) distance = 1.79 Å
Br – F(a) distance = 1.68 Å
F(b) – Br – F(b) angle = 89º 48'
F(b) – Br – F(a) angle = 86º 30'
F(b) – Br – e angle = 93º 30'

25. NO2+ Number of electron pairs = 2

Number of bond pairs = 2
Number of lone pair = 0
So, the species is linear with sp hybridisation.

O N O
sp

NO3– Number of electron pairs = 3

Number of bond pairs = 3
Number of lone pair = 0
So, the species is trigonal planar with sp2 hybridisation.

 sp2

NH4+ Number of electron pairs = 4

Number of bond pairs = 4
Number of lone pair = 0
So, the species is tetrahedral with sp3 hybridisation.

 sp3

RESONANCE Chemical Bonding # 18

26. The structure is pentagonal bipyramid having sp3d3 hybridisation as given below :

Fb – I – Fb = 72º (5 number) ; Fb – I – Fa = 90º (10 number)

Fb – I bond length = 1.858 ± 0.004 Å ; Fa – I bond length = 1.786 ± 0.007 Å.
27. Calcium carbide exists as Ca2+ and C22–. According to the molecular orbital model, C22– should have a bond
order of 3 (configuration u2u2 g2). MOT configuration suggests that it contains one  and two
-bonds .

28. XeF2 : ; XeF4 :

XeF6 : ; XeO3 :

29. XeO2F2 has trigonal bipyramidal geometry. Due to presence of lone pair on equitorial position, the shape is
see-saw.

30. As electronegativity of central atom decreases, bond angle decreases.

(Hybridisation and number of lone pair on cental atom are same in all options)
31. PF5 trigonal bipyramidal
BrF5 square pyramidal (distorted)

SOLUTION OF ADVANCED LEVEL PROBLEM

7. Two terminal carbons can be assumed to be at A and B, while the central
carbon at O. Then, AB = 2AP

AP 
But = sin  
AO 2

 109 o 28 
 
= sin  2   (in tetrahedral structure  = 109o28)
 
= sin (54o44’)
 AP = AO sin (54o44’) = 1.54 × 0.82 = 1.26Å
 AB = 2AP = 2.52Å
Ans. 2.52 Å

RESONANCE Chemical Bonding # 19

8.

d1 = 2 × 134 × sin 60° pm = 227.8 pm = 228 pm

d2 = 134 × 3 + 2 × 134 cos 60° pm = 536 pm

Chemical Bonding Part-2

EXERCISE # 1
PART - I
A-4. Boron trimethyl is a weaker Lewis acid than the boron trihalides or monoborane. The electron donating effect
of the methyl groups hinders the complex formation with trimethyl amine. Hence the bond N  B is weakest
in [(CH3)3 N  B(CH3)3]. Me3N as donor (capacity). BBr3 > BCl3 > BF3 ~ BH3 > BMe3.

A-6.

A-12*. Cl2O > F2O and F2O < H2O

111° 102° 102° 104°
NO2+ > NO2–
sp sp2
AsI3 > AsBr3 > AsCl3 (due to size of halogen)

B-3. (A) (B) (C)

B-5*. (A) Structure is similar to that of ethane. Each N atom is tetrahedrally surrounded
by one N, two H and a lone pair. The two halves of the molecules are rotated 95º
about N – N bond and occupy a gauche (non-eclipsed) conformation. The bond
length is 1.45 Å.

(B) Has partial double bond character due to p-d delocalisation.

(C) OF2=103º (approximate) and OCl2 = 112º (approximate).

(D) Exist in polymeric structure as in solid state.

B-7. There is p–d delocalization of lone pair of electron on nitrogen atom and empty d-orbital of silicon but not
p– p, one of the 2s-orbital electrons jumps to the last Pz orbital and does not participate in sp2 hybridisation.

RESONANCE Chemical Bonding # 20

B-9. In BF3 the B - F bond length is shorter than normal bond character on account of p – p back bonding (1.30
Å). In 1 : 1 complex there is no p – p back bonding and hence the B –F bond length is longer,(1.35 Å).

Steric number 4 4
Hence both N and B have tetrahedrdal geometry with sp3 hybridisation.
B-12*. (A) Steric repulsions of bulkier groups and p–d dative bonding favour for a linear Si–O–Si group.
(B) Due to stabilization of the conjugate base anion by O(p)  Si(d) bonding motion.
(C) It is pyramidal because p–d bonding is not effective on account of bigger phosphorus atom.
(D) It has most effective p-d overlapping due to small size of Cl and O.
C-7. S1 : as it does not have d–orbitals.

S2 : ClF3

S3 : In B2 mixing of the g(2s) orbital with the g(2p) orbital lowers the energy of the g(2s) orbital and
increases the energy of the g(2p) orbital to a higher level than the  orbitals. As a result, the last two
electrons are unpaired in the degenerate (having the same energy)  orbitals, and the molecule is paramagnetic.
In N2 the g(2s) and g(2p) levels of N2 interact (mix) less than the B2 and C2 levels, and the g (2p) and u(2p)
are very close in energy.
C-9. N22– : 1s2 *1s2 2s2 *2s2 2px2  2py2 2pz2 2px1 *2py1.
10 – 6 10 – 6
B.O. N22– = = 2. ; B.O. O2 = = 2.
2 2
10 – 6
NO– isoelectronic with O2 so B.O. = = 2.
2
All have same number of electrons (i.e. 16) so isoelectronic.

D-1. M.O for C2 = 1s2 < 1*s2 < 2s2 < 2*s2 <  p 2 y   2 p 2 z   2p x
2  
HOMO LUMO
It is important to note that double bond in C2 consists of both pi bonds because of the presence of four
electrons in two pi molecular orbitals C22– .

D-3. N2 : (1s)2 (*1s)2 (2s)2 (*2s)2 (2p2x = 2p2y ) 2pz)2

The bond order of N2 is 1/2(10 – 4) = 3.
N2+ : (1s)2 (*1s)2 (2s)2 (*2s)2 (2p2x = 2p2y ) 2pz)1
The bond order of N2+ is 1/2(9 – 4) = 2.5.
O2 : (1s)2 (*1s)2 (2s)2 (*2s)2 (2pz)2 (2p2x = 2p2y ) (*2px1 = *2p1y)
The bond order of O2 1/2(10 – 6) = 2.
O2– : (1s)2 (*1s)2 (2s)2 (*2s)2 (2pz)2 (2p2x = 2p2y ) (*2px2 = *2p1y)
The bond order of O2 1/2(10 – 7) = 1.5.
NO+ derivative of O2 and isoelectronic with O22+ ; so (1s)2 (*1s)2 (2s)2 (*2s)2 2pz)2 (2p2x = 2p2y )
The bond order of NO+ 1/2(10 – 4) = 3.
NO derivative of O2 and isoelectronic with O2+ ; (1s)2 (*1s)2 (2s)2 (*2s)2 2pz)2 (2p2x = 2p2y ), *2px)1
The bond order of NO is 1/2(10 – 5) = 2.5.
bond order  1/bond length  bond dissociation energy..

1 1
D-8. (A) O2– B.O = 1 (B) O2 B.O = 2 (C) O2+ = 2 (D) O22 – = 1
2 2
1
Bond order  
bond length

RESONANCE Chemical Bonding # 21

D-11. (A) H2O2 = 1.48 Å due to repulsions between non-bonded pairs of electron on O-atoms and O2F2 = 1.217 Å.
(B) In O 22 very slightly increases due to charge (–ve) on two O atoms.

(C)

D-15. NO– > NO > NO+ (bond length)

Bond order 2.0 2.5 3
H2 > H2+ > He2+ (bond energy)
Bond order 1 0.5 0.5
(In He2+ more electron in antibonding MO's)
NO2+ > NO2 > NO2– (bond angle)
Bond angle 180º 133º 115º
O22– < O2+ < O2 (paramagnetic moment)
No. of unpaired e– 0 1 2
D-19.* O22+ bond order = 3, NO+ bond order = 3, CN– bond order = 3, CN+ bond order = 2
D-20.*_ (A) Nitrogen is more electronegative than phosphorus.

So, dipole moment of trimethylamine is greater than trimethy phosphine.

(B)
In trisilyl ether the lone pair of electron on oxygen atom is less easily available for donation because of p-d
delocalisation due to presence of the vacant d-orbital with Si. This however is not possible with carbon in
CH3– O – CH3 due to the absence of d-orbital making it more basic.
(C) Bond order of C2 and O2 are same i.e., 2. In C2 molecules both bonds are -bonds whereas, there is one
and one -bond in O2 molecule
C2 = 131 pm ; O2 = 121 pm.

(D)

D-22*. In FO+ total no. of electrons = 16, so bond order will be 2.

In FO– total number of electrons = 18, so bond order will be 1.

2 1 1 10  7
D-25. He2+ bond order =  ; O – bond order =  1 .5
2 2 2 2
84 10  5
C2 bond order =  2 ; NO bond order =  2 .5
2 2
Bond order  bond dissociation energy..
D-27*. (A) O2+ : (1s)2 (*1s)2 (2s)2 (*2s)2 (2pz)2 (2p2x = 2p2y ) (*2px1 = *2py)
(B) NO is derivative of O2: NO(O2+) (1s)2 (*1s)2 (2s)2 (*2s)2 (2pz)2 (2p2x = 2p2y ) (*2px1 = *2py)
(C) O2– : (1s)2 (*1s)2 (2s)2 (*2s)2 (2pz)2 (2p2x = 2p2y ) (*2px2 = *2p1y)
(D) B2 : (1s)2 (*1s)2 (2s)2 (*2s)2 (2p1x = 2p1y) (pz)0

RESONANCE Chemical Bonding # 22

D-28*. NO– > NO > NO+ (bond length)
Bond order 2.0 2.5 3
H2 > H2+ > He2+ (bond energy)
Bond order 1 0.5 0.5 (more antibonding electron in He2+)
NO2+ > NO2 > NO2–
Bond angle 180º 133º 115º
O22– = O22+ > O2 (paramagnetic moment)
No. of unpaired e–
0 0 2

E-3. (A) N2O3 Dinitrogen trioxide

(B) N2O22– Hyponitrite ion

(C) N2O5 Dinitrogen pentoxide

(D) N2O4 Dinitrogen tetroxide

E-4. The correct formula of borax is Na2[B4O5(OH)4]. 8H2O. The structure of anion is :

E-8.* P4O10

The P – O bond lengths shows that the bridging bonds on the edges are 1.60 Å but the P = O bonds on the
corners are 1.43 Å and this P = O is formed by p – d back bonding. A full p-orbital on the oxygen atom
overlaps sideway with an empty d-orbital on the phosphorus atom. The bond angle POP is 127º and there is
no P – P bonds.

RESONANCE Chemical Bonding # 23

E-11. (I) [PCl4]+  sp3

(II) has  102° bond angle due to lp – lp repulsion, as bond pairs are closer to F-atoms.

(III) All have sp3 hybridisation and one lone pair.

(IV)

E-12.

E-13. (A) O  C  C  C  O
| | |
sp sp sp

O O
Resonance
O
(B) takes place O Cr Cr O
Resonance ; Therefore, six Cr – O bond lengths are not equal.
takes place
No resonance
O O

(C)

This is an example of 3-centre 2-e– bond which is also known as Banana bond.
But Al2Cl6 have covalent bond only and there is no electron deficient bonding as depicted in the given
structure.
Cl Cl Cl
Al Al
Cl Cl Cl
(D) AgI is bright yellow coloured compound due to the polarisation of anion, I–
.The bigger anions are more polarised and hence their electrons get excited by
partial absorption of visible light.

E-17. (A) NO B.O = 3 triple bond.

O = N – Cl there is a double bond between N and ‘O’ atom
(B) CaC2  Ca2+ + C22– (–C  C–)
H H
C2H4  C=C
H
H
(C) KO2 O2– B.O = 1.5
Na2  O22– B.O = 
H H
(D) py
C = C = C
py pz pz

H
H
(S + Pz + Px) (Spx) (S + Py + Px)
xz - plane (xy – plane)

RESONANCE Chemical Bonding # 24

E-18.

general formula of cyclic silicates is [Sin O3n]2n–

PART - II

1. (A)

Bond order  stability (i.e., bond strength)

(B) Helium molecule (He2) : He2 : (1s)2 (*1s)2
Bond order of He2 is ½(2 – 2) = 0
The molecular orbital description of He2 predicts two electrons in a bonding orbital and two electrons in an
antibonding orbital, with a bond order of zero - in other words, no bond. The noble gas He has not significant
tendency to form diatomic molecules and, like the other noble gases, exists in the form of free atoms.
(C) Carbon molecule (C2) : (1s)2 (*1s)2 (2s)2 (*2s)2 (2p2x = 2p2y) or KK (2s)2 (*2s)2 (2p2x = 2p2y )
Lithium molecule (Li2) : (1s)2 (*1s)2 (2s)2
Peroxide (O22–) : (1s)2 (*1s)2 (2s)2 (*2s)2 (2pz)2 (2p2x = 2p2y ) (*2px2 = *2p2y)
As all electrons are paired so C2, Li2 and O22– are diamagnetic.
(D) Fluorine molecule (F2) : (1s)2 (*1s)2 (2s)2 (*2s)2 (2pz)2 (2p2x = 2p2y ) (*2px2 = *2p2y)
2. (D) It is correct statement.

3.

4. Oxygen molecule (O2) : O2 : (1s)2 (*1s)2 (2s)2 (*2s)2 (2pz)2 (2p2x = 2p2y ) (*2px1 = *2p1y)

Bond order = 1/2(10 – 6) = 2.0,

O2+ : (1s)2 (*1s)2 (2s)2 (*2s)2 (2pz)2 (2p2x = 2p2y ) (*2px1 = *2p0y)

Bond order = 1/2(10 – 5) = 2.5.

Nitrogen molecule (N2) : (1s)2 (*1s)2 (2s)2 (*2s)2 (2p2x = 2p2y ) 2pz)2

The bond order of N2 is 1/2(10 – 4) = 3.

N2+ : (1s)2 (*1s)2 (2s)2 (*2s)2 (2p2x = 2p2y ) 2pz)1

Bond order = 1/2(9 – 4) = 2.5.

RESONANCE Chemical Bonding # 25

5. (I) O2+ : (1s)2 (*1s)2 (2s)2 (*2s)2 (2pz)2 (2p2x = 2p2y ) (*2px1 = *2p0y)

Bond order = 1/2(10 – 5) = 2.5.

(II) NO is derivative of O2 and isoelectronic with O2+ :
so (1s)2 (*1s)2 (2s)2 (*2s)2 (2pz)2 (2p2x = 2p2y ) (*2px1 = *2p0y)

Bond order = 1/2(10 – 5) = 2.5.

(III) N2+ : (1s)2 (*1s)2 (2s)2 (*2s)2 (2p2x = 2p2y ) 2pz)1

Bond order = 1/2(9 – 4) = 2.5.

O2+ , NO and N2+ have same bond order i.e. 2.5 and have same magnetic property having one unpaired
electron.
10. (A) N2+ : BO=2.5 (4 electron in antibonding MO) 1 unpaired electron (Paramagnetic)
N2– : BO=2.5 (5 electron in antibonding MO) 1 unpaired electron (Paramagnetic)
(B) NO : BO=2.5 (5 electron in antibonding MO) 1 unpaired electron (Paramagnetic).Last electron in antibonding
MO.So, easily removed.
N2 : BO = 3 (4 electron in antibonding MO) 0 unpaired electron (diamagnetic).Last electron in bonding
MO.So, not easily removed.
(C) NO+ : BO = 3 (0 unpaired electron) diamagnetic [BO   BL ].
(D) He2+ : BO = 0.5 (1 unpaired electron) paramagnetic [1 electron in antibonding MO].
H2+ : BO = 0.5 (1 unpaired electron) paramagnetic [0 electron in antibonding MO].

EXERCISE # 2

11. (a) Hydrogen molecule (H2) : H2 : (1s)2

N  Na 2  0
Its bond order, therefore, is = b  1
2 2
(b) Cation of hydrogen molecule (H2 ) : H2 : (1s)1
+ +

Its bond order, therefore, is = 1/2 (1 – 0) = 1/2

(c) Helium molecule (He2) : He2 : (1s)2 (*1s)2
Its bond order, therefore, is ½(2 – 2) = 0
(d) Lithium molecule (Li2) : (1s)2 (*1s)2 (2s)2
Its bond order, therefore, is 1/2(4 – 2) = 1.
(e) Beryllium (Be2) : (1s)2 (*1s)2 (2s)2 (*2s)2
Its bond order, therefore, is 1/2(4 – 4) = 0.
(f) Boron (B2) : (1s)2 (*1s)2 (2s)2 (*2s)2 (2p1x = 2p1y) (pz)0
Its bond order, therefore, is 1/2(6 – 4) = 1.

13. * 3p – – – –
* 3p    
3p    
3p  
*3s  
 3s  
S2 S22–
8–4
Bond order S2 = = 2 (paramagnetic with two unpaired electrons)
2

S  S.
8–6
Bond order S22– = = 1 (diamagnetic, as all electrons are paired).
2

16. Complex exists as NO+ and [BF4]– . NO+ is isoelectronic with N2 ; so 1s2, *1s2, 2s2, *2s2, 2p2x = 2p2y,
10 – 4
2pz2 , then its bond order is =3
2

RESONANCE Chemical Bonding # 26

20. (a) 6 shaired ‘O’ atoms.

(b)

(c)

(d) 4 equivalent N – O bonds due to resonance.

(e) 3 S—O—S bond

22. (a) (SiO32–)n (b) ((Si4O111)6–)n

(c) = (Si3O10)8– (d) (SiO32–)3

(e) (Na+ (PO3–))6 = Na6(PO3)6

RESONANCE Chemical Bonding # 27

 EXERCISE # 3

1.

According to the structure of cyclic metaphosphoric acid, (HPO3)3, three are there P – O – P bonds.
2. Molecular orbital electronic configuration of O2 is as follows (Z is taken as molecular axis).
1s2  *1s 2  2s2  * 2s2 2p 2  2p 2   2p 2  * 2p 1   * 1
z x y x 2p y

10 – 6
Bond order = = 2.
2
As it contains two unpaired electrons in bonding  molecular orbitals O2 is paramagnetic.
So, Magnetic moment = n (n  2) = 2 ( 2  2) = 2.83 B.M.

3. There is no S-S bond in S3O9 .

4. CN–, CO and NO+ all have same number of electrons i.e. 14. So all are isoelectronic species. Further all the
species are isoelectronic with N2 which have molecular orbital electronic configuration as follows
1s2  *1s2  2s2  * 2s2  2p x 2  2py 2  2p z 2 ;

10 – 4
So, Bond order = = 3.
2
Hence all will have same bond order and that is three.
5. Here ammonia acts as a lewis base and boron trifluoride as lewis acid as represented below. Hence in this
complex both N and B acquire tetrahedral geometry and sp3 hybridisation.

  or [NH3.BF3].

sp3 (steric number = 4) sp3 (steric number = 4)

6. O2– is derivative of O2 and has 17 electrons. So its molecular orbital electronic configuration is
1s2  *1s2  2s2  * 2s2  2p z 2  2p x 2  2py 2  * 2p x 2  * 2p y1
As it contains one unpaired electron in *2py1 molecular orbital so it is paramagnetic. Rest all species have
paired electrons so diamagnetic.
7. O2 bond order = 2 ; O2– bond order = 1.5 ; O22– bond order = 1.0 ; O2+ bond order = 2.5.

8. In diethyl ether (C2H5— —C2H5) oxygen atom has two lone pairs of electrons, thus acts as lewis base while
in anhydrous AICI3 aluminium has vacant 3p-orbital of valence shell and thus acts as Lewis acid. AlCl3
C2H5
accepts a lone pair of electrons from diethyl ether to complete its octet forming a complex O: AlCl3 .
:

C2H5
Hence, anhydrous AICI3 is more soluble in diethyl ether by means of solvolysis in comparison to hydrous
AICI3 (i.e., AICI3 . 6H2O). Hydrous AICI3 is a polar compound, while ether is non-polar, so on basis of Thumb`s
rule, like dissolve in like solvents. Hence hydrous AICI3 is least soluble in ether.

RESONANCE Chemical Bonding # 28

9. It is peroxodisulphuric acid, the Marshall’s acid and contains one – O – O – linkage as given in structure
O O
|| ||
HO — S — O — O — S — OH
|| ||
O O

(H2S2O8)

10. Molecular orbital electronic configuration is 1s 2  *1s 2  2s2  * 2s2  2p z 2  2p x 2  2p y 2  * 2p x1  * 2p y 0

As it contains one unpaired electron it is paramagnetic and bond order = (10 – 5) / 2 = 2.5 (O2 = 2.0).

11. The electronic configuration of O2 will be:

O2 = 1s2 *1s2 2s2 *2s2 2p2z 2p2x = 2p2y *2p1x = *2p1y
Nb  Na
Now bond order =
2
Where, Nb = Number of electrons in bonding orbitals Na = Number of electrons in antibonding orbitals
10  6
bond order = =2
2
Similarly electronic configuration of O2– (in KO2) will be
1s2 *1s2 2s2 *2s2 2p2z 2p2x = 2p2y *2p2x = *2p1y
10  7 3
Bond order = = = 1.5
2 2
In O2 [AsF4]–, O2 is O2+ .
The electronic configuration of O2+ will be
1s2 *1s2 2s2 *2s2 2p2z 2p2x, = 2p2y *2p1x
10  5
bond order  =2.5
2
1
Hence bond length order will be O+2 < O2 < O–2 because Bond order  Bond length .

13. NO and NO+ are derivative of O2.

NO(isoelectronic with O2+) : (1s)2 (*1s)2 (2s)2 (*2s)2 (2pz)2 (2p2x = 2p2y ) (*2px1 = *2py)
Bond order = 1/2(10 – 5) = 2.5.
NO+(isoelectronic with O22+) : (1s)2 (*1s)2 (2s)2 (*2s)2 (2pz)2 (2p2x = 2p2y ) (*2px = *2py)
Bond order = 1/2(10 – 4) = 3.
Bond order  1/bond length.
So NO+ has shorter bond length.

14. (A) In two dimensional sheet silicates, three oxygen atoms of [SiO4]4– are shared with adjacent tetrahedral
[SiO4]4– units,
(B) One oxygen atom is shared between two adjacent tetrahedra, [SiO4]4–.
(C) All four oxygen atoms are shared between adjacent tetrahedra, [SiO4]4–.
(D) Two oxygen atoms are shared between adjacent tetrahedra, [SiO4]4– forming a linear chain.

17.

18. He2+   (1s)2 * (1s)1, one unpaired electron.

H2  (1s)2 , * (1s)0 , no unpaired electron.
H2+  (1s)1 , * (1s)0, one unpaired electron.
H2– (1s)2, * (1s)1, one unpaired electron.
19. The electronic configuration of oxygen atom is 1s2, 2s2, 2p4. Each oxygen atom has 8 electrons. Hence in
each O22– ion there are 16 + 2 = 18 electrons. The electronic configuration of O22– ion is
KK (2s)2 * (2s)2  (2pz)2  (2px) p (2py)2*(2px)2 * (2py)2
Here KK represents non-bonding molecular orbital of 1s orbital. O22– contains no unpaired electrons.

RESONANCE Chemical Bonding # 29

 The electronic configuration of B2 molecule is
KK (2s)2 *(2s)2 (2px)1 (2pz)1
it contains 2 unpaired electrons. The electronic configuration of N2+ ion is
KK (2s)2 *(2s)2 (2px)2 (2py)2 (2pz)1
it contains one unpaired electron.
The electronic configuration of O2 molecule is
KK (2s)2 *(2s)2 (2px)2 (2py)2 (2pz)2 *(2px)1 *(2py)1
It contains 2 unpaired electron.

Nb – Na
20. Bond order =
2

CO = 1s 2  *1s 2  2s2  * 2s2 2p2x  2py 2  2p 2

z

Bond order of CO = 10 – 4 / 2 = 3
NO–  1s 2  *1s 2  2s2  * 2s2  2p z 2  2p x 2  2py 2  * 2p x1  * 2p y1
Bond order of NO– = 10 – 6 / 2 = 2
NO+  1s 2  *1s 2  2s2  * 2s2  2p z 2  2p x 2  2p y 2
Bond order of NO+ = 10 – 4 / 2 = 3
CN–  1s2  *1s2  2s2  * 2s2  2p x 2  2py 2  2p z 2
Bond order of CN– = 10 – 4 / 2 = 3
N2  1s2  *1s2  2s2  * 2s2  2p x 2  2p y 2  2p z 2
Bond order of N2 = 10 – 4 / 2 = 3.
21. KO2 exists as K+ & O2– .
In O2–, superoxide ion there are total number of electrons = 16 + 1 = 17.
MOT configuration = 1s 2  *1s 2  2s2  * 2s2  2p z 2  2p x 2  2p y 2  * 2p x 2  * 2p y1
O2– has one unpaired electron in antibonding *2py1 . So it is paramagnetic.
22. Steric number = 4 ; thus sp3 hybridisation in P4 . As each phosphorus is sp3, so
3
% p character will be = × 100 = 75.
4

23. O22– (8 + 8 + 2 = 18) : 1s2 *1s2 2s2 *2s2 2pz2 2px2 2py2 *2px2 *2py2 ; all electrons are paired. So
diamagnetic.
24. Molecular orbital configuration of
O2  1s2* 1s2 2s2 *2s2 2pz2 2py2 *2p1x *2p1y
 Paramagnetic
10 – 6
Bond order = =2
2
O2+  1s2* 1s 2s2* 2s2 2p2z 2px2 2py2 * 2p1x
 Paramagnetic
10 – 5
Bond order = = 2.5
2
N2  1s2* 1s2 2s2 *2s2 2p2x 2p2y 2p2z
 paramagnetic
10 – 4
Bond order = =3
2
N2+  1s2 * 1s2 2s2 * 2s2 2p2x 2p2y 2p1z
 Paramagnetic
9–4
Bond order = = 2.5
2

RESONANCE Chemical Bonding # 30

 C2  1s2 * 1s2 2s2 * 2s2 2p2x 2p1y
 Paramagnetic
8–4
Bond order = =2
2
C2+  1s2 * 1s2 2s2 * 2s2 2p2x 2p1y
 Paramagnetic
7–4
Bond order = = 1.5
2
NO  1s2 * 1s2 2s2 * 2s2 2p2z 2p2x 2p2y * 2p1x
 Paramagnetic
10 – 5
Bond order = = 2.5
2
NO+  1s2 * 1s2 2s2 * 2s2 2p2z 2p2x 2p2y
 Diamagnetic
10 – 4
Bond order = = 3.
2

25. NO+ is derivative of O2 ; NO+ (isoelectronic with O22+) 1s2 * 1s2 2s2 * 2s2 2p2z 2p2x 2p2y
10 – 4
Bond order = = 3.
2
CN– is derivative of N2 ; CN– (isoelectronic with N2) 1s2 * 1s2 2s2 * 2s2 2p2x 2p2y 2p2z
10 – 4
Bond order = = 3.
2

26. (A) B2 1s2 *1s 2 2s 2 *2s 2 2px1 = 2py1

64
Bond order = =1 Paramagnetic with two unpaired electrons.
2
It undergoes oxidation as well as reduction which can be explained by taking the following reactions.
2B + 3Cl2  2BCl3 ; 2B + 3Ca  Ca3B2 (boride)
Mixing of 's' and 'p' orbitals takes place.
(B) N2 1s2 *1s 2 2s 2 *2s 2 2px2 = 2py2 2pz2
10  4
Bond order = =3 Diamagnetic
2
It undergoes oxidation as well as reduction which can be explained by taking the following reactions.
N2 + O2  2NO ; 6Li + N2  2Li3N
Mixing of 's' and 'p' orbitals takes place.
(C) O2– 1s2 *1s 2 2s 2 *2s 2 2pz2 2px2 = 2px 2 *2px2 = *2py1
10  7
Bond order = = 1.5 Paramagnetic with one unpaired electron.
2
It undergoes oxidation as well as reduction which can be explained by taking the following reactions.
O2–  O2 + e– ; O2– + e–  O22–
Mixing of 's' and 'p' orbitals does not take place.
(D) O2 1s2 *1s 2 2s 2 *2s 2 2pz2 2px2 = 2px2 *2px1 = *2py1
10  6
Bond order = =2 Paramagnetic with two unpaired electrons.
2
It undergoes oxidation as well as reduction which can be explained by taking the following reactions.
O2  O2+ + e– ; O2 + e–  O2–
Mixing of 's' and 'p' orbitals does not take place.

RESONANCE Chemical Bonding # 31

27. (A) (B)

(C) (D)

N2 O 4 N2 O 5

28.

Decrease in B – F bond length which results in the higher bond dissociation energy of B – F in BF3 is due to
delocalised p–p bonding between filled p-orbital of F atom and vacant p-orbital of B atom.
29. Bond Order Bond Order
10  5 10  7
(1) O 2+ = 2.5 (2) O 2– = 1.5
2 2
10  8 10  4
(3) O22– =1 (4) O22+ =3
2 2
1
Bond order 
bond length
So, O22+ has the shortest bond length.
30. B2 ; total number of electrons = 10. The MOT electron configuration violating the Hund's rule will be thus :
2 2 2 2 2 0 0
1s  *1s  2 s  * 2s  2px   2p y  2pz

64
So, bond order = =1
2
As all electrons are paired, the molecule is diamagnetic.

SOLUTION OF ADVANCED LEVEL PROBLEM

3. Phosphorous acid (H3PO3) Dibasic  x = 2
Di meta phosphoric acid (H2P2O6) Dibasic  y = 2
Pyro phosphoric acid (H4P2O7) tetrabasic  y = 4
Ans. 224

13. (P) Molecular orbital electronic configuration ;

NO+ is derivative of O2, so MOT configuration is :
1s2 *1s2 2s2 *2s2 2px2 2py2 = 2pz2 (x is taken as molecular axis)
10  4
Bond order = =3
2
One  bond and two  bonds.

RESONANCE Chemical Bonding # 32

 –
(Q) Number of  bonds in NO+ is one and in BF4 are four. So total number of  bonds are five.

(R) Number of  bonds in NO+ are two.

(S)

Steric number of central atom boron is 4 + 0 = 4 ; so its hybridisation is sp3 and thus the number of hybrid
orbitals involved in sp3 hybridisation is four.

Ans.

V
15. O2[AsF6]  O2+ + [ As F6 ]–

1
O22– peroxide ion B.O = (10 – 8) = 1.
2

O – O bond is non polar so 2 polar bond.

carbon suboxide is C3O2

O = C = C = C = O.

Number of l.p is present in N(SiMe3)3 is zero.

16.

The P – O bond lengths shows that the bridging bonds on the edges are 1.60 Å but the P = O bonds on the
corners are 1.43 Å and this P = O is formed by p – d back bonding. A full p-orbital on the oxygen atom
overlaps sideway with an empty d-orbital on the phosphorus atom. The bond angle POP is 127º and there is
no P – P bonds.
(i) P = O have bond length of 1.43 Å (8 covalent bonds)
(ii) P – O have bond length of 1.60Å (12 covalent bonds)
(iii) Number of P – O – P linkage = 6.
(iv) Number of lone pair on each phosphorus atom is zero.

Ans. 4 12 6 0
(i ) (ii) (iii) (iv )

RESONANCE Chemical Bonding # 33

 Chemical Bonding Part-3
EXERCISE # 1
PART - I
2+
A-2. As Pb has low polarising power. So PbCl2 is ionic.
A-3. As charge on cations increases, their polarising power increases and thus covalent character increases.
 2 3 4
Li Cl  Be Cl2  BC l3  C Cl4
A-5. As the size of anions decrease the distance of valence shell electrons from nucleus decreases and so
polarizability decreases.
A-6. Sn4+ has highest polarising power amongst Na+, Pb2+ , Sn4+ and Al3+ because of smaller size and higher
charge. So SnCl4 is most covalent and thus has least melting point.
A-7. Because of high charge density on Sn4+ it has high polarising power and thus leads to greater polarisation of
anion i.e., greater distortion of electron clouds of the Cl– ions. So SnCl4 is most covalent.
A-9. Solubility BaCO3 and MgCO3 can be explained on the basis of their hydration and lattice energies.
A-10. AgI is less soluble than AgF due to covalent nature. LiI is more soluble then LiF due to high size difference
of ions more ionic nature, more melting point. Higher the charge density , larger will be the hydrated radii.
A-12. Polarisation of the I– by the Cu2+ results in the transference of an electron towards Cu2+ makes it as oxidising
agent and I– as a reducing agent, reduces Cu2+ to Cu+ and itself oxidised to I2 .
B-2. Metallic bond results from the electrical attractions among positively charged metal ions and mobile, delocalised
electrons belonging to the crystal as a whole.
B-4. (A) N2 contains one  and two  bonds but C2 contains only two  bonds as four electrons are present in
bonding  molecular orbitals.
(B) Cu2+ has higher hydration energy then Cu+ so Cu2+ is more stable than Cu+ . Moreover, Cu+ undergoes
disproportionation. 2Cu+  2Cu2+ + Cu. (a fact)
(C) Can be explained by electron sea model as it is due to the presence of mobile electrons.
B-6*. (A) It results from the electrical attractions among positively charged metal ions and mobile, delocalised
electrons belonging to the crystal as a whole.
(B) In general, greater the number of (n–1)d and ns electrons, stronger is the resultant bonding.
(C) Strength of metallic bond depend on the type of hybrid orbitals participating in metallic bonding.
(D) As the size of atom increases the attraction between the positive part of the atom and delocalised
electrons decreases and thus the strength of the metallic bond decreases.

PART - II

1. For more covalent character, small cation and large anion are favourable factors. In MgS, Mg2+ will have
higher polarising power and S2– will have higher polarisability. Hence there will be higher polarisation of anion
resulting in higher covalent character.
2. Due to smaller size of Be2+ and largest size of – amongst all anions i.e. F– , Cl– , Br– and –, there will be
greater polarisation of anion. Thus Be2 will be most covalent i.e. least ionic.
3. As the size of the cations increases in the order
Si4+ < Sn4+ < Sn2+
and for size of anions
F– < Cl–
so the order of increasing ionic character is
SiCl4 < SnCl4 < SnF4 < SnCl2 < SnF2
4. As polarizability of anion increases covalent character increases.
5. Larger anion has higher polarisability.

RESONANCE Chemical Bonding # 34

 Solution of Exercise # 2 already given in sheet booklet

EXERCISE # 3
1. Statement-1 : Germanium is a semiconductor, where the energy gap between adjacent bands is sufficiently
small for thermal energy to be able to promote a small number of electrons from the full valence band to the
empty conduction band. This leaves both bands partially filled, so the material can conduct electricity.
Statement-2 : Incorrect statement.
2. The elements of group 14 show an oxidation state of +4 and +2. The compounds showing an oxidation state
of +4 forms covalent compound and have tetrahedral structures. e.g. SnCl4, PbCl4, SiCl4, etc. whereas those
which show +2 oxidation state are ionic in nature and behave as reducing agent. e.g. SnCI2, PbCI2 etc.
Further as we move down the group the tendency of the element to form covalent compound decreases but
the tendency to form ionic compound increases.

3. High charge and small size of the cations increases polarisation.

As the size of the given cations decreases as
K+ > Ca2+ > Mg2+ > Be2+
Hence, polarising power increases as
K+ < Ca2+ < Mg2+ < Be2+

4. Covalent character in ionic compounds is governed by Fazan’s Rule. AlCl3 will show Maximum covalent
character on account of higher polarising power of Al3+ because of its having higher positive charge and
smaller size.

Solution of advanced level problem already given in sheet booklet

Chemical Bonding Part-4

EXERCISE # 1
PART - I

A-5. XeF2 SF2Cl2

XeOF2 ICl2–

IOCl4– F2ClO+

A-9*. Polarity depend on net dipole moment. If diple moment  = 0 it is nonpolar.

(A) XeF4 =0 non polar

RESONANCE Chemical Bonding # 35

 (B) XeF6  0 polar

(C) XeOF4   0 polar

F
F

(D) Xe F XeF5–  0 non polar

F
F

A-16.  ; So dipole moment of NH3 is greater than NF3.

A-19. Dipole moment of compound if it would have been completely ionic

= (4.8 × 10–10 esu) (2.67 × 10–8 cm) = 12.8 D
4 .0
so % ionic character = × 100% = 31.25 %
12.8

A-22. This is based on the decreasing electronegativity difference between H (2.1) and Sb (1.9) , As (2.0) , P (2.1)
and N (3.0).

B-1. S1 : Due to resonance , both bonds are equal.

S2 : Hydration of ions due to force of attraction between ion and water molecule. Which is a dipole.
S3 : Due to intermolecular H-bonding, boiling point increases.
S4 : A symmeetrical molecule with identical bonds have zero dipole moment.
B-2. All molecules have London dispersion force because of number of polarizable electrons.
Non polar molecules have only London dispersion force because of polarisable electron. Benzene is non
polar molecule.
Polar molecules have dipole-dipole attraction in addition to London dispersion force.

and so on
Molecules with, O–H, N–H, or F – H bond have hydrogen bonding in addition to London dispersion force.
Molecule IC is polar, so in addition to London dispersion force it has dipole-dipole attraction also.
B-3. Graphite has layered structure. Layers are held by van der Waal’s forces and distance between two layers is
340 pm. Each layer is composed of planar hexagonal rings of carbon atoms. C – C bond length within the
layer is 141.5 pm Each carbon atom in hexagonal ring undergoes sp2 hybridisation and make three sigma
bonds with three neighbouring carbon atoms. Fourth electron forms a  bond. The electrons are delocalised
over the whole sheet.

RESONANCE Chemical Bonding # 36

B-9. (A) As + charge on central atom increases, the attraction between + and – increases and thus Xe–F bond
length decreases. The correct order is XeF2 > XeF4 > XeF6
(B) PH5 can not undergo sp3d hybridisation as there is much large difference in size of s, p and d orbitals.
PH5 does not exist as no partial positive charge develops on P atom.
(C) Dipole moment of CH3Cl is greater than CH3F due to greater charge sepration on carbon and chlorine
atoms in CH3Cl.
(D) it is a correct order.
The strength of hydrogen bond depends upon :
(i) size (ii) electronegativity and (iii) ease of donation of electron pair by electronegative element.
Higher the value of electronegativity and smaller the size of the covalently bonded atom to H atom stronger
is the hydrogen bonding.

B-13*. maleic acid fumaric acid

O
C H
O
–
C

C O H
H C
O

O2[AsF4] = O2+ B.O = 2.5 so O2 + has smaller bond length than O2–
KO2 = O2 –
B.O = 1.5
Greater the size of the halogen atom greater will be bond angle.
F F
Pz Py
C C C
(s+px+py) (s+px) (s+px+pz)
F F

C-1 S1 : Due to intermolecular H-bonding in HF it boils at higher temperature than HCl

S2 : Mol. wt. of HBr < Mol. wt. of HI
S3 : Bond order of N2 is more than N2+ .
S4 : Molecular mass of F2is less than that of Cl2

C-3. S1 : Polarising power of a cation is inversely proportional to its size.

1
S2 : H2+ : 1s1 B.O. =
2
1
He2+ : 1s2 1s1 B.O. =
2
But He2+ has electron in antibonding molecular orbital so its is unstable.
S3 : H-bond formation requires the availability of lone pair of electron.
S4 : In Cl2O, the bond angle is more than 109º28’ due to steric repulsion.
C-4. As molecular weight increases, magnitude of Van der Waal's force of attraction increases.
Therefore, boiling point increases. Though NH3 has strong H-bonding but boiling point of SbH3 is highest due
to highest molecular weight. Boiling point NH3 = 238.5 K and SbH3 = 254.6 K.
C-6. (A) in S8 hybridisation of each S-atom is sp3 , in P4 hybridisation of each P-atom is sp3

(B) due to bp-lp repulsions

(C) Inter molecular H-bonding (PO43– groups are bonded by many H-bonds)

(D)

RESONANCE Chemical Bonding # 37

C-7*. (A) Boiling point of ICl > Br2 as ICI is polar and Br2 is non-polar in nature.

(B) pyramidal about each N-atom.

(C)

(D) identical due to resonance.

C-8*. (A) SbH3 > NH3 > AsH3 > PH3 ( order of B.Pt)
(B) As D2O has higher molecular mass than H2O so its density is more.
(C) Mn  4s23d5
Ca  [Ar] 4s2
Sr  [Kr]5s2
Rb  [Kr]5s1
Refer notes
(D) H2 weak VDW forces
CO2  weak VDW force but stronger than H2.
H2O  H-bonding.
C-9*. (A) Ethyne being non-polar is more soluble in acetone.
(B) CD3F is more polar than CH3F. In CD3F, C–D bond is more polar as deuterium is more electropositive than
hydrogen.
(C) Silyl isocyanate (SiH3NCO) is linear in shape because of p-d delocalisation of lone pair of electrons on
nitrogen. While in methyl isocyanate (CH3NCO) there is no p-d delocalisation of electron as carbon does
not have empty d-orbital and thus is bent in shape.
In CH2=C=C=C=CH2, the 2H–atoms on one C–atom lie in a plane perpendicular to the plane in which 2H–
atoms on other C–atom lie.

C-12. (I)

As a result of H-bonding, number of sulphuric acid molecules are associated to form cluster. Hence it has
high boiling point and viscosity.
(II) All S — O bond lengths are equal due to resonance.

(III) (IV)

RESONANCE Chemical Bonding # 38

C-13. (A) A fact
(B) In the solid state and in liquid HF , the HF2 – ion is held together by hydrogen bonding. In aqueous
solutions there is hydrogen bonding but each HF molecule forms hydrogen bonds with the much more
prevalent H2O present, instead of with other HF molecules and H3O+ and F – are much more likely to be
formed.
(C) H3BO3 (solid) has inter molecular hydrogen bonding.

H B H H

H B H H B

H H H H

H B H H B H

B
H H
H
H

C-14. (A) Like hydrated copper sulphate (CuSO4 .5H2O) in which one water molecule is hydrogen bonded to
coordinated water molecule, one water molecule is coordinated to lone pair of electrons on SnCl2 and the
other is hydrogen bonded to coordinated water molecule.
C-15 (A) intermolecular hydrogen bonded. (true)

(B) structure of anions are different CO32– – trigonal planar (sp2)

SO32– – trigonal pyramidal (sp3) (false)

(C) no lone pair of electrons (false)

(D) True. D2O = 374.4 K ; H2O = 373.0 K

C-16. S2O32– ion :

Individual O.N. of S atoms = +6 and –2. Average O.N. = +2
SbH3 has higher bp than NH3, due to vander waal forces.
In hydracids, the acidity increases down the group while for oxyacids, the acidity decreases down the
group.

RESONANCE Chemical Bonding # 39

C-17*.

The P = O contain one p-d bond. The PO43– ion show resonance.
Due to the presence of H-bonded to O, it show intermolecular H-bonding due to which it is syrupy.
C-24. (i) H2O has highest boiling point because of H-bonding.
(ii) Boiling point also depends on the magnitude of van der Waal's force of attraction, which in turns depends
on molecular weight of the compounds. Thus the correct order is H2O > H2Te > H2Se > H2S.

C-28 D is less electronegative than H-atom so the results

PART - II

4. = a 2  a 2  2a.a cos 120

= 2a 2  a 2 = a

5. IF7 has symmetrical Pentagonal bipyramidal shape.

6.

7. o-nitrophenol has intramolecular H-bonding so it will be vaporised first.

8. D2O has different physical properties than H2O max. density of D2O is at approximately 10°C

10. (A) sp3d ;  F – I – F = 1800 ;  = 0

(B) sp3d; polar;  F – Cl – F  180º

(C) sp3d, non–polar,  F – Xe – F = 1800

(D) sp3d , polar; F – S – F  1800 ; one lone pair..

RESONANCE Chemical Bonding # 40

11. HF shows stronger H-bond than H-Cl.
Dipole moment of HF is more than of HCl. (fact) Due to H-bond, boiling point of H–F is more than that of HCl.
Due to differences in electro negavitivity, the H–F bond is stronger than H–Cl bond.
(B) N is more electronegative than P. So the strength of H-bond is more in NH3. Due to this boiling point of
NH3 is more. For the same reason, boiling point and bond energy are also more for NH3 than PH3.
12. (A) CuSO4. 5H2O SO42– is resonance stablized
2+ 2–
(B) Ca / SO4 are held together by electrostatic force of attraction i.e., ionic bond but alternate layers
by H – bonds with water molecules
1
CaSO4 . H2O
2

(C) H3PO4  (D)

13. (A) Br2 is non-polar in nature. All molecules experience London dispersion forces which results from the
motion of electrons.
(B) HF has hydrogen bonding in liquid as well as in solid state. HF molecules also experience dispersion
forces.
(C) Ion-dipole forces are found in the solutions of ionic compounds in polar solvent where solvated species
such as Na(OH2)x+ and F(H2O)y– exist. Hydrogen bond exist between water molecules. In addition they also
experience dispersion London forces.
(D) CH3NH2 is a polar molecule that can form hydrogen bonds. In addition, it has dispersion forces.
(E) Induced dipole-dipole interaction exists between non-polar molecules and polar molecules such as
clathrate compound of Xe gas with water, when water is frozen under a high pressure of the gas. They have
formulae approximating to 6H2O : 1 gas atom (i.e. Xe.6H2O).
In addition, Xe.6H2O has H-bonding and dispersion forces.

EXERCISE # 2
6.32  10 18
6. % ionic character =  100 = 84.5 %
4.8  10 10  156  10 10
7._ Nitrogen is more electronegative than phosphorus.

So, dipole moment of trimethylamine is greater than trimethy phosphine.

12. Very strong hydrogen bonding occurs in the alkali metal hydrogen fluorides of formula M[HF2]; there is a liner
symmetrical anion having an over all, F–H–F distance of 2.26 Å.
[F – H – – – F]–  [F – – – H – F]–
F– + HF  [FHF]– ; H = – 161 ± 8 kJ mol–1

EXERCISE # 3
1. Intermolecular forces between H2S, H2Se and H2Te molecules are purely Van der Waal’s force of attraction
while in water there is stronger H-bonding between the water molecules. H-bond is stronger than Van der
Waal's force of attraction and thus more energy is required for converting H2O() to (H2O)(g).

RESONANCE Chemical Bonding # 41

2. (i) In carboxylic acid H-bonding is stronger than that in alcohol.
(ii) In aldehyde there is dipole-dipole attraction.
(iii) H-bonding is stronger than dipole-dipole attraction.
(iv) Boiling point  strength of intermolecular force of attraction.

3.

4. The reason for the lesser volatility of alcohol than ethers is the intermolecular association of a large number
of molecules due to hydrogen bonding as – OH group is highly polarised.
R R R R
----O – H ---- O – H ---- O – H ---- O –

hydrogen bonding
No such hydrogen bonding is present in ethers.

5. (A) (B)

(C) (D)

6.
For planar BO3 groups, the B–O bond length is usually close to 1.36 Å
but for tetrahedral BO4 groups the length increases to about 1.48 Å.
This suggests that in the planar grouping -boding involving lone pairs
of electrons from the oxygen atoms occurs; this -boding is necessarily
lost in the tetrahedral group, in which a lone pair from the extra oxygen
atom occupies the previously empty orbital on the boron atom.

7. Because of highest electronegativity of F, hydrogen bonding in F – H - - - - F is strongest.

SOLUTION OF ADVANCED LEVEL PROBLEM

 obs
1. % Ionic character =   100
Th

1.44  10 18 esu cm

=  100 = 20%
4.8  10 10  1.2  10 8 esu cm
 % covalent character = 100 – 20 = 80%

6  10 18
3. Percentage of IC = × 100 = 50%
4.8  10 10  2.5  10 8

RESONANCE Chemical Bonding # 42

4. Dipole moment of compound would have been completely ionic
= (4.8 × 10–10 esu) (2.25 × 10–8 cm) = 4.8 x 2.25 D
9
so % ionic character = × 100% = 83.33 %
4.8  2.25

5.

R = 2 2 ; R =
2 S – H  2 S –H  cos 97º 2 × S–H × 1 – 0.12

1.5
R = 2 × S–H × 0.88 ; S–H = D
2  0.94

0.15  10 9  1.6  10 19

(S–H)Cal = 10
 10 30
3
(S–H)Cal = 3 × 0.15 × 1.6 × 10 D
1 .5  1 
So % Ionic character = 
0 . 15 16 3  × 100 = 16 %
2  0.94    

7. (P) No of p-d bonds = 6.

(Q) NOHSO4 exists as NO+ and HSO4– ; NO+ is derivative of oxygen and isoelectronic with O22+ . Bond order
is 1/2 (10 – 4) = 3.

(R)

No of vacant sp3 hybrid orbitals participating in the formation of banana bonds are 2.

(S)

9. Theoretical value of dipole moment of a 100% ionic character = e × d

= (1.60 × 10–19 C) (1.41 × 10–10 m)
= 2.26 × 10–29 Cm

RESONANCE Chemical Bonding # 43

 Observed value of dipole moment = 2.60 × 10–30 Cm
observed value 2.60  10 30
Percent ionic character = × 100 = × 100 = 11.5% Ans.
theoretica l value 2.26  10 29

10. For a diatomic molecule dipole moment µ = e × d

 1.2  10 18 esu cm
 Electronic charge = =
d 1.0  10 8 cm
Actual value of electronic charge = 4.8 × 10–10 esu
1.2  10 10
 Fraction of the electronic charge = = 0.25
4.8  10 10

11. (i) Bond order of N2 = 1/2 (10 – 4) = 3

Bond order of O2 = 1/2 (10 – 6) = 2
Bond order of F2 = 1/2 (10 – 8) = 1
Bond order of O2+ = 1/2 (10 – 5) = 2.5
Bond order is directly proportional to the bond strength and so, the increasing order of their bond dissociation
energies is :
F 2 < O 2 < O 2 + < N2 .
(ii) The strength of H – bond mainly depends on the electronegativity of the atom attached to the H atom and
it increases with increasing electronegativity of the atom attached to polar H atom. So the increasing order
of strength of hydrogen bonding (X – H – – – X) is : S < CI < N < O < F

(iii) , , ,

So, the increasing order of bond angles is XeF4 < NH3 < BF3 > N3–

13. (i) H3 C

I = 3 C–CI × cos 70.5 + CH = 1.5 + 0.4 = 1.9 D

3
II = 3 C–CI × cos 70.5 – C–H = 1.5 – 0.4 = 1.1 D
III = 3 C–H × cos 70.5 + C–CI = 1.9 D

(ii) 2CH cos 60

3

net = 2.5 + CH = 2.5 + 0.4 = 2.9 D.

3

RESONANCE Chemical Bonding # 44

 LIQUID & GASEOUS STATE
EXERCISE # 1
PART - I
A-2. The pressure on the bubble = 1 atm (when it is at the surface)
1
The volume of the bubble =  (0.4)3 ml.
6
The pressure on the bubble = P atm (say) (when it is at the bottom)
1
The volume of the bubble =  (0.1)3
6
1 1
P×  × (0.1)3 =1×  (0.4)3
6 6
or P = 64 atm. Thus the pressure due to water is 63 atm ( atmospheric pressure = 1 atm)
Now, consider the depth of pond is h cm
 63 × 76 × 13.6 × g = h × 1 × g
 or h = 63 × 76 × 13.6 cm = 65116.8 cm = 0.65116 km.
 The depth of the lake is 0.65116 km.

A-3. Since the vessel is open, the gas can escape out on heating. In this case we can imagine a imaginary
boundary to trace the final volume of the gas.
(a) Now in the given situation, 3/5th of the gas (by amount) has escaped which means only 2/5th of the
amount is occupying the complete volume of the open container.
n 2 T1 2n / 5 300
And the Pressure is constant,  
n1 T2  n T2  T2 = 750 K.

n 2 300
(b) Similarly, n  900  1/3rd of the gas remained in the container. Hence, 2/3rd of the gas escaped.
1

(c) Half of the gas will escape out by doubling the temperature. Hence, the final temperature = 600 K.

A-6. P0 = 76 cm P0 = 76 cm

45 cm 10cm 45 cm
Initially : (A) 76 × 45 × A = 76 × 45 × A (B)
A = Area of cross section.
When tube is made vertical, let Hg column gets displaced by x cm towards A.
For A side : P1 × (45 – x) × A = 76 × 45 × A
For B side : P2 × (45 + x) × A = 76 × 45 × A
also P1 = P2 + 10
76  45 76  45  1 1 
( 45  x )
= ( 45  x ) + 10  76 × 45  ( 45  x )  ( 45  x )  = 10
 

 45  x  4s  x 
76 × 45  ( 45  x ) ( 45  x )  = 10
 

A-9.
Let the total number of molecules of the gas be n , of which n1 are in the
larger sphere and n2 in the smaller sphere after the stopcock is opened
V V/2
n = n1 + n2 and pV = nRT
pV pV pV
RT1 = RT1 + 2T2R

2pT2
p = 2T  T
2 1

RESONANCE Liquid & Gaseous State - 45

 n1T1 n2T2 10  300 n2  400
A-11. P1 = P2  =
24.6 1
 n2 = 0.3
 Mass of oxygen left = 0.3 × 32 = 9 g
 Mass of oxygen escaped = 320 – 9.6 = 310.4 g.

B-2. PV = nRT
 400  10 3 60  10 3 
 
P × 1.5 =  32

2  × 0.082 × 373
 
 P = 0.867 atm
2H2 + O2  2H2O
initial 0.03 0.0125 0
final 0.03 – 2(0.0125) 0
= 0.005 0 2(0.0125) = 0.025
 mH2 left = 0.005 × 2 = 0.01 g

& mH2O produced = 0.025 × 18 = 0.45 g

nH2  R  T 0.005  0.0821  373

PH2  = = 1.102 atm.
V 1 .5

nH2O  R  T 0.025  0.0821  373

PH2O  = = 0.509 atm.
V 1 .5

C-1. At constant volume and temperature P  W (here, volume of balloon is assumed to be constant)
Thus, for N2 : P1 = 2 atm P2 = 1/2 atm at t = 1 hr
P1 w 1 P2 ½ 14
 or w2 = P × w1 or w2 = × 14 =
P2 w 2 1 2 4
14 21
 wt of N2 diffused = 14 – = kg
4 4
For H2 : P1 = 2 atm P2 = ½ atm at t = t hr
w1 = 1 kg w2 = ?
P2
w2 = P × w1 = ¼ kg
1
Hence wt of H2 diffused = 1 – ¼ = ¾ kg
Now, we are to conclude one point as
rA B

rB  A , as per Graham law

VA
tA B VA t B B VA t B  A
= or   or   B
VB A VB t A A VB t A  A B
tB

VA B t B A w A tB A
or  or  
VB B t A B wB tA B
For our problem we can write,

w H2  t N2 MH2 ¾ 1 2 1 6 1 1
 or   or  
w N2  t H2 MN2 21/  t
2 28 14 21 4 t 14

1 1 14 1 60 60
or  or t=  hr = mins = mins = 16 mins
14 t 14 14 14 14 3.741
 for H2, 16 mins are required Ans.

RESONANCE Liquid & Gaseous State - 46

C-3. Change in pressure = 2000-1500 = 500 torr; time-taken = 40 min
500 500
rate1 = torr/min; similarly rate2 = torr/min
40 80

rate1 M

rate 2 32

nN2 mx
C-4. = M .........(i)
nx N2

PT VT = n T RT ........(ii)
2. 8  4
Here nT = = 0.5 and nx + nN2 = 0.5  nx = 0.1
0.0821  273
From (1)
0 .4 Mx
=  Mx = 448 .
0 .1 28

 n1u12 u12 x n1  u 22 x n 2  u 23 x n 3
D-1. urms = =
n n1  n 2  n3

2 x 10 23 x (10 4 )2  2 x 10 23 x (2 x 10 4 )2  2 x 10 23 x (3 x 10 4 )2
 urms = = 2.16 x 104 cm/sec
6 x 10 23

(UMPS )2 T2 2 T2
D-3. UMPS  T  (UMPS )1 = T1  =
1 400
T2 = 1600 K = 1327ºC.

3RT 3R  308 3RT

D-4. Urms = T1
 =  T = 22 K.
28 2

18
E-1. Volume of one mole of given vapour = L =50 L
0.36
RT 0.082  500
volume of one mole of an ideal gas = = = 41 L
P 1
Vm , real 50
so value of. Z = V , ideal =
m 41

E-3. TC = 273 + 31 = 304 K, PC = 728 atm

8a a
TC = 27 Rb and PC =
27 b 2

TC 8a 27 b 2 8b
   
PC 27 Rb a R

304 8b
On substitution 
728 0.082
304  0.082
 b= = 4.28 × 10–3 litre/mole
728  8
8a
Now, TC = 27 Rb

RESONANCE Liquid & Gaseous State - 47

 27 RbTC 27  0.0082  4.28  10 3  304
 a=  = 0.36 atm litre2 mole–2 Ans.
8 8

 2 
 P  n  4 .2 
E-5.  2  (V – nb) = n RT
 (10) 

 2 
 P  (10)  4.2 
(10 – 10 × 0.037) = 10 × 0.082 × 300

 (10 )2 

F-1. CO2 + C  2CO

At t = 0 x L (1 – x) L
At = t 0 2x L
1 – x + 2x = 1.6
1 + x = 1.6
x = 0.6 L
1 – x = 0.4 L
F-3. In the mix., volume of O3 = 20 ml
Volume of O2 = 80 ml
on heating 2O3  3O2
3
20 ml O3 will give × 20 = 30 ml O2
2
total volume = 80 + 30 = 110 ml
increase in volume = 110 – 100 = 10 ml.

F-6. Balanced chemical equation: CxHy + (x + y/4)O2  x CO2 + y/2 H2O

22.4 Lt of CxHy gives = 44 a gram CO2
1.12 Lt of CxHy gives = 44 a × 1.12 / 22.4 gram CO2
44 a × 1.12 / 22.4 = 2.2
a=1
22.4 Lt of CxHy gives = 18 × b/2 gram H2O
1.8 Lt of CxHy gives = 18 × b/2 × 1.12 / 22.4 gram H2O
18 b/2 × 1.12 / 22.4 = 1.8
b=4
 Hydrocarbon is CH4
wt of 1.12 Lt CH4 at NTP = 16 × 1.12 / 22.4 = 0.8 gram
mole of O2 used in the 22.4 Lt. hydrocarbon combustion = a + b/4 = 2 mole
mole of O2 used in the 1.12 Lt. hydrocarbon combustion = 2 × 1.12 / 22.4 = 0.1
volume of O2 used in the 1.12 Lt. hydrocarbon combustion = 0.1 × 22.4 = 2.24 Lt.

PART - II
A-3. Initial N2 + 3H2  2NH3
1 3
final – – 2
4 2
ratio =  .
2 1
A-6. Two flask initally at 27º and 0.5 atm, have same volume and 0.7 mole thus each flask has 0.35 mole
Let n mole of gas are diffuse from II to I on heating the flask at 127ºC
Mole in I flask = 0.35 + n, Mole in II flask = 0.35 – n
If new pressure of flask is P then
for I flask P × V = (0.35 + n) × R × 300 ; for II flask P × V = (0.35 – n) × R × 400
n = 0.5
mole in I flask = 0.40 mole in II flask = 0.30
0.5 × 2V = 0.7 × 0.0821 × 300 (initially) V = 17.24 Lt.
P × 17.24 = 0.30 × 0.0821 × 400 (finally) P = 0.57 atm.

RESONANCE Liquid & Gaseous State - 48

A-7. Let vol. of each flask is 'V' L, Initially
0.5 × 2V = 0.7 × 0.0821 × 300
V = 17.24 L
Let T is final temperature of flask when pressure in each flask becomes equal, it happens. when
nTotal = n1 + n2
P  ( 2V ) PV PV 2 1 1 34 7
= +  = + = =
RT R  400 R  300 T 400 300 1200 1200
2400
T= = 342.85 K
7
P × 2 × 17.24 = n1 × 0.0821 × 400  n1 = 0.3
0.5714 × 17.24 = n2 × 0.0821 × 300  n2 = 0.4

3RT 1.5 RT
A-12. PA = M ; PB = MB
A

PA 2 MB 2  2 MA
PB = MA = MA = 4.

B-2. (D) Weight of H2 = 20 g in 100 g mixture ; Weight of O2 = 80 g

20 80 5
 Moles of H2 = = 10 ;  Moles of O2 = =
2 32 2
5 25
 Total moles = 10 + =
2 2
10
 PH' 2 = PT x mole fraction of H2 = 1 x = 0.8 bar
25 / 2

B-3. Since A and A2 are two states in gaseous phase having their wt ratio 50% i.e. 1 : 1
96 1 96 1 1
moles of A =  =1 Moles of A2 =  
2 48 2 96 2
Total mole = 3/2
P = nRT/V.

1
C-3. r  So, NH3 diffuses with faster rate.
M

rA 16 wA 2
C-5.*– Given rB = ; wB = 3
3

rA nA MB
we have r = n MA
B B

16 w A MB MB
= M w MA
3 A B

3/2 3/2
16 2  MB   MB  MB
=     =8
3 3  MA 

 MA 
 MA = 4

8
 mole ratio =
3

D-3. mA = 2 mB
uA = 2 uB
nA = nB
vA = vB
1 2
PA VA mA nA uA
3
PB VB = 1 2
mBnBuB
3

RESONANCE Liquid & Gaseous State - 49

 3 N
  R  150
2 32 x N 1 1
D-4. K.EO = 3 N' =  K.EO = =
2   R  300 2 x 2 N' 2 2
2 32

N  N' Therefore, (A) option is correct.

( Vrms )1 T1 M2
D-8. ( Vrms )2 = M1 T2

D-9.*_ K.E. is a function of temperature. If temperature is constant, K.E. will be constant.

 a 
E-4. P   (V) = RT
V2 
 


a
PV + = RT
V
PV a
=1–
RT VRT

4 3
E-5. 4× r × NA = 24
3

a 64 a2
E-10.*_ PC = 2 T C2 =
27b 27  27 R2b2

TC2 64 a2 27 b2
VC = 3b = 2 2 
PC 27  27 R b a

8a 27 R2TC2
TC = 27 Rb a= 64 PC

y
F-3. CxHy + O2  x CO2 + + H2 O
2
357  21
15 ml ml
100
75 ml
 y y 75
 x    15 = 75 x+ =
 4  4 15
y y
x+ =5 x+ =5
4 4
y
3+ =5 15 x + 15x + 282 = 327
4
y=8 x=3
Formula = C3H8

 y y
F-4. CxHy +  x   O2  XCO2 + HO
 4 2 2
7.5 ml 36 ml
 y
36 – 7.5  x   + 7.5 x = 28.5
 4 

RESONANCE Liquid & Gaseous State - 50

  y
36 – 7.5  15   + 7.5 x = 28.5
 4 
y=4
x=2
So formula = C2H4

13
F-6. C4H10 + O2  4 CO2 + 5 H2O
2
x ml n-butane
y ml isobutane
13 13
Volume of O2 = x  +y
2 2

EXERCISE # 2
PATR - I
 P1V1   P2V2 
   
1.  T 
 1 Inside cylinder
=  T 
 2 Outside cylinder

20  2.82 1 V2
=
300 273
V2 = 51.324 L
Volume of gas at STP in cylinder = 51.324 L
Volume of gas left inside cylinder = 2.82 L
Volume of gas available to be filled in balloon = 48.504 L
Let n balloons are filled
3
4  21  n
 ×   × = 48.504  n = 10
3  2 1000

3. PV = nTotal RT
105 × 0.02 = nTotal × 8.314 × 300
nTotal = 0.8
m Ar mNe
+ = 0.8
40 20
mAr + mNe = 28
mAr = 24 ; mNe = 4

8 RT
5. uAV =
M
8RT 16  10 4    1 10 3
For He : 4 x 102 = 3 so RT = = 80 
 x 4 x 10 8

8 RT 16 x 10 4 x  x 20 x 10 3
for Ne : 4 × 102 = so RT = = 400
  20  10 3 8

3 3 6
 KE = nRT  Total KE of He = x x 80 = 565.71 J/mol
2 2 4
3 12
 Total KE of Ne = x x 400 = 1131.42 J/mol
2 20
Total K.E. of mixture = 565.71 + 1131.42 J = 1697.13 J/mol
6 12
Total mole in mixture = + = 1.5 + 0.6 = 2.1.
4 20
1697 .13
KE / mole of mixture = = 808.16 J/mol
2.1

RESONANCE Liquid & Gaseous State - 51

6. For the gaseous mixture
PV = nRT 1×40 = n × 0.0821×400 n = 1.219
Total mole of mix. = 1.219
Suppose moles of C2H6 and C2H4 are a and b respectively
a + b = 1.219 ...................... (1)
7
C2H6 + O  2CO2 +3H2 C2H4 +3O2  2CO2 +2H2O
2 2
a 7a/2 b 3b
moles of O2 required for the combustion of mix. = 7a/2 + 3b
7a 130
+3b =  (2)
2 32
by solving eq. (1) and (2) we get
a = 0.808 b = 0.4115
0.808 0.4115
mole fraction of C2H6 = = 0.66 ; mole fraction of C2H4 = = 0.34
1.219 1.219

7. Before effusion
Moles of CO = 0.5
Moles of CO2 = 0.5
Total moles diffused out = A
Let moles of CO effused out = a
Let moles of CO2 effused out = b
 a+b=A
28a  44b 28a  44b
 M1 = 
ab A
Mean molar mass of residual gases in the vessel
28(0.5  a)  44(0.5  b) 14  28a  22  44b 36 (28a  44b)
M2 = or M2 = = 
0.5  a  0.5  b 1  (a  b ) 1 A 1 A

36 (28a  44b ) 36 MA
or M2 =  or M2 =  1
1 A 1 A 1 A 1 A
or M2 (1 – A) = 36 – M1 A or M1 A + M2 (1 – A) = 36 Ans.
9. Let moles of Ar = x
Moles of O2 = y
Moles of SO2 = 1 – (x + y)
1 22.4
Total moles of mixture =
0.08  273
1 – (x + y) = y + x  1 = 2 x + 2y
y=2x 1 = 2x + 4x
1 1
x= ; y=
6 3
1 1 1
 40   32   64
6 3 2
Mmix = 1 1 1 = 49.33
 
6 3 2

 Mmix 1 49.33
f= = = 2.2 g/L
RT 0.0821  273

10. (a) By Dalton's partial pressure

PN2  PH2O = 760 mm
From given data PN2 = 745 mm
So PH2O = 760 – 745 = 15 mm
745
% Mole of N2 = % of pressure of N2 = × 100 = 98.02
760

RESONANCE Liquid & Gaseous State - 52

  Mole % of H2O = 100 – 98.02 = 1.98% Ans.
(b) Increase weight of drying agent due to absorption of water (H2O).
Hence, Wt. of H2O = 0.15 g
0.15
 Mole of H2O =
18
15
Pressure of H2O( (PN2 ) = 15 mm = atm
760
From gas equation PV = nRT
15 0.15
×V= × 0.0821 × (273 + 20)
760 18
V = 10.156 litres Ans.
12. Based on Dalton law of partial pressure, partial pressure of H2 is determined hence, its number of moles.
Partial pressure of H2 and water vapour are known, hence, mole fraction can be determined. Since number of
moles of dry H2 is known, mass of dry H2 can be determined.
19
PH2O V  0.300
760
(a) nH2O (vapour) = = = 0.31 m mole
RT 0.0821 294

n H2 PH2 729
(b) XH2    = 0.975
n Total PTotal 748

(c) PTotal = PH2  PH2O  748 = PH2 + 19

729
 PH2 = 748 – 19 = 729 Torr = atm
760
729
PH2 V  0.300
n H2   760 = 0.0119 mol H2
RT 0.0821  294
mass of gas (H2) = nH × Mgas = 0.0119 × 2 = 0.24 g
2

14. (a) Under low pressure region, V is high

 a  a
(V – b)  V   P  2  V = RT  PV + = RT
 V  V
PV a PV  a 
 + =1  Z= =  1  RTV 
RT RTV RT  
20.39
Z=1– = 0.98
0.0821  350  35
(b) Under high pressure region, P is high,
 a 
P  2   P  P (V – b) = RT
 V 

PV Pb
 PV – Pb = RT   =1
RT RT
PV Pb
 Z= =1+
RT RT
b  PV
 1,
P 1 
Z=1 + by approximation   
V  RT RT V 

0.1383
=1+ = 1 + 0.004 = 1.004
35

15. CaCO3 (s) 


CaO (s) + CO2(g)
25
Moles of CaCO3 used =
100
25
Moles of CaO formed = = moles of CO2 formed
100

RESONANCE Liquid & Gaseous State - 53

 25
Mass of CaO formed = × 56 g = 14 g
100
14
Volume occupied by CaO = cc ~_ 4.2 mL
3 .3
 Volume available for CO2(g) = 504.2 – 4.2 mL = 0.5 L
Now applying the van der waals equation of state
2
 p  an
 

 v 2  (v – nb) = nRT
 
 4  (0.25)2 
p   [0.5 – 0.25 × 0.04] = 0.25 × 0.082 × 1500
 (0.5)2 

4  (0.25)2
 p = 62.83 – = 61.83 atm.
(0.5)2

PART - II
3. N2  2N
1 .4 1
at t = 0 = 0
28 20
1
at t = tf –x 2x
20
1 3
but, x = 30% of =
20 200
1 1 1 3 13
Final number of mole = – x + 2x = +x= + =
20 20 20 200 200
13 0.0821  1800
 P= × = 1.92 atm.
200 5

rmixture 32 20  60
4. rO2 = =
M 311
M = 2.16
V.D. = 4.32

7.

rHCl 17 x 17
rNH3 = 36.5
 200  x
=
36.5
 x = 81.13 cm

8. Let both gases meet at nth row

rNO2 x 179
rC6H10Br = 12  x = 44 = 2
x = 24 – 2x
3x = 24
x=8=n–1
n = 9th Row
10. PV = nRT
1
PV = RT
M

RESONANCE Liquid & Gaseous State - 54

12. Max capacity of balloon = 600 ml
P1V1 = P2V2
500  1 = 600  P2
5
P2 =  760 mm = 633 mm
6
Height above which balloon will burst.
= (760 – 633)  100 cm
= 127  100 cm = 127 m
14. 76  13.6 = x  13.6 + 1  13.6 + 3.4  20 + 6.8  30 + 13.6  15
76  13.6 = x  13.6 + 13.6 + 13.6  5 + 13.6  15 + 13.6  15
76 = x + 1 + 5 + 30
x = 40 cm
17. H2 +1/2O2 H2O(l)
a b 0
a–2b 0 b
Reaction is studied at constant P &T.
a+b = 40 a–2b = 10
a = 30 ml b = 10ml
mole fraction of H2 = volume fraction of H2 =30/40 = 0.75.
20. – Slope of isotherm below critical point < 0.
Slope of isotherm above critical point < 0.
Slope of isotherm at critical point = 0.
So slope of isotherm at critical point is maximum.
8a
 – TC = 27 Rb
TC  a
Larger value of TC It means less decreases in temperature is required to liquifly the gas. Gas will
liquify at higher temperature. So, easier'll be liquification.
 – When gas is below critical temperature. It is 'liquid' so vander waal equation of state is not valid.
So, Answer (B).

4
25. VC = 3 × N × r3 × 0.44
3

27.

(a) at T = 500 K, P = 40 atm corresponds to 'a' substance - gas

(b) at T = 300 K, P = 50 atm corresponds to 'b' substance - liquid
(c) at T < 300 K, P > 20 atm corresponds to 'c' substance - liquid
(d) at T < 500 K, P > 50 atm corresponds to 'd' substance - liquid
So, Answer (D)
28. Suppose the cylinder will burst at T2K
P2T1 14.9  300
T2 
P1 (V1 = V2) = 12
= 372.5 K

RESONANCE Liquid & Gaseous State - 55

 T2 T T2 MB
29. Clearly from the diagram (vMPS)B > (vMPS)A   1  
MB M A T1 M A
hence if T1 > T2. MA is necessarily greater than MB
31. With increase in temperature, most probable velocity increases & fraction of molecules with velocity equal to
M.P. velocity decreases. Total no. of molecules remain same.

EXERCISE # 3
1. (A) PV = K (Boyle's law)
P1V1 = P2V2 = P3V3
(B) From charle's law
V
VT  =K
T
V1 V2
 T1 = T2
(C) From Graham's law
1 PM
r and d=  d  M.
M RT

1
So, r .
d
(D) From Dalton's law of partial pressure at constant temperature.
P = P1 + P2 + .......
(E) Vander Waal's equation (real gas equation)
 a 
 P   (V – b) = RT (For 1 mole)
 V2 
R
(F) = K (Boltzmann constant)
N
(G) Molar volume = 22.4 L at STP
(I) Constant temperature P – V curve is called isotherm.
(J) Graph between V and T at constant pressure called isobar.
2. (A) PV = nRT
At constant temperature
PV = K (T = constant)
Higher the value of PV, higher the temperature.
So, T3 > T2 > T1
Since, P1 = P2 = P3
So, VT  V3 > V2 > V1
PM
d=
RT
Since, P1 = P2 = P3
1
d  d1 > d2 > d3
T
(B) From Graph,
V3 > V2 > V1 and T1 = T2 = T3
Higher the volume, lesser the pressure because temperature is same for all.
P1 > P2 > P3
PM
d=
RT
Since, T1 = T2 = T3
So, dP  d1 > d2 > d3
(C) From the graph,
P3 > P2 > P1 and T1 = T2 = T3
Higher the pressure, lesser the volume because temperature is same for all.
V1 > V2 > V3

RESONANCE Liquid & Gaseous State - 56

 PM
d=
RT
Since, T1 = T2 = T3
So, dP  d3 > d2 > d1
(D) From the graph,
d3 > d2 > d1 and P1 = P2 = P3
PM 1
d=  d
RT T
So, T 1> T2 > T 3
PV = nRT
Since, P1 = P2 = P3
VT
So, V1 > V2 > V3
3. (A) At low pressure, b is negligible in comparison to Vm.
 
P  a 
 2  (Vm) = RT
 Vm 

PVm a
 = Z = 1 – V RT < 1
RT m
So, gas is more compressible than ideal gas.
a
(B) At high pressure, 2 is negligible in comparison to P..
Vm
 P (Vm – b) = RT
PVm Rb
 =Z=1+ < 1.
RT RT
So, gas is less compressible than ideal gas.
a
(C) Low density of gas means pressure is low so, at low pressure Z = 1 – V RT < 1 and gas is
m
more compressible than ideal gas.
(D) At 0ºC H2 and He have a  0.
Pb
So, Z=1+ and gas is less compressible than ideal gas.
RT
Patm
5. P1 = 75 cm of Hg, V1 = 24 × A
0.4  10
P2 = 75 + 10 + = 100 cm of Hg
13.6
 75 × 24 = 100 × x
x = 18 cm
P2

6. Case  Case 
P1 = (P0 + h) P2 = (P0 – h)
P1V1 = P2V2
Now in both the cases, the gas is the same and temperature is also constant, hence boyles law can be
applied.
1 A (P0 + h) = 2 A (P0 – h)
h(1   2 )
P0 = (    ) cm of Hg column.
2 1

PVm
8. Z= >1
RT
PVm 1 22.4
=
RT RT

RESONANCE Liquid & Gaseous State - 57

 At same pressure = 1 atm.
1 Vm 1 22.4
>  Vm > 22.4 L at STP for real gas.
RT RT
For, Vm = 22.4 L of real gas, we have to increase the pressure.
11. PC, VC and TC are given hence ‘a’ and ‘b’ should be calculated using PC and TC as it is more reliable.
a 8a
PC = 2 , TC =
27b 27Rb

PC R 300 x 1/ 12 1
TC = 8b  b= 8 x 50 =
16
1/ 3
4 1  3 
4 x r3 . NA =  r=  
3 16  256 Na 

12.

At 100 K and pressure below 20 atm it may have liquid or gaseous state depending on the pressure.

1
13. P  PV = K
V

1
Pressure is directly proportional to .
V

14. From Charle's law, volume is theoretically zero at 0 K and kinetic energy is directly proportional to absolute
temperature. So, it is zero at 0 K.

1
16. Rate of diffusion 
Molar mass
3 3 w
Total K.E. = nRT = RT
T
2 2 M

22. On collision, K.E. redistributes, one molecule acquires and other looses the K.E. so, average K.E. remains
the same at the same temperature.

1
24. Rate of diffusion 
Molar mass

27. Increase in volume per degree rise in Celsius temperature at constant pressure is V0/273.15, where V0 is the
volume of gas at 0ºC .

PA
28. Rate of diffusion 
TM

32. At NTP, PT = 1 atm, T = 0ºC

PMmix 1.3  0.082  273
dmix =   Mmix = 29.1.
RT 1

RESONANCE Liquid & Gaseous State - 58

 x  28  (100 – x )  32 3200 – 2910
Mmix = 29.1 =  x= = 72.5%
100 4

 PN2 = 0.725 atm.

20  wH2
33. =2  wH2 = 2 g.
11

20  2
Mavg = 20 2 = 11.

20 2

 2
 P  an 
35. (V – b) = nRT

 V 2 

PV 2 Pam6
Unit of a will be unit of = .
n2 mol2

37. At constant temperature,

P1V1 = P2V2
875 V 875  3
× V = P2 ×  P2 = atm = 3.454 atm.
760 3 760

39. Case  Case 

P1 = (P0 + h) P2 = (P0 – h)
P1V1 = P2V2
Now in both the cases, the gas is the same and temperature is also constant, hence boyles law can be
applied.
1 A (P0 + h) = 2 A (P0 – h)
h(1   2 )
P0 = (    ) cm of Hg column.
2 1

40. (i) From KTG assumption, no effect of gravity on motion of molecules.

PM dRT 1.8  0.082  300
(ii) d =  M= = = 44.3.
RT P 1

U27 ºC 300 1 0.25 1

(iii) U = =  U927 ºC = 2  U927ºC = 0.5 ms–1.
927 ºC 1200 2

2 8 22  0.082  273
(iv) Ptotal = PH2  PO2  PCO2 =  2  32  44  = 1.75 atm.
  22.4

PMmix dRT 1.146  0.082  300  760

44. d=  Mmix = =
RT P 740
x  28  (100 – x )  32
 Mmix = 28.95 =  x = 76.25%
100

PV 750  200
45. n=  n= = 0.0082 moles.
RT 760  1000  0.082  293
weight of gas = x × 30 + 58 (0.0082 – x) = 0.3846.
0.091
x= = 0.00325.
28
(0.0082 – 0.00325 )
mole % of butane = × 100 = 60.36%.
0.0082

RESONANCE Liquid & Gaseous State - 59

 EXERCISE # 4
PART - I
P V
1. Compressibility of an ideal gas (Z) =
nRT
P  22.4
For a mole of ideal gas at STP, (Z) =
RT
P  Vm
For other gases Z < 1. It is equal to
RT
Hence Vm < 22.4 litre.

3RTH2 3RTN2 3RT

2. Given that : = 7 (because Urms = )
2 28 M

3RTH2 3  RTN2
So =7×  TN2 = 2TH2 or TN2 > TH2 .
2 28

3. Mass of steam = 1000 × 0.0006 = 0.6 gm

Mass of water () = 0.6 gm
Volume of liquid water = 0.6 cm3

3 RT
4. Urms = using ideal gas equation,
M

w RT RV P
PV = nRT = RT;;   where d is the density of the gas
M M w d

3P 1
 Urms = at constant pressure, Urms 
d d

PV 100  V
5. We know that, Compressibility factor, Z =  0.5 = 0.082  273  V = 0.1119 L
RT

 a 
Further when volume of a gas molecule is negligible, van der Waal's equation becomes  P   (V – 0) = RT
 V2 

a
or PV = RT – or a = RTV – PV2
V
Substituting the values
a = (0.082 × 0.1119 × 273) – (100 × 0.1119 × 0.1119) = 1.253 atm L2mol–2.

6. (C) At const P,
V1 V2 22.4 V2
T1 = T2  = .  V2 = 30.6 litre.
273 373

r1 M2 32
7. (a) (i) r2 = M1 or, 1.33 = M1  M1 = 18.09.

M1 18.09  10 3
(ii) Vm = molar density = = 50.25 × 10–3 m3.
0.36

PVm 1 50.25
(iii) Z= = = 1.224.
RT 0.0821 500
(iv) Since Z > 1.  Force of repulsion dominates over force of attraction.
3 3
(b) Av. translation K.E. = kT = × 1.38 × 10–23 × 1000 J = 2.07 × 10–20 J.
2 2

RESONANCE Liquid & Gaseous State - 60

 8 RT 3 RT
8. Uav = M
and Urms =
M

Uav 8 RT M 8
3 RT = = 0.9216 or Uav = 0.9216 × Urms
  
Urms M 3

400
Given, Uav = 400 m/s or Urms = = 434.02 m/s
0.9216

3 RT
9. urms =
M

3 2E 2E
E= RT  RT =  urms =
2 3 M

rate of diffusion 2 M1 rHe 16

10. rate of diffusion 1 = M2 rCH4 = =2
4

11.* The vander waals equation of state is -

(for 1 mole of gas)
 
P  a 
 2  (Vm – b) = RT
 Vm 
When a is negligible, then
pVm b
Z=  1 P
RT RT
that is Z increases with increaser in p.
when b is negligible, then
pVm a
Z=  1
RT VRT
increasing p implies decrease in V, which is turn, implies increase in the value of a/VRT and hence decrease
in the value of Z.
The curve IV is applicable provided temperature of the gas is near but larger than it’s critical temperature
Hence, the choice (a), (b) and (c) are correct.
12. (A) For H2 gas at high pressure Z > 1.
(B) For any gas at P ~ 0, Z ~ 1 i.e. ideal behaviour.
(C) For CO2 gas at normal pressure and temperature Z < 1.
(D) For any gas at very large molar volume i.e. P ~ 0, Z ~ 1 i.e. ideal behaviour of gas.
13. (A) At very large molar volume
a
P+ P and Vm – b = Vm
Vm2
(C) According to van der Waals equation 'a' and 'b' are independent of tempt.

an2
14. Correction factor for attractive force in to the real gas is given by .
V2

15. Vrms = Vmp

3RT 2RT 3R  400 2R  60
MX = MY 
40
= MY
MY = 4.

3RT
16. (A) Fact (B) P = MV = M = 3MRT
M
(C) Max well distribution (D) Fact

RESONANCE Liquid & Gaseous State - 61

17. PHe = 1 – 0.68 = 0.32 atm
V=?
n = 0.1
nRT 0.1 0.0821 273
V= = =7
P 0.32

PART - II
1. R = 8.3 J mol–1 K–1 = 2 cal mol–1 K–1 = 8.314 × 107 erg mol–1 K–1 = 0.082 litre atm K–1 mol–1
2. Various gas laws can be easily derived from kinetic equation obtained as a result of kinetic theory of gases.

n P
3. =
V RT

4. It is one of the assumption of kinetic theory of gas.

5. 2BCl3 + 3H2  2B + 6HCl

2 mol 3 mol 2 mol

21.6 g B = 2 mol B = 3 mol H2

PV =nRT
nRT 3  0.0821  273
 V= = = 67.2 L
P 1

3
6. K.E. = RT
2
3 3 313
E1 = R 293 and E2 = R 313  E2 = × E1
2 2 293

7. b = 4N × v i.e., total volume occupied by molecules of one mole of gas in motion.

8. Helium is not used to produced and sustain powerful superconducting magnets. All others are the uses of
helium.
9. Distribution of molecules (N) with velocity () at two temperature T1 and T2 (T2 > T1) is show below:

N T1
T2

u
At both temperatures, distribution of molecules with increase in velocity first increases, reaches a maximum
value and then decreases.
10. Let the mass of methane and oxygen be m gm. Mole fraction of oxygen xo
2

m
m 32
32 1
= m m =  = Let the total pressure be P.
 32 3m 3
32 16

1 1
 Partial pressure of O2, Po2 = P× xo2 P× = P..
3 3

RESONANCE Liquid & Gaseous State - 62

 CHEMICAL EQUILIBRIUM
EXERCISE # 1
PART - I
K1 bx
A-1. A B Kc = =
K2 ax

K1a  K 2b
a-x b+x x = K K Therefore, (A) option is correct.
1 2

A-5. X2 + Y2 2XY
1 2
x x 2x 2x = 0.6  x = 0.3
3 3
1 2
[x2] = - 0.3 [y2] = - 0.3
3 3
Therefore, (A) option is correct.
A-9. N2 + O2 2NO
Initial 2 moles 4moles
1 1 1
At Eq. 2– 4– 2× = 1 mol
2 2 2
1
Molar concentration of NO at equilibrium = = 0.4
2.5
2
2 x
B-1. SO3(g) + CO(g) SO2 (g) + CO2 (g) 9=  
2x
2 2 2 2
2+x 2+x 2-x 2-x x=1
n(SO 2 ) 1
neq = 3 + 3 + 1 + 1 = 8 n(SO3) + n(CO2) = 4 = <1
n(CO) 2
Therefore, (D) option is correct.
B-3. (I) N2O4 2NO2 Kc = 4
at point — A
Product 
Q = Re ac tan t  = 0
So, Q have minimum value at point A.
(II) at point [N2O4] = [NO2] = 0.1 M

NO2 2 0.1 0.1

Q= = = 0.1
N2O 4  0 .1

Q < Kc
So, reaction proceeds left to right
(III) Kc = Q at point [D & F].

B-4. 2O3(g) 3O2(g) Kp = 4 × 1014 pO >> pO

2 3
3
p o2
Kp = p 2 pO + PO = 8  PO ~ 8 atm.
o3 2 3 2 

83
4 × 1014 = p2O = 11.3 × 10-7 Therefore, (B) option is correct.
p2O3 3

conc. of isobu tan e

B-6. From given information, Q = tan 75º = > Kc = 3
conc. of n  bu tan e
so backward reaction

RESONANCE Chemical Equilibrium - 63

B-7. S (s) + S2– (aq) S22– (aq) K1 = 12
2S (s) + S2– (aq) S32– (aq) K2 = 132
K2 132
Now, S22– (aq) + S (s) S32– (aq) Keq = K = = 11
1
1 12

B-9. Ni+2 + 6NH3  [Ni (NH3)]+6 Kf = 6 × 108

t =0 0.01 mole 0.1 mole 0
At equilibrium x (0.1 – 0.06) 0.1
6
Ni(NH )  (0.1)
3 6
Kc = = 6 × 108 . [Ni+2] = 4 × 10–8.
Ni NH  = Ni 0.4
2
3
6 2 6

B-10. C(s) + CO2(g) 2CO(g)

3P
P–P/2 P= = 12
2

P2
so KP = = 2P = 2 × 8 = 16 atm.
(P / 2)

B-12. Kp = 0.800 atm = PCO2 = maximum pressure of CO2 in the container to calculate maximum volume of

container the PCO2 = 0.8 atm and none of CO2 should get converted into CaCO3(s).
so V(0.800 atm) = (10 L) (0.2 atm)
so v = 2.5 L

2 4 2 4 2 1
C-3. KP = 0.667 atm = atm = .P= .
3 1 2 1 2 2

4 2 4
so , =  32 = 1 – 2
1 2 3

1 1
so , 2 =  =
4 2

C-10. P1 = 15 atm ; T1 = 300 K.

Equilibrium temperature is 300ºC that is 573 K.
So first of all we have to calculate pressure of NH3 at 573 K.
P1 P2 15 P2
T1 = T2 = 300 = 573
P2 = 28.65 atm at 300ºC.
1 3
NH3 (g) N (g) + H2(g).
2 2 2
t=0 28.65 atm 0 0
x 3
t = teq. [28.65–x] atm x
2 2
But according to question.
x 3
Ptotal = 28.65 – x + + x
2 2
or 28.65 + x = 40.11.  x = 11.46.
11.46
Degree of dissociation of NH3 = = 0.4.
28.65

D-5. CuSO4 . 5H2O(s) CuSO4 . 3H2O(s) + 2H2O(g) KP = 2.25 × 10-4

KP = p 2 H2O = 2.25 × 10-4 p H O = 1.5 × 10-2
2

RESONANCE Chemical Equilibrium - 64

 22.8 PH2O
Vapour Pr = = 3 × 10-2 R.H. = × 100 = 50%
760 V.P.
Therefore, (B) option is correct.

D-7. SrCI2 . 6H2O(s) SrCI2 . 2H2O(s) + 4H2O(g) Kp = 16 × 10-12

( pH2O )4 = KP pH2O = (KP)1/4 = 2 × 10-3 atm

7 .6
H2O () H2O(g) p H2 O = = 1.0 × 10-2
760
PV 10  2  1
nH2 O = = = 4.45 × 10–4
RT 0.082  274
2  10 3
nH2 O = = 8.9 × 10-5  nH2O absorbed = 3.56 × 10-4
0.082  274
 wt absorbed = 6.4 mg. Therefore, (A) option is correct.
D-8. From thermodynamics.

5 PV 10 2  2.5
D-12* 10–10 atm = PH2O  PH2O = 10–2 atm. n= = 1 = 10–3
RT  300
12

E-5. Solubility of gas is directly proportional to the pressure of gas above liquid.
E-7. N2 (g) + O2 (g) 2NO (g)
1mole 2mole 3mole
(3 ) 2 9
KC = = 2.
1 2  
Let a mole of O2 is added, Then,
N2 (g) + O2 (g) 2NO (g)
1mole 2mole 3mole
t=0 1 (2 + a) 3
(1–x) (2 + a)–x (3 + 2x)

[NO] =  3  2x  = 0.04 ; (3 + 2x) = 4.

 100 
2x = 1, x = 0.5.

(3  2 x )2 9 ( 4)2 9
KC = = . ; KC = = .
(1 – x )(2  a – x ) 2 0.5[(1.5) – a] 2
16 9 35
= = . ; = = [1.5 + a]
0.5(1.5  a) 2 4 .5
101
7.11 = 1.5 + a . ; a= = 5.61
18

E-10. H2O() H2O(g)

KP = (PH2O )
When neon is added at constant pressure, we have to increase volume of the container. So more water will
evaporate to mantain equilibrium.

F-1. AB A+ + B– AB + B– AB2–

[ A  ][B  ] [ AB 2 ]
K1 = K2 =
[ AB] [ AB][B  ]

[ A  ][B  ] [ AB][B ] [A  ] [A  ] K1 1
K1/K2 = .  =  . [B–]2   = . 2
[ AB] [ AB 2 ] [ AB 2 ] [ AB 2 ] K2 B 
Therefore, (D) option is correct.
RESONANCE Chemical Equilibrium - 65
F-2. AB A+ + B– AB + B– AB2–
a–x–y y (y–x) (a–x–y) y–x x
y( y – x ) x
K1 = (a – x – y ) K2 = (a – x – y )( y – x )

 y( y – x ) 
 
 (a – x – y ) 
K1 K1 y
= x 2
K2 (a – x – y )( y – x )
 K 2 = x (y–x)

F-3.*_ AB A+ + B¯ K1
y y–x
AB + B¯ AB2– K2
y–x x
x
 K1 = (y – x)y K2 = y  x

k1 y
 k = (y – x)2
2 x

F-8. A(s) X + Y
 +
B(s) Y + Z
+ 
 K P1 =  ( + )
K P2 =  ( + )
Ptotal = ( + ) +  +  = 2 ( + )
 2 ( + ) = 50   +  = 25
 250 25    = 10 ,  = 15
 K P2 =  ( + ) = 15 × 25 = 375

PART - II
(7 to 9)
2A2(g) A4(g)
3p – x – y x/2

A2 + 2C A2 C2
3p – y-x P–2y y– z
A2 C2 2AC
y– z 2z
1
PA 4 PA 4
 K P1 2 2 81
PA2 2  PA 2

K P1
 
2 / 81 4

9
 PA 2 = atm.
2
9
 3p – x – y = ... (i)
2
x 1
= ... (ii)
2 2
 x = 1 atm
1
also given 2Z = .... (iii)
2

RESONANCE Chemical Equilibrium - 66

 1
Z= atm
4
Ptotal = 3p – x – y + x/2 + p – 2y + y – z + 2z = 4p – x/2 – 2y + z
1 1 1 27
=4×p– –2× + = atm.  P = 2 atm.
2 2 4 4

9
Sol. 7. 3P – x – y =
2
1 9
6– – y=
2 2
y = 1 atm.
1 3
PA 2C2 = y – z = 1 –  atm.
4 4
9
nA2 PA 2 3P  x  y 2
Sol. 8.   = 1/ 2  9
n AC PAC 2z

PA 2C2 3/4
Sol. 9. K p   3
2 2
PAC  1
 
2

EXERCISE # 2
4. H3BO3 + glycerine (H3BO3 + glycerine complex)
t=0 0.1 a 0
t=eq 0.04 (a – 0.06) (0.06)
0.06
Given : = 0.9
(0.04) (a  0.06)
6 1
so, (a – 0.06) = =
4  0.9 0 .6
1
Hence, a = + 0.06 = 1.73 M
0 .6
5. 2HI (g) H2 (g) + I2 (g)
t=0 a 0 0
t (a – 2x) x x
x2 1
Given : 2 =
(a  2 x ) 54.8
a  2x
so, = 54.8 and (a – 2x) = 0.5 M
x
0.5 0.5
so, x= = = 0.0675 M
54.8 7.40

6. NH2 COONH4(s) 2NH3(g) + CO2(g)

2Po Po Kp = (2Po)2 × Po = 4Po3
3Po P’ Kp = (3Po)2 × P’ = 9Po2.P
4
P’ = P
9 o

Pf 3Po  94 Po 31
i
 
P 3Po 27

RESONANCE Chemical Equilibrium - 67

9. C(s) + H2O(g) CO(g) + H2(g)
t=0 – 1 2 3
carbon solid will start forming when there will be equilibrium in the container
Pco .PH2 (2P) (3P)
Kp = PH2O = 3 atm = = 6 P = 3 atm
P

1
So P= atm
2
So Total pressure in the container will be
PT = P + 2P + 3P = 6P = 3 atm Ans. 3

11. LiCI. 3NH3 (s) LiCI. NH3 (s) + 2NH3 (g) Kp = 9 atm2 = p2NH
3
0.1 a  pNH = 3 atm
3

35
no. of moles of NH3 at equilibrium = = 0.5844
0.082  313
For 0.1 mol of LiCI NH3 to convent 0.2 mol of NH3 must be needed.
Total number of mol of NH3 req. = 0.7844.
12. Let initial equilibrium concentration of C = x M
A 2B + C
t = teq 3 4 x
x  42 16 x
KC = = ..........(i)
3 3
Now on doubling the volume concentrations will become half of initial so
A 2B + C
3 x x.4  2 4x
after doubling volume 2 QC = = < KC
2 2 23 3
x 
Conc. at new equilibrium (1.5 – a) 2 + 2a   a Hence forward shift.
2 
Now given that (2 + 2a) = 3
so a = 0.5
1
so [A] = 1M [B] = 3 [C] = (x + 1)
2
(1  x )  9 16 x
so KC = =
2 1 3
so 27x + 27 = 32x
27 16 27 144
so x= = 5.4 and KC = × × = 28.8. Ans.
5 3 5 5

13. 2AB2 (g) 2AB (g) + B2 (g)

t=0 a 0 0
(a  )
a(1–) (a)
2
 a[2   ]
Total mole = a[1 –  +  + ]
2 2
a(1 –  )  2 a  2
PAB 2 = ×P ; PAB = ×P
a(2   ) a(2   )

 a 
 
 2    
PB2 = a(2   ) =   × P..
2   
2

RESONANCE Chemical Equilibrium - 68

 2
 2    
  P   P
2  2 
KP = 2
 2(1 –  ) 
  P
 2P 
 << 1.
1/ 3 1/ 3
 3P  2K P   2K P 
KP = ; =   i.e. x =  
2  P   P 

14. N2O4(g) 2NO2(g)

a (1-) 2a
(i) Mobs = 38.33 × 2 = 76.66
a(1   )  92  2a  46
(ii) 76.66 =
a(1   )
 = 0.2
2a
(iii) % of NO2 =  100 = 33.33%
a(1   )

2
 2 
2   2
p NO2  1  
(iv) Kp = = 1  = 0.33
p N2 O 4 
 2


 1  

16. PCl5 (g) PCl3 (g) + Cl2 (g)

8.34
t=0 208 .5
0 0
8.34 8.34
teq. 208 .5
 x x x nT = 208 .5
 x

 8.34 
Given, (1 atm) (2.05 L) =   x mole  (0.082 L atm mole–1 K–1) (500 K)
 208 .5 

8.34 2.05
so, +x= = 0.05 mole
208.5 0.082  500
x = 0.05 – 0.04 = 0.01
0.01
so, = = 0.25 = 25%
0.04

2  1/ 16 
 = 6 atm.
Kp = . P = 
1 2  1  (1 / 16 )  15

17. PCl5(g) PCl3(g) + Cl2(g)

t=0 a 0 0
teq 0.61 a 0.39 a 0.39 a nT = 1.39 a
208.5 a
so, Mmix = = 150
1.39 a

PMmix 1 150 150

so, density = = = g/L
RT 0.082  500 41

19. T = 445oC = 445 + 273 = 718K

P = 207atm
n = 1 mole
1
Ag2O 2Ag (s) + O (g)
2 2

RESONANCE Chemical Equilibrium - 69

 Kp = PO2 = (207)1/2 = 14.39
G0 = G0 + 2.303 RT log Keq.
But at eq. G = 0
G0 = – 2.303 RT log Keq.
But for formation
1
2Ag (s) + 2
O2 (g) Ag2O (s)
1 Mole
1 1
Kp = 1/ 2 = (207)1/ 2
(Po 2 )

1
G0 = – 2.303 × 8.312 × 718 log ( 207 )1/ 2

2.303  8.312  718

G0 = × log 207
2
G0 = 6872.17 log 207
G0 = 15915.75 J
G0 = 3789.46 Cal
G0 = 3.789 KCal
G0 = 3.8 KCal

1
20. So2 (g) + O So3 (g)
2 2
H0 = – 98.32 KJ/mole = – 98.32 × 103 J/mole
S0 = – 95.0 J/mole 0K
G0 = H0 – T S0 = – 98.32×103 – [298 × (– 95)] = – 98.32 ×103 + 28.310×103
G0 = – 70.01×103
G0 = – 2.303 RT log Kp
– 70.01×103 = – 2.303×8.312×298 log Kp
70.01×103 = 5.705×103 log Kp
12.27 = log KP
Kp = 1.86 × 1012 (atm)1/2

3 .8 10 2
21. (PH2O )3 = 10–6  (PH2O ( g) )eq = 10–2 atrm PH2O = =
760 2
0.01
P = 0.01 – = 5 × 10–3
2

PV 5  10 3
number of moles of H2O(g) absorbed = = × 15 = 3 × 10–3 moles
RT 25

3  10 3
 moles of CuSO4 . 5H2O formed = = 10–3 = x
3
 105 x = 105 × 10–3 = 100

28. A(s) A'(g) + H2S(g) B(s) B'(g) +H2S(g)

A(s) A'(g) + H2S(g) P = 50 mm  PH2S = PA’’ = P/2 = 25 mm

B(s) B'(g) +H2S(g) P = 68 mm  PH2S = PB’ = P/2 = 34 mm

(i) K p1 = (25)2 = 625 mm2

K p2 = (34)2 = 1156 mm2
(ii) Ratio of moles is same as that of partial pressure so
A(s) A'(g) + H2S(g)
P1 P1+ P2

RESONANCE Chemical Equilibrium - 70

 B(s) B'(g) + H2S(g)
P2 P2+ P1
K P1 = PA' x PH2S = P1(P1 + P2) ......... (i)

K P2 = PB' x PH2S = P2(P1 + P2) ......... (ii)

K P1 P1 625
K P2 = P2 = 1156

(iii) total pressure = P1 + P2 + (P1+ P2) = 2(P1 + P2)

(i) + (ii) = (P1 + P2)2
Kp  Kp = P1 + P2
1 2

PT = 2 × ( K p1  K p2 ) = 84.4 mm.

29. N2(g) + 3H2(g) 2NH3 (g)

9P – x – y 13P – 3x – 2Y 2x
N2(g) + 2H2(g) N2H4(g)
9P – x – y 13p – 3x – 2Y Y
given 9P – x – y + 13P – 3x –2y + 2x + y = 7Po
 22P – 2x – 2y = 7Po ........(1)
then 2x = Po .........(2)
and 13P – 3x – 2y = 2Po .........(3)

Po
P=
2

9Po Po 3Po 5Po 13  7

9P – x – y = – – = 2y = Po = 3Po
2 2 2 2 2
13Po 3Po 6Po 3
13P – 3x – 2y = – – = 2Po y= P
2 2 2 2 o

(2x )2 Po
2
1
K1 = 3 = 5 = 2
(9p  x  y )(13p  3 x  2y ) 20Po
Po .( 2Po )3
2
3
Po 3
2
K2 = = 2
 5  2 20Po
 Po 2Po 
2 
30. For I equilibrium 2NO2 N2 O 4
P`N2O 4
Kp = (P` 2 = 6.8 .... (1)
N2 O 4 )

 P`N2O 4 = 1.7 atm  By Eq. (1) ; P`NO 2 = 0.5 atm

The equilibria are maintained using NO and NO2 in the ratio 1 : 2
For II equilibrium NO + NO2 N2O3
Initial pressures P 2P 0
Pressures at equi. (P – x) (2P – x– 3.4) x
 3.4 atm of NO2 are uesed for I equilibrium to have P`N2O 4 =1.7 atm
At equilibrium (P – x) 0.5 x
( P`NO 2 is same for both the equilibria since both reactions are at equilibrium at a time.)
Total pressure at equilibrium (Given 5.05 atm)
= P`NO  P`NO2  P`N2O3  P`N2O 4 = P – x + 0.5 + x + 1.7
RESONANCE Chemical Equilibrium - 71
  5.05 = P + 2.20
 P = 5.05 – 2.20
 P = 2.85 atm
 2P – x – 3.4 = 0.5
2 × 2.85 – x – 3.4 = 0.5
 x = 5.70 – 3.90
 x = 1.80 atm
 P`NO = 2.85 – 1.80 = 1.05 atm
Now KP for NO + NO2 B2O3
P`N
2 3 O 1.80
KP = P`  P` 
1.05  0.5 = 3.43 atm
–1
NO NO 2

EXERCISE # 3
3.06
1. Mole of NH4HS = = 0.06 mol
18  1  32
NH4HS(s) NH3(g) + H2S(g)

t=0 0.06 mol 0 0

t = teq. 0.06 –0.3 × 0.06 0.3 × 0.06 0.3 × 0.06
= 0.018 mol = 0.018 mol.

Ptotal × 2 = 2 × 0.018 × 0.0821 × 300

Ptotal = 0.4433 atm
2
0.443  0.443 
PNH3 = PH2S = atm kp =   = 0.049 atm2
2  2 

kp 0.049
kc = = (24 .63 )2 = 8.1 × 10–5 (mol/lit)2
(RT)2
(ii) No effect of addition of NH4HS(s) on equilibrium as active mass of solid is one.
2. Equilibrium is affected by pressure and temperature but not by catalyst.

KP 1.44  10 5
3. KP = KC (RT)ng  KC = ng

(RT ) (0.082  773 ) 2

[C] [D]
4. QC = [ A ] [B] , < KC

QC  with time

5. With change of pressure, x will change in such a way that Kp remains a constant.
6. N2O4 (g) 2NO2.
moles t=0, 1 0
moles at eq. 1– 2
2
 2 
  P 
 (1   )  4 2
KP = = × P..
1– 
P 1– 2
1 
Let total pressure at eq. = P.
4 2
or KP =
× P..
1– 2
When volume is halved, P is double.
  will change as KP is independent of pressure change.

RESONANCE Chemical Equilibrium - 72

7. In this reaction the ratio of number of moles of reactants to products in same i.e., 2 : 2, hence change in
volume will not alter the number of moles .
8. If in the reaction the ratio of number of moles of reactants to products in same i.e., 1 : 1, then change in
volume will not alter the number of moles .
9. The conversion of SO2 to SO3 is an exothermic reaction, hence there is no need to increase the temperature.
There is also a decrease in volume or moles in product side. Thus the reaction is favoured by low temperature
and high pressure. (Le-Chatelier’s principle).

10. C[N2O 4 ] = 4.8 × 10–2 mol L–1, C[NO2 ] = 1.2 × 10–2 mol L–1

[NO 2 ] 2 1.2  10 2  1.2  10 3

Kc   = 0.3 × 10–2 = 3 × 10–3 mol L–1
[N2O 4 ] 4.8  10 2
[P4 O10 ( s)]
11. P4(g) + 5O2 (g) P4O10(g) Kc 
[P4 ( s)][O 2 ( g)]5

12. CO(g) + CI2(g) COCI2(g)

Kp 1
n = 1 – 2 = – 1; Kp = Kc(RT)n   (RT ) 1 
Kc RT

[NO] 2
13. N2(g) + O2(g) 2NO(g) ; Kc =  4  10  4
[N2 ][O 2 ]

1 1 [N2 ]1/ 2 [O 2 ]1/ 2 1 1 1 100

NO(g) N (g) + O2(g) ; Kc     2
  50
2 2 2 [NO] Kc 4  10 4 2  10 2

14. Kp = Kc (RT)n n = 3 – 2 = 1.
Kp = Kc (0.0821 × 457)1 . Kp > Kc.
15. CI2(g) + 3F2(g) 2CIF3(g) ; H = – 329 kJ. Favourable conditions:
(i) Decrease in temperature, (ii) Addition of reactants, (iii) Increase in pressure i.e., decrease in volume.
16. NH4HS(s) NH3(g) + H2S(g)
Initial presens 0 0.5 0
At equi. 0 0.5+x x
Total pressure = 0.5 + 2x = 0.84  x = 0.17 atm
Kp = PNH3  PH2S = 0.11 atm . 2

17. When nitrogen is added at equilibrium condition, the equilibrium will shift according to Le-chatelier principle
at equilibrium G = 0 and catalyst changes the rate of forward and backward reactions by equal extent. KP
of reaction is a function of temperature only.

18. Given : PCI5(g) PCI3(g) + CI2(g)

t=0 1 0 0
teq 1–x x x
Total number of moles = 1 – x + x + x = 1 + x
 x 
Thus partial pressure of PCI3 =  1  x  P..
 

1
19. SO3(g) SO2(g) + O (g)
2 2

[SO2 ][O2 ]1/ 2

= KC = 4.9 × 10–2 ...........(i)
[SO3 ]
SO3(g) + 1/25 O2(g) SO3(g) ...........(ii)
[SO 3 ] 1
[SO 2 ][O2 ]1 / 2
= K'C = For 2SO2(g) + O2(g) 2SO3(g)
4.9  10 – 2

RESONANCE Chemical Equilibrium - 73

 [SO 3 ]2 1 10000
2 = KC2 = 4 = = 416.49
[SO 2 ] [O 2 ] 4.9  4.9  10 24.01

20. Gº = Hº – TSº = – 54.07 × 1000 – 298 × 10 = – 54070 – 2980 = – 57050
Gº = – 2.303 RT log10 K
– 57050 = – 2.303 × 298 × 8.314 log10K = – 5705 log10 K
log10 K = 10

21. At equilibrium G (Gibbs energy) = 0 but G° (standard Gibbs energy)  0

As G (Gibbs energy) is more negative reaction will be more spontaneous.

22. c=a+b

23. X 2Y Z P + Q
1– 2 1–  
2
 2     
PT2  

PT2 
 PT1  
 1     1    1   
Kp =  1   Kp =  1  
1 2
 PT1   PT 
 1    1  2 

2
 2   1  
K P1  PT1   PT2 
 1    1  
K P2 = 1  ×     
 
 PT   PT   PT 
 1  2   1  2   1  2 

1 4PT1 PT1 1
= P ; PT2 = 36
9 T2

24. PV = nRT
V = 1 dm3 = 10–3 m3
P = 3170 Pa
R = 8.314 J K–1 mol–1
T = 300 K
3170 × 10–3 = n × 8.314 × 300
3170  10 3
n= = 1.27 × 10–3 mol.
8.314  300

25. CO2(g) + C(s) 2CO (g)

0.5 atm
0.5–p 2p

Total pressure = 0.5 – P + 2P = 0.8

P = 0.3
2
PCO (2P)2 (0.6)2
Kp = P = =
CO2 (0 . 5  P ) (0.5  0.3)
Kp = 1.8

26. N2 + O2  2NO K = 4 × 10–4

1 1 1 1
NO  N2  O 2 K’ = = = 50
2 2 K 4  10  4

RESONANCE Chemical Equilibrium - 74

 SOLUTION OF ADVANCED LEVEL PROBLEM
1. (i) CO(g) + 2H2 (g) CH3OH (g)
0.15 a
0.15 – x a – 2x x  x = 0.08
0.15 – x + a – 2x + x = 0. 5 PV = n RT
8.2  2.5
a – 2x = 0.35 n= = 0.5
0.082  500

0.08
2 .5 20000
Kc = 2 = = 58.3
0.07  0.35  343
 
2 . 5  2 .5 

58.358.3
Kp = 58.3 × (RT)–2 = =
= 0.035
(0.082  500 )2
41 41
(ii) Total pressure will remain 8.2 atm as catalyst reduces only time taken to achieve equilibrium, does
not affect equilibrium condition / concentrations.

x 2
2. 2.0 × 10–37 =  x = 6.6 × 10–20
0.482 2  0.933 
 [N2] = 0.0482 mol L–1 ; [O2] = 0.0933 mol L–1 ; [N2O] = 6.6 × 10–21 mol L–1

3. Ag+ (aq) + Fe2+ (aq) Fe3+ (aq) + Ag(s)

Millimole before reaction 500 × 0.150 500 × 1.09
or = 75 = 545 0 0
Millimole after reaction (75 – x) (545 – x) x x
 mM = Meq. (both Ag+/Ag and Fe2+/Fe3+ have valency factor unity)
[Fe3  ]
KC =
[ Ag ] [Fe2  ]


x
1000
 KC = .... (1)
 75  x   545  x 
  
 1000   1000 
Mil lim ole
 Conc. = Total volume

75  x 545  x x
[Ag+] = ; [Fe2+] = ; [Fe3+] =
1000 1000 1000
Now 25 mL of mixture requires 30 mL of 0.0832 M or 0.0832 × 5 N KMnO4.
 Fe2+ is oxidized by KMnO4.
 Milliequivalent of Fe2+ left at equilibrium in 1000 mL
= Milliequivalent of KMnO4 for 1000 mL
30  0.0832  5  1000
= = 499.2
25
 545 – x = 499.2
 x = 545 – 499.2 = 45.8
Thus, by Eq. (1),
45.8
1000 45.8  1000
Kc  
 75  45.8   545  45.8  29.2  499.2
   
 1000   1000 
KC = 3.1420.

RESONANCE Chemical Equilibrium - 75

4. For the reaction,
Fe2+ + 3dipy [Fe(dipy)3]2+
rforward = Kf = [Fe2+] [3 dipy]
= 1.45 × 1013 [Fe2+] [dipy]3
rbackward = Kb × [Fe(dipy)3]2
= 1.22 × 10–4 [Fe(dipy)3]2+
Kf
At equilibrium rf = rb and KC = K = [Fe(dipy)3]2+ /Fe2+] [dipy]3
b

Kf 1.45  1013
Also, stability constant of complex = Equilibrium constt. of reaction = K = = 1.188 × 1017
b 1.22  10 4

5. (a) A + 2B 2C
a 2a
a–x 2a – 2x 2x
Total moles at equilibrium 3a – x
2x
Mole fraction of C = = 0.4
3a  x
2x = 1.2a – 0.4x
1.2a
x=
2.4
a
x=
2
Now A + 2B 2C
a
a a
2
5a
Total moles =
2
a
8 a 16
PA = 2 x 8 = atm ; PB = x8= atm
5a 5 5a / 2 5
2

a 16 (PC )2 5
PC = x8= atm ; KP = =
5a / 2 5 (PB )2 . PA 8
KP = 0.625 atm–1

(b) A + 2B 2C
Mole fraction 0.16 0.32 0.52
Partial pressure 0.16 P 0.32 P 0.52 P

(0.52P)2 5
KP = =
0.16P x (0.32P)2 8

0.52 x 0.52 x 8
P = 0.16 x 0.32 x 0.32 x 5 = 26.4 atm

6. (i) From the graph 0.3 × n = 0.6

n=2
(ii) K = (0.6)2 / 0.3 = 1.2 mol / L
0 .6  0 .5
(iii) initial rate of conservation of A = = 0.1 M hr–1
1

RESONANCE Chemical Equilibrium - 76

 4
 3   3 
   
 10   10  243
7._ QC = 2 =  10 – 2 = 7.59 × 10–2 > K
 2  4  32 c

  
 10  10 
so, reaction will proceed in backward direction.

8. A(g) B(g) + C(g) Kc = 4

1 2 2
0.5 1 1 Qc = 2 < Kc
1  x 2
0.5 - x 1+x 1+x 4=
0.5  x
x = 0.162 [A] = 0.338 [B] = [C] = 1.162
9. Ag+ + 2CN– [Ag(CN)2]–
t=0 0.1 0.5 0
10
teq 10–6 0.3 0.1 K1 = × 106
9
Zn2+ + 4CN– [Zn(CN)4]2–
t=0 0.1 0.5 0
0 .1
eq. 10–12 0.1 0.1 K2  = 1015
(0.1)4  10 –12
Substracting two times Ist reaction from IInd reaction, we will get the required reaction, so

1015 10 3  81
Keq = 2
= = 810 Ans. 810
 10  12
100
   10
 9 
2 2
 0.55   0.76 
10. Kp =   = 1.49 ; Kp =   = 10.03
 0.45   0.24 
Higher temperature ( Kp > Kp).

10 5
11. 2HBr(g) H2(g) + Br2(g) Kp =
1.6
10 – 2p p p
2
 p  10 5
  = p = 2.5 × 10–2
 10  2p  1.6
(pH )eq = (pBr )eq = 2.5 × 10–2 bar ; (pHBr)eq = 10.0 bar
2 2

12. The equilibrium reaction would involve 2 moles of CO, 1mole of O2 and 2 moles of CO2 as the unit of KC is
lit/mole.
So the equilibrium equation is
2CO(g) + O2 (g) 2CO2 (g)
1
The equation, CO(g) + O (g) CO2 (g) would have an equilibrium constant with units (lit/mole)1/2.
2 2
2CO(g) + O2 (g) 2CO2(g)
1 1
Initial conc. = 0.5 = 0.5 0
2 2
x
Conc. at equil. 0.5 – x 0.5 – x
2
[CO 2 ] 2
 Kc = = 5 × 103
[CO] 2 [O 2 ]

RESONANCE Chemical Equilibrium - 77

 x2
 5 × 103 =
 x
(0.5  x )2  0.5  
 2
Since, the value of equilibrium constant is pretty high so we can assume that almost entire CO goes to CO2.
Thus, value of x would be close to 0.5. But concentration of CO, (0.5 – x) would not be zero but would be a
 y
small value. Let this value be y. Then the concentration of O2 at equilibrium would be  0.25  2  .
 

( 0. 5 ) 2
 5 × 103 =  y
y 2  0.25  
 2 
y
As value of y is very small, can be easily ignored with respect to 0.25
2
( 0 .5 ) 2
5 × 103 =
y 2  0.25
y = 1.4 × 10–2
[CO] = y = 1.4 × 10–2 M.

13. CH3COOH() + C2H5OH() CH3COOC2H5() + H2O()

1 – 0.5 1 – 0.5 0.5 0.5
0 . 5  0 .5
So, KC = =1
0 . 5  0 .5
Now let a moles of CH3COOH and b moles of C2H5OH are taken :
a a a a
a– b–
3 3 3 3
(a / 3 )  (a / 3 )  a a
KC = a
or 2  b  3  =

2a / 3   b  
3
 3

a 2
or 2b = a or =
b 1

(30.8)2
14. H2 + I2 2HI Kp = = 38
9 .6  2 .6
25 – x 18 – x 2x = 30.8
(30.8 )2
2HI H2 + I2 Kp = = 38
9 .6  2 .6

  1 2
1– =  = 0.245
2 2 38 4 (1   )2

15. PCl5 PCl3 + Cl2

a 0 0
a(1-) (a) (a)
Total moles at equilibrium = a(1+) ........ (i)
PV 1 1.7
From n=  = 0.03959 ........ (ii)
RT 0.0821 523
From (i) and (ii) a(1+) = 0.03959
4 .5
Here a= Hence  = 0.8329
208 .5

16. 4PH3(g) P4(g) + 6H2(g)

1–0.4 0.1 0.6
0.6  34  0.1 124  0.6  12
Meq. = = 30.76
1 .3
Vapour density = 15.38
RESONANCE Chemical Equilibrium - 78
17. PCl5(g) PCl3 + Cl2 4.678 × 110 = ntotal × 0.082 × 523
5(1–) 5 5 ntotal = 11.998
3
5(1–) + 4 = 12 = = 0.6
5

4.768
Peq mix. = × 8 = 3.18
12

2 P 0.6 2  3.18
Kp = = = 1.78
1 2 1  0 .6 2

18. (a) The given equilibrium is ,

CO2 (g) + C (s) 2 CO(g)
Initial mole 1 0
Final mole (1 – ) 2
(nCO ) 2 P
1
( 2 ) 2  5 
KP = n ×   = ×  
CO 2  n  (1 –  ) 1   

20  2
10 =
(1 –  )
or 10 – 10 2 = 20 2 .
10
 2 =
30

1
 = = 0.577 .
3
Thus, mole of CO2 at equilibrium = 1 –  = 1 – 0.577 = 0.423.
and mole of CO at equilibrium = 2 = 2 × 0.577 = 1.154
Total mole present at equilibrium = 0.423 + 1.154 = 1.577.
At equilibrium, PV = nRT
P = 5 atm ; n = 1.577, T = 817 + 273 = 1090.
5 × V = 1.577 × 0.0821 × 1090.
 V = 28.22 litre.
1.154
 [CO] at equilibrium = = 0.041 mol litre–1.
28.22
0423
 [CO2 ] at equilibrium = = 0015 mol litre–1.
28.22
(b) For CO2 (g) + C(s) 2CO (g)
Initial mole 1 0
Final mole (1 – a) 2a
Total mole at equilibrium = 1 – a + 2a = 1 + a.
1– a 5
Given =
1 a 100
95
 a=
100

(nCO ) 2 P
1

KP = (n ×  
CO 2 )  n 

2 1
 2  95   P 
 
 100   
10 =  5  ×  105 
   100 
 100   

 P = 0.145 atm.
RESONANCE Chemical Equilibrium - 79
19. Pentyne-1 Pentyne-2 + Pentadiene-1-2.
(A) (B) (C)
At eq. 1.3 95.2 3.5
[B] [C] 95.2  3.5
Keq. = [A]
= = 256.31 .....(i)
1 .3
Now, for B A
[A]
K1 = [B]

[C] 3. 5
then from Eqs. (i) and (ii), K1 = K = = 0.013.
eq. 256 .31
 Gº= – 2.303 RT log10 K = – 2.303 × 8.314 × 448 log 0.013 = 16178 J = 16.178 kJ.
Stability order for A and B is B >A.
Similarly for B C
[C ] K eq. [ A ] 256.31 1.3
K2 = [B] = = = 0.037.
[B]2 95.2  95.2
 Gº = – 2.303 R log10 K = – 2.303 × 8.314 × 448 log 0.037 = 12282 J = 12.282 kJ.
Thus, stability order for B and C is B > C.
Given the values of Gº1 and Gº2 , the total stability order is B > C > A.
KOH alc.
CH3.CH2.CH2.C  CH    [CH3CH2CH = C = CH2]  [CH3CH2C  C – CH3].

20. Gº = Hº – TSº ; K = e–Gº / RT

At 300 K, Gº = (– 41.16 – 300 × – 0.0424) × 1000 = – 28440 J/mol
At 1200 K, Gº = (– 32.93 – 1200 × – 0.0296) × 1000 = – 2590 J/mol
KP (300 K) = 8.935 × 104
KP (1200 K) = 0.37753
Q=1
at 300 K : Q < K , Hence forward direction.
at 1200 K : Q > K , Hence backward direction.

21. CaCI2(s) + 2H2O(g) CaCI2.2H2O(s)

0.07 mm of Hg = 0.07 / 760 = 9.21 × 10–5 atm
KP = 1 / (9.21 × 10–5)2 = 1.18 × 108 atm–2.
Gº = – RT ln KP = – 35.489 kJ.

22. CO(g) + H2O(g) CO2(g) + H2(g)

GR = (–394.36) – (137.17 – 228.57) = – 28.62 kJ = – RT ln k
28.62
log K = =5
8.314  248  2.303
K = 105
PCO 2  PH2
K = P P
CO H2 O

CO + H2 O CO2 + H2
1–x PH2O 1+x 1+x

(1  x )2 (1  x )2
5
10 = (1  x ) P =
H2 O (1  x ) 1.22  10  3

(1  x )2
122 =
(1  x )

H2O() H2O(g) kp = PH2O (vp)

Gºrxn. = –28.62 kJ
kp = 105

RESONANCE Chemical Equilibrium - 80

 CO + H2 O CO2 + H2
101.325 – x 3.16 kp 101.325 kp – x 101.325 kp – x

H2O() H2O(g)
G = –8.56
–8.56 = –2.303 RT log kp
log kp = 1.5
kp = 3.16 = PH2O
(101.325  x ) (101.325  x )
kp = 105 = (3.16 ) (101.325  x )

x = 101.201 kpa ; PCO = 0.124 kPa ; PCO 2 = 202.65 kPa

23. C2H6(g) C2H4(g) + H2(g)

initial 20 0 0
eq. 20 – x x x
2
 x 
 
 20  x 
0.5 20  x = 0.05  x = 6.02
 
 
 20  x 

26.02
mole percentage = × 100 = 24.5
106.02
Hº = Gº + TSº = 144.01 kJ
From the equation,
 0.05  144 .01 1000  1 1 
log  K  =   
 2  2.303R  300 900 
Gº (300 K) = – R × 300 × 2.303 log K2 = 103.47 kJ/mol.
24. (a) Because Fe2O3 is a solid, its "concentration" doesn't change when more Fe2O3 is added. Therefore,
there is no concentration stress, and the original equilibrium is undistrubed.
(b) Le Chatelier's principle predicts that the concentration stress of removed CO2 will be relieved by reaction
from left to right to replenish the CO2.
(c) Le Chatelier's principle predicts that the concentration stress of removed CO will be relieved by reaction
from right to left to replenish QC = [CO2]3 / [CO]3.
When the equilibrium is disturbed by reducing [CO], QC increases, so that QC > KC. For the system to move
to a new state of equilibrium, QC must decrease-that is, [CO2] must decrease and [CO] must increase.
Therefore the reaction goes from right to left, as predicted by Le Chatelier's principle.
25. (a) Because the forward reaction is endothermic, an increase in temperature favours the formation of NF2.

[NF2 ] 2
The equilibrium constant KC =
[N2F4 ]
will therefore increase with increasing temperature.
(b) The stress here is the removal of NF2 gas. To offset it, more N2F4 will decompose to form NF2. The
equilibrium constant Kc remains unchanged, however.
(c) A decrease in pressure (which is accompained by an increase in gas volume) favors the formation of more
gas molecules, that is, the forward reaction. Thus, more NF2 gas will be formed. The equilibrium constant will
remain unchanged.
(a) Adding helium to the equilibrium mixture of constant volume will not shift the equilibrium.
26. (a) Consider only the gaseous molecules. In the balanced equation there are 3 mol of gaseous reactants and
2 mol of gaseous proudct. Therefore the net reaction will shift toward the products (to the right) when the
pressure is increased.
(b) The number of moles of products is 2 and that of reactants is 1 ; therefore the net reaction will shift to the
left, toward the reactants.
(c) The number of moles of products is equal to the number of moles of reactants, so a changes in pressure
has no effect on the equilibrium.

RESONANCE Chemical Equilibrium - 81

27. (a) The stress applied to the system is the addition of NH3. To offset this stress, some NH3 reacts to produce
N2 and H2 until a new equilibrium is established. The net reaction therefore shifts from right to left that is:
N2(g) + 3H2(g)  2NH3(g)
(b) At the instant when some of the NH3 is added, the system is no longer at equilibrium. The reaction

[NH3 ]20 (3.65)2

quotient is given byQc = = = 2.86 × 10–2
[N2 ]0 [H2 ]30 (0.683)(8.80)3
Because this value is greater than 2.37 × 10–3, the net reaction shifts from right to left until Qc equals Kc.

28. NH4I (s) NH3 (g) + HI

initial eq. 150 150
final eq. 750 30
1 1
HI (g) H (g) + I2 (g)
2 2 2
eq. 150 – 2x x x
x x
=2  x = 60
150  2x
Final pressure = 750 + 30 + 60 + 60 = 900 mm of Hg.
29. A(g) B(g) + 2C(g)
1–x x + 3y 2x – y
C(g) 2D(g) + 3B(g)
2x – y 2y 3y + x
neq = 1 – x + x + 3y + 2x – y + 2y
neq 1  2x  4 y 13 7
ni
= =  2x + 4y =
1 6 6

1  2x  4 y 13
=
1 6
7
2x + 4y =
6
12x + 24y = 7 ........(i)
2x  y 4
=
1 x 9
18x – 9y = 4 – 4x
8
(22x – 9y = 4) ........(ii)
3
176 32
x – 24y = ........(iii)
3 3
(1) + (3)
176 32
12x + x= +7
3 3
212 53
x=
3 3
53
x=
212
1
x = 0.25 =
4
use in eq. (1)
1
312 × + 24y = 7
4
24y = 4
1
y=
6
RESONANCE Chemical Equilibrium - 82
 A(g) B(g) + 2C(g)
1 3 1 1 3 2 1 1
1– 4 = 4 4 +3× 6 = 4 4 – 6 = 3

C(g) 2D(g) + 3B(g)

2 1 1 2 1 3 1 3
4 – 6 = 3 6 = 3 6 + 4 = 4

2
3  1
 
4 3 1
K c1 = 3 = = 0.111
11
9
4

2 2
 1 3 
   
3 4 1 27
K c2 = 1 = × = 0.14
3 64
3
30. Let xA , xB and xC are the mole fractions of A, B and C respectively.
A 
B KB/A = xB / xA
A C KC/A = xC / xA
KB/A + KC/A = (xB + xC) / xA = (1 – xA) / xA
1
 xA = 1k
B / A k C / A

kB / A kC/ A
xB = 1k , x =
B / A k C / A 1k B / A k C / A
C

31. 3A2 (g) A6 (g) KP = 1.6 atm–2

PA 2
KP = 1.6 = (P )3
A2

0.2 3
PA 2 =
= 0.5 atm
1.6
Also pressure of A2 used for the formation of A6 = 0.6 atm
For A2 (g) + C(g) A2C (g)
t=0 2P P 0
At eq. 2P – P1 – 0.6 P – P1 P1
Also for 3A2 (g) A6 (g)
t=0 2P 0
At eq. 2P – P1 – 0.6 0.2
2P – P1 – 0.6 = 0.5
(since PA 2 at eq. is 0.5 for similataneous equilibria)
Also pressure of A2 + C + A2C + A6
= (2P – P1 – 0.6) + (P – P1) + P1 + 0.2
= 1.4
0.5 + P + 0.2 = 1.4
P = 0.7 atm
 2P – P1 – 0.6 = 0.5
 P1 = 2 × 0.7 – 0.6 – 0.5
P1 = 0.3 atm
 PA 2 = 0.5 atm, PC = 0.7 – 0.3 = 0.4 atm, PA 2C = 0.3 atm
Also KP for A2 (g) + C(g) A2C (g)
PA 2C 0. 3
KP = P  P = = 1.5 atm–1
A2 C 0 .5  0 .4

RESONANCE Chemical Equilibrium - 83

 IONIC EQUILIBRIUM
EXERCISE # 1
PART - I
A-1. HCl (aq) + CH3COOH (aq) Cl– (aq) + CH3 COOH2+(aq).
Acid-1 base-2 base-1 acid-2
A-7.* pKw = – logKw = – log 1 × 10–12 = 12.
Kw = [H+][OH–] = 10–12 .
[H+] = [OH–]
 [H+]2 = 10–12 ; [H+] = 10–6 ; pH = – log[H+] = – log 10–6 = 6.
H2O is neutral because [H+] = [OH–] at 373 K even when pH = 6.
(D) is not correct at 373 K. Water cannot become acidic.
B-1. (A) At 25ºC, [H+] in a solution of 10–8 M HCl > 10–7 M.
(B) [H+] = 10–8 M.
(C) [OH–] = 4 × 10–6 M  [H+] = 2.5 × 10–9 M.
+
(D) [H ] = 10 M.
–9

B-3. Inital Final

pH = 12 pH = 11
[H+] = 10–12 M [H+] = 10–11 M
[OH ] = 10 M
– –2
[OH–] = 10–3 M
Inital No. of mole of OH = 10
– –2
Final No. of mole of OH– = 10–3
So no. of mole of OH removed = [.01 – 0.001] = 0.009
–

B-8. In this solution, source of OH– is water

 C = [OH–]
109
= = 1.8 × 10–111 M
1000 / 18
% ionisation = 1.8 × 10–9 M
B-11. Given density of formic acid = 1.15 g/cm3
 Weight of formic acid in 1 litre solution = 1.15 × 103 g
1 .15  10 3
Thus, [HCOOH] = = 25 M
46
Since in case of auto ionisation
[ HCOOH2 ] = [HCOO–] and [HCOO–] [ HCOOH2 ] = 10–6  [HCOO–] = 10–3

[HCOO  ]  100 103

Now % dissociation of HCOOH = = × 100 = 0.004%.
[HCOOH] 25

B-13. N2 H4 + H2 O N2H5– + OH–

1 0 0
1–  
Kb = C2.

Kb 4  10 –6
 a= = 0.16 1000
= 0.02 or 2%.
C

32 500

 Ka 
 1
C-2. Relative strengths of weak acids =  K 
a  2
Assume C1 and C2 are same (Although not given).

 K a1   2.1 10 – 4 
   
 Relative strength =  K  =  1.1 10 – 5 
 a2   
Relative strength for HCOOH to CH3COOH = 4.37 :1.
RESONANCE Ionic Equilibrium - 84
C-3 to C-5
Final volume of solution become double and concentration becomes half.
C1 = 0.01, C2 = 0.1
[H+] = K a1C1  K a 2C 2

=2  10  4  0.01  2  10 5  0.1 = 2  10  6  2  10  6 = 2 × 10
–3

pH = 3 – log2 = 3 – 0.3 = 2.7

2  10 4 2  10 5
1 = = 10–1 ; 2 = = 10–2
2  10  3 2  10  3
HOCl H+ + OCl– CH3COOH H+ + CH3COO¯
C1(1 – 1) C11+C22 C11 C2(1 – 2) C11+C22 C22
[OCl–] = C11 [CH3COO–] = C2 2
= 0.01 × 10–1 = 0.1 × 10–2
= 1 × 10–3 = 1 × 10–3
Kw 10 14
[OH–] = = = 5 × 10–12 M
2  10  3

[H ]
[HOCl] = 10–2(1 –0.1) = 9 × 10–3 M
[CH3COOH] = 10–1 (1 – 0.01)  10–1

1 1
C-7. Initial pH = (pKb – log C) = (5 – log 2 – log 0.1) = 2.85
2 2
After adding NaOH, pOH of solution = 1
Change in pOH = 1.85

D-4. CH3COOH + OH–  CH3COO– + H2O

t=0 20 20
t = eq – – 20
20
So, [CH3COO–] = = 0.1 M
200
1 1 1
pH = 7 + pKa + log C = 7 + 2.37 + log 10–1 = 7 + 2.37 – 0.5 = 8.87
2 2 2

D-7.* Let BA be this salt BA  B+ + A–

A does not undergo hydrolysis because HA is strong acid. B+ undergoes hydroysis
–

Kh Kw
h= h = degree of hydrolysis where Kh = Hydrolysis constant = K b .
c

h Kh greater the hydrolysis constant greater the h(degree of hydrolysis).

1
h greater the Kb lesser the h.
Kb
Hydrolysis is endothermic, Kh increases with temperature and h also increase with temperature.
Kw
h V V = volume of salt solution hence h increases with dilution. Kh = K
b
Both Kw and Kb change with temperature, hence Kh changes with temperature.
Hence, statement(B) is correct. h increases if Kb decreases, statement(C) correct.
It is found that as temperature increase, Kw and Kb increase but increase in Kw is greater than increase in Kb.
Hence, h increases with increase in temperature. or h decrease in temperature., hence statement.
(D) is correct.
(D) is not correct from explanation of (B).

RESONANCE Ionic Equilibrium - 85

D-10. HS– + H2O H2S + OH–

K wC Kw K wK a
 [OH–] = Ch =  [H+] = =
Ka K w .C C
Ka
or pH = 1/2[pKw + pKa + logC]

E-2. Ka = 5 × 10–10 pKa = 10 log 5 = 9.3

 CN 
pH = pKb + log  HCN 
 

 5  Vml   Vml 
9 = 9.3 + log  10  2   – 0.3 = log  4 
   

 4  4
0.3 = log  V   Vml = 2  Vml = 2 ml
 ml 

E-3. HCOOH + KOH 

 HCOOK + H2O
milimole 20 10
10 – 10
[HCOO– ]  10 
pH = pKa + log = 3.74 + log  10   pH = 3.74
[HCOOH]  

E-4. CH3COOH + NaOH   CH3COONa + H2 O

time t = 0 40 mmole 20 mmole
time t = t 20 mmole – 20 mmole
 20 
pH = pKa+ log    pH = pKa  [H+] = Ka = 1.8 × 10–5 M
 20 

E-6. (a) NH4OH + HCI  NH4CI + H2O

0.2 M 0.1 0 0
0.1 0 0.1 0.1
pOH = pKb
(b) NH4OH + HCI  NH4CI + H2O
0.1 0.05 0 0
0.05 0 0.05
 0.05 
pOH = pKb + log  0.05  = pKb
 
(c) NH4OH + HCI   NH4CI + H2O
0.3 0.15
0.15 0 0.15
pOH = pKb So all solution have same pH

 ab 
E-9. Maximum buffer capacity of a solution is given by, buffer capacity = 2.303  a  b  . Hence the result.
 

(0.5 )2
and a = b = 0.5, BC = 2.303 × = 0.57
1

E-10. Mole of NaOH is required for 1 lit solution = x

 Mole of NaOH is required for 100 ml of solution = 0.1 x
Now, 0.1x = 1 × V  V = 0.1x lt = 100x ml.

F-4. pKa = 5.45

[Base form]
pH = pKHIn + log [ Acid form]  pH = pKHIn = 5.45

RESONANCE Ionic Equilibrium - 86

 For a Buffer solution
[CH3COONa] [CH3COONa]
pH = pKa + log [CH COOH]  5.45 = 4.75 + log [CH COOH]
3 3

[CH3COONa] 5 [CH3COONa]
0.7 = log [CH3COOH]  = [CH COOH]
1 3

[OH – ] [ In  ]
F-7. Kb = ; The colour is provideds when indicator 50% dissociated. Also indicator giving coloured
[ InOH ]
cation in base InOH.
 [OH–] = Kb = 1 × 10–5.
 pOH = 5
 pH = 9.

[H ] [ In ]
F-8. Ka =
[HIn]

[H  ]  80 1
1 × 10–5 =  [H+] = × 10–5
20 4
 pH = 5.6.
G-2. (a) Initially pH will decrease fast, then slowly due to buffer formation and then will decrease fast as buffer
action diminishes.
(b) For a weak electrolyte
C 2
Ka =
(1   )

Ka
when  << 1 then  =
C
as C increases   decreases
as C is tending to zero   will be unity
(c) At 1/4th neutralisation
CH3COOH + NaOH  CH3COONa + H2O

 3  1
 0 .1    0 .1  
 4  4

[CH3 COO  ]  1
pH = pKa + log = pKa + log  
[CH3 COOH] 3
At 3/4th neutralisation
pH = pKa + log 3
1
so difference in pH = (pH) = log 3 – log = 2 log 3
3

G-9. Initial decrement is due to consumption of free OH– ions, then slow decrement in pH is due to basic buffer
solution and minimum slope will be there when there is best buffer action ([salt] / [base] = 1)
H-2. Ksp of Mg (OH)2 = 2.56 × 10–13
4 s 13 = 2.56 × 10–13  s1 = 4 × 10–5 M
Ksp of Al (OH)3 = Ksp = 4.32 × 10–34
27 s24 = 4.32 × 10–34  s2 = 2 × 10–9 M
s1 4  10 –5
s2 = = 2 × 104
2  10 9

RESONANCE Ionic Equilibrium - 87

H-6. Let Ksp of AgCI = x
x
(a) solubility of AgCl in pure water = s1 = x (b) solubility of AgCl in 0.01 M CaCl2 = s2 =
0.02
x x
(c) solubility of AgCl in 0.01 M NaCl = s3 = (d) solubility of AgCl in 0.05 M AgNO3 = s4 =
0.01 0.05
So s1 > s3 > s2 > s4

H-8. Solubility of BaSO4 = K SP =

1.1 10 10 = 1.05 × 10 M
–5

 wt. of BaSO4 = 1.05 × 10–5 × 233 = 244.37 × 10–5 g/litre.

1
 Volume of water needed to dissolve 1g BaSO4 is equal to = 410 litre
244.37  10  5

H-10. Ca3(PO4)2 + 6HCI  CaCI2 + 2H3PO4

soluble

I-2. KSP (Ba CrO4) = 2.4 × 10–10 M2

[CrO4–2] = 6 × 10–4 KSP (BaCrO4) = [Ba+2] [CrO4–2] 2.4 × 10–10
+
 [Ba ] × 6 × 10–4 = 2.4 × 10–10
[Ba+] = 4 × 10–7 M Ans.
I-3. pH = 4  [H+] = 10–4 M  [OH–] = 10–10 M
Al (OH)3 Al+3 + 3 OH–
Ksp (Al (OH)3) = [Al+3] [OH–]3
[Al3+] [OH–]3 = 1 × 10–33
[Al3+] (10–10)3 = 1 × 10–33  [Al+3] = 10–3 M

I-7.  Ag+ + CI–

AgCI   Ag+ + CNS–
AgCNS 
(x + y) x (x + y) y

K SP ( AgCI) x [CI ] [CI ] x 1.8  10 –10

K SP ( AgCNS) = y = So = y =
[CNS  ] [CNS  ] 1.6  10 11
= 1.125 × 10 = 11.25
x
 y = 11.25 x = 11.25

KSP (AgCI) = [Ag+] [CI–] = (x + y) x = 1.8 × 10–10

12.25 y × 11.25 y = 1.8 × 10–10

1.8  10 –10
y2 =
12.25  11.25

180  10 –12
y2 =
12.25  11.25
y2 = 1.3 × 10–12
y = 1.14 × 10–6
x = 11.25 × 1.14 × 10–6 = 12.83 × 10–6
+
[Ag ] = [x + y] = 12.83 × 10 + 1.14 × 10–6 = 13.97 × 10–6 = 1.4 × 10–5 M
–6

K sp 10 –10
I-8.* [Ag+] ion required to precipitate Cl– ion = – = = 2 × 10–9 mol/L.
[Cl ] 0.05
K sp 4  10 –16
—
[Ag+] ion required to precipitate I ion = – = = 8 × 10–15 mol/L.
[I ] 0.05
Since [Ag+] ion conc. required to precipitate AgI is less than the [Ag+] ion conc. required to precipitate AgCl,
AgI precipitates first.
Hence choices (A),(B) and (D) are correct while (C) is incorrect.

RESONANCE Ionic Equilibrium - 88

 K SP 6.9  10 –12
I-10. For precipitation of Ag2CO3. [ CO 32  ] =  2 = = 6.9 × 10–2
[ Ag ] [10 5 ] 2

K SP 8.1 10 –9
and for precipitation of BaCO3. [ CO 32  ] = 2 = = 8.1 × 10–5
[Ba ] 10  4

I-12. (i) Ag+ + NH3 [Ag(NH3)]+ K1 = 3.5 × 10–3 .

(ii) [Ag(NH3)]+ + NH3 [Ag(NH3)2]+ , K2 = 1.8 × 10–3 .
on the basis of above reaction,

[ Ag(NH3 ) ] [ Ag(NH3 ) ]
K1 =  ; K2 = .
[ Ag ] [NH3 ] [ Ag(NH3 ) ] [NH3 ]
For the formation of
Ag+ + 2NH3 [Ag(NH3)2]+
Formation constant
[ Ag(NH3 )2  ]
Kf =
[ Ag ] [NH3 ]2
Kf = K1 × K2 = 3.5 × 10–3 × 1.8 × 10–3 = 6.3 × 10–6 .
I-13.* In AgNO3 solution, the solubility of AgCN will decrease as compared to pure water because of common ion
effect of Ag+ ion.
In NH3 solution and buffer of pH = 5, the solubility of AgCN will increase due to complex formation in case of
NH3 solution and hydrolysis of CN– ions in case of buffer of pH = 5.

I-15.* (a) Zn(OH)2 Zn+2 + 2OH¯

S 2S
(S)1 (2S)2 = 4.1 × 10–17
 4S3 = 4.1 × 10–17  S = 2.172 × 10–6 mol/L
Now [OH¯] = 4.344 × 10–6 M
 pOH = 5.362  pH = 8.64
(b) Zn(OH)2 +2
Zn + 2OH¯ Ksp = 4.1 × 10–17
+2
Zn + 4OH¯ Zn (OH)4 2– Kf = 3 × 1015
Add Zn(OH)2 + 2OH¯ Zn(OH)4 2– K = 0.123
 Kf is v. large almost all the dissolved salt will form the complex.
2
Hence
Zn OH 4
= 0.123 
x
= 0.123 (if x is the solubility)
[OH¯] 2 (0 . 1  x ) 2

i.e. x2 – 8.33 x + 0.01 = 0  x = 1.2 × 10–3 mol/L

PART - II
4. For SrF2 in pure water
4s13 = Ksp
For SrF2 in 0.1 M NaF solution
s2 (0.1)2 = Ksp  4s13 = s2 (0.01)
256
 4s13 = s1 × (0.01)  s1 = 8 × 10–4 M
106
 Ksp = 4s13 = 2.048 × 10–9
5. [Sr2+]i = 0.0011 = 11  10–4 M
[Sr2+]f = 2  10–4 M
 [Sr2+] precipitated = (11 – 2)  10–4 M = 9  10–4 M
[F–] needed for this precipitation = 2  9  10–4 = 18  10–4 M
Also, [Sr2+]f [F–]2f = Ksp = 2.048  10–9
But, [Sr2+]f = 2  10–4 M
 [F–]f = 3.2  10–3 M
 Total [F–] needed = 3.2  10–3 + 18 10–4 = 5  10–3 M

5  10 3  42
 NaF needed for 100 ml solution = = 0.021 g
10
RESONANCE Ionic Equilibrium - 89
6. SrF2  Sr2+ + 2F–
s 2s
F– will react with H+ to produce HF
F – + H+ HF
1 [HF] 7
K= K =  =
10 5

a [H ][F ]
 [HF] = 7  105 [F–] [H+] ( [H+] = 10–5 ; pH=5)
= 7  105 [F–]  10–5 = 7 [F–]
Here [F ] + [HF] = 2s
–

s
 [F–] =
4
2
s
Ksp = s   = 2.048  10–9
4
 s = 3.2  10–3 mol/L

11. (A) [H+] in HCl solution = 10–5 M

[H+] in H2S solution = K a  C = 10–4 M
so [H+] in HCl solution < [H+] in H2S solution
& [OH–] in HCl solution > [OH–] in H2S solution
& degree of dissociation of water in HCl solution > degree of dissociation of water in H2S solution
pH of HCl solution > pH of H2S solution.
(B) At pH = 4.74 in CH3COOH solution, [CH3COO–] = [CH3COOH]
1
 degree of dissociation of CH3COOH =
2
At pH = 9.26 i.e. pOH = 4.74 in NH4OH solution, [NH4+] = [NH4OH]
 degree of dissociation of CH3COOH = degree of dissociation of NH4OH
degree of dissociation of water in CH3COOH solution > degree of dissociation of water in NH4OH solution.
(C) [H+] in CH3COOH solution = 1.8  10 5  0.1 = 1.8 × 10–3 M

[H+] in HCOOH solution = 1.8  10  4  1 = 1.8 × 10–2 M

so, degree of dissociation of CH3COOH = degree dissociation of HCOOH.
(D) [H+] in HA1 solution = 10 5  0.1 = 10–3 M

[H+] in HA2 solution = 10  6  0.01 = 10–4 M

so [OH–] in solution of HA1 < [OH–] in solution of HA2
pH in solution of HA1 < pH in solution of HA2
& degree of dissociation of water HA1 < degree of dissociation of water HA2.

12. (A) H2C2O4 + OH–  HC2O4– + H2 O

m.moles 50 25
25 – 25
Buffer solution pH = pKa1
(B) H2C2O4 + OH–  HC2O4– + H2 O
m.moles 50 50
– – 50
pK a1  pK a2 13
Amphiprotic, pH = = = 6.5.
2 2
(C) H2C2O4 + OH–  HC2O4– + H2 O
m.moles 50 75
– 25 50
HC2O4– + OH–  C2O42– + H2 O
m.moles 50 25
25 – 25
Buffer solution pH = pKa2.

RESONANCE Ionic Equilibrium - 90

 (D) H2C2O4 + OH–  HC2O4– + H2 O
m.moles 50 100
– 50 50
HC2O4– + OH–  C2O42– + H2 O
m.moles 50 50
– – 50
Salt hydrolysis, pH > 7.

EXERCISE # 2
4. H2 O H+ + OH–
t=0 C
teq C (1 – ) C C
1000
So, [H+] = [OH–] = C = × 3.6 × 10–9
18
 pH = 7 – log 2 = 6.7 and Kw = [H+] [OH–] = 4 × 1014

2 . 21
6. (i) [TIOH] = = 5.0 × 10–3 . (mol. wt. TIOH = 221).
221  2
 pOH = log[OH–] = – log 5.0 × 10–3 = 2.3 ;
 pH = 11.7.
0.37  1000
(ii) [Ca(OH)2] = = 0.01 M.
74  500
 [OH–] = 2 × 0.01 M = 0.02 M
 pOH = – log[OH–] = 1.7 ;
 pH = 12.3.
0.32  1000
(iii) [NaOH] = = 0.04 M.
40  200
 [OH–] = 0.04 M ; pOH = 1.4 ;
 pH = 12.6.
1  12
(iv) [HCl] formed = = 12 × 10–3 M. (M1V1 = M2V2)
1000
 [H+] = 12 × 10–3 ; pH = 1.92.
10._ (a) HN3 H+ + N3 –
c 0 0
c [1–]  

c 2 Ka 2  10 5
= Ka  < < 1   = = = 1.4 × 10–3
1–  c 0 .1
[H+] = c= 1.41 × 10–4.
pH = 3.85
pOH = 10.15

2  10 5
(b) = = 0.141 > 0.1
10 3
 cannot be neglected.
c 2
= Ka
1– 
c2 + Ka – Ka = 0

 K a  K a2  4cK a
=
2c
 = 0.13.
[H+] = c = 1.3 × 10–2.

RESONANCE Ionic Equilibrium - 91

 1.725  2 
 
14. C=  1    = 10
–3
138  

 2 
 
12.5 × 10–3  1    = 10–3
 
 = 0.245
[H+] = 12.5 × 10–3 × 0.245 = 3.07 × 10–3
pH = 3 – log 3.07 = 2.52

15. (i) CH3COOH = 0.2 M

[H+] = Ka  C = 2  10 5  0.2 = 4  10 6 = 2 × 10–3
pH = 3 – log 2 = 2.7
2  10 3
C  = [H+]  =   = 0.01
2  10 1
(ii) HCI 
 H+ + CI–
0.1 0.1 0.1
[H+] = 0.1 pH = 1
CH3COOH CH3 COO– + H+
0.2 O 0.1
0.2 (1 – ) 0.2  0.1 + 0.2  = 0.1
0 . 2  0 . 1
Ka = = 2 × 10–5  = 2 × 10–4
0.2
(iii) [CH3COO–] = 0.2 × 2 × 10–4 = 4 × 10–5
1 102  2  10 4 2  100
(iv) % change in  =
1 10 2

× 100 = 1 – 100 
= 98 %

21. C5H5NH+ CI– It is salt of SAWB

1 1 1 1
pH = 7 – pKb – logC  pH = 7 – pKb – log 0.25
2 2 2 2
 pKb = 9.1
Kb = Antilog (– 9.1) = 8 ×10–10

[salt ]
24. (a) We have pH = – logKa + log
[acid]
4.1 60 3
 pH = – log 1.8 × 10–5 + log = 4.74 + log = 4.62
82  4 4

[salt]
(b) pOH = – logKb + log
[base]
2 .5
 pOH = – log 1.8 × 10–5 + log = 4.74 + log 5 = 5.43
0 .5
 pH = 14 – pOH = 8.57
[Salt] 0 .4 8
(c) pH = – log Ka + log = – log 1.8 × 10–4 + log = 4.74 + log = 4.94
[Base] 0.25 5

 50  C  50  C
25. pH = pKa+ log    4 = 5 + log
 50  0.2  50  0.2

C C
 log = –1  = 0.1  C = 0.02 M
0 .2 0 .2

RESONANCE Ionic Equilibrium - 92

26. NaCN + HCI   HCN + NaCI
0.01 x mole 0 0
(0.01–x) 0 x mole –
 0.01 – x  0.01 – x
pH = pKa + log    8.5 = 9.4 + log
 x  x

 x  x
 log   = 0.9  =8  x = 8.9 × 10–3 mole
 0 . 01 – x  0.01 – x

0 .1
28. pOH = 4.74 + log = 4.74
0 .1
 pH = 9.26
(a) NH4+ + OH–   NH3 + H2O
t=0 0.1mole 0.05 mole 0.1 mole
0.05 mole – 0.15 mole
0.05
pOH = 4.74 + log = 4.26
0.15
 pH = 9.74
(b) NH3 + H+   NH4+
t=0 0.1 mole 0.05 mole 0.1 mole
0.05 mole – 0.15 mole
0.15
pOH = 4.74 + log = 5.22
0.05
 pH = 8.78

29. A buffer solution show best buffering action when the pH of solution is near to Ka of acid component of buffer
solution
There for the above buffer can be best prepared by taking H2PO4– and H PO42–

[HPO 4 2  ]
(a) pH = pKa2 + log =7
[H2PO 4 – ]

[HPO 4 2 ] [HPO 4 2 ]
 log = – 0.22  = 0.6
[H2PO 4 – ] [H2PO 4 – ]
(b) In 50 ml buffer solution
[H2PO4–] = 0.1 M = 5 milimole, [HPO42–] = 0.06 = 3 milimole
milimole of NaOH added = 20 × 0.01 = 2
H2PO4– + OH– 
 HPO42– + H2 O
5 2 3 0
3 0 5 0
5
pH = pKa2 + log  3  = 7.44.
 

30. Kb (NH3) = 1.8 × 10–5

CH3COOCH3 (aq) + 2H2O (aq)  CH3COO–(aq) + H3O+ (aq) + CH3OH(aq)
[NH4+]0 = 0.1 M, [NH3] = 0.06 M, [CH3COOCH3]0 = 0.02 M
[NH4 ]  0 .1 
pOH = pKb + log = 4.74 + log  0.06 
[NH3 ]  
(pOH)initial = 4.74 + 0.22 = 4.96  (pH)initial = 9.04
NH3 (aq) + H+ (aq)  NH4+ (aq)
0.06 0.02 0.1 mole
0.04 – 0.12 mole

RESONANCE Ionic Equilibrium - 93

 0.12  0.12 
(pOH)final = 4.74 + log = 4.74 + log   = 4.74 + log 3 = 4.74 + 0.48 = 5.22
0.04  0.04 
 (pH)final = 8.78
pH = 9.04 – 8.78 = 0.26
Yes this is satisfactory buffer.

33. For this indicator, pH = pKIn = 2

Now, at [H+] = 4 × 10–3 M,

( 4  10 3 ) [In – ] [HIn]
KIn =  = 0.4
[HIn] [In – ]

[HIn] 0 .4
 % of HIn = – × 100 = × 100 = 28.57 %.
[In ]  [HIn] 1.4

37. NH4OH + HCI 

 NH4CI + H2O
Milimole 2.25 2.25 2.25
at mid point
2.25
Milimole = N1 × VHCI = 2.25 VHCI = = 22.5
0 .1
 2.25 
[NH4CI] =  37.5  = 0.06M and pKb = 5 – log 1.8 = 4.74
 

1 1 4.74 1
 pH = 7 – pKb – log C = 7 – – log 0.06 = 5.24
2 2 2 2

38. HCOOH + OH–   HCOO– + H2 O

t=0 20 mmol 10 mmol
10 0 10
pH = pKa = 3.7
 20  1
At end point [HCOONa] =  40  = M
  2

1 1 3 .7 1
pH = 7 + pKa + log1/2 =7+ – × 0.30 = 8.7
2 2 2 2

40. (a) At eq. point

No. of milieq. of Base = No. of milieq. of HCI
0.252  1000
= 0.14 × 40
Molarmass
 Molar mass of base = 45
(b) BOH + HCI   BCI + H2O
t=0 5.6 0.14 × 20
5.6 2.8 0 0
2.8 0 2.8
Basic buffer
pH = 10.7 So pOH = 3.3
pOH = pKb = 3.3
Kb = Anti log (– 3.3) = Anti log (1 – 0.3) × 10–4 = 5 × 10–4
44. Let V ml of each is mixed.
0.002  V 0.002  V
[Cu+2] = 2V = 0.001 and [IO3–] = 2V = 0.001
Ksp = (0.001) ( 0.001)2 = 10–3 × 10–6 = 10–9
KIP < Ksp  NO PPT formation

RESONANCE Ionic Equilibrium - 94

45. FeSO4 + Na2S  FeS + Na2SO4
a a
a  a 
KSP =  2   2  = 6.25 × 10–18
   
a2 = 4 × 6.25 × 10–18 = 4 × 625 × 10–20
a = 2 × 25 × 10–10 = 5 × 10–9 M.

46. Ca F2 Ca+2 + 2F–

Let Solubility is s mole/lit
CaF2 Ca+2 + 2F–
s 2s
The F– react with H+ to produce HF
F – + H+ HF
1 [HF] [F  ] [H ] [F  ] [H  ]
K1 = K =    [HF] = =
a [F ] [H ] Ka 3.45  10  4
[HF] = 2.9 × 103 [F–] [H+]
(A) at pH = 7 [HF] = 2.9 × 10–4 [F–]
But the solution contain [HF + F–] = 2 [Ca+2]
[2.9 × 10–4 + 1] [F–] = 2s [F–] = 2s
3
Ksp = 4s = 0.4 × 10 –11 s = (10 × 10–12)1/3 = 2.15 × 10–4
(b) At pH = s
[HF] = 2.9 × 103 [F–] × 10–5 = 2.9 × 10–2 [F–]
[F ] + HF = 2s
–  [F–] + 0.029 [F] = 2s
 1 
[F] [1.029] = 2s  [F–] =   × 2s
 1.029 
2
 1 
Ksp = 4 s3   = 4 × 10–111  s3 = (1.29)2 × 10–11
 1.029 
1
s = (10.6  10 12 ) 3 = 2.2 × 10–4

48. concentration of H2S = 0.1 M concentration of MBr2 = 0.05 M

So concentration of M+2 = 0.05 Ksp of (MS) = [M+2] [S–2] = 6 × 10–21
100  6  10 21
[S2-] = = 120 × 10–21 = 1.2 × 10–19 M
5
Precipitation of MS will start when H2S provide 1.2 × 10–19 M ion of S–2
[H ] 2 [S 2 ]
+
For H2S H2 S 2H +S –2
K = K1. K2 =
[H2 S]
[H ] 2  1.2  10 19
10–7 × 1.2 × 10–13 = [H+]2 = 10–2
0.1
So [H+] = 0.1M  pH = 1
49. (1) [NaI] = 0.1 M
NaI   Na+ + I–
0.1 M 0.1 M 0.1 M
(2) Na2SO4   2Na+ + SO4–2
0.1 0.2 0.1
For precipitation of PbI2
Ksp (PbI2) = [Pb+2] [I–]2 = 9 × 10–9  [Pb+2] × (0.1)2 = 9 × 10–9
 [Pb+2] = 9 × 10–7
For Precipitation of PbSO4
Ksp (PbSO4) = [Pb+2] [SO4–2] = 1.8 × 10–8  [Pb+2] × 0.1 = 1.8 × 10–8
 [Pb+2] = 1.8 × 10–7
+2
For Preci pitation of PbSO4 required conc. of Pb is less So PbSO4 is Precipitate first.

RESONANCE Ionic Equilibrium - 95

 where PbI2 (more soluble compound) start precipiting conc of [Pb2+] = 9 × 10–7
conc. of anion of less soluble salt
Ksp (PbSO4) = [Pb+2] [SO4–2] = 1.8 × 10–8 = (9 × 10–7) [SO4–2] = 1.8 × 10–8
[SO4–2] = 0.02 M

50. Let solubility of CaC2O4 is s mole/lit

CaC2O4 (s) Ca+2 (aq) + C2O42– (aq)
s s
C2O42– react with H+ to produce HC2O4– & H2C2O4
1
H+ + C2O42– HC2O4– K'1 =
K2

1 [HC2O 4 ] [H ] [C 2O 24 ]

K 2 = [H ] [C2O 24 ]  [HC2O4–] =
K2
Again this HC2O4– react with H+ as.
1
HC2O4– + H+ H2C2O4 K1' = K
1

1 [H2C 2O 4 ] [HC 2O 4 ] [H ]

K 1 = [HC 2 O 4 ] [H  ]  [H2C2O4] =
K1

[H ] 2 [C 2O 24 ]
Puting the value of [HC2O4–]  [H2C2O4] =
K1 K 2
Now [C2O42–] + [HC2O4–] + [H2C2O4] = s
 [H  ]  [H  ] 2   10 4 10 8 
[C2O4 ] 1  K
2–  
K 1 K 2  = s ; [C2O4 ]2–
 1  5
  =s
 2  5  10 25  10 7 

s
[C2O42–] =    Ksp = [Ca+2] [C2O42–] = 2.7 × 10–9
3

s2
= 2.7 × 10–9  s = 9 × 10–5 M
3

52. Kd [(Ag (CN)2 )– ] = 1 × 10–21 Kf [Ag (CN)2–] = 1 × 1021

Inital [Ag+]i = 9 × 10–4 M [Ag+]f = 1 × 10–19 M
Almost all Ag+ get precipitated,
Ag+ + 2CN– [Ag (CN)2]–
t=0 9 × 10 –4
b o
t = teq 1. 0 × 10–19 (b – 18 × 10–4) 9 × 10–4
9  10 4
Kf = = 1 × 1021
(1 10 19 ) (b  18  10  4 )2
 b = 4.8 × 10–3
So Amount of CN– added = 4.8 × 10–3 mole

54. Given, AgI(s) Ag(aq) + I(aq ) ,

KSP = [Ag+] [I–] = 1.2 × 10–17 .........(1)
Ag(aq) + 2CN(aq ) [Ag(CN)2] (aq) ;

[ Ag(CN) 2 ]
Kf = = 7.1 × 1019 .........(2)
[ Ag  ][CN  ] 2

RESONANCE Ionic Equilibrium - 96

 Let x mole of AgI be dissolved in CN– solution then,
Now AgI(s) + 2CN– [Ag(CN) 2 ] + I–
mole before reaction I 0 0
mole after reaction (1–2x) x x
By Eqs. (1) and (2), Keq = KSP × Kf
[ Ag(CN) 2 ][I ]
= = 1.2 × 10–17 × 7.1 × 1019
[CN  ] 2
Keq = 8.52 × 102 .......(3)
2
x.x x x2
 Keq = 8.52 × 102 = 2 = or = 29.2
(1 – 2x ) (1  2 x ) 2 1  2x
Thus, x = 29.2 – 52.4x or x = 0.49 mole

EXERCISE # 3
1. (A) ApBq(s) pA+q + qB–p
pS qS
LS = (pS)p. (qS)q = pp.qq.S(p+q)

2. (a) CH3COOH CH3COO– + H+ .

conc. 0.1 (1-) 0.1 (0.1+ 0.1)
approximations
Let 1-  1
and 1+  1
[CH3COO  ] [H ]
Ka 
[CH3COOH]

[CH3COO – ]  0.1
or 1.75 × 10–5 = .
0 .1
or [CH3COO–] = 1.75 × 10–5 . ; or C = 1.75 × 10–5 .
or 0.1  = 1.75 × 10–5. ; or  = 1.75 × 10–4 .
or = 0.0175%.
or pH = – log[H+] = – log(0.1). ; or pH = 1.

(b) HCl + NaOH  NaCl + H2O.

m mole before reaction 100 150
m mole after reaction 0 50 100

CH3COOH + NaOH  CH3COONa + H2O

m molebefore reaction 100 50
m mole after reaction 50 0 50 (buffer sol.)
[CH3COO – ]
pH = pKa + log = – log (1.75 × 10–5) = 4.757 Ans.
[CH3COOH]

3. Solution is acidic in nature but not a buffer solution.

4. HSO4– – can accept and donate a proton. HSO4– + H+  H2SO4 ; HSO4–  H+ + SO 24

5. Mg(OH)2 Mg2+ 2OH– Ksp = [Mg2+] [OH–]2 Ksp = s (2s)2 = 4s3.

6. At 25°C, Ionic product of water (Kw)

= 1 × 10–14, So pKw = 14
 [H+] × [OH–] = 1 × 10–14
or – log [H+] – log [OH–] = 14
pH + pOH = 14
It is neutral compound, so in it pH = pOH = 7 at 25°C. On decreasing the temperature, Kw decrases, so pKw
increases. Hence at 4°C pKw is higher than 25°C and at higher pKw, pH will be higher i.e, at 4°C pH of water
is higher than 7.

RESONANCE Ionic Equilibrium - 97

7. Lesser the Ksp, more is the precipitation.

8. AB2 A2+ + 2B– s = 1.0 × 10–5 mol L–1

2+ – 2 –5 2
Ksp = [A ] [B ] = 1.0 × 10 × (2.0 × 10 ) = 4.0 × 10–15
–5

9. We know for acids, pH must be less than 7.

10. When rain is accompanied by a thunderstorm,
HO
N2 + O2  NO  NO2 2 HNO2 + HNO3
11. NaX + H2O NaOH + HX
In it HX is weak acid, so NaX is a salt of weak acid and strong base.
Kw 1 10 14
 Hydrolysis constant of NaX is Kh = = = 1 × 10–9
Ka 10 5
For this type of salt Kh = Ch2
C = molar concentration
h = degree of hydrolysis
 1 × 10–9 = 0.1 × h2
1 10 9
or h2 = = 1 × 10–8 h = 1 × 10–4
0 .1
 percentage hydrolysis of NaX salt = 1 × 10–4 × 100 = 1 × 10–2 = 0.01 %

12. HA + OH–  A– + H2 O

0.1 V 0.1 V m. moles
– – 0.1 V
0 .1 V 0 .1
[A–] = 2 V = M,
2

1 1 1  0. 1 
pH = 7 + (pKa + log c) = 7 + (6 – log 5.6) + log  2   9
2 2 2  

13. Congugate base is formed by the removal of H’ from acid

H2PO 4  HPO24  H

14. MX4 (solid) M 4  ( aq )  4 X  ( aq ) Solubility product, Ksp = s × (4s)4 = 256 s5

1/ 5
 K ps 
 s =  

 256 

15. CH3NH2 + HCI  CH3 NH3 + CI– .
Initial moles 0.1 0.08
moles after reaction 0.02 0 0.08 mole in 1 lt
[OH– ] [CH3NH3 ]
Kb =
[CH3NH2 ]

[OH– ]  0.08 5
or, 5 × 10–4 = or, [OH–] = × 10–4 .
0.02 4

Kw 10 14  4
 [H+] = or, [H+] = = 8 × 10 – 111 M.
[OH– ] 5  10 – 4

16. Conjugate base of OH– OH– O2– +H+

17. MX2(s) M2+ (aq) + 2X– (aq)

Ksp = s . (2s)2 = 4s3  4 × 10–12 = 4s3  s3 = 1 × 10–12
 s = 1 × 10 M 
–4
[M2+] = 1 × 10–4 M

18. pH = – log[H+]  [H+] = antilog (–pH) = antilog (–5. 4) = 3.98 × 10–6

RESONANCE Ionic Equilibrium - 98

 [H ] [HA  ]
19. H2 A H+ + HA– ; K1 = = 1 × 10–5
[H2 A ]
[H ] [H2 ]
HA– H+ + A2– ; K2 = 5 × 10–10 =
[HA  ]
[H ]2 [H2 ]
K= = K1 × K2 = 1 × 10–5 × 5 × 10–15
[H2 A ]

20. For acidic buffer, pH = pKa +

A 


HA 
when the acid is 50% ionised, [A–] = [HA] or pH = pKa + log 1 or pH = pKa
given pKa = 4.5  pH = 4.5  pOH = 14 – 4.5 = 9.5.

21. AgIO3(s) Ag+(aq) + O–3(aq) [s = Solubility]

Ksp = s2
or s = 1.0 × 10–4 mol/lit = 1.0 × 10–4 × 283 g/lt = 2.83 × 10–3 gm/100 ml.

22. BOH + HCl  BCl + H2O (in titration)

B+ + H2O BOH + H+
For titration
Nacid Vacid = Nbase Vbase
2 2
x V = 2.5 x
15 5
V = 3 x 2.5 = 7.5 mL
In resulting solution
2
x 2.5
5 2
[B+] = = = 0.1
10 20

Kw 10 14
Kh = K = = 10–2
b 10 12

0 .1 h 2
or Kh = = 10–2 (solve quadratic equation to get 'h', as we can't write 1 – h  1 since h is > 0.1)
(1  h)
or h = 0.27
[H+] = 0.1 × 0.27 = 2.7 × 10–2

23. MX MX2 M3X

s12 = 4 x 10–8 4s23 = 3.2 x 10–14 27s34 = 2.7 x 10–15
s1 = 2 x 10–4 s23 = 8 x 10–15 s34 = 10–16
s2 = 2 x 10–5 s3 = 10–4
 s1 > s3 > s2
 MX > M3X > MX2

1 1 4.8 4.78
24. pH = 7 + pKa – pKb = 7 + – = 7.01
2 2 2 2

25. Given Ka = 10–4

pKa = 4
C = 0.01 M
1 1 1 1
pH = 7 + pKa + log C = 7 + (4) + (–2) = 8 Ans.
2 2 2 2

RESONANCE Ionic Equilibrium - 99

26. Na2CO3  2Na+ + CO32–
1 × 10 M
–4
1 × 10 M 1 × 10–4 M
–4

+2 2–
Ksp[BaCO3] = [Ba ] [CO3 ]
5.1 × 10–9 = [Ba+2] × 1 × 10–4
[Ba+2] = 5.1 × 10–5M

27.* (C) HNO3 + CH3COONa mixture can act as buffer solution if volume of HNO3 solution taken is lesser than
volume of CH3COONa solution because of following reaction :
CH3COONa + HNO3  CH3COOH + NaNO3
(D) CH3COOH + CH3COONa - mixture will act as buffer.

28. Basic solutions will convert red litmus blue.

, their aqueous solution will be basic due to anionic hydrolysis.

29. In IInd equation H2PO4– give H+ ion to the H2O therefore in the IInd equation it act as an acid.

30. H2CO3 H+ + HCO3– K1 = 4.2 × 10–7

+ 2–
HCO3 –
H + CO3 K2 = 4.8 × 10–11
K1 >> K2
 [H+] = [HCO3–]
[H ][CO 23  ]
K2 =
[HCO 3 ]
but [H+] = [HCO3–]
[CO32–] = K2 = 4.8 × 10–11

31. Ksp = [Ag+] [Br–] = 5.0 × 10–13

[Ag+] = 0.05 M
[0.05] [Br–] = 5.0 × 10–13
5.0  10 13
[Br–] = = 1 × 10–111 M
0.05
moles of KBr = M × V = 1 × 10–11 × 1 = 1 × 10–11
weight of KBr = 1 × 10–11 × 120 = 1.2 × 10–9 g

32. KSP = 1.0 × 10–11 = (Mg+2) (OH–)2

1.0 × 10–11 = (0.001) (OH–)2
(OH–) = 10–4
POH = 4
PH = 14 – 4 = 10.

33. AgCl (s) Ag+ + Cl– Ksp(AgCl) = 1.6 × 10–10

Z Z+Y
CuCl (s) Cu+ + Cl– Ksp(CuCl) = 10–6
Y Z+Y
Z (Z + Y) = 1.6 × 10–10
Y (Z + Y) = 10–6
 (Z + Y)2 = 1.6 × 10–10 + 10–6  (Z + Y)2  10–6
 Z + Y = 10–3  Z (Z + Y) = 1.6 × 10–10
 Z × 10–3 = 1.6 × 10–10  Z = 1.6 × 10–7
 1.6 × 10–x = 1.6 × 10–7
 x=7

34. O2– (base) + H2O (acid)  OH– (C.B) + OH– (C.A.)
O2– acts as Lewis base.

RESONANCE Ionic Equilibrium - 100

 SOLUTION OF ADVANCED LEVEL PROBLEM
1. C6H5OH  C5H5N C6H5O– + C5H5NH+
K aK b
Kn = K = 2.34 × 10–5
w
Kn being small and thus neutralisation does not proceed very far towards completion.

2. Since [H+] = K w , therefore

1
pH = – log [H+] = – log KW
2
Thus, the calculated values of pH at the given tempratures are as follows.
Temprature pH
1
0ºC – log (0.114 × 10–14) = 7.472
2
1
10ºC – log (0.292 × 10–14) = 7.267
2
1
25ºC – log (1.008 × 10–14) = 7.002
2
1
40ºC – log (2.919 × 10–14) = 6.767
2
1
50ºC – log (5.474 × 10–14) = 6.631
2

3. For a solution to have twice alkalinity, we have

[OH–] = 2.0 × 10–7 M
Thus, pOH = – log {[OH–]/M} = – log (2.0 × 10–7) = 7 – 0.301 = 6.699
and hence pH = 14 – pOH = 7.301
4. (a) meq. of H+ = 10 × 0.1 + 40 × 0.2 × 2 = 17.
17
[H+] = = 0.34.
50
pH = 0.47
10 – 9.9 0.1
(b) [H+] = = = 9.1 × 10–4
109.9 109 .9
pH = 4.0 – log 9.1 = 3.04

(c) pV = nRT
(740 – 23.7 ) 1
n= × 100 × × 10–3 = 3.85 × 10–3 M
760 0.0821  298
[HCl] = 3.85 × 10–3 M = [H+].
pH = 3 – log3.85 = 2.41

(d) pH of Final Solution = 1

pH = 1
[H+] = 10–1
P  d  10 36.5  10  1.25
Initial  M = = M = 12.5
M.W. 36.5
N1V1 = N2V2  12.5 × V1 = 10–1 × 2.5
2 .5
V1 = V1 = .02 lit = 20 ml
125

5. (a) HA H+ + A–
c(1 – ) c c

[A ] c
pH = pKa + log = pKa + log c (1   )
[HA ]
RESONANCE Ionic Equilibrium - 101
     1  
 pH = pKa + log   = pK – log  
 1    a
  

 1    1   1
 log 
  
 = pK – pH.
a
 
  
 =
10(pK a pH)  =
1  10 ( pK a pH)

(b) HA H+ + A—
Cº – x x+y x
+
H2 O H + OH–
x+y y

[H  ] x
Ka = , [H+] y = 10–14 = Kw Where [H+] = x + y.
c0 – x

KW K ac 0
y= ,x= .

[H ] K a  [H  ]

KW K ac 0
[H+] = x + y = + .
[H ] 
K a  [H  ]

0 .1 K a
10–3 = 10–11 +
K a  10 – 3
Ka + 10–3 = 100 Ka
10 3
Ka=  10–5 .
99
(c) HA + H2O H3+O + A–

[H3 O  ][ A – ] C 2 2
Ka = =
[HA ] C(1 –  )
with in an error of 10% C(1 – ) or C – C = 0.90 C.
or C = 0.10 C.
(0.10C)2 C
Ka = = or C = 90 Ka.
0.90C 90

6. (CH3)2NH2 + H2O (CH3)2NH3+ + OH–

base acid
[(CH3 )2 NH3 ][OH – ] c.c c 2
Kb = = =
[(CH3 )2 NH2 ] c (1 –  ) (1 –  )
5.4 × 10–4 = 0.02 × 2 .
  = 0.164.
c 2 0.02   2
Since  > 0.1, we will use Kb = or 5.4 × 10–4 =
(1 –  ) (1 –  )
Now  = 0.151
In presence of NaOH, the dissociation of diethylamine will decrease due to common ion effect. Thus 0.1 + ca
= 0.1 + c ~
 and 0.1 & (1 –) ~
1
c  (0.1  c )
Thus Kb = 5.4 × 10–4 = =  × 0.1.
c(1 –  )
or  = 5.4 × 10–3 = 0.0054.

7. CH3COOH CH3COO– + H+
1 0 0
1–  
(pKa = – logKa = 4.74,  Ka = 1.82 × 10–5)

RESONANCE Ionic Equilibrium - 102

 c 2
Ka = = c2 (1 –  1).
(1 –  )

Ka 1.82  10 –5
 = = = 0.019 or 1.9%.
c 0.05
Always calculate a first by Kb = c2, if  > 10% then use again.
c 2
K=
(1 –  )
(a) If H+ are already present (due to HCl)
CH3COOH CH3COO– + H+
1 0 0.01
c(1 – ) c c
[CH3 COO – ][H  ] c  (0.01  c )
Kb = =
[CH3 COOH] c(1 –  )
Since prsence of H+ will favour the reverse reaction or  will decrease.
i.e., 0.01 + c = 0.01 and 1–=1 (due to common ion effect).
0.05    0.01
 1.82 × 10–5 = .
0.05
  = 1.82 × 10–3 = 0.0018.
(b) Similarly solve for 0.1 M HCl
 = 0.00018.

C 2
8. Ka =
1 
40 2 +  – 1 = 0
 = 0.146
[H+] = C = 1.75 × 10–3 M
pH = 2.76

9. HA H+ + A—
c–x x x
[H+] = x = 1.5 × 10–3 M
x2
Ka =
c–x
1.5  10 –3 )2
2.5 × 10–3 = .
c – 1.5  10 – 3
c = 2.4 × 10–3 M.

10. B2H6 + 6H2O  2H3BO3 + 6H2 .

1 1000
concentration H3BO3 = c = 2 × × = 0.725
27.6 100

HA H+ + A—

[H+] = K ac = 7.3  10 10  0.725 = 2.3 × 10 .

–5

pH = – log[H+] = 4.64.
11. Ka = c2 = 0.1 × (0.01)2 = 10–5.
HA H+ + A—.
0.1(1 –) 0.1  0.1+ 0.2 .
0.1  (0.1  0.2)
10–5 =
0 .1
 = 5 × 10–5
(Therefore, 0.1 is neglected).

RESONANCE Ionic Equilibrium - 103

12. HSac H+ + Sac–
0.002  10 3
10–2 0
250
8 × 10–3 10–2 0
8 × 10 (1 – ) 10–2
–3 8 × 10–3 

10 2 [8  10 3  ]
Ka = = 2 ×10–12   = 2 × 10–10
8  10  3 (1   )
[Sac–] = 8 × 10–3 × 2 × 10–10 = 16 ×10–13 = 1.6 × 10–12 M

13. C6H5OH (Phenol)   Weak acid Ka = 1 × 10–10

C6H5OH C6H5O– + H+
C 0 0
C–C C C
Ka = C  2 = 1 × 10–10

1 10 –10
= = 20  10 10  = 4.47 × 10–5
0.05
[C6H5O–] = 4.47 × 10–5 × 0.05 = 2.42 × 10–6
[C6H5ONa] = 0.01 M
C6H5ONa 
 C6H5O– + Na+
0.01 0.01 0.01
C6H5OH 
 C6 H5 O – + H+
0.05 0.01 O
0.05 (1 – ) 0.01 0.05 
[0.05 ] 0.01
= 1 × 10–10  = 10–8
0.05

14. [H+] = (3  108  106 )  (2  109  105 )  10 14

= 6  107 = 2.44 × 10 M
–7

for HA, [H+] = [A–] = 3 × 10–3 M

[H ] [B ]
for HB, Ka = 10–10 =
[HB]
 [B–] = 3.33 × 10–9 M

15. [H+] = (0.1 2.4  10 4 )  (0.1 4  10  4 ) = 8 × 10 M

–3

[H ] [HCOO  ]
for HCOOH, Ka = 2.4 × 10–4 =
[HCOOH]
 [HCOO¯] = 3 × 10–3 M
[H ] [OCN ]
for HOCN, Ka = 4 × 10–4 =
[HOCN]
 [OCN¯] = 5 × 10–3 M
16. HCI  H+ + CI–
0.01 0.01 0.01
CHCI2COOH CHCI2COO– + H+
0.01 0 0.01
0.01 (1 – ) 0.01  0.01 + 0.01 
0.01 [0.01  0.01 ]
Ka = 0.01(1   ) = 2 × 10–2
0.01 2 + 0.01  = 2 × 10–2
10–2 2 + 10–2  = 2 × 10–2
2 +  – 2 = 0

RESONANCE Ionic Equilibrium - 104

  2  1 8 2  3
= 2 = 2   = 0.56
[H+] = 10–2 + 10–2 × 0.56 1.56 × 10–2 M
[CHCl2COO–] = 0.01  = 5.6 × 10–3 M

17. Dissociation of H2S can be represented as

(a) H2S H+ + HS–
(b) HS– H+ + S2–

[H ][HS 1 ]
From the first ionisation of H2S = = Ka1
[H2S]
Since H2S is weakly ionised and its ionisation is further decreased in presence of highly ionised HCl,
concentration of H+ in solution will be mainly due to HCl. Thus [H+] = 0.2 M.
Substituting the value in the above reaction

0.2 [HS  ]
= 1 × 10–7 ; [HS–] = 5 ×10–8 M
0 .1
From the second ionisation of H2S,

[H ][S2 – ] 0.2  [S 2 ]

= Ka2 or = 1.3 ×10–13
[HS ] 5  10 8
[S2–] = 3.25 ×10–20 M

18. H3PO4 H2PO4— + H+ .

0.1 – x x–y x+y+z.
H2PO4– HPO42– + H+ .
x–y y–z y + x + z.
HPO42– PO42– + H+.
y–z z x + y + z.
( x – y ) ( x  y  z) x2
Ka1 = = (y + z are very small compared to x)
0 .1 – x 0 .1  x

x2
7.5 × 10–3 =  x = 0.024 M
0.1 – x

( y – z) ( x  y  z ) y.x
Ka2 = x–y = =y  y = 6.2 × 10–8 (here z < < y)
x
z( x  y  z ) z.x y
Ka3 = y–z = y  z = Ka3 . . = 9.3 × 10–19 M
x
 [H3PO4] = 0.1 – x = 0.076 M
[H+] = [H2PO4–] = x = 0.024 M
[HPO42–] = 6.2 × 10–8 M
[PO43–] = z = 9.3 × 10–19 M
Kw
[OH–] = = 4.17 × 10–13 M
[H ]
wt. of NH3 10
19. Given, =
wt. of solution 100
 100 g dsolution contains 10 g NH3
 MNH = (10 × 1000) / [17 × (100/0.99)] ( V = mass / density)
3
Now NH3 + H2O  NH4OH NH4+ + OH–
Before dissociation 1 0 0
After dissociation (1–)  
 [OH–] = C. = C (K b / C) = (K b .C )
[ C = 5.82 M and Kb = kw / Ka = 10–14 / (5 × 10–10) = 2 × 10–5]

RESONANCE Ionic Equilibrium - 105

  [OH–] = [2  10 5  5.82] = 1.07 × 10–2 M
 [H+] = 10–14/1.07 × 10–2
= 0.9268 × 10–12 M
+
 pH = – log [H ] = – log 0.9268 × 10–12 = 12.0330

20. NO2– + H2O HNO2 + OH–

c(1 – h) ch ch where h is degree of hydrolysis
[OH–] = ch ;

Kh Kw 10 14
Also; h= = K a .c = = 2.36 × 10–5
c 4.5  10  4  0.04
 [OH–] = 0.04 × 2.36 × 10–5 or pOH = 6.025
 pH = 14 – pOH = 7.975
21. Asc– + H2O HAsc + OH–

Kh Kw 10 14  0.02
 [OH–] = C.h = C = Kh .C = .C = = 2 × 10–6
C Ka 5  105

1 10 14
 [H+] = = 5 × 10–9 M
2  10  6

 Kh  Kw 1014
Also h= C = Ka  C = = 10–4 or 0.01 %
  5  10 5  0.02

22. pH of (Na2C2O4) C = 0.5 × 10–3

1 1
pH = 7 + pKa2 + log C Here pKa2 = [6 – log 5]
2 2
1 1 1 1
pH = 7 + [6 – log 5] + [log 5 × 10–4] = 7 + [6 – log 5] + [log 5 – 4] = 8
2 2 2 2
[H+] = 10–8 So [OH–] = 10–6 M

23. AlCI3 C = 0.15 M (AlCI3 is SAWB)

[A (H2O)6]3+ + H2O() [A(H2O)5 OH]2+(aq) + H3O+(aq) Ka = 1.5 × 10–5
At t = 0 0.15 – O O
At t = teq 0.15 (1– ) 0.15  0.15 
0.15   0.15 
Ka = 0.15 [1   ] = 1.5 × 10
–5

 1.5 × 10–1 2 = 1.5 × 10–5  2 = 10–4   = 10–2

+
[H3O ] = 0.15 × 10 = 1.5 × 10 M
–2 –3

 pH = 3 – log 1.5 = 3 – 0.18 = 2.82

24. (a) Let V mL of NH4OH be mixed with NH4Cl to have a buffer of pH 8.65.
The total volume after mixing becomes (V + 30) mL.
0.3  V
m mole of NH4OH = 0.3 × V  [NH4OH] =
( V  30)

0.2  30
m mole of NH4Cl = 0.2 × 30  [NH4Cl] =
( V  30)
Also pOH of buffer mixture is given by :
[Salt]
pOH = pKb + log .
[Base]

(0.2  30) /( V  30)

or 14 – 8.65 = 4.74 + log . (pOH = 14 – pH).
(0.3  V ) /( V  30)
RESONANCE Ionic Equilibrium - 106
 6
0.6 = log 0.3 V .

 V = 5 mL.
 0.2  30 /( V1  30 ) 
Similarly calculate 14 – 10  4.74  log 
 0.3  V1 /( V1  30 )  for pH = 10 ;
V = 111.11 mL.
(b) HA H+ + A–
t=0 0.2 0.1
teq. 0.2 – x x 0.1 + x

[H ] [ A  ] x (0.1  x )
Ka = = ( 0 .2  x )
[HA ]

x 2  0 .1 x
 0.05 =
0 .2  x
 0.01 – 0.05 x = x2 + 0.1 x
x2 + 0.15 x – 0.01 = 0
x = 0.05 M
(c) Let V mL of 0.1 M HCOONa be mixed to 50 mL of 0.05 M HCOOH.
0.1 V
 In mixture [HCOONa] =
( V  50)

50  0.05
[HCOOH] =
V  50
[Salt]
 pH = – log Ka + log
[ Acid]

(0.1 V ) /( V  50)
 4.0 = 3.7 + log
2.5 /( V  50)
 V = 50 mL
(d) NaCN + HCI is not a buffer but if HCI is in less amount then, it gives a buffer as it produces HCN.
NaCN + HCI  NaCI + HCN
Mole added 0.01 a 0 0
Mole after reaction (0.01 – a) 0 a a
This is buffer ofHCN + NaCN
Let a mole of HCI be used for this purpose
0.01  a
 pH = – log Ka + log
a
0.01  a
8.5 = – log (4 × 10–10) + log
a
 a = 8.89 × 10 mole of HCI
–3

(e) We know,
[Salt]
pOH = – log Kb + log
[Base]
a
5 = 4.7 + log
b
a
=2  a = 2b
b
Given a + b = 0.6
2b + b = 0.6
 3b = 0.6
or b = 0.2 mole or 0.2 × 17 = 3.4 g/L
 a = 0.4 mole or 0.4 × 53.5 = 21.4 g/L
Thus, [Salt] = 0.4 M and [Base] = 0.2 M
RESONANCE Ionic Equilibrium - 107
25. (a) initial pH of solution when,
0.1 0.1
[NH3] = and [NH4CI] =
1 1
[Salt] 0 .1
pOH = – log 1.8 × 10–5 + log = – log 1.8 × 10–5 + log = 4.74
[Base] 0 .1
 pH = 9.26

(i) Now 0.02 mole of HCI are added then

HCI + NH4OH  NH4CI + H2O
Mole before reaction 0.02 0.1 0.1
Mole after reaction 0 0.08 (0.1 + 0.02)
 Volume = 1 litre
0.08 0.12
 [NH4OH] = and [NH4CI] =
1 1
0.12
 pOH1 = – log 1.8 × 10–5 + log = 4.92
0.08
 pH1 = 9.08
Change in pH = pH – pH1 = 9.26 – 9.08 = + 0.18
 Change in pH = 0.18 and pH decreases
(ii) Now 0.02 mole of NaOH are added
NaOH + NH4CI  NaCI + NH4OH
Mole before reaction 0.02 0.1 0 0.1
Mole after reaction 0 0.08 0.02 0.12
0.08
 pOH2 = – log 1.8 × 10–5 + log = 4.57
0.12
 pH2 = 9.43
Change in pH = pH – pH2 = 9.26 – 9.43 = – 0.18
 Change in pH = 0.18 unit i.e., pH increases

(b) HCOONa + HCl  HCOOH + NaCl

Initially mM 6.25 0.25 0 0
Finally mM 6 0 0.25 0.25
6
 pH = 3.75 + log = 3.75 + log 24 = 5.13
0.25
0.25
Also [HCOOH] = = 4.17 × 10–3 M
60
(c) Let Acid is H2A
K a2 K
H2A   a1
  HA–    A–2
For HA ,
– pKa2 = 9.7
and pKb = 11.7 So pKa1 = 14 – 11.7 = 2.3
HA– + HCI  H2A + CI–
t=0 10 milimole x milimole 0 0
(10 – x) 0 x x
This solution Act as Buffer solution

[HA – ] [HA – ]
So pH = pKa1 + log  2.6 = 2.3 + log
[H2 A ] [H2 A ]

(10 – x )  10 – x 
0.3 = log  2=    2x = 10 – x
x  x 
3x = 10  x = 3.33 milimole

RESONANCE Ionic Equilibrium - 108

 31.8
26. (a) m. mole of CO32– = × 1000 = 300
106
m. mole of H+ = 150 × 1 = 150
CO32– + H+  HCO3–
t=0 300 150
150 – 150

[CO 3 2 ]
so pH = pKa + log = 10.3.
[HCO3  ]
(b) Mole balance equation
[HCO3–]0 = [H2CO3] + [HCO3–] + [CO32–]
K a1[H2CO 3 ] K a1 K a2 [H2CO 3 ]
 [HCO3–]0 = [H2CO3] + +
[H ] 
[H  ]2

 K a1 K a1 K a2 
[HCO3–]0 = [H2CO3] 1   
 
  2 
 [H ] [H ] 

 4.9  10 7 4.9  10 7  10 12 

[HCO3–]0 = [H2CO3] 1 
 

 10 8 (10 8 ) 2 

 [HCO3–]0 = [H2CO3] (1 + 49 + 4.9 × 10–3)

[HCO 3  ]0
 [H2CO3] =
50
0.0005
 nH2CO3 = = 10–5 mole.
50
K a1[H2CO 3 ]
[HCO3–] =
[H  ]

n 4.9  10 7  10 5
 HCO3  = = 4.9 × 10–4 mole
10 8
K a1 K a2 [H2CO 3 ]
[CO32–] =
[H  ]2

4.9  10 7  10 12  10 5
n 2 = = 4.9 × 10–8 mole
CO3
(10 8 ) 2
x
27. pH1 = pKa + log
a
y
pH2 = pKa + log .
a
y
pH2 – pH1 = 0.6 = log .
x
y = x 100.6 4x.
x : y = 1 : 4.

28. pKa = 11 – log 4.7 = 11 – log 4.7 = 11 – 0.672 = 10.328

 n Na 2 CO 3
  n Na 2 CO 3

pH = pKa + log  0 .3

 10 = 10.328 + log  0 .3


   

0 .3 0 .3
log n Na CO = 0.328  n Na 2 CO 3 = 2.13
2 3

 0 .3 
WNa2CO3 =   × 106 = 14.94  15 gram
 2.13 

RESONANCE Ionic Equilibrium - 109

29. For sodium butyrate
1 1  5  log 1.5  1
pH = 7 + pKa + log C = 7 +  2
 + log (0.1)
2 2   2
= 7 + 2.41 – 0.5 = 8.91
For Indicator

[H ] [In- ]
KIn =
[HIn]

[In- ] K In 3.16  10 10

 =  = = 0.257
[HIn] [H ] 10 8.91
30. Case I: BOH + HCI  BCI + H2O
Millimole before reaction a 0.1 × 5 = 0.5 0 0
Millimole after reaction (a – 0.5) 0 0.5 0.5
[BCI]
 pH = 10.04  pOH = – log Kb + log ....(1)
[BOH]

0.5
 pOH = 3.96  3.96 = – log Kb + log ...(2)
( a  0. 5 )
Case II : BOH + HCI  BCI + H2O
Millimole before reaction a 0.1 × 20 = 2
Millimole after reaction (a – 2) 0 2 2
[BCI]
 pH = 9.14  pOH = – log Kb + log ...(3)
[BOH]

2
 pOH = 4.86  4.86 = – log Kb + log ...(4)
a2
Kb = 1.81 × 10–5
1
31. pH of CH3COOH = (pKa – log c)
2
1
3= (pKa – log 0.1)  pKa = 5
2

1 1/ 4
stage of neutralisation : pH = 5 + log = 4.52
4 3 /4
3 3/4
stage of neutralisation : pH = 5 + log = 5.48
4 1/ 4
32. We know that pH of a mixture of solution containing weak acid and strong base can be calculated as below
1 1
pH =7+ pKa + log c
2 2
1 1
=7+ × 4.72 + log 0.05
2 2
= 7 + 2.36 –0.65 = 8.71
33. C6H5NH2 + H2O C6H5 NH3 + OH–
[C 6H5NH3 ][OH  ]
Thus , Kb =
[C 6H5NH2 ]
10 14 10 8  [OH ]
5 =
2.4  10 0.24
 [OH ] = 10 M
– –2

RESONANCE Ionic Equilibrium - 110

34. Let NaHCO3 + Na2CO3 + KCl
xg yg

At Ist equivalent point

Na2 CO3 + HCI   NaHCO3 + NaCI
Milimole HCI consumed = 0.15 × 10 = 1.5
 Y  1.5  106
 106  × 1 × 103 = 1.5 y= = 0.159 g
  1000
At IInd equivalent point
m. eq. of Na2CO3 + m. eq. of NaHCO3 = m. eq. of HCl = 35 × 0.15
 x   y 
  84  +  106  × 2 = 0.15 × 35 × 10–3
   

x ( 2.25  84 )
 + (1.5 × 10–3) × 2 = 5.25 × 10–3  x= = 0.189 g
84 1000
mass of KCI = 0.152 g
0.159  100
mass % of Na2CO3 = = 31.8 %
0. 5
0.189  100
mass % of NaHCO3 = = 37.8 %
0. 5
0.152  100
mass % of KCI = = 30.4 %
0 .5

35. Let Molarity of C6H4 (OH) COOH = M1

C6H4 (OH) COOH + NaOH   C6H5 (OH) COONa
At end point
No. of eq. of C6H4(OH)COOH = No. of eq. of NaOH = 16.24 × .02
0.3248
25 × M1 = 0.3248  M1 = = 0.013
25
Half neutrilazation
C6H4 (OH) COOH + NaOH  C6H5 (OH) COONa
0.3248 0.1624 0 0
0.1624 0 0.1624
[C 6H5 (OH)COONa]
pH = pKa1 + log [C H (OH)COOH]  4.7 = pKa1  Ka1 = 2 × 10–5
6 5
Complate Neutrilization
C6H5 (OH)COOH + NaOH  C6H5 (OH)COONa + H2O
0.3248 0.3248 0
0 0 0.3248
0.3248
[C6H5 (OH) COONa] = = 7.88 × 10–3
41.24
C6H5(OH)COONa This species is amphiprotic species.
pK a1  pK a2 4.7  pK a2
So pH =  7.5 =
2 2
15 – 4.7 = pKa2  pKa2 = 10.3  Ka2 = 5 × 10–11

36. [Sr(OH)2]  Sr2+ + 2OH–

19.23
[Sr(OH)2] = = 0.158 M
121 .62  1
 [OH–] = 2 × 0.158 M = 0.316 M

RESONANCE Ionic Equilibrium - 111

 or pOH = 0.5.  pH = 13.5
[Sr2+] = 0.158 M.

37. (a) BaSO4 Ba2+ + SO42–

s s (where s M/litre is soluble of BaSO4)
(i) KSP = s × s
s= K SP = 1.6  10 9 = 4 × 10 mol litre
–5 –1

(ii) In presence of 0.10 M BaCl2, let s mol/litre BaSO4 is disolved
KSP = [Ba2+] [SO42–]
1.6 × 10–9 = (0.1 + s) (s) [(0.1 + s) = 0.1 as s <<< 0.1]
 s = 1.6 × 10–8 M
(b) For CaSO4, Let solubility be s mol/litre
Them s = 9  10 6 = 3 × 10 mol litre
K SP = –3 –1

Thus, 3 × 10–3 mole of CaSO4 is soluble in water = 1 litre

1 1
 mole (1 g) of CaSO4 is soluble in = = 2.45 litre water
136 136  3  10 3

(c) Let solubility of Mg(OH)2 be s mol litre–1

Mg(OH)2 Mg2+ + 2OH–
2+ – 2
 [Mg ] [OH ] = KSP
4s3 = 8.9 × 10–12
 s = 1.305 × 10–4 mol litre–1
 [OH–] = 2 × 1.305 × 10–4 mol litre–1
 pOH = 3.58
 pH = 10.42

38. (a) For Ag2CrO4 (s) 2Ag+ + CrO42–

2s s
KSP = 4s3  s = 2 × 10–4 mol/lt.
Now,
CrO42– + Pb2+  PbCrO4 (s)
m. moles of CrO42– = m. moles of Pb2+
50 × 2 × 10–4 = 20 X
 X = 5 × 10–4 M.
(b) Pb2+ + 2Cl–  PbCl2 .
10 1
–x – 2x  0.
101 101

 1 1 9.5
[Pb2+] =  10 –  × = = 9.4 × 10–2 M.
 2 101 101

(c) Taking density of water to be 1 g/cc.

136 1000
[CaSO4] = 6 × = 10-10 M.
10 136

Concentration of CaSO4 in saturated solution. = K SP = 3 × 10–3.

M1V1 = M2V2.
10-10 × V1 = 3 × 10–3 × V2 .
V2 1 V1 – V2
V1 = 3  V1 = 0.67.

RESONANCE Ionic Equilibrium - 112

39. PbBr2 Pb2+ + 2Br–.
0.8 s 2 × 0.8s
8 × 10–5 = 4 × (0.8)3 × s3  s = 5 × 10–3 mol/lt.
solubility of salt = 5 × 10 × 368 = 1.84 g/lt.
–3

40. (a) BaSO4 Ba2+ + SO42– .

s + s s
BaCrO4 Ba2+ + CrO42–
s + s s

[Ba2+] = 1.4 × 10–5 = K sp1  K sp2

 Ksp1 + Ksp1 = (1.4 × 10–5)2
K sp1 1
& K sp2 = 2.5
On solving, Ksp1 = 5.6 × 10–11
Ksp2 = 1.4 × 10–10

5.6  10 11
Solubility of BaSO4 in 0.01 M Na2SO4 = = 5.6 × 10–9 M.
0.01

3
7.1 10 9
(b). milli moles of I— = 25 × 2 × .
4
milli moles of Ag + = 13.3 × M.
Ag+ (aq) + I– (aq)  AgI (s)
Equatiing both M = 4.55 × 10–3.

2.8  10 9
(c). [F—] concentration when [Sr2+] is 2.5 × 10–3 = = 1.058 × 10–3 M.
2.5  10  3
Total m. moles of F— added = 100 × [1.058 × 10–3 + 2 (0.016 – 0.0025)] = 2.8
Mass of NaF added = 2.8 × 10–3 × 42 = 0.1776 g.

41. Given, MBr2(g) MBr2(aq) ® M2+ + 2Br–

MBr2 + H2S  MS + 2HBr
KSP of MS = [M2+] [S2–]
6 × 10–21 = [0.05] [S2–]
 [S–2] = 1.2 × 10–19 M
Thus, MS will be precipitated if H2S provides 1.2 × 10–19 M ions of S2–
Now for H2S H2 S 2H+ + S2–
[H  ] 2 [S 2  ]
K1 × K2 =
[H2 S]

[H ] 2 [1.2  10 19 ]

10–7 × 1.3 × 10–13 =
[0.1]
 [H+] = 1.04 × 10–1 and pH = 0.983

42. Volume of both AgNO3 & HCN are equal so. There concentration is half
[AgNO3] = 0.01 M [HCN] = 0.01 M
HCN H+ + CN– Ka = 4 × 40–10 ....... (i)
1
Ag+ + CN– AgCN K= K ....... (ii)
a
on adding equation (i) & equation (ii)
Ag+ + HCN H+ + AgCN K' = 106

RESONANCE Ionic Equilibrium - 113

 As the volue of K' is very high so almost all Ag+ & HCN converted in product
Ka
Ag+ + HCN H+ + AgCN(s) K' = K = 1 × 106
sp

0.01 0.01 0 0
x x  0.01  0.01

0.01
K' = ( x )2 = 106

X2 = 10–8  X = 10–4
Conc. of [Ag+] = 10–4

43. For the precipitation of Mg(OH)2

[Mg2+][OH–]2 = Ksp
[OH–] = 5 × 10–5.
For NH3 - NH4+ buffer solution,

[OH ][NH4  ] (5 10 6 )(0.4)

Kb =  [NH3] = = 0.1 M.
[NH3 ] 2  10 5

44. Let final concentration of SO42- in solution = [SO42-]left = x

Mole balance equation for SO42-

[SO42-]initial = [SO42-]left + [SO42-]combined

0.3 10
= 0.1 = [SO42-]left + [SO42-]combined
30
0.1 = x + [Ca2+]combined + [Sr2+]combined
 0.1 = x + ([Ca2+]initial – [Ca2+]left ) + ([Sr2+]initial – [Sr2+]left )

 0.2 K sp of CaSO 4   0.2 K sp of SrSO 4 

   
0.1 = x +  3 – + –
[SO 4 2 ]left [SO 4 2 ]left
   3 
   

 0 .2
 2.4  10 5 

 0 .2
 7.6  10 7 

 0.1 = x +  3 – x  +  3
–
x 
   

 3x2 + 0.1x + 7.428 × 10–5 = 0

on solving, x = [SO42-]left = 7.26 × 10–4 M

2.4 10 5
[Ca2+]left = = 0.033 M
7.26 10  4

7.6 10 7
[Sr2+]left = = 1.05 × 10–3 M
7.26 10  4

100 3
1.4  10 5
45. [Ag+] concentration = ×2× = 8.68 × 10–3.
350 4
100 3
1.4  10 5
[SO42–] concentration = × = 4.34 × 10–3.
350 4
250
[Pb2+] = × 2.8  10 13 = 3.78 × 10–7.
350
[CrO42–] = 3.78 × 10–7.
[Ag+]2 [CrO42–] = 2.85 × 10–11 > KSP of Ag2CrO4 .
[Pb2+] [SO42–] = 1.64 × 10–9 < KSP of PbSO4 .
Only Ag2CrO4 will precipitate.

RESONANCE Ionic Equilibrium - 114

46. [Ag+] [Cl–] = 1.75 × 10–10
[Ag+] [Br–] = 5.25 × 10–13

5.25  10 13 5.25  10 13

 [Br–] = × [Cl–] = × (0.075) = 2.25 × 10–4 M.
1.75  1010 1.75  1010

47. (a) 500 mL of 0.4 M NaOH are mixed with 500 mL of Ca(OH)2 a saturated solution having Ca(OH)2 solubility
as s M.
For Ca(OH)2 Ca2+ + 2OH–
KSP = s × (2s)2 = 4s3
Then, 4s3 = 4.42 ×10–5

 4.42  10  5 
 s= 3    0.0223M
 4 
 
Now Ca (OH)2 + NaOH are mixed
 Solution has Ca2+ and OH– out of which some Ca2+ are precipiated
0.0223  500
On mixing, [Ca2+] = = 0.01115 = 111.5 × 10–4 M
1000
0.0223  2  500 500  0.4
[OH–] = + = 0.2223 M
1000 1000
[from Ca (OH)2 ] [from NaOH]
 [Ca2+] [OH–]2 = KSP
[Ca2+]left [0.2223]2 = 4.42 × 10–5
4.42  10 –5
[Ca2+]left = = 8.94 × 10–1 mol litre–1
[0.2223 ] 2
 Mole of Ca(OH)2 precipitated = Mole of [Ca2+] precipitated
= 111.5 × 10–4 – 8.94 × 10–4 = 102.46 × 10–4
 Wt. of Ca(OH)2 precipitated from Ca(OH)2 solution
= 102.46 × 10–4 × 74 = 7582.04 × 10–4 g = 759 mg
(b) For CaSO4 Ca2+ + SO 24

[Ca2+] [ SO 24 ] = KSP

Let [ SO 24 ] = a, just sufficient to precipitate CaSO4 from a solution having [Ca2+] = 0.005 M

2.4  10 5
Then, [0.005] [a] = 2.4 × 10–5  a=
0.005
[ SO 24 ] = 4.8 × 10–3 mol litre–1
(c). The minimum [OH–] at which there will be no precipitation of Mg(OH)2 obtained by
KSP = [Mg2+] [OH–]2
6.0 × 10 = [0.05][OH–]2
–12

 [OH–] = 1.34 × 10–5 M

Thus, a solution having [OH–] = 1.34 × 10–5 M will not show precipitation of Mg(OH)2 in 0.05 M Mg2+ solution.
These hydroxyl ions are to be derived by a buffer of NH4CI and NH4OH i.e.,
NH4OH NH4 + OH–
NH4CI  NH4 + Cl–

[NH 4 ][OH  ]
For NH4OH Kb =
[NH 4 OH]

In presence of NH4CI; all the [ NH4 ] are provided by NH4CI since common ion effect decreases dissociation
of NH4OH.
[NH4 ][1.34  10 5 ]
 1.8 × 10–5 =
[0.05]

RESONANCE Ionic Equilibrium - 115

  [ NH4 ] = 0.067 M
or [NH4CI] = 0.067 M
(d). AgCI Ag+ + CI– AgI Ag+ + I–
(x + y) x (x + y) y
x x
K sp ( AgCI) x 1 10 –10 10 +6
K sp ( AgI) = y = –17 = 8 .5 × 10
8.5  10
x = 1.8 × 106 y
AgCI Ag+ + CI– AgI Ag+ + I–
(x + y) x x+y y
x x
x2 = 10–10 xy = 8.5 × 10–17
x = 10–5 y = 8.5 × 10–12

(e). Ksp = 4 × (6.7 × 10–6)3 = 1.203 × 10–15

s × (10–6)2 = 1.203 × 10–15
s = 1.203 × 10–3 M
 7  10 3 
48. Concentration of CaCO3 =  100  mole/lit = 7 × 10–5 mole/lit
 
Ksp of CaCO3 = 49 × 10–5 mole/lit
when only [Ba+2] is 90% precipitated then only CaCO3 starts precipitation
then if & solution contain a mole/lit of Ca+2 & Ba+2
 49  10 10 
[Ca+2] [CO3–2] = 49 × 10–10 [CO3–2] =  a

 

a  10 49  10 10
Now for BaCO3 Ksp = [Ba+2] [CO3–2] = × = 4.9 × 10–10
100 a
49. Al (OH)3 (s) Al+3 + 3 OH– KSP = 5 × 10–33
[Al (OH)4]– Al+3 + 4OH– Kd = 1 × 10–34
K sp
Al (OH)3 (s) + OH– [Al(OH)4]– , K1 =
Kd
1× 10–3 0
0 1 ×10–3
[ A (OH) 4 ]  5  10 33 1 10 3
K1 = = = 50  [OH–] = = 2 × 10–5
1 10  34

[OH ] 50
pOH = 5 – log 2 = 4.7  pH = 14 – 4.7 = 9.3  pH = 9.3
(b) Al(OH)3  Al+3 + 3OH–
5 × 10–3
5  10 33
[Al+3] [OH–]3 = KSP  [OH–]3 =
5  10 3
[OH–]3 = 1 × 10–30  [OH–] = 10–10 pOH = 10 pH = 4

50. Cu2+ + 4NH3 () [Cu(NH3)4]2+ ; Kƒ = 5.6 × 1011

Initial mole 0.005 0.5 × 0.4 0
= 0.2
Kƒ is large and thus all the Cu2+ will give [Cu(NH3)4]2+
Let Cu2+ left is a, than
0.005
[Cu(NH3)4]2+ = 0.005 mole = M (0.005 >> a)
0 .5

RESONANCE Ionic Equilibrium - 116

 a
[Cu2+] = M (Let)
0 .5
[NH3] = 0.2 – 4 × 0,005 + 2a
= 0.2 – 0.02 + 2a (0.18 >> 2a)
0.18
= 0.18 mole = M
0. 5

0.005
0.5
[Cu (NH3 ) 4 ] 2 4
Kƒ = 5.6 × 1011 = =

[Cu 2 ] [NH3 ] 4 Cu   00.18
2 
.5 
 [Cu2+] = 1.06 × 10–12 M

51. Zn(OH)2(s) Zn+2(aq.) + 2OH–(aq.) Ksp = 1.2 × 10–17 ...... (i)

2+
Zn + 4OH –
[Zn(OH)4]2– Kf = 1016 ...... (ii)
2 × [eq.(i) & eq.(ii)]

2Zn(OH)2(s) Zn+2 + [Zn(OH)4]2– K' = (Ksp)2 Kf  K' = 1.44 × 10–18

2Zn(OH)2(s) Zn+2 (aq.) + [Zn(OH)2]2– K' = 1.44 × 10–18

s s
   
2 2

 s2 
 
 4  = 1.44 × 10
–18
 
s2 = 4 × 144 × 10–20  s = 2.4 × 10–9 M
But Ksp [Zn(OH)2] = [Zn2+] [OH–]2 = 1.2 × 10–17

 (1.2 × 10–9) [OH–]2 = 1.2 × 10–17

[OH–] = 10–4 M

RESONANCE Ionic Equilibrium - 117

 EQUIVALENT CONCEPT & TITRATION
EXERCISE # 1
PART - I
A-2. In S2Cl2
2 × 35.5 g Cl  2 × 32 g S
 35.5 g Cl  32 g S
 Equivalent mass of S in S2Cl2 is 32.

N  VL 0.5  70
A-11. Moles of pure NaOH required = = = 35
v.f 1
Mass of pure NaOH required = 35 × 40 = 1400 g = 1.4 kg.
100
Mass of wet NaOH required (containing 15% water) = 1.4 × = 1.65 kg.
85

A-12. eq. = NVL = 1/2×1

eq. × eq. mass = mass (g)
1
 36.5  18 .25( g)
2
mass remained = 18.25 – 2.675 = 15.575 g
15.575 / 36.5
New normality =  0.569 N
750 / 1000

2 6
B-8. Na2 S 2 O3  Na 2 S O 4
the total change in oxidation number = 4 × 2 = 8
mol. wt. M
 ENa2S2O3 = =
V. f 8

C-3. Eq. of Na2CO3 = Eq. of H2SO4

1 . 06 25
2  N
106 1000
N = 0.8 N
C-4. H2C2O4 NaOH
63  1000 40  1000
M= M=
126  100 40  100
M=5 M = 10
N = 10 N = 10
V = 125 mL V = 125 mL
N1V1 = 1250 milli equivalent N2V2 = 1250 milli equivalent
so, resulting solution will be neutral.

C-9. eqHNO3 = eqNaOH

18.9 3 .2
× 1 × V1 = × 1 × V2
63 40
V1 4
V2 = 15

C-10. eqacid = eqbase (VF = 1 for both)

CHCl2COOH + NH3  CHCl2COONH4

From reaction, m.moles of NH3 = m.moles of dichloroacetic acid = 100

RESONANCE Equivalent Concept & Titration - 118

 100
 Moles of NH3 = = 0.1
1000

D-4. 1.68 × 10–3 × 6 = 3.36 × 10–3 × x

x=3
So, oxidation number of A increases by 3.
 New oxidation number of A = –n + 3 = 3 – n.
D-7. K2Cr2O7 + Sn2+  Sn4+ + Cr3+
Sn4+ + Fe2+  Sn2+ + Fe3+
4.9
Milli equivalent of K2Cr2O7 in 10 mL solution = ( 294 / 6)  0.1
× 10 = 10
10
so, milli mole of Fe3+ = = 10 (V.F. of Fe3+ = 1)
1

D-10. (A) Formula of silver chromate (VI) will be Ag2 CrO4

0 .1
(B) Minimum mass of zinc required for reduction of 0.1 mole of Cr3+ to Cr2+ = moles of Zn
2
6.54
(v.f. of Zn = 2 & v.f. of Cr3+ = 1) = g = 3.27 g
2
(C) CrO42– Cr2O72–
in both ions, chromium is in +6 oxidation state.
(D) Given reaction is correct.

D-11. MnO4– + 5e– + 8 H+  Mn2+ + 4 H2O

 1 mole of MnO4– accepts 5 mole of e–
1/5 mole of MnO4– accepts 1 mole of e–
 0.2 mole of MnO4– accepts 1 mole of e –
 0.6 mole of MnO4– accepts 3 mole of e –
Fe2+  Fe3+ + e –
 1 mole of Fe2+ will liberate 1 mole of e –
Cr2O72 – + 6e – + 14 H+  2 Cr+3 + 7 H2O
 1 mole of Cr2O72– will accept 6 moles of e –
1 mole of FeC2O4  Fe3+ + CO2 + 3 e –
 1 moles of ferrous oxalate gives 3 moles of e –
 0.2 moles of KMnO4 = 1/5 moles of KMnO4 oxidises 1 mole of Fe2+ ion. (Tallies with statement A)
0.6 moles of KMnO4 = 3/5 moles of KMnO4 will oxidise 1 mole of ferrous oxalate (Tallies with
statement C)
1 mole of K2Cr2O7 will oxidise 2 moles of ferrous oxalate. (Tallies with statement D)
Hence ,(A) , (C) , (D) are correct while (B) is incorrect.

D-12. 5As2S3 + 28KMnO4 + H+  10H3AsO4 + 28Mn2+ + SO42–

m.moles of KMnO4 = 50 × 0.1 = 5

28 m.moles of KMnO4  5 m.moles of As2S3

 1 m.mole of KMnO4  5/28 m.moles of As2S3
55
 5 m.mole of KMnO4  m.moles of As2S3
28
55
Mass of As2S3 = x = 246 × × 10–3 = 0.22 g
28

E-2. The weight % of available Cl2 from the given sample of bleaching powder on reaction with dil acids or CO2 is
called available chlorine.
CaOCl 2  H2SO 4  CaSO 4  H2 O  Cl 2
71
Max. % of available of Cl2 = × 100 = 55.9%.
127

RESONANCE Equivalent Concept & Titration - 119

E-3. The weight % of available Cl2 from the given sample of bleaching powder on reaction with dil acids or CO2 is
called available chlorine.
CaOCl 2  H2SO 4  CaSO 4  H2 O  Cl 2

3.55  10  0.125
% of available Cl2 = = 5%.
3.55
 25
100

E-5. Excess of Mohr's salt = 30 × 0.1 × 5 meq.

= 15 meq
Mohr's salt consumed = [(35 × 1.0 × 1) – 15] meq
= 20 meq.
Now Cl2 + 2Fe2+  2Fe+ + 2Cl– (balanced equation)
1 1 1
So moles of Cl2 = × moles of Fe2+ = eq. of Fe2+ = × 20 m moles = 10 mmoles
2 2 2
= 10 × 10–3 × 71 gm = 0.71 gm
0.71
So, required % = × 100 = 7.1%
10

E-6. C + O2  CO + CO2 ......(i)

t=0 0.1 – –
t=t 0 x (0.1 – x)
5CO + 2O5  5CO2 + 2 ......(ii)
t=0 x
t=t 0 x/5
2 + 2Na2S2O3  Na2S4O6 + 2Na
1 1
 moles of 2 liberated = × moles of hypo consumed = × 120 × 10–3 × 0.1 = 60 × 10–4
2 2
So, x = 5 × 60 × 10–4 = 0.03 moles (from reaction (ii) : 5 × mole of I2 = mole of CO)
0.03  12
So, % of C forming CO = × 100 = 30%
1 .2

E-7. From given reactions :

m.moles of hypo = m.moles of iodine × 2 = m.moles of Cu2+ ions = 24.5 × 0.1 m.moles
so, mass of copper = 24.5 × 0.1 × 10–3 × 63.5 g

24.5  0.1 10 3  63.5

so, % of copper = × 100 = 51 %
0.305

E-8. 2 moles of Cu2+ = 1 mole of 2

= 2 moles of hypo.
so moles of hypo used = 20 × 10–3 × 0.1 = 2 m moles = moles of copper hence
2  10 3  63.5
% of copper = × 10% = 63.5%
0.2


E-9. Ni(CO)4  Ni + 4CO
5CO + 2O5  2 + 5CO2
2S2O32– + 2  2– + S4O62–
so moles of 2 produced = 4 moles
so moles of hypo used = 8 moles = (4 M) (2 litres).

F-3. BrO3– + 6I–  3I2 + Br–

moles of I2 = 3 × moles of KBrO3
 moles of I2 = 0.02 × 3 = 0.06
Eq of I2 = Eq of Hypo
0.06 × 2 = 0.1 ×V
V = 1.2 L = 1200 mL.

RESONANCE Equivalent Concept & Titration - 120

F-4. Eq. of Hg5 (IO6)2 = Eq. of I2 = Eq. of Na2S2O3
 (moles of Hg5 (IO6)2) × 16 = 0.004 × 1
 moles of Hg5 (IO6)2 = 2.5 × 10–4.

F-5. 6e– + 10H+ + V2O5  2V2+ + 5 H2O

(Zn  Zn2+ + 2e– ) × 3
–––––––––––––––––––––––––––––––––––––
V2O5 + 3 Zn + 10 H+  3 Zn2+ + 2V2+ + 5H2O .....(1)
Now, H2O + V2+  VO2+ + 2H+ + 2e–
2e– + 2  2–
––––––––––––––––––––––––––––––––––––––
V2+ + 2 + H2O  2– + VO2+ + 2H+
so, we have overall 1 mole of V2O5 reducing 2 moles of iodine
 10  10
so,   moles of V O will be reduce = × 2 = 0.11 moles of 2
 102  80  2 5 182

F-7. m.eq of (NH4)2 SO4 + m.eq of H2 SO4 = m.eq of NaOH

250
(m.moles × 2) + (0.1 × 10 × ) = 0.2 × 100
25
 m.mole of (NH4)2 SO4 = 5
5
wt. of (NH4)2 SO4 = × 132 = 0.66 g
1000
0.66
 % of (NH4)2 SO4 = × 100 = 94.28 %  94.3 %
0. 7

F-8. KOH + Na2CO3

a m.moles b m.moles
m.eq. of KOH + m.eq. of Na2CO3 (v.f. = 1) = m.eq. of HCl (in presence of phenolphthalein)
1
a × 1 + b × 1 = 15 ×
20
 a + b = 0.75 ...(i) (in presence of phenolphthalein)
m.eq. of KOH + m.eq. of Na2CO3 (v.f. = 2) = m.eq. of HCl (in presence of methyl orange)
1
1 × a + 2 × b = 25 ×
20
 a + 2 × b = 1.25 ...(ii) (in presence of methyl orange)
by solving (i) & (ii), a = 0.25 m.moles.
0.25
 mass of KOH = × 56 = 0.014 g
1000

F-9. meq of H2SO4 = meq of NaOH + meq of Na2CO3

0.265
N × 25 = 0.5 × 50 + × 103 or N = 1.2
106 / 2
In original H2SO4 solution
N1V1 = N2V2 or N1 × 10 = 1.2 × 100 or N1 = 12 N

PART - II

2. (A) Eq of Sn2+ = Moles × v.f. = 3.5 × 2 = 7.

Eq of MnO4– = Moles × v.f. = 1.2 × 5 = 6.
Since MnO4– (O.A) is the LR, so the amount of oxidant available decides the number of electron transfer.
Also, electron involved per mole of OA (5) > electron involved per mole of RA (2).
(B) Eq of H2C2O4 = Moles × v.f. = 8.4 × 2 = 16.8.
Eq of MnO4– = Moles × v.f. = 3.6 × 5 = 18.
Since H2C2O4 (RA) is the LR, so the amount of reductant available decides the number of electron transfer.

RESONANCE Equivalent Concept & Titration - 121

 Also, electron involved per mole of OA (5) > electron per mole of RA (2).
(C) Eq of S2O32– = Moles × v.f. = 7.2 × 1 = 7.2.
Eq of I2 = Moles × v.f. = 3.6 × 2 = 7.2.
Since S2O32– (RA) and I2 (OA) both completely get consumed, so both the amount of reductant and oxidant
decides the number of electron transfer.
Also, electron involved per mole of OA (2) > electron involved per mole of RA (1).
(D) Eq of Fe2+ = Moles × v.f. = 9.2 × 1 = 9.2.
Eq of Cr2O72– = Moles × v.f. = 1.6 × 6 = 9.6.
Since Fe2+ (RA) is the LR, so the amount of reductant available decides the number of electron transfer.
Also, electron involved per mole of OA (6) > electron involved per mole RA (1).

3. 10 e– + 2MnO4–  2Mn2+ ; v.f. = 10

M
 Eq. mass of Ba(MnO4)2 =
10

4. Fe0.9 O + K2Cr2O7  Fe+3 + Cr+3

 2 
n factor of Fe0.9 O = 0.9  3   = 0.7
 0 .9 

M 10M
 Eq mass = =
0 .7 7

5. n factor is 2
M 128
Eq. weight = = = 64.
2 2

EXERCISE # 2

23 27 30
1._ (a) E = = 23 (b) E = =9 (c) E = = 30
1 3 1
35.5 60 96
(d) E = (e) E = = 30 (f) E = = 48
1 2 2
95
(g) E = = 31.67
3

M2
6. v.f. of Cu2S is 2 + 6 = 8  Eq. wt. of Cu2S =
8
M1
v.f. of CuS is 6  Eq. wt. of CuS =
6
M3
v.f. of KMnO4 is 5  Eq. wt. of KMnO4 =
5

8.

Now, 233.34 g BaSO4  96 g SO42–

96
 0.95 g BaSO4   0.95 or 0.39 g SO42–
233 .34
 Mass of metal in metal sulphate = 0.98 – 0.39 = 0.59 g
Now, eqmetal = eqSO2–
4
0.59 0.39
E metal = 96 / 2
Emetal = 72.61

RESONANCE Equivalent Concept & Titration - 122

10. Final No. of eq. of H2SO4
Initial No. of eq. of H2SO4
No. of reacted Eq. of H2SO4
So, No. of equivalent of NH3
No. of Mole of NH3
Volume at S.T.P
= 0.2 × 30 × 10–3
= 6 × 10–3
= 1 × 30 × 10–3
= 30 × 10–3
= 24 × 10–3
= 24 × 10–3
= 24 × 10–3 (v.f. = 1)
= 24 × 22400 × 10–3
= 24 × 22.4 mL
= 537.6 mL

3+ +3
15. Fe
+2
+ Cr2O7
–2 Cr + Fe
+6 +3
v.f. = 6
v.f. = 1
No. of m.eq. of Fe+2 = No. of m.eq. of Cr2O7–2
[M × 25] × 1 = [0.01 × 50] × 6
0.01  50  6
M=
25
M = 0.02 × 6 = 0.12

18. Lets mole of FeSO4 = x

Now, KMnO4 oxidises only FeSO4
equivalent of FeSO4 = equivalent of KMnO4
100
x×1= ×2×5  x=1
1000

nFeSO4 1
so, mole fraction of FeSO4 = n = .
mixture 3

20. Excess of Mohr's salt = 30 × 0.1 × 5 meq. = 15 meq

Mohr's salt consumed = [(35 × 1 × 1) – 15] meq = 20 meq.
Now Cl2 + 2Fe2+  2Fe3+ + 2Cl– (balanced equation)
1 1
So moles of Cl2 = × moles of Fe2+ = × 20 × 10–3 moles = 10 × 10–3 moles
2 2
Mass of Cl2 = 10 × 10–3 × 71 = 0.71 g
0.71
So, required % of available Cl2 = × 100 = 7.1%
10

22. Let moles of As2O3 and As2O5 are x and y respectively. In first step, only As2O3 react with I2.
So, eq. of As2O3 = eq. of I2
x × 4 = 20 × 0.05 × 10–3
x = 0.25 × 10–3
wt. of As2O3 = x × Mol. mass
= 0.25 × 10–3 × 198
wt. of As2O3 = 0.0495 g
In second step, As2O5 react with I–
So, total eq. of As2O5 = eq. of I– reacted = eq. of I2 released = eq. of hypo used
wt. of Hypo  v.f .
Total moles of As2O5 × v.f. = Mol. Mass
(Total moles of As2O5 = moles of As2O5 formed in 1st stage + moles of As2O5 initially present)
1.116
(25 × 10–5 + y)4 = ×1
248
0.25 × 10–3 + y = 1.125 × 10–3
y = 0.875 × 10–3

RESONANCE Equivalent Concept & Titration - 123

 mass of As2O5 = y × Mol. mass
= 0.875 × 10–3 × 230
= 0.20125 g
Total mass of mixture = 0.20125 + 0.0495 = 0.25075 g Ans.

23. 2– + O3 + H2O  2OH– + 2 + O2

2 + 2Na2S2O3  Na2S4O6 + 2Na
From the above reaction :
2Na2S2O3  2  O3
40 x 0.1
moles of Na2S2O3 = = 0.004
1000
moles of 2 = moles of O3= 0.002
volume of O3 at STP = 0.002 × 22.4 = 0.0448 L (present in 1 L mixture)
0.0448
Percentage of O3 = × 100 = 4.48% (by volume)
1

24. MnO2  HCl KI Na 2S 2 O 3

 Cl2  2    Na + Na2S4O6
Redox changes are : 2e + 20  2–
2S2+2  S4+5/2 + 2e
2e + Mn+4  Mn+2
The reactions suggest that :
m.eq. of MnO2 = m.eq. of Cl2 formed = m.eq. of I2 liberated = m.eq. of Na2S2O3 used
w
 × 1000 = 0.1 × 1 × 30 [v.f. : MnO2 = 2, Na2S2O3 = 1]
M/ 2
0.1 1 30  M 0.1 1 30  87
or w= = ( MMnO2 = 87)
2000 2000
0.1305
w MnO2 = 0.1305 g  Purity of MnO2 sample = × 100 = 26.1%
0 .5

25. At phenolphthalein end point

eq. of Na2CO3 + eq. of NaOH = eq. of HCl used
Let x mole of Na2CO3 and y mole of NaOH present in 25 mL solution
x × 1 + y × 1 = 19.5 × 0.995 × 10–3
x + y = 19.4 × 10–3 .... (i) (The v.f. of Na2CO3 is 1 when phenolphthalein is used)
At Methyl orange (MeOH) end point,
eq. of Na2CO3 + eq. of NaOH = eq. of HCl used
x × 2 + y × 1 = 25 × 0.995 × 10–3
2x + y = 24.875 × 10–3 .... (ii) (The v.f. of Na2CO3 is 2 when methyl orange (MeOH) is used)
On solving eq. (1) and (2),
x = 5.475 × 10–3 and y = 13.925 × 10–3
or wt. of Na2CO3 in 25 mL = 5.475 × 10–3 × 106
5.475  10 –3  106
wt. of Na2CO3 in 1 litre = × 1000 = 23.2 g Ans.
25
wt. of NaOH in 25 mL solution = 13.925 × 10–3 × 40
13.925  10 –3  40
wt. of NaOH in 1 litre = × 1000 = 22.28 g Ans.
25

26. CH3(CH2)nCOOH + O2  (n + 2)CO2(g) + H2O(g)

excess
moles of CO2
moles of CH3(CH2)nCOOH = (n  2 )
...... (1)
When CO2(g) is passed into excess of NaOH solution, then Na2CO3 will form according to reaction :
2NaOH + CO2  Na2CO3 + H2O
 moles of NaOH reacted = 2 × moles of Na2CO3 ...... (2)
Now solution contain remaining NaOH and Na2CO3 formed.
Let moles of NaOH and Na2CO3 are x and y respectively and solution divided into two equal parts.

RESONANCE Equivalent Concept & Titration - 124

 Part I : At Ph end point,
Eq. of NaOH + eq. of Na2CO3 = Eq. of HCl used
x y
×1+ × 1 = 50 × 1 × 10–3
2 2
x + y = 0.1 ........... (1)
Part II : At MeOH end point,
Eq. of NaOH + eq. of Na2CO3 = Eq. of HCl used
x y
×1+ × 2 = 80 × 1 × 10–3
2 2
x + 2y = 0.16 ........... (2)
On solving equation (1) and (2),
y = 0.06
x = 0.04
Since moles of CO2 = moles of Na2CO3 = 0.06
 From equation (1),
1.16 0.06
=
48  14n n2
On solving, we get n = 4 Ans.
Amount of NaOH remaining = 0.04 mole
Amount of NaOH reacted = moles of Na2CO3 × 2
= 0.06 × 2 = 0.12
Total moles of NaOH taken = 0.04 + 0.12 = 0.16
wt. of NaOH taken = 0.16 × 40 = 6.4 g.

28. millimoles of K2Cr2O7 = 25 × 0.002 = 0.050

meq or millimoles of Fe2+ present in water sample = 25 × 0.002 × 6 – 7.5 × 0.01 = 0.225
 Mass of Fe2+ in water sample = 0.225 × 56 × 10–3 = 12.6 x 10-3 grams
assuming 100 mL water = 100 gram water
12.6  10 –3
ppm = × 106 = 126 ppm
100

29. Each mole of K2Cr2O7 releases 6 moles of electrons which is used by Fe for its reduction
so assuming the sample conatins x grams of CuFeS2 originally.
K Cr O
( CuFeS2 Fe2+ 22
7
Cr3+ + Fe3+)
3
40 × 0.01 × 6 = (x /183.5) × 1000
x = 0.4404 g
% of CuFeS2 in sample = (0.4404/0.5) × 100 = 88.08%

30. Let m.moles of Fe2(SO4)3 and FeC2O4 are x and y. In first reaction, only FeC2O4 react with KMnO4 as :
FeC2O4 + KMnO4  Fe+3 + CO2 + Mn+2
v.f. = 3 v.f. = 5
m.eq. of FeC2O4 = m. eq. of KMnO4
1
y × 3 = 40 ×
16
40
y= ......... (1)
48
In IInd reaction, all Fe+3 is convert into Fe+2 :

Fe+3 from FeC2O4 + Fe+3 from Fe2(SO4)3  Zn / H
 Fe+2
t=0 y 2x 0
t=t 0 0 (y + 2x)
In IIIrd reaction all Fe+2 again react with KMnO4 as :
Fe+2 + KMnO4  Fe+3 + Mn+2
v.f. = 1 v.f. = 5
m.eq. of Fe+2 = meq of KMnO4
1
y + 2x = 60 × 16

RESONANCE Equivalent Concept & Titration - 125

 Putting the value of y from equation 1st ,
60 40
2x = –
16 48
140
2x =
48
70
x= ......... (2)
48
From eq. (1) and (2),
x 7
y = 4 Ans.

31. Balanced reactions are :

5SeO3–2 + 2BrO3– + 2H+  5SeO4–2 + Br2 + H2O
BrO3– +3 AsO2– + 3H2O  Br– +3 AsO4–3 + 6 H+
total millimoles of BrO3– = 20 × 1 /60 = 1/3
millimoles of BrO3– backtitrated = 5 × 1/25 × 1/3 = 1/15
millimoles of BrO3– consumed for SeO3–2 = 1/3 – 1/15 = 4/15
5 millimoles of SeO3–2 = 2 millimoles of BrO3– (from 1st reactions)
millimoles of SeO3–2 for reaction = 4/15 × 5/2 = 2/3
mass of SeO3–2 = 2/3 × 127 = 84.67 mg

EXERCISE # 2

Molecular weight Mol. wt. Mol. wt.

1. Eq. mass = Change in oxidation No. of Mn = =
4–2 2
(O.N. of Mn in MnSO4 = +2; O.N. of Mn in MnO2 = +4).
2. (A) Equilivalents of H2C2O4.2H2O in 10 mL = Equivalents of NaOH
 6 .3 1000  10
    = 0.1 × V (in litre)
 126 / 2 250  1000
 V = 0.04 L = 40 mL.

3. 2KMnO4 + 5H2O2 + 3H2SO4  K2SO4 + 2MnSO4 + 8H2O + 5O2

2KMnO4 + 3MnSO4 + 2H2O  5MnO2 + 2H2SO4 + K2SO4
MnO2 + Na2C2O4 + 2H2SO4  MnSO4 + 2CO2 + Na2SO4 + 2H2O.
 meq. of MnO2 = meq of Na2C2O4 = 10 × 0.2 × 2 = 4

4
 Mn 4   2e  Mn2 
 millimoles of MnO2 = =2  
2  Valency factor of MnO 2  2

Now, 2KMnO4 + 3MnSO4 + 2H2O  5MnO2  + K2SO4 + 2H2O

Since MnO2 is derived from KMnO4 and MnSO4 both, thus it is better to proceed by mole concept
millimoles of KMnO4 =millimoles of MnO2 × (2/5) = 4/5
Also, 5H2O2 + 2KMnO4 + 3H2SO4  2MnSO4 + K2SO4 + 8H2O + 5O2
5 4 5
 millimoles of H2O2 = millimoles of KMnO4 ×   2
2 5 2
 MH2O2 × 20 = 2 or MH2O2 = 0.1 M
5. Dilute nitric acid converts chromate into dichromate and H2O.
2K2CrO4 + 2HNO3  K2Cr2O7 + 2KNO3 + H2O.

6. 2MnO4– + I— + H2O  2MnO2 + IO3– + 2OH—.

7.

RESONANCE Equivalent Concept & Titration - 126

8. Cr2O72– + Fe2+  2Cr3+ + Fe3+ + 7H2O
n=6 n=1
1 mole of Cr2O72– will require six moles of Fe2+ ions.
9. HCl reduces MnO4– to Mn2+ and itself oxidises to Cl2.
10. Weight of organic compound = 29.5 mg
NH3 + HCl  NH4Cl
HCl (remaining) + NaOH  NaCl + H2O
(1.5 m mole)
Total milimole of HCl = 2
mili mole of HCl used by NH3 = 2 – 1.5 = 0.5
mili mole of NH3 = 0.5
weight of NH3 = 0.5  17 mg = 8.5 mg
14
weight of nitrogen =  8.5 mg = 7 mg
17
7
 % of Nitrogen in compound =  100 = 23.7 %.
29.5

11. milli mole of Hypo = 0.25 × 48

= 2 × milli mole of Cl2
0.25  48
milli mole of Cl2 = = 6 milli mole
2
= milli mole of Cl2 = milli mole of CaOCl2
6
So, molarity = M = 0.24 M
25

12. CaOCl2 = Ca(OCl)Cl

OCl– – Hypochlorite ion
which is anion of HOCl
Anhydride of HOCl = Cl2O.

SOLUTION OF ADVANCED LEVEL PROBLEM

1. 85.5 = Emetal + EOH–
or 85.5 = Emetal + 17
or Emetal = 68.5

31 27 56 32
2. (a) EP = = 10.33 (b) EAl = =9 (c) EFe = = 28 (d) ES = = 5.33
3 3 2 6

3. 40 g, O  60 g metal
 8 g, O  12 g metal (E)
4. v.f. of Na2S2O3 = 2 (2.5 – 2) = 1
 Eq. wt. = M/1
5. v.f. of KBrO3 = 1 (5 – (– 1)) = 6
M
 Eq. wt. =
6

6. v.f. of oxalic acid = 2 (4 – 3) = 2

M
 Eq. wt. =
2

7. meqH = meqNaOH
2SO4
0.2 × V = 0.02 × 20
V = 2 mL

RESONANCE Equivalent Concept & Titration - 127

8. m eq. of HCl reacted with alkalline earth metal carbonate = (25 × 1) – (50 × 0.1) = 20
 m eq. of alkalline earth metal carbonate = 20
1
 Eq. wt. × 1000 = 20

1000
 Eq. wt. of metal carbonate = = 50
20
Eq. wt. of Metal = Eq. wt. of metal carbonate – Eq. wt. of carbonate
60
= 50 – = 20
2
At wt. of metal = (Eq. wt. of metal) × Valency of metal
= 20 × 2 = 40

9. 2NH3 + H2SO4  (NH4)2SO4

2NaOH + H2SO4  Na2SO4 + 2H2O
 m.eq of H2SO4 neutralized by NH3 = (50 × 1) – (24.5 × 1) = 25.5
 m.moles of NH3 present in double sulphate = 25.5
 25.5 
 Mass of NH3 present in double sulphate =  1000 17  = 0.4335 g
 
0.4335
 % of NH3 in double sulphate = × 100 = 8.67%
5
10. KMnO4 + Fe+2  Fe+3 + Mn+2
milli equivalent of KMnO4 = milli equivalent of Fe2+
140
1 × 5 × M = 1×
56
140  1
M= = 0.5
56  5
KHC2O4.H2C2O4 = 2 C2O42– + KMnO4  Mn2+ + CO2
milli eq. of KMnO4 = milli eq. of KH2 C2O4 . H2C2O4
100 × 5 × 0.5 = 1 × 2 × 2 × M
M = 0.0625
KHC2O4.H2C2O4 + 3NaOH  3H2O + Na2C2O4 + KNaC2O4
meq of KHC2O4.KHC2O4 = meq of NaOH
3 × 1 × 0.0625 = 0.20 × V
3  0.0625 15
V= = 0.9375mL or mL.
0.20 16

11. milli eq. of FeSO4 = milli eq. of KMnO4

N1V1 = N2V2
1
N1 × 25 =  20
10
20
N1 = = M1 (V.f. = 1)
10  25
20
Weight of FeSO4.7H2O, W = × 278 = 22.24g
10  25
22 .24
% of FeSO4 .7 H2O =  100 = 88.96 %
25

12. Redox changes are :

Fe  Fe+2 + 2e– (in H2SO4)
Fe+2  Fe+3 + e– (with K2Cr2O7)
6e + Cr2+6  2Cr+3
1
m.eq. of Fe+2 in 20 mL = m.eq. of K2Cr2O7 = 30 × =1
30
1 100
 m.eq. of Fe+2 in 100 mL = =5
20

RESONANCE Equivalent Concept & Titration - 128

 meq 5
 m.moles of Fe+2 = = = 5 = m.moles of Fe
v.f . 1
 Mass of pure Fe in wire = 5 × 10–3 × 56 = 0.28 g
0.28
% of Fe in wire = × 100 = 99%
0.2828

13. On balancing the reaction,

MnO4– + Fe+2 + H+  Mn+2 + Fe3+
MnO4– + 5Fe2+ + 8H+  Mn2+ + 5Fe3+ + 4H2O
or
KMnO4 + 5FeCl2 + 8HCl  MnCl2 + 5FeCl3 + 4H2O + KCI
10 500
moles 1.07 x 3 = 1.5
158 1000
So, KMnO4 is limiting reagent.
mole of KMnO 4 Mole of FeCl3
 =
1 5
10
mole of FeCl3 = x 5 = 0.316
158

14. Let V mL of reducing agent be used for KMnO4 in different medium which act as oxidant
Acid medium, Mn7+ + n1 e–  Mna+
 n1 = 7 – a
Neutral medium, Mn7+ + n2 e–  Mnb+
 n2 =7 – b
Alkaline medium, Mn7+ + n3 e–  Mnc+
 n3 = 7 – c
meq of reducing agent = meq. of KMnO4 in acid
= meq. of KMnO4 in nautral
= meq. of KMnO4 in alkali
= 1 × n1 × 20 = 1 × n2 × 33.3 = 1 × n3 × 100
 n1, n2,n3 are integers and are  7,
 n1 = 5, n2 = 3 and n3 =1
Therefore, different oxidation state of Mn are :
Acid media, Mn7+ + 5e–  Mna+
 a=+2
Netrual media, Mn7+ + 3e–  Mnb+
 b=+4
Alkaline media, Mn7+ + 1e–  Mnc+
 c=+6
Now, same volume of reducing agent is treated with K2Cr2O7 and therefore,
m.eq. of reducing agent = m.eq. of K2Cr2O7
But, m.eq. of reducing agent = m.eq. of KMnO4 in acid
 m.eq. of KMnO4 in acid = m.eq. of K2Cr2O7
20 × 5 = 1 × 6 × V (v.f. for Cr2O72– = 6)
100
V= = 16.67 mL
6
It is important to note that the conditions are valid only when Mn in each medium exist as monomeric atom,
i.e. not as Mn2.
Balanced equations for three half reactions :
MnO4– + 8H+ + 5e–  Mn2+ + 4H2O (Acidic medium)

MnO4– + 2H2O + 3e–  MnO2 + 4OH– (Neutral medium)

MnO4– + e–  MnO42– (Basic medium)

RESONANCE Equivalent Concept & Titration - 129

15. Sn2+  Sn4+ + 2e
6e + Cr2+6  2Cr+3
Since Sn+2 is oxidized by K2Cr2O7
 m.eq. of Sn+2 = m.eq. of K2Cr2O7 used for oxidation of tin = N × Vin mL

 
 2 .5 
2 .5  N  
= 294 294
× 10 = 1.02   0 .5 
 0.50 
 6 

6
w Sn2
 × 1000 = 1.02
119 / 2
WSn  2 = 0.0607 g

0.0607
 % Sn = × 100 = 15.17 %
0 .4

HCl
16. KIO3 + 5KI  3I2
v.f. = 5 v.f. = 1

0.214
mole (excess) 3×10–3mole
214
I2 + 2Na2S2O3 
v.f. = 2 v.f. = 1, 50 ml, M(say)

3×10–3mole 6×10–3= 50 × M × 10–3  M = 0.12 M.

17. Used millimoles of I2 = 0.05 – 0.002x10/2
= 0.04 = millimoles of Sn2+
wt of tin = 0.04 × 119 = 4.76 mg.

80  0.2
18. Moles of iodine = moles of chlorine = × 10–3 = 8 × 10–3
2

8  71 10 3
so required % = × 100% = 8 %
7.1

19. Excess of Sn2+ = 30 × 0.1 × 5 meq.= 15 meq

Sn2+ consumed = [(35 × 0.5 × 2) – 15] meq
= 20 meq.
Now Cl2 + Sn2+  Sn4+ + 2Cl– (balanced equation)
1 1
So molesof Cl2 = moles of Sn2+ = eq. of Sn2+ = × 20 m moles = 10 mmoles
2 2
= 10 × 10–3 × 71 g = 0.71 g.
0.71
So, required % = × 100 = 7.1%
10

3 KI  CH COOH
2 2 3 Na S O
20. Bleaching powder   I2 
  I– + Na2S4O6

The redox changes are 2e– + I2  2 I–

2S2+2  S4+5/2 + 2e–
m.eq. of available Cl2 = m.eq. of I2 liberated = m.eq. of Na2S2O3 used.
 m.eq. of available Cl2 in 20 mL bleaching powder solution
= m.eq. of Na2S2O3 used
1
= 20 ×
10
1 500
 m.eq. of available Cl2 in 500 mL bleaching powder solution = 20 × × = 50
10 20

RESONANCE Equivalent Concept & Titration - 130

 w
 × 1000 = 50 (w = weight of available Cl2)
71/ 2
50 71
 w= × = 1.775 g
1000 2
1.775
 % of available Cl2 in bleaching powder = × 100 = 35.5%
5

21. H+ + IO3– + I–  I2

On balancing the reaction,
6H+ + IO3– + 5I–  3I2 + 3H2O
Let normality of HCl is X.
I2 + 2S2O3–2  2I– + S4O62–
m.eq. of I2 = m.eq. of Na2S2O3
 (millimoles of I2) × 2 = M × v.f. × V
0.021 x 24  1
milli moles of I2 = = 0.252
2

m.mole of HCl m.mole of  2

Now, =
6 3
25  X / 1 0.252
= (v.f. for HCl = 1)
6 3
 X = 0.02 N

m.mole of IO3 m.mole of  2

=
1 3
0.252
0.2 × V =
3
V = 0.42 mL

1 2
22. Mole of KMnO4 = 20 × 10–3 × = × 10–3
50 5
2
so, mole of Fe2+ = 5 × × 10–3 = 2 × 10–3
5

1 1
so, mole of N2H4 = × 2 × 10–3 = ×10–3
4 2
Now mole of N2H6SO4 = mole of N2H4
1
so, mass of N2H6SO4 = × 10–3×130 = 65 × 10–3 g
2
so, in 10 mL solution, quantity of N2H6SO4 = 65 × 10–3 g
65  10 3
 in 1 liter solution, quantity of N2H6SO4 = ×1000 g = 6.5 g
10

23. Fe3O4 , Fe2O3 , Impurity

  
x mole y mole
In first reaction,

H
Fe3O4 + I–  Fe+2
v.f. = 2
x mole 3x mole

H
Fe2O3 + I–  Fe+2
v.f. = 2
y mole 2y mole

RESONANCE Equivalent Concept & Titration - 131

 (Eq. of Fe3O4 + Eq. of Fe2O3) in 10 mL solution = Eq. of Hypo
10
2(x + y) × = 4.8 × 1 × 10–3
50
2x + 2y = 4.8 × 10–3 × 5
x + y = 12 × 10–3 .....(1)
In IInd reaction,
H
Fe+2 + KMnO4   Fe+3 + Mn+2
v.f. = 1 v.f. = 5
moles 3x + 2y 3.2 × 10–3 × 1
eq. of Fe+2 in 25 mL solution = eq. of KMnO4
10
(3x + 2y) × = 3.2 × 1 × 5 × 10–3
20
3x + 2y = 32 × 10–3 .....(2)
On solving eq. (1) and (2),
x = 8 × 10–3
y = 4 × 10–3
wt. of Fe3O4 = 8 × 10–3 × 232 = 1.856 g
wt. of Fe2O3 = 160 × 4 × 10–3 = 0.64 g
1.856 0.64
% Fe3O4 = × 100 = 30.93 % Ans. ; % Fe2O3 = × 100 = 10.67 % Ans.
6 6

24. Let , weight of H2C2O4 = 'a' g and weight of NaHC2O4 = 'b' g

for acid base reaction
(meq. of H2C2O4 + meq . of NaHC2O4 ) in 10 mL = 3 × 0.1
 meq. of H2C2O4 + meq. of NaHC2O4 in one litre = 3 × 0.1 × 100 = 30
a b
 × 1000 + × 1000 = 30
90 / 2 112 /1
1000 a 1000 b
 + = 30 ......(1)
45 112
For redox change :
C23+  2 C4+ + 2e–
Mn + 5e–  Mn2+
7+

(meq. of H2C2O4 + meq. of NaHC2O4) in 10 mL = 4 × 0.1

 meq. of H2C2O4 + meq. of NaHC2O4 in 1 litre = 4 × 0.1 × 100 = 40
a b
 × 1000 + × 1000 = 40
90 / 2 112 /2

M M
(eq. wt. of H2C2O4 = and eq. wt. of NaHC2O4 = as reductant)
2 2
1000 a 2000 b
 + = 40 ......(2)
45 112
Solving equation (1) and (2), we get :
a = 0.9 g and b = 1.12 g
(Also given : a + b = 2.02 and thus equation (1) or (2) can be used to find a and b by using a + b = 2.02)
25. Let 'a' mole of Cu+2 and 'b' mole of C2O42– be present in solution.
Case I :The solution is oxidized by KMnO4 which reacts with only C2O42–.
5e + Mn+7  Mn+2
C2+3  2C+4 + 2e
 m. eq. of C2O4 = m. eq. of KMnO4
–2

 b × 2 × 1000 = 0.02 × 5 × 22.6

 b = 1.13 × 10–3
Case II : After oxidation of C2O4–2 , the resulting solution is neutralized by Na2CO3, acidified with dilute
CH3COOH and then treated with excess of KI. The liberated I2 required Na2S2O3 for its titration :
KI Na S O 3
Cu+2  Cu+ + I2 22 
 Na2S4O6 + I–

RESONANCE Equivalent Concept & Titration - 132

  m. eq. of Cu+2 = m. eq. of I2 liberated = m. eq. of Na2S2O3 used
 m. eq. of Cu+2 = m. eq. of Na2S2O3 used
a × 1 × 1000 = 11.3 × 0.05 × 1
 a = 5.65 × 10–4
Cu2 a 5.65  10 4 1
 Molar ratio = = = =
C2O 42 b 1.13  10  3 2

26. Number of millimoles of KIO3 in 30 mL of solution = Molarity × Volume in mL

1
= × 30 = 3
10
Given equation : KO3 + 2K + 6HCl  3CI + 3KCl + 3H2O
According to the equation of the reaction given, 1 mole of KIO3 is equivalent to 2 moles of KI
No. of millimoles of K in 20 mL of stock solution = 2 × 3 = 6
50
 No of millimoles of K in 50 mL of the same solution = 6 × = 15
20

1
No . of millimoles of KO3 in 50 mL of solution = × 50 = 5
10
 No . of millimoles of K used with 50 mL of KO3 solution = 2 × 5 = 10 (from reaction)
 No. of millimoles of K used with AgNO3 = 15 – 10 = 5
Ag NO3 + K  AgI + KNO3
1 mole of AgNO3 reacts with 1 mole of KI. Therefore,
 No. of millimoles of AgNO3 is equal to 5 .
 Weight of AgNO3 = 5 × 10–3 × 170 g = 0.85 g
0.85 100
 % of AgNO3 = = 85 %
1

27. Assume 10 mL of titrant, so there is 0.1 × 10 = 1 m.mole NaOH or KMnO4. The acidity is due of
KHC2O4.H2C2O4(KH3A2)
m.eq. of KH3A2 = m.eq. of NaOH
3 × m.mole of KH3A2 = m.mole of NaOH x 1
1
 m.moles of KH3A2 = 1 × = 0.33 ....... (1)
3
m.eq. of KMnO4 = m.eq. of Na2A + m.eq. of KH3A2
5 × m.mole of KMnO4 = m.mole of Na2A × 2 + m.mole of KH3A2 × 4 (C2O42–  2CO2, v.f. = 2)
 5 × 1 = m.mole of Na2A × 2 + 0.33 × 4 (from (1))
 m.mole of Na2A = 1.83 ....... (2)
From (1) and (2),
mNa 2 A 1.83  103  134
mKH3 A 2 = = 3.38
0.33  103  218
 Mixing proportion by mass = 3.38 : 1.
28. The redox changes are :
for reducing of Fe2O3 by zinc dust
Fe23+ + 2e–  2Fe2+
Fe2+  Fe3+ + e–
oxidant + ne–  product
meq. of Fe2O3 in 25 mL
= meq. of Fe3+ in Fe2O3
= meq. of Fe2+ formed
= meq. of oxidant used to oxidize Fe2+ again
 meq. of Fe2O3 in 25 mL = meq of oxidant
= 17 × 0.0167 × n
Where, n is the number of electron gained by 1 mole of oxidant
100
 meq. of Fe2O3 in 100 mL = 17 × 0.0167 × n ×
25

RESONANCE Equivalent Concept & Titration - 133

 1 55.2  1000
 M = 17 × 0.0167 × n × 4
100 
2
molecuar wt. of Fe2O3 = 160
1 55.2  1000  2
 n = 100  160  17  0.0167  4 = 6
Hence, number of moles of electrons gained by one mole of oxidant = 6 .
29. Let total mole of Mg used for MgO and Mg3N2 be 'a' and 'b' respectively.
2Mg + O2  2MgO
Before reaction a 0
After reaction 0 a
3Mg + N2  Mg3N2
Before reaction b 0
After reaction 0 b/3
Now (a + b/3) mole of MgO and Mg3N2 are present in the mixture.
MgO + 2HCl  MgCl2 + H2O ; Mg3N2 + 8HCl  3MgCl2 + 2NH4Cl
'2b'
or the solution contains 'a' mole of MgCl2 from MgO and 'b' mole of MgCl2 from Mg3N2 and mole of NH4Cl.
3
8b
Also mole of HCl used for this purpose = 2a +
3
(for MgO) (for Mg3N2 )
60  12
Now mole of HCl reacted with MgO and Mg3N2 = = 0.048
1000
8b
2a + = 0.048 ... (1)
3
Further, mole of NH4Cl formed = mole of NH3 liberated
= mole of HCl used for absorbing NH3
= Total equivalent of acid – equivalent of base used for back titration
10  6
= = 4 × 10–3
1000

2b
 = 4 × 10–3 or b = 6 × 10–3 ... (2)
3

8  6  10 3
From (1) 2a + = 0.048 or a = 16 × 10–3
3
6
Thus, % of Mg burnt to Mg3N2 = (6  16 ) × 100 = 27.27 %

30. In presence of Hph indicator

m. eq. of HCl = m. eq. of Na2CO3 + m.eq. of NaOH
30  0.1 = (a  1) + (a  1)
 a = 1.5
In presence of MeOH indicator
m. eq. of H2SO4 = m. eq. of Na2CO3 + m. eq. of NaOH
0.15  2  V = (a  2) + (a  1)
V = 15 ml

RESONANCE Equivalent Concept & Titration - 134

 HYDROCARBONS
EXERCISE # 1
PART - I

A-1.

A-2. Symmetrical alkane with even no. of carbon atoms can be prepared by Wurtz reaction.

A-5. CH3CH2Cl CuLi

CH3CH2Li   2CH3CH2 Li + CuI  (CH3CH2)2 CuLi (X)


CH3 – CH2 – CH2 – CH2 – CH2 – CH2 – CH2 – CH2 – CH3

n-nonane
A-6. -keto acid decarboxylate readily.

CH3
|
B-3. Br2 / h CH  C  CH3
    3
|
Br

B-5. Bromine atom has a much higher regioselecvity than chlorine atom in abstracting 30 hydrogen.
B-7. Initial and final energy difference will be –134 kJ/mol.

Electrolysis
C-4.    + 2CO2 + H2 + 2NaOH

C-5. Zn dust
  CH3 – C  C – CH3 (But -2-yne)

C-6.  CH  CH + 6AgI

Electrolysis
C-7.    + 2CO2 + 2NaOH + 2H2O

– H O
C-9. 2Mg+2 ( C  C – C3–) 3 
 Mg (OH)2 + CH  C – CH3 (Propyne)

D-1. Electron releasing group and stability of carbocation will decide rate of reaction in electrophilic addition
reaction.

D-3. C=C at position 1 is more reactive towards electrophile Br  as this is adjacent to O atom to provide +m
effect. C=C at position 3 is more substituted as compared to C=C at position 2. Alkyne is less reactive
towards Br  as compared to alkene.

RESONANCE Hydrocarbon - 135

 
Br – Br –H
E-2.     

Br – Br
E-3.   

Cl H O
E-5. CCl3CH = CH2 2 2

H2 O Migration of CH
3
E-8*. (A)      
 


H shift
(B)    


OH
(C) H2 O / H  
 


H O / H OH
(D) 2  

E-9.

RESONANCE Hydrocarbon - 136

 1. Ring exp .
H O     HO
E-10. 3 
 2. 1, 2CH3 shift 2

BH3 THF H O / OH

E-14. R – CH = CH2   2 
2


NBS
I
E-16. CH2 = CH – CH2 – CH = CH2   CH2 = CH – CH – CH = CH2



NBS
CH2 = CH – CH = CH – CH2 – Br   CH2 = CH – CH = CH – CH2


Zn
F-4.  + Br2


Note : Addition of HBr by free radical mechanism.

– H2O
G-2.  

G-5.* (I) CH2 = C = CH2

CH3  C  CH3 CH2  C  CH3

|| |
O OH

(II) CH3 – C  CH CH3  C  CH 2 CH3  C  CH 3

| ||
OH O
BH / THF tautomeris ation
(III) CH3 – C  CH  3   CH3 – CH  CH – OH 
anti Markonikov
   CH3 CH2 – CHO

(1) BH .THF
G-6. CH3 – CH2 – C  CH ( 2 3
) CH COOD
3

H-2.* (A) when H+ add to the Buta-1, 3-diene in the r.d.s., an allylic carbocation is formed, however from But-1-ene,
an 2º carbocation will form which will be less stable.
(B) At room temperature, product will be TCP.


(C)  C H2 – CH  C  CH2
(carbocation as more stable)
RESONANCE Hydrocarbon - 137
I-5.

I-6. Re agent R 2 Re agent R

         1

Syn addition with Baeyer's Reagent, So cis will form meso compound however peroxy acid in anti addition
gives enantiomer.

I-7. CH3 – CH2 – C  CH   

KMnO 4 CH3CH2COOH + CO2 + H2O

H

(1) O3 CO
I-8.    2
  2CH3COOH
(2) H2O

I-10.


J-1. CH3 – CH2 – CH2 – CH3 +

J-3. +

+ +

J-8. Primary monochloride can be which is chiral

6 (1º H) × 1 = 6 (Chiral) 2 (2º H) × 3 = 6 1 (3º H) × 5 = 5 3 (1º H) × 1 = 3

6
% yield = ×100 = 30%
20

H – H
J-10._ 
  +
– H 2O

RESONANCE Hydrocarbon - 138

 Trans + Br2 Meso
Cis + Br2 d + l (enantiomer)
But-1-ene + Br2

J-11.

J-13.

H
|
Li / NH3 ( ) Br2
J-14.      CH3  C  C  CH3  
CH3–CC–CH3 Birch  (Meso)
reduction | Anti addition
Trans H

K-1.  H (  H O )
2 (Aromatic carbocation)
    
(H2SO 4 )

K-3. () +PhMgBr 

() + PhMgBr  (Not formed)

L-4. Rate of electrophilic substitution  Stability of arenium ion.

Br2 / Fe
L-5.   
 +

L-7.

RESONANCE Hydrocarbon - 139

L-11. (1) Strong activity group (–NH2 and –OH) and –M groups do not shows friedal craft recation.
(2) Vinyl halide and aryl halide do not gives friedal craft recation.

3 AlCl
L-13. + CH3Cl 
 

Br
Br / Fe Br / Fe CH2
L-15. 2
    
monobro mination
2
    
monobro mination

COOH NH2 Br

AlCl3
L-18._ + CH2 = CHCH2Cl  

CH3 CH2Br CH2OH MnO

CH3Cl NBS - 2
L-19._ HO
AlCl3  

L-20._

L-22._ conc. HNO conc. H SO

3   
2 4 + +
 

PART - II
COOH O
1. (A)
COOH
COOH

(B)
O
COOH

(C)
COOH

(D) + 2NaCl

RESONANCE Hydrocarbon - 140

2. (A) CaC2 + H2O  Ca(OH)2 + CH  CH
(B) Mg2C3 + H2 O  Mg (OH)2 + CH3 – C  CH
Kolbe 's
(C)  
Electrolys is

Kolbe 's
(D)  
Electrolys is

(E) 2HCI3 + 6Ag 

Zn
(F) 
 CH – C  CH + 2 Zn Br
powder 3 2

NaI
(G)  CH3 – C  C – CH3 But -2-yne
Acetone

3. (A) –CH=CHCOOH is deactivating due to –I of –COOH group, but o,p-directing due to stability of carbocation.
(B) –CCl3 is electron withdrawing group due to –I nature.
(C) –OH is electron donating due to +m.
–NO2 is electron withdrawing due to –m.

4. (A) Con. H PO
3 
   4


Zn –Hg / HCl
   


(B) AlCl

3 Pd– C / 
  


(C) H Pd– C / 
   


(D)  
HCl ( dry )

– H

RESONANCE Hydrocarbon - 141

(5 to 6)
1
Heat of hydrogenation  stability of alkene

7. Solution by reverse synthesis: W must be terminal alkyne, since it gives white Precipitate with Tollen's
Reagent
Br2
 

– H
10.  

11.

12.

13. + NO2 

EXERCISE # 2

1_. (i)

(ii)

(iii) Ph–Br + CH3–Br Ph–Ph + CH3–CH3 + Ph–CH3

These are wurtz reaction.

RESONANCE Hydrocarbon - 142

 NaOH
4.  
Electrolys is

6. Soda lim e


Br / h
2 five products

1
8._ Stability of alkene  heat of hydrogenation

10._ (i) or R–CC–R

(ii) CH3–CH=CH–CH3 CH3–CC–CH3

NH OH  AgNO
11. 4
CaC2 + H3O  Ca (OH)2 + CH  CH  3
  Ag+ C–  C– Ag+
White ppt.
13. Since the reactivity towards ionic addition  stability of carbocation intermediate formed.

I CH3 – CH = CH – CH3 H 
 CH3  C H  CH2  CH3

II H 


CH3 CH3
| |
H
III Ph  C  CH  CH3  Ph  C  CH2  CH3


Ph CH3
| |
IV H Ph  C  CH2  CH3
Ph  C  CH  CH3 


Stability of carbocation intermediate : IV > III > II > I. reactivity of alkene : IV > III > II > I.

Hg ( OAc )
2 NaBH / NaOH
16. (a) C3H7CH = CH2   
 4
 
THF / H2O

(b) Self explanatory.

(c) Self explanatory.
(d) Self explanatory.

RESONANCE Hydrocarbon - 143

 CH3 H CH3
| | |
dil. aqueous H SO 4 
18. H3 C  C  CH  CH2      2   H3 C  C  C  CH3  H3 C  C  C  CH3
| | | | |
CH3 CH3 OH CH3 CH3
3,3  dim ethyl  1  butene 2, 3  dim ethyl  2  bu tanol 2, 3  dim ethyl  2  butene

23.

HBr  Br 
24. (a) CH3CH2C  CH  CH3CH2 C = CH2  CH3CH2 C = CH2
|
Br
HBr  
H
(b) CH3CH2C  CH  CH3CH2 C = C HBr 
 CH3CH2CH = CHBr
peroxide

Br
(c) CH3CH2C  CH 
2
 CH3CH2 C = CHBr
|
Br

26. This reaction proceeds through a carbocation. Since the alkyl carbocation from the alkene group is more
stable than the vinyl carbocation from the alkyne group.

31. CH3C  C(CH2)3CCCH3  CH3COOH, HOOC(CH2)3COOH, HOOCCH3

32. and

34. CH3 – CH2 – CH –  CuLi + CH3–CH2–Br  CH3 – CH2 – CH – CH2 – CH3  Cl / h
 |  2
 | 
 CH2 – CH3   CH2 – CH3 
2
( X)

4 isomers Fractional distillation

 3 fractions
      
( with one dlpair )

35. After addition of HBr, we get two chiral centres, so total isomers will be four.

36._ H2C  CH  CH  CH3 (d/ by 1,2-addition)

|
Br
H3C–CH=CH–CH2–Br (E/Z by 1, 4-addition)
Thus total isomers is 4.

RESONANCE Hydrocarbon - 144

 EXERCISE # 3
ALKANE
1. Clemmensen’s reagent or Wolf kishner reagent are preferred for reduction of > C = O group into – CH2. With
Zn(Hg) /HCl OH group will also undergo SN reaction.

Pd / H2
2. H3C – H2C – HC = CH2     CH3 – CH2 – CH2 – CH3

Cl / hv
3. 2  

Neopentane only one monochloro product

4. + Cl2  +

Zn / HCl
5.   
Clemmensio n
Re duction

6. + 2 Na  

hv
7. + Br2  

2-Bromo-2-methyl butane

Cl 2 / hv
8.    +

+ +

N=6 ,P=4

9. Cl / h
2

RESONANCE Hydrocarbon - 145

 +

Total = 8

10.

Four monochloro derivatives are chiral.

11. single product.

ALKENE & ALKYNE

O
HgSO4 ||
Tautomerise
4. (A) CH3 – CH2 – C  CH + H2O   CH3  CH2  C  CH2     CH3  CH2  C  CH3
Dil. H2SO4
|
OH
(Because keto form is more stable than enol)
5. Terminal alkyne gives white ppt with ammonical silver nitrate.
CH3 —C  CH + NH3 + AgNO3  CH3 —C  C. Ag + NH4NO3
white ppt.

while propene does not give any reaction with ammonical AgNO3 due to absence of acidic hydrogen.
6. Addition of bromine to an alkene is an anti addition a symmetrical trans alkene on anti addition forms a meso
compound. Also in addition of alkene first of all Br attacks therefore it is an electrophilic addition.

7. CH3–CH2–CCH + NH4Cl + H2O

8. CH3–CH2–CH2–Br CH3–CH=CH2

9. H
Ph – C  C – CH3 

H O
 2

O
||
Ph  C  CH2  CH3

' A'
(Keto  form)

RESONANCE Hydrocarbon - 146

10. Pd / H2
CH3– CH2 – CH = CH2    CH3 – CH2 – CH2 – CH3

11. 2HOCl
HC  CH   
  
 H2O

12. H O
3

1
14. Boiling Point  surface area  Branching
Iso butene has smallest vander wall surface area of contact so its boiling point least.

HBr
15. CH2 = CH – CH = CH2 
 CH3 – CH = CH – CH2 – Br
40 º C
(80%) (1,4)
Thermodynamically product

16.

17. CH2  CH  CH3

| |
NO Cl

18.

19.  

20.
RESONANCE Hydrocarbon - 147
 Na / Liq NH
3
21. CH3CH2 CCH     


3 O Zn, H O
2
22. CH3CH=CHCH3 
        
Re ductive ozonolysis

23. CnH2nO = 44
CnH2n = 44 – 16
CnH2n = 28
n=2
O / Zn
CH3–CH=CH–CH3 3 CH3–CH=O
Sol. (24 & 25)

26.
Presence of one vinyl group gives formaldehyde as one of the product in ozonolysis.
BENZENE
1. 'N' has lone pair, so it is activating and o/p directing % p > % O.

3. It is ArSE 2 reaction, N has lone pair so it is activating and subtitutions accurs at most activated position.

4. Reaction involved are

(1) A  B
3H2SO 4 + 2NaBr + MnO2  Br2 + MnSO4 + 2NaHSO4 + 2H2O
(A ) (B )
(2) A  C

2H2SO4 + H  O  N  O  


O

RESONANCE Hydrocarbon - 148

5.

Note : (–NH– part is p-directing).

CH3
CH3 CH3

FeCl 3
Cl
6. + Cl2   +

o–chlorotoluene Cl
p–chlorotoluene
The reaction proceeds by electrophilic substitution mechanism. The CH3 group is o/p directing.
7. –NO2 group in benzene ring shows –  and – R effect, which deactivates the ring towards electrophilic
substitution but activates it towards nucleophilic substitution.

SOLUTION OF ADVANCED LEVEL PROBLEM

1. Na /(Dry ether ) +
      

Cl / hv (i) Li
2. 2 
(ii) CuI

3.  +

CH3 CH3 CH3

|
| Li | CuI CH3 – CH– CH2 –I
4. CH3CH  Br  CH3CH  Li        2,4-Dimethylpentane.

5. 

CH3
|
6. Products are CH3  C  Cl and CHCl3
|
CH3

RESONANCE Hydrocarbon - 149

9. 1° C – H = 12 × 1 = 12
2° C – H = 2 × 3 = 6
3° C – H = 2 × 6 = 12
----------------------------
6
Minimum yield = × 100 = 20%
30
Ans. 20 %
10. 1º halides : BrCH2CH2CH2CH3  CH2=CHCH2 CH3
BrCH2CH(CH3)2  CH2 = C(CH3)2
3º halides : (CH3)3 CBr CH2 = C(CH3)2

alc.KOH
11. C5H11X   
 CH3–CH2–CH2–CH=CH2 / CH3–CH2–CH=CH–CH3
– HX
pent-1-ene pent-2-ene
Thus possible structure of halide may be
(a) CH3CH2–CH2–CH2–CH2–X (b)

Pent -1-ene only Pent-2-ene only

13. Pentene exist in the following isomeric forms :
; ;

and the stability order is :

Pent-1-ene < pent-2-ene (cis) < pent-2-ene (trans) < 2-methylbut-2-ene
(Since stability increase with increasing number of electron releasing alkyl group).

1. Ring exp ansion

16.     

2. H

17.

 –
 Cl
18. 

RESONANCE Hydrocarbon - 150

20. (A) HBr (B)


31.BD .
21. D2 / Lindlar's catalyst
CH3C  CCH3     CH C  CCH
 2. CH3 COOD
3 3

1.BD .THF 1.BH .THF

22. CH3C  CCH3 3  3
    CH3C  CCH3

2. CH3 COOH 2. CH3 COOD

26._ Cl h alc. KOH /  NBS alc. KOH / 

2   

Br
27._ H2C=CH–CH=CH–CH=CH2 
 +

(C) will be thermodynamically controlled.

KMnO / H
28.   4  O = C = O +

29. The products of ozonolysis are 2-pentanone and acetaldehyde. Writing the structure of both the carbonyl
compounds.

Removing =O of the compounds and linking both through double bond, we get the alkene.

Thus, the alkene is 3-methylhex-2-ene.

Reaction :

RESONANCE Hydrocarbon - 151

31.

32.

33. (a)

(b)

RESONANCE Hydrocarbon - 152

 (c)

(d)

34. (A) But-2-yne + Na / liq. NH3  trans But-2-ene + Br2  Meso-2,3-dibromobutane
(B) But-2-yne + Lindlar  cis But-2-ene + HOCl/H+  Racemic -3-chloro-2-butanol
(C) But-2-yne + Lindlar  cis But-2-ene + Beyer’s reagent  Meso - 2,3-butanediol
(D) But-2-yne + Birch  trans But-2-ene + (i) HCOOOH / (ii) H3O+  Racemic-2,3-butanediol

COOH
H OH
36. (A) and its enantiomer - a case of syn addition.
HO H
COOH
Mixture is optically inactive (racemic mix).
COOH
H OH
(B) meso form by anti addition
H OH
COOH
COOH
H OH
(C) and its enantiomer by anti addition.
HO H
COOH
COOH
H OH
(D) meso by syn addition
H OH
COOH

RESONANCE Hydrocarbon - 153

38. 3 2 1

'X' will be :

H H
| + |
H (H 2SO 4) CH 2= C – CH2CH3 + CH3– CH = CH – CH 3
H3 C  C  CH2 CH3
| (cis + trans)
OH 3 alkenes

H H
| | -
HCl / ZnCl2 Cl
CH3  C  CH2 CH3     CH3  C  CH2  CH3 CH 3 – CH – CH 2 – CH 3
| 
|
OH Cl
(R +S) 2 isomers

H
|
CH3  C  CH2CH3 3CrO / H
   CH3  C  CH2  CH3 (one oxygen atom)
| Oxidation ||
OH O

SOCl2 anhydrous
42. o-HOOC–C6H4–CH2–C6H5     
AlCl3

Zn  Hg
  

HCl

H
O -
CH2 – CH2OH
+
O ---- AlCl3
43. AlCl3 + CH 2 CH2 
CH 2 CH 2

Ph HO – CH – CH2 – Cl CH = CH2
C CH2 NaOH +
  HOCl / H
H O



44. 2NO
 


RESONANCE Hydrocarbon - 154