DPP-1

Electrochemistry
SECTION – 1 : STRAIGHT OBJECTIVE TYPE

1.1

The E° in the given diagram is,

(A) 0.5 (B) 0.6 (C) 0.7
(D) 0.8

1.2 What is cell entropy change of the following cell?

Pt(s) | H2(g) | CH3COOH, HCl || KCl (aq) |Hg2Cl2| (s) | Hg
P = 1 atm 0.1M 0.1M
Emf of the cell is found to be 0.045 V at 298 K and temperature coefficient is
3.4  10 – 4 V K – 1
Given Ka (CH3COOH) = 10 – 5 M
(A) 60 (B) 65.2 (C) 69.2 (D) 63.5

1.3 Following cell has EMF 0.7995 V.

Pt | H2 (1 atm) | HNO3 (1M) || AgNO3 (1M) | Ag
If we add enough KCl to the Ag cell so that the final Cl- is 1M. Now the
measured emf of the cell is 0.222 V.
The Ksp of AgCl would be :
(A) 1  10 – 9.8 (B) 1  10 – 19.6 (C) 2  10– 10 (D)
–14
2.64  10

1.4 Zn Amalgam is prepared by electrolysis is aqueous ZnCl2 using Hg cathode

(9gm). How much current is to be passed through ZnCl2 solution for 1000
seconds to prepare a Zn Amalgam with 25% Zn by wt. (Zn = 65.4)
(A) 5.6 amp (B) 7.2 amp (C) 8.85 amp (D) 11.2 amp

1.5 The solubility of [Co(NH3)4Cl2] CIO4_________ if the λ Co(NH ) Cl = 50, λ CIO =
3 4 2 4

70, and the measured resistance was 33.5  in a cell with cell constant of
0.20 is ____.
(A) 59.7 mmol/L (B) 49.7 mmol/L (C) 39.7 mmol/L (D) 29.7 mmol/L

1.6 We have taken a saturated solution of AgBr.Ksp of AgBr is 12  10 – 14 . If 10 –

7
mole of AgNO3 are added to 1 litre of this solution then the conductivity of
this solution in terms of 10 – 7 Sm – 1 units will be
[Given λ°(Ag ) = 4  10 – 3 Sm2 mol – 1 λ°(Br  ) = 6  10 – 3 Sm2 mol – 1,
5  10 – 3Sm2mol-1]
(A) 39 (B) 55 (C) 15 (D) 41
1.7 At 298K the standard free energy of formation of H2O(  ) is – 237.20kJ/mole
while that of its ionisation into H+ iion and hydroxyl ions is 80 kJ/mole, then
the emf of the following cell at 298 K will be
H2(g,1 bar) | H+ (1M) || OH– (1M) | O2 (g, 1bar)
(A) 0.40 V (B) 0.81 V (C) 1.23 V (D) – 0.40 V

1.8 Which of the following cell can produce more electric work.
(A) pt,H2|NH4Cl||0.1MCH3COOH|H2,pt (B) pt,H2|0.1MHCl||0.1MNaOH|H2,pt
(C) pt,H2|0.1MHCl||0.1MCH3COOK|H2,pt(D)
pt,H2|0.1MCH3COOK||0.1MHCl|H2,pt

1.9 A hydrogen electrodes is immersed in a solution with pH = 0 (HCl). By how

much will the potential (reduction) change if an equivalent amount of NaOH is
added to the solution. (Take PH2 = 1 atm) T = 298 K.
(A) increase by 0.41V (B)increase by 50mV (C)decrease by 0.41V
(D)decrease by 59mV

[Br - ]
1.10 At what does the following cell have its reaction at equilibrium?
[CO32  ]
Ag(s) | Ag2CO3(s) | Na2CO3 (aq) || KBr(aq) | AgBr(s) | Ag(s)
KSP = 8  10 – 12 for Ag2CO3 and KSP = 4  10 – 13 for AgBr
(A) 1  10 – 7 (B) 2  10 – 7 (C) 3  10 – 7 (D) 4  10 – 7

1.11 Calculate the EMF of the cell at 298 K

Pt|H2(1atm)|NaOH(xM),NaCl(xM)|AgCl(s)|Ag
If E°cl-/AgCl/Ag = + 0.222 V
(A) 1.048 V
(B) – 0.04 V
(C) – 0.604
(D) Emf depends on x and cannot be determined unless value of x is given

1.12 A current of 0.1A was passed for 2hr through a solution cuprocyanide and
0.3745g f copper was deposited on the cathode. Calculate the current
efficiency for the copper deposition.
(A) 79% (B) 39.5% (C) 63.25% (D) 63.5%

1.13 With t taken in seconds and I taken in Amp, the variation of I follows the
equation
t2 + I2 = 25
what amount of Ag will be electrodeposited with this current flowing in the
interval 0-5 second ? (Ag : 108)
(A) 22mg (B) 66mg (C) 77mg (D) 88mg

1.14 The following cell has a potential of 0.55 V at 25°C

Pt(s) | H2(1atm)| H+ (? M) || Cl- (1M)| Hg2Cl2(s)| Hg(  )
What is the pH of the solution in the anodic chamber? E° Cl-/Hg2Cl2/Hg = 0.28 V
(A) 4.57 (B) 14.07 (C) 9.15 (D) 7.15
1.15 A resistance of 50  is registered when two electrodes are suspended into a
beaker containing a dilute solution of a strong electrolyte such that exactly
half of the them are submerged into solution. If the solution is diluted by
adding pure water (negligible conductivity) so as to just completely submerge
the electrodes, the new resistance offered by the solution would be
(A) 50  (B) 100  (C) 25  (D) 200 

1.16 The standard reduction potential of a silver chloride electrode is 0.2 V and that
of a silver electrode is 0.79 V. The maximum amount of AgCl that can
dissolve in 106 L of a 0.1 M AgNO3 solution is
(A) 0.5 mmol (B) 1.0 mmol (C) 2.0 mmol (D) 2.5 mmol

1.17 Calculate the cell EMF in mV for

Pt|H2(1atm) |HCl(0.01M)|AgCl(s)| Ag(s) at 298 K
If  G°r values are at 25°C
kJ kJ
- 109.56 for Agcl(s) and – 130.79 for (H+ + Cl-) (aq)
mol mol
(A) 456 mV (B) 654 mV (C) 546 mV (D) None of
these.

1.18 Adiponitrile is manufactured electrolytically from acrylonitrile

CH2 = CHCN   CN – (CH2)4 – CN
How many kg of adiponitrile (molecular mass = 108) is produced in 9.65 hr
using a current of 3750 A with 80% efficiency/
(A) 30 kg (B) 58 kg (C) 60 kg (D) 80 kg

1.19 It is observed that the voltage of a galvanic cell using the reaction M(s) +
x
xH+   Mx+ + H2 varies linearly with the log of the square root of the
2
hydrogen pressure and the cube root of the Mx+ concentration. The value of x
is
(A) 2 (B) 3 (C) 4 (D) 5

1.20 During the electrolysis of 0.1 M CuSO4 solution using copper electrodes, a
depletion of [Cu++] occurs near the cathode with a corresponding excess near
the anode, owing t inefficient stirring of the solution. If the local concentrations
of [Cu++] near the anode & cathode are respectively 0.12 M & 0.08 M,
calculate the back e.m.f. developed. Temperature = 298 K.
(A) 22 mV (B) 5.2 mV (C) 29 mV (D) 59 mV

1.21 Acetic acid has Ka = 1.8  10 – 5 while formic acid had Ka = 2.1  10–4. What
would be the magnitude of the emf of the cell
0.1M acetic acid  0.1M formic acid 
Pt(H2) Pt(H2) at 25°C
0.1M sodium acetate 0.1M sodium formate
(A) 0.0315 volt (B) 0.0629 volt (C) 0.0455 volt (D) 0.0545 volt
1.22 Consider the cell Ag(s)|AgBr(s)|Br-(aq)||AgCl(s)|Cl-(aq)|Ag(s) at 25°C. The
solubility product constants of AgBr & AgCl are respectively 5  10 – 13 & 1 
10 – 10. For what ratio of the concentrations of Br- & Cl- ions would the emf of
the cell be zero ?
(A) 1 : 2000 (B) 1 : 100 (C) 1 : 500 (D) 200 : 1

1.23 Value of  m  for SrCl2 in water at 25°C from the following data:
Conc. (mol/lt) 0.25 1
-1 2 -1
 m (  cm mol ) 260 250
(A) 270 (B) 260 (C) 250 (D) 255

1.24 Calculate the useful work of the reaction Ag(s) + 1/2Cl2(g)  AgCl(s)
Given E°cl2/cl- = + 1.36 V, E°AgCl/Ag,Cl- = 0.22 V
If Pcl2 = 1 atm and T = 298 K
(A) 110 kJ/mol (B) 220 kJ/mol (C) 55kJ/mol (D) 1000 kJ/mol

1.25 Which of these ions Cu+, Co3+, Fe2+ is stable in aqueous medium.
Given : E°Cu2+/Cu+ = 0.15 volt ; E°Cu+/Cu = 0.53 V ; E°Co3+/Co2+ = 1.82
V;
E°Fe3+/Fe2+ = 0.77 V ; E°Fe2+Fe = - 0.44 V ; E°O2,H+/H2O = 1.23 V
(A) Cu , Co3+
+
(B) Co3+ (C) Cu+ (D) Co3+, Cu+
2+
,Fe

1.26 Select the correct statement if -

E°Mg2+/Mg = - 2.4V, E°Sn4+/Sn2+ = 0.1 V, E°MnO4-,H+/Mn2+ = 1.5 V, E° I2/I- = 0.5 V
Here,
(A) MnO4– is the strongest Oxidizing Agent and Mg is the strongest Reducing
Agent.
(B) Sn4+ + 2I-   Sn2+ + I2 is a spontaneous reaction.
(C) Mg2+ + Sn2+   Mg + Sn4+ is a spontaneous reaction.
(D) Here, Weakest oxidizing agent is Sn4+ and weakest reducing agent is
Mn2+.

1.27 What is the value of pKb (CH3COOH-) if λ m = 390 & λ m = 7.8 for 0.04 of a
CH3COOH at 25°C
(A) 9.3 (B) 9.2 (C) 4.7
(D) 4.8

1.28 The temperature coefficient of a standard Cd-cell is – 5.0  10– 5 Vk– 1 whose
emf at 25°C is 1.018 V. During the cell operation, the temperature will -
(A) increase (B) decrease (C) either (D) remains
constant

1.29 A cell Ag | Ag+ || Cu++ | Cu initially contains 2M Ag+ and 2M Cu++ ions. The
charger in cell potential after the passage of 10 amp current for 4825 sec is:
(A) – 0.000738 V (B) – 1.00738 (C) – 0.0038 V (D) none
1.30 For the cell (at 298 K)
Ag(s) | AgCl(s) | Cl-(aq) || AgNO3(aq) | Ag(s)
Which of the following is correct –
(A) The cell emf will be zero when [Ag+]a = [Ag+]c ([Ag+] in anodic compartment
= [Ag+] in cathodic compartment)
(B) The amount of AgCl(s) precipitate in anodic compartment will decrease
with the working of the cell.
(C) The concentration of [Ag+] = constant, in anodic compartment during
working of cell.
0.059 1
(D) Ecell = E°Ag+ | Ag – E°Cl-|AgCl|Ag  log 
1 [Cl ]a

1.31 Acetic acid is titrated with NaOH solution. Which of the following statement is
correct for this titration?
(A) Conductance increases upto equivalence point, then it decrease.
(B) Conductance decreases upto equivalence point, then it increase.
(C) First conductance increases slowly upto equivalence point and then
increases rapidly.
(D) First conductance increases slowly upto equivalence point and then drops
rapidly.

1.32 During an electrolysis of conc. H2SO4, perdissulphuric acid (H2S2O8) and O2

from in equimolar amount. The amount of H2 that will form simultaneously will
be (2H2SO4  H2S2O8 + 2H+ + 2e-)
(A) thrice that of O2 in moles (B) twice that of O2 in moles
(C) equal to that of O2 in moles (D) half of that of O2 in moles

SECTION – II : MULTIPLE CORRECT ANSWER TYPE

1.33 In which of the following cell (s) : Ecell = Ecell° ?

(A) Cu(s)|Cu2+ (0.01M)||Ag+(0.1M)|Ag(s)
(B) Pt(H2)|pH = 1 ||Zn2+(0.01M)|Zn(s)
(C) Pt(H2)|pH = 1 ||Zn2+(1M)|Zn(s)
(D) Pt(H2)|H+ = 00.1 ||Zn2+(0.01M)|Zn(s)

1.34 Which one is/are correct among the following?

Given, the half cell emf’s E°Cu+2|Cu = 0.337, E°Cu+1|Cu = 0.521
(A) Cu+1 disproportionates
(B) Cu and Cu2+ comproportionates (reserve of disproportionates into Cu+).
(C) E°Cu|Cu+2 + E°Cu+1|Cu is positive
(D) All of these

1.35 Indicate the correct statements:

(A) Conductivity cells have cell constant values independent of the solution
filled into the cell.
(B) DC (direct current) is not used for measuring the resistance of a solutn.
(C) Kohlrausch law is valid both for strong and weak electrolytes.
(D) The k decreases but λ M and λ E increase on dilution.
1.36 The standard redox potential E° of the following systems are
System E° (volts)
(i) MnO4 + 8H+ + 5e- 
-
 Mn2+ + 4H2O 1.51
2+ 4+ -
(ii) Sn   Sn + 2e - 0.15
(iii) Cr2O7 + 14H+ + 6e- 
2-
 2Cr3+ + 7H2O 1.33
(iv) Ce3+   Ce4+ + e- - 1.61
The oxidizing power of the various species are related as
(A) Cr2O72- > MnO4- (B) Ce4+ > Sn4+ (C) Ce4+ > MnO4- (D) MnO4- > Sn4+

1.37 Mark out the correct statement(s) regarding electrolytic molar conductivity.
(A) It increase as temperature increases.
(B) It experiences resistance due to vibration of ion at the mean position.
(C) Increase in concentration decrease the electrolytic molar conductivity of
both the strong as well as the weak electrolyte.
(D) Greater the polarity of solvent, greater is the electrolytic molar conduction.

SECTION - III : ASSERTION & REASON TYPE

1.38 Statement-1: In electrochemical cell, we cannot use KCI in the salt bridge if
anodic or cathodic compartment consists of Ag+ of Pb2+ ion.
Statement-2: Salt bridge is employed to maintain the electrical neutrality and
to minimize the liquid-liquid junction potential.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct
explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct
explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

1.39 Statement-1: Zinc protect the iron better than tin even after it cracks.
Statement-2: E°OPzn < E°OPfe But E°OPSn > E°OPfe
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct
explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct
explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

1.40 Statement-1: On increasing dilution, the specific conductance keep on

increasing.
Statement-2: On increasing dilution, degree of ionization of weak electrolyte
increase and mobility of ions also increase.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct
explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct
explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.
1.41 Statement-1: For the reaction : Ni++ + 2e--  Ni
++
Fe + 2e-- 
 Fe
 E°Fe++ |Fe < E°Ni++ | Ni and E°red > 0
 So Fe electrode is cathode and Ni electrodes and Ni electrode is
anode.

Statement-2: Because  G° < 0 and E°cell > 0, so cell is possible.

(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct
explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct
explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

SECTION-IV : TRUE & FALSE TYPE

1.42 Identity the ture and false statement and answer in given options
1. During electrolysis of 1M NaCl solution Cl2 does not form at the anode.
2. For a concentration cell with its reaction at equilibrium both Ecell and
E°cell are zero.
3. In a solution of HCN the concentration of CN- ions is given by 10-pH.
(A) FTF (B) TTT (C) FFF (D) FTT

1.43 KMnO4 librates O2 from water in presence of an acid.

Given, E°MnO4,Mn+2,H+|Pt = 1.51 V
E°H+|O2|Pt = 1.223 V

1.44 The standard potentials of some metal-insoluble salt-anoin electrode are as

given below
Ag – AgCl E°red = 0.222
Ag – AgBr = 0.03
Ag – AgI = - 0.151
Ag – Ag2S = - 0.69
Then the KSP values must follow:
KSP (AgCl) > KSP (AgBr) > KSP(AGI) > KSP (Ag2S)

1.45 If the E° for N2O4 + 2H+ + 2e 

 2HNO2 is 1.07 V. Then the standard cell
emf of the cell 2N2O4 + 2H2  4HNO2 will be 2.14 volt:

1.46 At 300 K specific conductivity of ethanol is 4  10-10 mho cm-1. The ionic
conductance of H+, C2H5O- at this temperature is 300 and 100 mho cm2
equivalent-1 respectively. Then the negative logarithm of ionic product of
alcohol will be 18.

1.47 Metallic sodium cannot be prepared from electrolysis of an aqueous solution

of NaCl because the SRP H2O < SRP Na+.

1.48 The process of AgCN + KCN 

 K[Ag(CN)2] involves the oxidation of Ag.
 SECTION – V : COMPREHENSIN TYPE

Comprehension # 1
A fuel cell is a cell that is continuously supplied with an oxidant and a
reductant so that it can deliver a current indefinitely.
Fuel cells offer the possibility of achieving high thermodynamic efficiency in
the conversion of Gibbs energy into mechanical work. Internal combustion
engines at best convert only the fraction (T2 – T1)/T2 of the heat of combustion
into mechanical work.
G
While the thermodynamic efficiency of the fuel cell is given by, η  , where
H
 G is the Gibbs energy change for the cell reaction and  H is the enthalpy
change of the cell reaction.
A hydrogen-oxygen fuel cell may have an acidic or alkaline electrolyte.
2.303RT
Pt|H2(g)|H+(aq.)||H2O(  )|O2(g)|Pt; = 0.06
F
The above fuel cell is used to produce constant current supply under constant
temperature & 30 atm constant total pressure condition in a cylinder. If 10
moles H2 and 5 moles of O2 were taken initially. Rate of combustion of O2 is
10 milli moles per minute.
The half cell reactions are
1
O2(g) + 2H+ (aq) + 2e-   H2O (  ) E° = 1.246V
2
2H+ (aq) + 2e-   H2(g) E° = 0
To maximize the power per unit mass of an electrochemical cell, the
electronic and electrolytic resistances of the cell must be minimized. Since
fused salts have lower electrolytic resistances than aqueous solutions, high-
temperature electrochemical cells are of special interest for practical
applications.

1.49 Calculate e.m.f. of the given cell at t = 0. (log 2 = 0.3).

(A) 1.255 V (B) 1.35 V (C) 1.3 V (D) 1.246 V

1.50 The above fuel cell is used completely as an electrolytic cell with Cu
voltameter of resistance 26.94  using Pt electrodes. Initially Cu voltameter
contains 1 litre solution of 0.05M CuSO4.[H+] in solution after electrolysis
(Assuming no change on volume of solution).
(A) 0.015 M (B) 0.03 M (C) 0.025 M (D) 0.01 M

1.51 If λ m  (Cu2+) = 0.01S m2 mole -1, λ m  (H+) = 0.035 S m2 mole-1 and λ m  (SO42-)
= 0.016 S m2 mole-1, specific conductivity of resulting solution left in sopper
voltameter after above electrolysis is
(A) 2.57 S m-1 (B) 1.75 S m-1 (C) 1.525 S m-1 (D)
-1
2.25 S m
Comprehension # 2

REDOX TITRATIONS

Titrations are one of the methods we can use to discover the precise
concentrations of solution. A typical titration involves adding a solution from a
burette to another solution in a flask. The endpoint of the titration is found by
watching a colour change taking place. However, a problem arises when a
suitable indicator cannot be found, or when the colour changes involved are
unclear. In cases redox potential may sometimes come to the rescue.

A particularly well known example (Fig.1) is a method of discovering the

concentration of iron in a solution by titrating them with a solution of cerium
(IV). The redox potential that are of interest here are E°Fe3+/Fe2+ = + 0.77 V and
E°Ce4+/Ce3+ = + 1.61 V. These tell us that cercium (IV) ions are the oxidizing
agents, and iron (II) ions are the reducing agent. They should react according
to the equation
Fe2+ (aq) + Ce4+ (aq)  Fe3+ (aq) + Ce3+ (aq)
Now imagine that we know the concentration of the cerium (IV) ions solution
in the burette. We want to measure the concentration of the iron (II) solution. If
we add just one drop of the cerium (IV) solution from the bruette, some of the
iron (II) ions will be oxidised. As a consequence the beaker would now contain
a large number of unreacted ions, but also some iron (III) ions as well. All of
the cerium (III). The solution in the beaker now represents an iron(III)/iron(II)
half cell, although not at standard conditions. Thus the e.m.f. of the cell will be
near, but not equal, to E°Fe3+/Fe2+.
If we continue to ad cerium (IV) solution, the number of iron (II) ions is
gradually reduced and eventually only a very few are left (Table).At this stage
the next few drops of cerium (IV) solution convert all the remaining iron (II)
ions into iron (III), and some of the cerium (IV) ions are left unreacted. Once
this happens we no longer ions and a smaller number of cerium (IV) ions. The
solution in the beaker now behaves as a cerium (IV)/cerium (III) half-cell
(although not a standard one).

Just before all the iron (II) ions are converted into iron (III) we have a cell with
an e.m.f.of around + 0.77 V. After all the iron (II) ions are oxidised, we have a
cell with an e.m.f. of about + 1.61 V. This rapid rise in e.m.f. occurs with the
addition of hust one drop of cerium (IV) solution. You should be able to
understand why a graph of cell e.m.f. against volume of cerium (IV) solution
added looks like that of Fig. 2. The end point of the titration can be read from
the graph and the concentration of the iron (II) solution calculated in the usual
way
1.52 When an ion is converted into a complex ion, the redox potential changes.
You can see this in the case of the e.m.f. of the iron (III)/ iron (II) system (+
0.77 V) and the hexacyanoferrate (III)/ hexacyanoferrate (II) system (+0.36 V).
The cyanide ion is said to stabilize the oxidation state of the iorn. If you were
to make up a cell
Fe(CN)6 3 (aq), Fe(CN)6 4  (aq) Fe3 (aq), Fe 2  (aq),
Pt(s) , Pt(s)
1mol dm 3 1mol dm 3

What would be the e.m.f. and what would be the cell reaction?
(A) 0.41V, Fe(CN)64- (aq.) + Fe3+(aq.) 
 Fe(CN)63-(aq.) + Fe2+ (aq.)
(B) 0.13V, Fe(CN)64- (aq.) + Fe3+(aq.) 
 Fe(CN)63-(aq.) + Fe2+ (aq.)
(C) 0.41V, Fe(CN)63- (aq.) + Fe2+(aq.) 
 Fe(CN)64-(aq.) + Fe3+ (aq.)
(D) 0.13V, Fe(CN)63- (aq.) + Fe2+(aq.) 
 Fe(CN)64-(aq.) + Fe3+ (aq.)

1.53 The cell shown below was set up

Fe3 (aq), Fe 2  (aq), Br(aq), Br2 (), Pt(s)
Pt(s)
1mol dm 3 1mol dm 3

What would be the cell e.m.f.? If potassium cyanide solution were added to
the left hand half cell (with due care!), what would you expect to happen to the
e.m.f. of the cell? E°Br2/Br- = 1.07V and use data of previousquestion, if
required.

(A) 0.30 V, emf will increase from 0.30V to 0.41V

(B) 1.84 V, emf will decrease from 1.84V to 1.43V
(C) 0.30 V, emf will increase from 0.30V to 0.71V
(D) 0.30 V, emf will increase from 0.30V to 0.43V
1.54 Imagine you were given a solution of potassium dichromate (VI) in a beaker,
and a solution of iron (II) sulphate in a burette. You do not know the
concentration of dichromate (VI) ions, but the concentration of the iron (II)
solution is known. Your task is to carry out a redox titration using the two
solutions in order to determine the concentration of dichromate(VI) ions.
Sketch a graph how the e.m.f. changes in the course of above titration.
E°Cr2O2-7/Cr3+ = 1.33 V, E°Fe3+/Fe2+ = 0.77 V.

Comprehension # 3
The molar conductance of NaCl varies with the concentration as shown in the
following table.
λ Cm  λ m  b C Where λ Cm = molar specific conductance
λ m = molar specific conductance at infinite
dilution
C = molar concentration
 Molar Concentration Molar Conductance
of NaCl In ohm-1 cm2 mole-1

4  10-4 107
9  10-4 97
16  10-4 87

When a certain conductivity cell (C) was filled with 25  10-4(M) NaCl solution.
The resistance of the cell was found to be 1000 ohm. At infinite dilution,
conductance of Cl- and SO4 – 2 are 80 ohm-1cm2mole-1 and 160 ohm-
1
cm2mole-1 respectively.

1.55 What is the molar conductance of NaCl at infinite dilution?

(A) 147 ohm-1cm2mole-1 (B) 107 ohm-1cm2mole-1
(C) 127 ohm-1cm2mole-1 (D) 157 ohm-1cm2mole-1

1.56 What is the cell constant of the conductivity cell (C)

(A) 0.3895 cm–1 (B) 3.85 cm–1 (C) 38.5 cm–1 (D) 0.1925 cm–1

1.57 If the cell (C) is filled with 5  10-3 (N) Na2SO4 the observed resistance was
400 ohm. What is the molar conductance of Na2SO4.
(A) 19.25 ohm-1cm2mole-1 (B) 96.25 ohm-1cm2mole-1
-1 2 -1
(C) 385 ohm cm mole (D) 192.5 ohm-1cm2mole-1

Comprehension # 4
METALLURGY OF COPPER

Electrolytic purification of copper is required since the product of the

Bessemer convert is impure. Sheets of pure copper are made the cathodes
and blister copper is used as the cathodes. The bath contains CuSO4, H2SO4
and NaCl. Metallic copper goes into solution as Cu+2 ions at the anode and
deposited at the cathode. Zinc and iron go into solution and do not deposit at
the cathode along with copper. Silver goes into solution as Ag+ ions, but
forms sludge in the electrolysis cell. The noble metals such as gold and
platinum do not dissolve; they fall to the bottom when released from the
copper anode. They help to pay for the copper refining process.

1.58 In what form will solver be recovered from the plating bath?
(A) Ag+ (B) AgCl (C) Ag (D) Ag – Cu alloy

1.59 The different chemical behaviour of various metal ions (for example only Cu is
deposited on the cathode) involved are explainable best using
(A) their amount in impure copper (B) the electrochemical series
(C) their ionization potentials (D) their hydration energies
1.60 The voltage is kept low enough during the operation. This is to ensure that
(A) Fe+2 and Zn+2 ions are kept in solution only
(B) there is no risk of electric shocks to the plant operators
(C) gold and platinum do not dissolve in solution and are recovered as solids
(D) temperature control is maintained to effect reaction rate control

1.61 What approximate purity may be achieved in this process ?

(A) 90% (B) 95% (C) 99% (D) 99.9%

1.62 The most important role of various electrolytes added to the electrorefining
bath in this case is
(A) to reduce the temperature of bath
(B) to result in good electrical connectivity so as to have high production rates
(C) so that the anode acts as an attackable electrodes
(D) to enhance the viscosity of electrolyte thus preventing leakage from bath.

Comprehension # 5
A solution that is relatively resistance to change in pH is called a buffer
solution. We can also say that the solution is buffered the simplest way to
achieve substantial conc. Of both acid and base in the same solution to use a
conjugate acid-base pair. The most common form of buffer solution contains a
weak acid and its conjugate base or a weak base and its conjugate acid.
By using buffer concept. A student prepare 2L buffer solution of 0.0330 M
NaH2PO4. The solution is divided in half between the two compartment (each
containing 1L buffe) of an electrolysis is carried out for 212 min with a
constant current of 1.25 A. [Assumes that pKa(H2PO4-) = 7.2]

1.63 The concentration of [H+] consumed by HPO42- at anode is:

(A) 0.165 M (B) 0.330 M (C) 1.00 M (D) 0.0825 M

1.64 pH in 1st compartment cell (at anode) is:

(A) 7.2 (B) 6.72 (C) 7.67 (D) 7.0

1.65 pH in 2nd compartment cell (at cathode) is:

(A) 7.2 (B) 6.72 (C) 7.67 (D) 7.0

SECTION – VI: Matrix – MATCH TYPE

1.66 Match Matrix

(A) Zn | Zn2+ (C) || Zn2+ (2C) | Zn (p) Spontaneous cell reaction
(B) H2(P) | HCl(1N) | H2(P) (q) Working cell representation
(C) Cu | Cu2+ (0.01M) || Ag+ (0.1M) | Ag (r) Concentration of cation in
cathodic Compartment
increases upto quilibrium

(D) AgCl | Ag (KCl, 0.1 M) || Ag+ (0.01M) | Ag (s) Concentration cell

1.67 Match the following:
Column I Column II
1
(A) Concentration cell (p) H 2 + O 2   H 2 O + electrical energy
2
(B) Spontaneous cell reaction (q) E 0 cell  0
(C) Daniel cell (r) Ecell > 0
(D) Hofmann voltameter (s) Galvanic cell
1
(E) Fuel cell (t) H2O + electrical energy   H2 + O2
2

1.68 Assume inert electrolyte used in salt bridge in all the given cells is KCl.(Ka of
HCOOH = 2 × 10–4)
Column I Column – II
(A) Zn | ZnSO4(1M)|| ZnSO4(2M) | Zn (p) Sponataneous cell reaction.
(B) Cu| CuCl2(1M) || CuSO4(2M) | Cu (q) Osmotic pressure of cathodic
solution is greater than that of
anodic solution .

(C) Ag|AgCl(sat.sol.) || AgNO3(1M)|Ag (r) At equilibrium condition of the

cell, freezing point of anodic
solution is higher than of
cathodic solution

(D) Pt|H2| HCOOH (1M) || HCl (1M)|H2|Pt (s) At equilibrium condition of the
cell, boiling point of cathodic
solution is higher than that of
anodic solution

1.69 Match the coloumn:

Column – I
Coloumn – II
(A) Molten PbCl2 using inert electrode (p) Metal of salt will
reduced
(B) Sodium chloride solution using inert electrode (q) H2O + 2e  H2(g) +
2OH–
(C) Silver nitrate solution with silver electrode (r) Solution becomes
basic after
electrolysis
(D) Sodium nitrate solution using inert electrode (s) Solution becomes
acidic after
electrolysis
(t) Solution become
acidic after
electrolysis
1.70 Column – I Column – II
(Quantities) (Factors on which dependency exist)
(A) Molar conductance (p) Temperature
(B) emf of a cell in operation (q) Concentration of species involved
(C) Electrode potential (r) Nature of substance involved
(D) Standard reduction potential (s) No. of electrons lost or gained in
the reaction

SECTION – VII: SUBJECTIVE ANSWER TYPE

SHORT SUBJECTIVE

1.71 In the acid base titration [H3PO4(0.1 M) + NaOH (0.1M)] e.m.f of the solution is
measured by coupling this electrodes with suitable reference electrode.When
alkali is added pH of solution is in accordance with equation , Ecell = E0cell +
0.059 pH.
For H3PO4 Ka1 = 10–3 ; Ka2 = 10–8 ; Ka3 = 10–13
What is the cell e.m.f. at the llnd end point of the titration if E0cell at this stage
is 1.3805 V.

1.72 100 ml, 0.05 M CuSO4 solution is electrolysed by using current of 0.965 Å for
100 min. Find the pH of solution at the end of electrolysis.

1.73 The e.m.f. of a cell corresponding to the reaction

An + 2H + (aq)   Zn 2+ (0.1M) + H 2 (g) (1atm)
is 0.26 volt at 25° C. Calculate the pH of the solution at the hydrogen
electrode
E0 zn2+ /zn = – 0.76 volt and E 0 H+ /H = 0
2

1.74 A fuel cell uses CH4 (g) and forms CO32– at the anode . It is used to power a
car with 80 Amp. For 0.96 hr. How many litres of CH4 (g) (stp.) would be
required ? (Vm = 22.4 L/mol) (F = 96500). Assume 100% efficiency.

1.75 Small spherical ball of silver metal used in jewellery having diameter 0.1 cm,
which is obtained by the electrolytic deposition. It total number of balls in
jewellery is 10,000, then calculate the applied amount of electricity in
coulombs, which is used on the depositon on electrodes having entire surface
0.12 m2 .[Density of Ag = 10.5]
It is assumed that 3.5% electricity consumed as wastage during electrolysis
and 60% of electrode body immessed in electrode. [Given your answer in
multiple of 104]

LONG SUBJECTIVE

1.76 The E°cell = 1.18 V for

Zn(s) | Zn+2(1M) || Cu+2 (1M) | Cu(s).
Determine the value of x if when excess granulated zinc is added to 1 M Cu2+
2.303RT
solution the [Cu+2] eq. becomes 10–XM. ( T = 298 K,  0.059)
F
1.77 For the cells in opposition
Zn(s) | ZnCl2(sol.) | AgCl(s) | Ag | AgCl (s) | ZnCl2(sol.) |Zn(s)
C1 = 0.02 M C2 = 0.5 M

Find out the emf (in millivolt) of the resultant cell ? (Take log 2 = 0.3,
RT
at 298K = 0.060 )
F
1.78 AT  + / T couple was prepared by saturating 0.1 M KBr with T  Br and
following the T   from the relatively insoluble bromide to equilibrate. This
couple was observed to have a potential of –0.443 V with respect to (Report
answer in multiplication of 10–8 ) (E 0Pb2+ /Pb = –0.126, E T0 + /T   0.336V)
2.303RT
(Take antilog (0.5509) = 3.55, = 0.059)
F
1.79 The following two cells with initial concentration as given are connected in
parallel with each other.
(1) Fe(s) | Fe(NO3)2(aq.) (1M) || SnCl2(aq.) (1M) | Sn(s)
(2) Zn(s) | ZnSO4(aq.) (1m) || Fe(NO3)2(aq.) (1M) | Fe(s)
After sufficient time equilibrium is established in the circuit . What will be the
concentrations (in mmoles/L) of Fe2+ ions in first and second cells
respectively?

(Take E 0Sn 2+ /Sn = – 0.14V, E 0Zn 2+ /Zn = – 0.76V, E 0Fe2 =  0.44V,2.3 × RT=6433, log2 = 0.3]

1.80 The conductivity of a solution may be taken to be directly proportional to the

total concentration of the charge carries (ions) present in it in many cases.
Using the above find the percent in conductivity (k) of a solution of a weak
monoacidic base BOH when its 0.1 M solution is diluted its original volume.

(Kb = 10–5 for BOH) (take 50 = 7.07) (Mark the answer to nearest integer )

1.81 At 0.04 M concentration the molar conductivity of a solution of a electrolyte is

5000  –1 cm2 mol–1 while at 0.01 M concentration the value is 5100  –1 cm2
mol–1 . Making necessary assumption (Taking it as strong electrolyte ) find the
molar conductivity at infinite dilution and also determine the degree of
dissociation of strong electrolyte at 0.04 M

1.82 A silver coulomb meter is in series with a cell electrolyzing water. In a time of
1 minute at a constant current, 1.08 g silver got deposited on the cathode of
the coulometer. What total volume (in mL) of the gases would have produced
in other cell if in this cell the anodic and cathodic efficiencies were 90% and
80% respectively. Assume STP conditions and the gases collected are dry.
(Ag – 108) (Molar volume of any ideal gas at STP = 22.4 L)
1.83 Calculate the emf of the cell in mV (atleast in fist two digits must match with
correct answer) (giving your answer in magnitude only).

Ag(s),AgIO3 (s) Ag + (xM),HIO3 (1M) Zn +2 (1M) Zn(s)

1
If KSP = 3 × 10–8 for AgIO3 and Ka = for HIO3 and E 0cell for 2Ag + Zn+2
6
 2Ag++ Zn is – 1.56 V.


RT
(log 3 = 0.48) (Take = 0.059)
F
 PHYSICAL CHEMISTRY
1. ELECTROCHEMISTRY

1.1 (B) ClO3- + 2H2 + 4e   ClO- + 4OH- ;  G1°

1
ClO- + H2O + e   Cl2 + 2OH- ;  G2°
2
1
Cl2 + e   Cl- ;  G3°
2
ClO3- + 3H2O + 3e   Cl- + 6OH- ;  G°

  G° =  G1° +  G2° +  G3°

- 6FE° = - 4F  0.54 – 1F  0.45 – 1F  1.07
3.68
 E° = + = + 0.61 V
6

1.2. (B) considering the cell reaction

H2 + 2e   2H+
Hg22+ + 2e   2Hg ) (  ) + 2Cl- (aq)
 E  -4
 S = nF =   = 2  96500  3.4  10 = 65.223 J/K/mole
 T  P

1.3 (A) 2Ag+ + H2 2H+ + 2Ag

0.0591 (H  )2
E = E° - log
2 PH2  (Ag + ) 2
0.0591 1
0.222 = 0.7995 - log
2 (Ag + )2
(Ag+) = 10-9.8
KsP = (Ag+) (Cl-) = (10-9.8)  (1) = 10-9.8

(C) Let  gm of Zn deposit on 9 gm of Hg

x
% of Zn in Amalgam = x100  25
9 x
 x = 3 gm
3x 2
Eq. of Zn =
65.4
6 96500
Current = x  8.85
65.4 1000

1.5 (B)
1.6 (A) The solubility of AgBr in presence of 10-7 molar AgNO3 is 3  10-7 M.
Therefore [Br] 3  10-4 M3, [Ag+] = 4  10-4 m3 and [NO3-] = 10-4 m3
Therefore Ktotal = kBr- + KAg + + KNO 3 = 39 Sm-1

1.7 (A) Cell reaction

1
Cathode: H2O(  ) +O2(g) + 2e-   2OH- (aq.)
2
Anode:  2H+ (aq.) + 2e-
H2(g) 
1
H2O(  ) + O2(g)   2H+ (aq.) + 2OH- (aq.)
2
Also we have
1
H2(g)(  ) + O2(g)  H2O(  )  G°f = - 237.2 kj/mol
2
H2O(  )   H+ (aq.) + OH-(aq.)  G° = 80 kj/mol
Hence for cell reaction
 G° = - 77.20 kj/mole
77200
So, E = - = 0.40 V
2  96500

0.0591 [H + ]
1.8 (D) Ecell = - log + a
1 [H ]c
For Ecell to be highest [H+]a should be lower and [H+]c should be higher
and that why anode compartment should be more basic and cathodic
compartment should be acidic.

1.9 (C) pH changes from 0 to 7.

 [H+] changes from 1 to 10-7 M.
Accordingly Ered. Decreases by 0.059 log 10-7 i.e. 0.059  (-7) = - 0.41
volt.

1.10 (B) anode : Ag(s)  Ag+ (aq) + 1e-

Cathode : Ag+ (aq) + 1e- 
 Ag


Net : Ag +(AgBr) 
1e +
 Ag (Ag 2Co3 )

 K SP AgBr 
 [Br  ]  K SP AgBr
0.059 K SP Ag 2 Co3
0=0+ log    =
1 K SP Ag 2 Co3 [Br  ] [CO32  ]
[CO32  ]
4 1013 [Br  ] [Br  ]
   = 2 107
12 2 2
8 10 [CO ]3 [CO ]3
 1
1.11 (A) Anode :  H +  1e-
H 2 
2
Cathode : AgCl + 1e-  Ag + Cl-

1 1e -
Net : H 2  AgCl   H +  Ag + C1-
2
0.059 
Ecell = + 0.222 + log 
1 [H ][Cl- ]
[OH  ]
= + 0.222 + 0.059 log = + 0.222 + 0.059 (14) = + 1.048 volt
[1014 ][Cl- ]

63.5  0.1 7200

1.12 (A) m (theoretical) =  0.4738g
96500
0.3745
 % efficiency =  100 = 79 %
0.4738

1.13 (A)

π(25) π  25
Q= C F
4 4  96500
108 π  25
 m=  g = 0.02197 g = 21.97 mg 22 mg
1 4  96500

1 
1.15 (A) R =
KA
The k is halved while the A is doubled. Hence R remain 50  .

1.16 (B) AgCl + 1e- 

 Ag + Cl- E° = 0.2 V
Ag  Ag+ + 1e- E° = - 0.59 V



1e
AgCl   Ag+ + Cl- E° = - 0.59 V
0.059 0.059
E° = log K  - 0.59 = log KSP
n 1
 KSP = 10-10
Now solubility of AgCl in 0.1 M AgNO3
S (S + 0.1) = 10-10  S = 10-9 mol/L
Hence 1 mole dissolves in 109 L solution
Hence in 106 L amount that dissolves in 1 mol.
1.17 (A) G 0cell reaction = 2 (- 130.79) – 2 (-109.56)
= - 42.46 KJ/mole
(for H2 + 2AgCl   2Ag + 2H+ + 2Cl-)
 42460
 E 0cell =   0.220 V
 2  96500
0.059 1
Now Ecell = + 0.220 + log = 0.456 V = 456 mV.
2 (0.01)4

1.18 (B) 2CH2 = CHCN + 2H+ + 2e-   CN – (CH2)4 CN

 108  3
  10  3000  9.65  3600
2
m=   = 58.32 kg
96500
Ans. 58 Kg

0.059 0.12
1.19 (B) Ebck = log = 5.19 mV
2 0.08

1e-
1.21 (B) Reaction is Hc+   HA+
0.059 2.1104
 E= log = 0.0629 V
1 1.8 105

0.059
1.22 (A) E0Br- /AgBr/Ag = E0Ag + /Ag/Ag  log KSPAgBr = E0Ag+ /Ag - 0.7257
1
0.059
and E0Cr- /AgCl/Ag = E0Ag + /Ag  log KSPAgCl = E0Ag+ /Ag - 0.59
1
Now cell reaction is
Ag + Br-   AgBr + 1e-
AgCl + 1e-   AgBr + C1-

-
1e
Br- AgCl   C1- + AgBr

0.059 [Br  ]
0 = (0.7257-0.59) + log
1 [Cl ]
[Br  ]
 = 0.005
[Cl ]

1.23 (A) m = m - b c

260 = m  - 0.5 b … (1)

250 = m  - b … (2)
 On solving (1) & (2), we get
m  = 270 1 cm2mol-1

1.24 (A) (1) AgCl(s) + e   Ag(s) + Cl- E° = 22 V

-
(2) 1/2Cl2 + e   Cl E° = 1.36 V
We get
Ag(s) + 1/2Cl2(g)   AgCl(s) E°cell = 1.14 V
  G = - nEF° = - (1) (96500) (1.4) = - 110 KJ/mol

1.25 (B) if reduction potential of metal ion is greater then O2/H2O couple, the ion
is stable in water. So Co3+ is stable in water

1.26 (A) [Hint: Reverse of (B) & (C) is spontaneous; weakest Oxidizing Agent
here is Mg2+]

λm 7.8
1.27 (B) α = 
= = 0.02
λm 390
 Ka(CH3COOH) = C 2 = 0.04  (4.8)
 pKa6 – log24 = 6 – 4  0.3 = 4.8
 pKa(= H3COO-) = 14 – pKa = 9.2

1.28 (A)  H = G + T S
 E 
= - nFEcell + nFT  
 T  p
= - 199.35 KJ/mol [n = 2 for Cd2+ +2e-  Cd & putting
other values]
Now H < O  Exothermic reaction
 Heat will be released increasing the temperature.

1.29 (A) Q = 10  4825 = 4825 = 48250 C

48250
no. of mole = = 0.5
96500
1 1
Ag + Cu++   Ag+ + Cu
2 2
2.00 2.00
2 - 025 2 + 0.50
0.0591 [Ag + ]
Ecell - E°cell - log
1 [Cu ++ ]1/ 2
0.0591 2.00
E1 = E°ell - log
1 (2.00)1/ 2
0.0591 2.50
E2 = E°ell - log
1 (1.75)1/ 2
 0.0591  2.50  0.0591
 E = E2 – E1 =  log 2  log 1.75   1 [log 1.41 – log
1  
1.88]
0.0591 0.0591
= [0.1492 – 0.2742] = -  0.125 = - .00738 V
1 1

1.30 (C) Conductivity is high due to [H+]

2H 2SO 4  H 2S2 O8 + 2H + + 2e- 

1.32 (A) Cathode  + - 
 2H 2 O  O 2 + 4H + 4e 
Cathode {2H2O  H2 + 2OH- - 2e-}  3.
Net: 2H2SO4 + 8H2O  H2S2O8 + O2 + 3H2 + 6H+ + 6OH-
Hence ratio of n O2 and n H2 is 1: 3.

1.33 (A, B, D)

1.34 (A, C) 2Cu+1 

 Cu + Cu+2
2Cu+1 + 2e 
 2Cu
 Cu+2
Cu – 2e 
2Cu+1   Cu+2 + Cu
2  0.521  2( 0.337)
 E° = 0.184
2

1.35 (A, B, C, D)

1.36 (B, C, D) the SRP should be high for a species to be a good oxidizing agent.

1.38. (B) Both (S – 1) & (S – 2) are true and (S – 2) is not the correct explanation
of (S – 1)

1.39. (C) 1.40 (D) 1.41 (D) 1.42 (A)

1.43 Tue The cell for oxidation reaction is,

Pt | O2 | H+, H2O || MnO 4 , Mn+2, H+ | Pt

 E 0cell = E0MnO- ,Mn +2 ,H+2 ,H + |Pt - E 0H+ |O |Pt = 1.51 – 1.223 = 0.287 V
4 2

Therefore true.

1.44 True

1.45 False 2N2O4 + 2H+ + 2e 

 2HNO2

H2   2H+ + 2e
--------------------------------------
N2O4 + H2   2HNO2
  E° = E0(N O + + E0H + = 1.07 V.
2 4 |H ,HNO2 2 |2H

1.46 True λ  = λ H + + λ C H O = 400

2 5

1000
 λ =K  [C = concentration of C2H5OH]
C
 Kalcohol = [H+][OC2H5] = (10-9)2
 pkalcohol = - log (10-18) = 18

1.47 False SRP H2O > SRP Na+ so H2O will be reduced in preference to Na+ ion.

1.48 False The oxidation number is not changing for Ag.

1
1.49 (C) Cell reaction is, H2(g) + O2 (g)  H2O(  )
2
0.06 1 0.06 1
Ecell = 1.246 - log = 1.246 - log
2 PH 2  PO2 2 20 10
0.06 1
= 1.246 + (1.3 + ) = 1.246 + 0.054 = 1.3 V.
2 2

V 1.3
150. (A) i= = = 0.04825 A.
R 26.94
5
Time of electrolysis = = 500 minutes.
10 103
1
Cu2+ (aq) + H2O   Cu+ (aq) + O2 + 2H+ (aq).
2
ixt 0.04825  500  60
 moles of H+ formed = = = 0.015 M
F 96500

1.51 (B) In resulting solution, [Cu2+] = 0.0075 = 0.0425 M, [H+] = 0.015 M and
[SO 2-4 ] = 0.05 M.
 2+  +
λ   [So 24  ]
κ = κ Cu2+ + κ H+ + κ SO 2  = λ Cu 2+ [Cu ] + λ H + [H ] + SO2-4
4
1000 1000 1000
4 4 4
0.0110  0.0425 0.35 10  0.015 0.016 10  0.05
 
1000 1000 1000
= 0.00425 + 0.00525 + 0.008
= 0.0175 S cm-1 = 1.75 S m-1.

1.52 (A) E 0cell = E0Fe3 + / Fe2 + - E 0Fe(CN)3 - / Fe(CN)4- = + 0.77 V – 0.36 V = + 41 V

6 6

4-
The reaction is: Fe (CN)6 (aq) + Fe3+ (aq)  Fe(CN)6 3-
(aq) + Fe2+
(aq)

1.53 (C) E 0cell = E0Br /Fe- - E0Fe3+ / Fe2+ = + 1.07 V – 0.77 = + 0.30V
2
 If cyanide ions are added, the left hand half cell would change its e.m.f.
to E0Fe(CN3- / Fe(CN)4- = + 0.36. Therefore the e.m.f. would change to + 0.71V.
6 6

1.54 (B) After one drop iron (II) solution is added the beaker will contain a
mixture of Cr2O 27  , Cr3+ and Fe3+ ions. The e.m.f. will be near to
ECr O2- / Cr3+ = + 0.77. The reaction is:
2 7

6Fe (aq) + Cr2O 2-7 (aq) + 14H+ (aq)  6Fe3+ (aq) + 2Cr3+ (aq) +
2+

7H2O(I)
The apparatus would be like that in figure. The graph is shown is
figure.

1.55 (C) λ Cm  λ m  b C
when C1 = 4 x 10-4 λ Cm = 107
and when C2 = 9 x 10-4 λ m = 97
so 107 λ m - b x 2 x 10-2 … (1)
97 = λ m - b x 3 x 10-2 … (2)
b = 1000
λ m λ m - b C
λ m = 127 ohm-1 cm2 mole-1

1.56 (D) For 25 x 10-4 (M) NaCl solution

λ m = λ m - b C
λ m = 127 – 103 (25 x 10-4)1/2
λ m = 127 – 103 x 5 x 10-2
λ m = 77
K x1000  1
But λ m = K=   x
M a R
 1 1000
λm=   x x
a R M
1000
λ m = [Cell constant] x
RxM
 1000
 77 = [Cell constant] x
1000 x 25 x104
Cell constant 77 x 25 x 10-4 = 0.1925 cm-1

1.57 (D) For Na2SO4 solution

 1 0.1925
K=   x = = 4.81 x 10-4 ohm-1 cm-1
a R 400
K x1000 4.81x10-4 x1000
λm= =
M 5
x103
2
λ m (Na2SO4) = 192.4 ohm-1 cm2 mole-1
1.58 (B) Ag+ + NaCl  AgCl + Na+.

1.59 (B) SRP zinc = - 0.76

SRP iron = - 0.44
SRP copper = + 0.34 (highest); Hence only copper deposits,
others do not.

1.60 (A) Increasing voltage would cause deposition of Fe+2 and Zn+2 also to
occur.

1.61 (D) 99.95% pure Cu in obtained.

1.62 (B) Water (pure) is a poor electrical conductor.

1.63 to 1.65
it 1.25  212  60
[H+] = [OH-] = =
96500 96500
= 0.165 M

At anode

HPO 24  + H+ H2PO4 –
0.330 M 0.165 M 0.330 M
0.330 M – 0.165 M 0.165 M 0.330 M + 0.165 M
0.165 M 0.495 M

[HPO --4 ] 0.165

pH = 7.2 + log -
= 7.2 + log = 7.2 – log3 = 7.2 – 0.4771 = 6.72
[H 2 PO 4 ] 0.495

At cathode

H2PO4 - + OH- HPO4 -- + H2O

0.330 0.165 0330
0.330 M – 0.165 M 0 0.330 M + 0.165 M
0.495
pH = 7.2 + log
0.165
 pH = 7.2 + log3 = 7.2 + 0.477
pH = 7.67.

1.63 (A) 1.64 (B) 1.65 (C)

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

Based on facts.

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

Factual question.

1.68 (A – p, q, r, s), (B – p, q), (C – p, q r, s), (D – p, q, r, s)

1.69 (A – p, s) ; (B – q, r) ; (C – p, s) ; (D – q, s)
A) PbCl2, Cathode: Pb2+ 2e-   Pb(s)
-
Anode: 2Cl   Cl2 (g) + 2e-
B) Cathode: H2O + 2e   H2(g) + 2 OH-
Anode: 2Cl-   Cl2 (g) + 2e-
(OH-) in increased solution become basic

(C) Cathode: Ag+ + e-  Ag(s)

Anode: Ag(s)   Ag+ + e-
Neutral solution

(D) Cathode: H2O + 2e  H2(aq) + 2 OH-

Anode: H2O   1/2 O2 + 2H+ + 2e-
Neutral solution

1.70 (A – p, q, r), (B – p, q, r), (C – p, q, r), (D – r)

pKa 2 + pKa 3
1.71 pH = =10.5
2
Ecell = E°cell + 0.059 pH = 1.3805 + 0.059  10.5 = 2V.

1.72 Time taken to electrolysed Cu-metal completely

ixt
= equivalents of Cu-deposited
96500
0.965  t
= 0.005  2
96500
t = 1000 sec.
after 1000 sec pH of solution is not change because after this time only water
is reduced and water is oxidized.
 equivalents of H+ produced = equivalents of Cu2+ ion deposited = 10-2.
pH = - log 10-2 = 2.

1.73 E° cell = 0.76 volt

Applying nernst equation
 - 0.0591 [Zn 2+ ][H 2 ]
Ecell = E°cell log
2 [H + ]2
- 0.0591 (0.1) (1)
0.26 = 0.76 log
2 [H + ]2
0.1 2  0.50
log + 2
= or log 0.1 – log [H+]2 = 17 or 2pH = 17 – log 0.1
[H ] 0.0591
18
pH = = 9.
2

1.74 CH4 + 10OH-   CO 32  + 7H2O + 8e-

80 x 3600 x 0.96
No. of Faradays required =
96500
1 80 x 3600 x 0.96
Hence mol. Of CH4 required x
8 96500
1 80 x 3600 x 0.96
VCH 4 = x x 22.4 L = 8.356 = 8.02 L
8 96500
Ans. 8

0.1
1.75 Radius of ball = = 0.5
2
Surface area of electrodes = 0.12 m2 = 1200 cm2
60% of 1200 = 2000 cm2.
4 4
Weight of jewellery = π r3  10,000  density =  3.14  (0.05)3
3 3
 10000  10.5 = 54.9 gram
wt. of Ag 54.9
Now amount of electricity in faraday =  = 0.50F =
Equivalent wt. of Ag 108
48250 coulomb.
48250 100
So applied electricity amount = = 50,000 coulomb = 5  104
96.5
coulomb
So, Ans is 5.

1.76 40

1.77 as cell reaction is

1st cell: Zn + 2AgCl   ZnCl2 + 2Ag

2nd cell: ZnCl2 + 2Ag   2AgCl + Zn
-----------------------------------------
Overall ZnCl2(C2)   ZnCl2(C1)
RT  0.5   0.059  0.5  
E= In   V=  log    V = 42 mV
2F  0.02   2  0.02  
1.78 Pb2+ + 2e-   Pb
0.0591 
E0Pb2+ / Pb  E 0Pb2+ / Pb - log
2 0.1
= - 0.1555 volt
Ecell = E Pb2+ / Pb = ET / T
0.443 = - 0.1555 - ET / T
ET / T = - 0.5985V
E   e   T
1
ET / T = E0T / T - 0.059 log
(T  )
- 0.5985 = - 0.336 + 0.059 log (Tl+)
T  + = 3.55 x 10-5 M
KsP = (T  +) (Br–) = 3.55 x 10-5 x 0.1 = 3.55 x 10-6 M2 = 355 x 10-8 M2

1.79 Fe(s) + Sn2+ (aq.) Fe2+ (aq) + Sn(s) E 0cell = 0.30V

Zn(s) + Fe2+ (aq.) Zn2+ (aq.) + Fe(s) E 0cell = 0.32V
If above cells are connected in parallel then first cell will get charged up and
second cell will get discharged so net cell reaction will be.
Fe 2 2+ (aq.)  Fe12+ (aq.) Zn 2+ (aq.)  Sn 2+ (aq.) E 0cell
t = 0 1M 1M 1M 1M
t(aq.) (1 – x) (1 – x) (1 + x) (1 + x)
G 0net = - nf E 0net
= - 2 x 96500 x 0.02 J/mole
So, -2.30 RT log keq. = -2 x 96500 x 0.02
2 x 96500 x 0.02
log keq. = = 0.6
6433
keq. = 4
(1+ 2)2 (1+ 2) 1
2
=4  =2  x=
(1- x) (1- x) 3
2+
So, concentration of Fe ions in the first cell
2
= concentration of Fe2+ ions in the second cell = M = 667
3
mmoles/L

1.80 Initially [OH-] = 105  0.1 = 10-3

[ions]total = 2  10-3 M
1
later [[OH-] = 105  = 50  10-4 M
20
 [ions]total = = 2 50  10-4 M
2 50  20
 % change on [ions]total =  100 = - 29.29% Ans.29
20
1.81

From the graph we can seen the λ M value of 5200 1 cm2 mol-1. Hence
5000
α = = 0.9615 0.96 Ans. 96
5200

1.82 Charge passed = 0.01 Faraday

 1 
At the anode  H 2O  O2  2H   2e   with 90% efficientcy 0.01  0.9 F
 2 
1
have been used and will produce  0.01 0.9 mole of O2 i.e. 0.00225 mol O2.
4
+2e-
At the cathode 2H2O   H 2 + 2OH -
0.01 0.8
Moles of H2 produced = mol = 0.004 mol
2
Total moles produced of gases = 0.004 + 0.00225 = 0.00625 mol
vol. at STP = 0.00625  22400 mL = 140 mL Ans. 140

Cα 2 1 α2
1.83 Ka =  =
1 α 6 1 α
 1  (1)2  4  6 1  1  1  24 1
 α = = 
12 12 3
1 1
 [IO3-] = 1  = M
3 3
8
3 10
 [Ag+] 1 = 9  10-8 M
1
3
+2 2e -
Now 2Ag + Zn   2Ag+ + Zn
0.059 1
Gives E = - 1.56 + log = - 1.144 V = - 1144 mV
2 (9 108 ) 2
Ans. 1144
 DPP-2
Ionic Equilibrium
SECTION - I: STRAIGHT OBJECTIVE TYPE
2.. . 1 The degree of dissociation of water in a 0.1 M aqueous solution of HC1 at a
cedain temperature t°C is 3.6 x 10-15 . The temperature t must be :
(A) < 25°C (B) = 25°C •
(C) > 25°C (D) insufficient data to predict

2.2 Which one is the correct expression below for the solution containing 'n' number
of weak acids?
n n
Ki
(A) [H  ]   (B) [H  ]  K C i i
i=1 Ci i=1

n
(C) [H + ]= K C i i (D) none of these
i =1

2.3 The pH of glycine at the first half equivalence point is 2.34 and that at second half
equivalence paint is 9.60. At the equivalence point (The first inflection point) The
pH is :
(A) 3.63 (B) 2.34 (C) 5.97 (D) 11.94

2.4 The pK, of a weak acid if titration progress is monitored as follows

(A) Data in sufficient (B) 8.15
(C) 3.88 (D)4.28

2.5 A 1.458 g of Mg reacts with 80.0 ml of a HCI solution whose pH is -0.477. The
change in pH after all Mg has reacted. (Assume constant volume. Mg = 24.3
g/mol.)(log 3 = 0.477)
(A) -0.176 (B) +0.477 (C) -0.2385 (D) 0.3

2.6 Equal volume of two solution having pH = 2 and pH = 10 are mixed together at
90°C. Then pH of resulting solution is : (Take Kw at 90°C = 10-12)
(A) 2 + log 2 (B) 10 - log 2 (C) 7 (D) 6

2.7 Find the ApH(initial pH -final pH) when 100 ml 0.01 M HCI is added in a solution
containig 0.1 m moles of NaHCO3 solution of negligible volume ( Kai =10-7, Ka,
=10-11 for H2CO3) :
(A) 6 + 2 log3 (B) 6 - log3 (C) 6 + 2Iog2 (D) 6 - 21°93

2.8 The ionization constant of benzoic acid is 6.46 x 10-5 and lc for silver benzoate
is 2.5 x 10-13. How many times silver benzoate more soluble in a buffer of pH =
3.19 as compared to its solubility in pure water ?
(A) 3.317 (B) 9.5 (C) 1000 (D) 7.5
2.9 30 ml of 0.06 M solution of the protonated form of an anion acid methonine (H2A+) is
treated with 0.09 M NaOH. Calculate pH after addition of 20 ml of base. pKa, = 2.28 and
pKa2 = 9.2.
(A) 5.5 (B) 5.74 (C) 9.5 (D) None
2.10 A certain acid-base indicator is red in acid solution and blue in basic solution 75% of the
indicator is present in the solution in its blue form at pH = 5. Calculate the pH at which the
indicator shows 90% red form?
(A) 3.56 (B) 5.47 (C) 2.5 (D) 7.4

2.11 Ionisation constant of HA (weak acid) and BOH (weak base) are 3.0 x 10-7 each at 298K.
The percent degree of hydrolysis of BA at the dilution of 10L is :
(A) 25 (B) 50 (C) 75 (D) 40

2.12 Which of the following concentrations of NH4+ will be sufficient to prevent the
precipitation of Mg(OH)2 from a solution which is 0.01 M MgCl2 and 0.1 M NH3 (aq).
Given that : K5 of Mg (OH)2 = 2.5 x 10-11 and Kb for NH3(aq) = 2 x 10-6.
(A) 0.01 M (B) 0.02 M (C) 0.001 M (D) 0.04 M

2.13 Calculate the molar solubility of zinc tetrathiocyanato-N-mercurate (II) if its Ksp = 2.2 x
10-7.
(A) 0.00380 (B) 0.000469 (C) 0.0095 (D) 0.0183

2.14 An acid-base indicator which is a weak acid has a pKa value = 5.45. At what
cocentration ratio of sodium acetate to acetic acid would the indicator show a colour
half-way between those of its acid and conjugate base forms? pKa of acetic acid = 4.75.
[log 2 = 0.3]
(A) 4 : 1 (B) 7 : 1 (C) 5 : 1 (D) 2 : 1

2.15 The indicator constant of phenolphthalein is approximately 10-10. A solution is prepared

by adding 100.01 c.c. of 0.01 N sodium hydroxide to 100.00 c.c. of 0.01N hydrochloric
acid. If a few drops of phenolphthalein are now added, what fraction of the indicator is
converted to its coloured form?
2 3 1 9
(A) (B) (C) (D)
3 4 2 11
2.16 A certain mixture of HCI and CH3 - COOH is 0.1 M in each of the acids. 20 ml of this
solution is titrated against 0.1M NaOH. By how many units does the pH change from
the start to the stage when the HCI is almpst completely neutralised? Ka for acetic acid =
1.8 x 10-6.
(A) 2.03 (B) 0.775 (C) 2.325 (D) 3.172

2.17 A buffer solution is made by mixing a weak acid HA (Ka = 10-6) with its salt NaA in
equal amounts. What should be the amount of acid or salt that should be added to make
90 ml of buffer solution of buffer capacity. 0.1 ?
(A) 10 mmoles (B) 22 mmoles (C) 9 mmoles (D) 11 mmoles
2.18 A sample of water has a hardness expressed as 80 ppm of Ca2+ . This sample is
passed through an ion exchange column and the Ca2+ is replaced by H+. What is the pH
of the water after it has been so treated? [Atomic mass of Ca = 40]
(A) 3 (B) 2.7 (C) 5.4 (D) 2.4
 SECTION - II : MULTIPLE CORRECT ANSWER TYPE

2.19 A 1 litre solution of pH = 1 diluted upto 10 times. What volume of a solution with pH = 2
is to be added in diluted solution so that pH does not change :
(A) 1 litre (B) 10 litre (C) 100 litre (D) 25 litre

2.20 The solubility of a sparingly soluble salt A. By in water at 25°C 1.4 x 10-4 M. The
solubility product is 1.1 x 10-11. The possibilities are :
(A) x = 1, y = 2 (B) x = 2, y = 1 (C)x= 1,y= 3 (D) x = 3, y = 1

2.21 The variation of pH during the titration of 0.5 N Na2CO3 with 0.5 N HCI is shown
in the given graph. The following table indicates the colour and pH ranges of
different indicators :

Indicator Range of colour change Colour in acid Colour in base

Thymol blue 1.2 to 2.8 Red Yellow
Bromocresol red 4.2 to 6.3 Red Yellow
Bromothymol blue 6.0 to 7.6 Yellow Blue
Cresolphethalein 8.2 to 9.8 Colouriess Red

Based on the graph and the table, which of the following statements are true?
(A) The first equivalence point can be detected by cresolphthalein.
(B) The complete neutralisation can be detected by bromothymol blue
(C) The second equivalence point can be detected by bromocresol red.
(D) The volume of HCI required for the first equivalence point is half the
volume of HCI required for the second equivalence point.

2.22 Which of the following solutions when added to 1L of a 0.1 M CH3COOH solution
will cause no change in either the degree of dissociation of CH3COOH or the pH of
the solution. Ka = 1.8 x 10-5 for CH3COOH?
(A) 3 mM HCOOH (Ka = 6 x 10-4) (B) 0.1 M CH3COONa
(C) 1.34 mM HCI (D) 0.1 M CH3COOH

2.23 Buffer solution A of a weak monoprotic acid and its sodium salt in the
concentration ratio x : y has pH = (pH),. Buffer solution B of the same acid and its
sodium salt in the concentration ratio y : x has pH = (pH)2. If (pH)2— (pH), =1
unit and (pH), + (pH)2 = 9.5 units, then
x x
(A) pKa = 4.75 (B) = 2.36 (C) = 3.162 (D) pKa = 5.25
y y
 SECTION - : ASSERTION AND REASON TYPE
2.24 Statement-1 : solubility of BaSO4 in 0.1 M Na2SO4 is 10-9 M hence its K8 is 10-18.
Statement-2 : because for BaSO4 Ksp = (s)2 [symbols have their usual meanings].
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correctexplanation
for Statement -1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct
explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement – 1 is False, Statement -2, is True.

2.25 Statement-1 : It is difficult to distinguish the strengths of the strong acids such
as HCI, H2SO4, HNO3,HBr, HI or HCIO4 in dilute aqueous solutions.
Statement-2 : In dilute aqueous solution all strong acids donate a proton to water
and are essentially. 100% ionised to produce a solution containing H30+ ions plus
the anions of strong acid .

(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation

for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct
explanation forStatement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

2.26 Statement-1 : The titration curve for weak acid and weak base is as follows :

For this titration no suitable indicator is present.

Statement-2 : Indicator should change it colour sharply for indication of reaction to be
complete so its pH-range should lie perfectly with in sharp change to avoid experimental error.

(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for

Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for
Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.
2.27 Statement-1 : 0.20 M solution of NaCN is more basic than 0.20 M solution of NaF.
Statement-2 : 0.20 M solution of NaCN is more basic than 0.20 M solution of
CH3COONa.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for
Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for
Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

2.28 Statement-1 : A substance that can either act as an acid or a base is called
ampholyte.
Statement-2 : Bisulphide ion (HS-) and biscarbonate ion (HCO3-) are ampholytes.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for
Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for
Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

2.29 Statement-1 : pH of amphiprotic anion is always independent upon concentration.

1
Statement-2 : pH of amphiprotic anion is given by  pK1 + pK 2  where as pK1 and pK2 are
2
the dissociation congt. of the acid in which amphiprotic anion is formed –
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for
Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for
Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.
1SECTION - IV : TRUE AND FALSE TYPE
2.30 (a) In any strong acid's solution, the concentration of [OH-] will be zero.
(b) If  G° of a reaction is positive, then the reaction will not proceed at all, in the forward direction for
any concentrations of reactants and products.
(c) When titration curves are drawn for
(i) 1M HCI (50 mL) with 1 M NaOH and
(ii) 0.01 M HCI (50 mL) with 0.01 M NaOH on the same graph paper they look like:

(A) T, T, F (B) F, F, T (C) F, T , F (D) T, F, T

2.31 (a) When 100 ml of 0.1 M NaCN solution is titrated with 0.1 M HCI solution the
variation of pH of solution with volume of HCI added will be

(b) Variation of degree of dissociation a with concentration for a weak

electrolyte at a particular temperature is best represented by :

(c) 0.1 M acetic acid solution is titrated against 0.1 M NaOH solution. The difference
in pH between 1/ 4 and 3/4 stages of neutralization of acid will be 2 log 3.
(A) T, F, T (B) F, F, F (C) T, T, T (D) F, T, F

SECTION - V : COMPREHENSION TYPE

Comprehension # 1
Radiochemical techniques can be used to determine solubility product
eslimation. The measurement of radioactivity can be used to find the
concentration in a solubthty equilibrium giving afak idea about various equilibrium
concentrations. In an experiment, 50.00m1 of a 0.010 81A*1103sdufion containing
a silver isotope with a radioactivity of 75,000 counts per min per mi were mixed
viii 100 ml of a 0.03 Na103 solution. The mixed solution was diluted 500 mi and
filtered to remove al oftheAg/03predpilateleavinig behind a radioactive solution.
Molar mass of AgI03 = 285 g/mol.
2.32 The remaining solution was found to have a radioactivity of 50 cane tsper min per
mi. Then find the mass of the ppt of AgI03 obtained separated.
(A) 183 mg (B) 283 mg (C) 383 mg (D)483 mg

2.33 The Ksp of AgI03 silver(radioactive) are :

(A) 3.5 x 10-16 (B) 3.5 x 10-12 (C) 5.3 x 10-i° (D) 5.3 x 104'

2.34 The % of unprecipitated silver ions is

(A) 0.15% (B) 0.37% (C) 0.67% (D) 0.97%
Comprehension # 2

Consider a solution of CH3COONH4 which is a salt of weak acid &weak base. The
equilibrium involved in the solutions are :

CH3C00– + H20 CH3COOH + OH– …………..(1)

NH4– + H2 O NH4OH + H+ ……………(2)

H+ + OH– H2O ……………(3)

If we add these three reactions, then the net reaction is

CH3C00- + NH4 + + H20 ----' CH3 COOH + NH4 OH ……………(4)

-
Both CH3C00 and NH4' get hydrolysed independently and their hydrolysis depends
on
(i) their initial concentration
K K
(ii) the value of Kh which is W for CH3COO- and W for NH 4 .
Ka Kb
Since both of the ions were produced from the same salt, their initial concentrations are
K
same . Therefore unless & untial the value of W and Kb is same, the degree of
Ka
hydrolysis of ion can't be same.

To explain why we assume that degree of hydrolysis of cation and anion is

same, we need to now look at the third reaction i.e., combination of H+ and OH– ions.
It is obvious that this reaction happens only because one reaction produced H+ ion
and the other produced OH– ions. We can also note that this reaction causes both the
hydrolysis reaction to occur more since their product ions are being consumed. Keep
this thing in mind that the equilibrium which has smaller value of equilibrium conxtant
is affected more by the common ion effect. For the same reason if for any reason a
reaction is made to occur to a greater extent by the consumption of any one of the
product ion, the reaction with the smaller value of equilibrium constant tends to get
affected more.

Therefore we conclude that firstly the hydrolysis of both the ions ocurs more in
the presence of each other (due to consumption of the product ions) than in each
other is absence. Secondly the hydrolysis of the ion which occurs to a lesser extent
(due to smaller value of Kh) is affected more than the one whose Kh is greater. Hence
we can see that the degree of hydrolysis of both the ions would be close to each other
when they are getting hydrolysed in the presence of each other.
235 In the hydrolysis of salt of weak acid & weak base :
(A) degree of hydrolysis of cation and anion is different
(B) degree of hydrolysis of cation and anion is same
(C) degree of hydrolysis of cation and anion is different and they can never be
assumed same.
(D) degree of hydrolysis of cation and anion is different but they are very close to each other
when they are getting hydrolysed in the presence of each other.

2.36 For 0.1 M CH3COONH4 salt solution given, K aCH COOH  K bNH OH  2  105.
3 4

In this case : degree of hydrolysis of cation and anion is

(A) exactly same (B) slightly different
(C) can't say (D) different but can be take approximatly
same

237 In a solution of NaHCO3 , the amphiprotic anion can under ionization to form H+
ion and hydrolysis to from OH– ion.
ionization
HCO3- + H20 CO3 2 - + H2 0
hydrolysis
HCO 3 - + H 2 0 HCO 3 2 + OH -

To calculat PH, suitable approximation is :

(A) [CO32-] = [HCO3] (B) degree of ionization = degree of
Hydrolysis
(C) both (A) and (B) (D) neither 'A' nore 'B'

Comprehension # 3
When aluminium salts are added to water, Ae3+ ions are immediately attracted to the
negative end of polar water molecules. They form hexaaquaaluminum(III) ions, [Al(H20)6]3+.
This is often written simply as Al+3(aq). However the electric field associated with small,
highly charged Al+3 ion is so intense that it draws electrons in the 0 – H bonds of water
towards itself. This enables the water molecules to become donors. In aqueous solution,
free water molecules act as bases and the following equilibrium is established ;
[Al(H2O )6 ]3  H2O [Al(OH)(H2O )5 ]2  H3O 

Thus, solutions of Al+3 salts are acidic, in fact as acidic as vinegar. When a base
stronger than H2O, e.g. S2-is added to aqueous aluminium salts further H+ ions are removed
from [Al(H20)6]3+ and insoluble aluminium hydroxide precipitates.
2[Al(H20)6]3+ (aq) + 3S2- (aq) 2[Al(OH)3(H20)3](s) + 3H2S(g)
More stronger base can remove 4H+ ions as follows :
[Al(H20)6]3+ + 40H– [ Al(OH)4(H20)]– (aq) + 4H20(  )

2.38 Which of [Al(H2O)6]3+, H2S or H20 is the strongest acid ?

(A) [Al(H2O)6]3+ (B) H2S (c) H2O (D) all same.
2.39 A base which will behave just like S2- :
(A) CO32- (B) CH3OH (C) NH4+ (D) NH2–

2.40 Another ion that would behave similar to AI+3 (aq) in forming an acidic salvation:
(A) Be4+2(aq) (B) Ba2(aq) (C) Na+1 (D) T  +

2.41 [Al(OH)3 (H20)3] (s) more simply written as Al(OH)3(s) is :

(A) acidic (B) basic (C) neutral (D) amphoteric

2.42 Which gas would get absorbed when passed into a solution of A!+3 (aq) ?
(A) NI13 (B) NO (C) CO (D) 02

SECTION - VI : MATRIX - MATCH TYPE

2.43 Match the following :

If ka of HCN = 5 x 10-10 , ka of HOCN = 3.2 x 10-4 , kb of NH3 = 1.8 x 10-5 , ka of CH3COOH
= 1.8 x 105

Column-I Column-II
(A)10-2 M NaA (P) pH > 7
(B)100 ml of 10-1 M NaCI + 100 ml of (q) pH # 7
10-1 M HCI + 300 ml of 10-1 M NaOH
(C)10-1 M HCI + 10-1 M HCN (r) pH < 7
(D) 10-1 M NH4OCN (s) pH = 7

2.44 Match the effect of addition of 0.1 M KOH to 0.1 M, 50 ml H3PO4 Ka1, Ka2 Ka3
are the I, II, III ionisation constant of H3PO4 :
Column-I Column-II
(A) 75 ml of KOH (p) pH = pKa1
(B) 25 ml of KOH (q) pH = pKa2
pK a 2 +PK a 3
(C) 150 ml of KOH (r) pH=
2
1
(D) 100 ml of KOH (s) pH=7+ [pK a3 +logC]
2

2.45 If we mix equal volume of two solution. Match the following :

Column I Column II
(A) 0.2 M KOH + 0.5 M HCOOH (p) 0.7
(B)0.1 M NaC1 + 0.1 M NaNO3 (q) between 1 to 7
(C)0.1 NI NH4CI + 0.1 M NaOH (r) 7
(D)0.5 M HCI + 0.1 M NH4OH (s) greater than 7
2.46 K1 and K2 are first and second ionisation constant of H2CrO4, K3 is dissociation
constant for NH3.
Match the following:
Column I Column Il
(A) 0.1 M H2Cr04 (p) pH = 7 + 1/2pK2 — 1/2pK3
(B) 0.1 M KHCrO4 (q) pH = 7 + 1/2pK2 + 1/2log C
(C) 0.1 M (NH4)2 Cr04 (r) pH = 1/2pK1 — 1/2log C
(D) 0.1 M K2Cr04 (s) pH = 1/2(pK1 + pK2)

247 (Use log 1.8 = 0.26, ka of formic acid = 1.8 x 10-4, ka of acetic acid = 1.8 x10-5, kb of
ammonia = 1.8 x10-5, ka1 of H2S =10–7 and ka2 of H2S =10-14, for the following
matchings)
Match the entries of column II for which the equality or inequality given in the column
I are satisfied.
Column I Column II
-5
(A)10 M HCI solution > 0.1 M H2S solution (p)  water(degree of dissociation of water)
(B)CH3COOH solution at pH equal to 4.74 (q) [OH-]
= NH4OH solution at pH equal to 9.26
(C)0.1 M CH3COOH solution = 1.0 M HCOOH solution
(r) a (degree of dissociation of weak
electrolytes)
-5
(D)0.1 M of a weak acid HA/ (kb = 10 ) solution (s) pH
< 0.01 M of a weak acid HA2(ka = 10-8) solution

SECTION - VII: SUBJECTIVE ANSWER TYPE SHORT SUBJECTIVE

2.48 The equilibrium constants for amino acids are given in terms of succesive
ionization constants of the protonated form for example, equilibrium constants
for Glycine (NH2CH2COOH) are Ka1 = 5 x 10-3 M and Ka2 = 2 x 10-10 M. What will
be the pH at the Isoelectric point for this amino acid and pH of 0.02 M protonated
Glycine in pure water respectively [Take log 2 = 0.30]

2.49 Given : Zn (OH)2 (s) Zn(OH)2 (aq) ; K1 = 10-6

Zn (OH)2 (aq) [Zn(OH)]+ + OH ; K2 = 10-7
-

[Zn(OH)]+ (aq) Zn+2+ OH- ; K3 = 10-4

Zn(OH)2 (aq) + OH- [Zn(OH)3]- ; K4 = 103
[Zn(OH)3]- (aq) + OH- Zn(OH)4]2- ; K5 = 10

Find out the negative of logarithm of the solubility of solid Zn(OH)2 at 25°C at pH
= 6. Consider Zn(OH)2 makes saturated solution at 25°C. (Write down in OMR
sheet if your answer is 1.23 then etc.)
2.50 200 mL of 0.2 M H2SO4 is diluted to 900 ml by adding water. Solution is then
reacted with 100 mL, 0.6 M NaOH solution. The resulting sample is further reacted
with 100 mL of 0.2 M Ca(OH)2 solution and then 100 mL H20 was vaporised.
Calculate final pH and write your answer in the from of pH x 101.

2.51 When NaOH solution is gradually added to the solution of a weak acid (HA), the
pH of the solution is found to be 5.0 at the addition of 10.0 mL of NaOH and 6.0 at
the further addition of 10.0 mL of same NaOH. (Total volume of NaOH = 20 mL)
calculate pKa for HA [log 2 = 0.3]
[Fill your answer in the form of multiple of 10-1 for example if your answer is 2.1
then fill 21 as your answer]

2.52 The Ks of Barium oxalate is 1 x 10-8. K1, K2 of oxalic acid are 1 x 10-3 and 1 x 10-5
respectively. Find the solubility of BaOx in water and the pH of the saturated
solution formed.
2.53 What is ratio of moles of Mg(OH)2 and Al(OH)3 in 1 litre. Their saturated
solution (lc of Mg(OH)2 = 4 x 10-12 and KSP of Al(OH)3 = 1 x 10-33) give answer by
multiplying it with by 10-16.

2.54 What is the solubility( in 10-4 mol/L ) of T  N3 in a solution prepared by shaking

excess of T  N3 and T  3PO4.The solution produced contains 1 mmol of PO43- per
200 mL solution. Ksp (T  N3) = 5.6875 x 10-4.

LONG SUBJECTIVE:

2.55 The pH at which in presence of a given indicator a titration is ended is

sometimes known as titration exponent and is denoted by pT. For phenolphthalein
and methyl orange pT values are 9.0 and 4.0 respectively. Calculate the indicator
(methyl orange) error if 0.1N HCI is titrated by 0.1 N NaOH. Can 0.01N HCI be
titrated with 0.01N NaOH using methyl orange or phenolphthalein as indicator
with the same accuracy. Explain (Temp. = 298 K)
 2. IONIC EQUILIBRIUM

2.1 (C) Kw = 55.5  3.6  10-15  0.1 = 2  10-14

Hence temperature must be > 25°C

[H + ][A - ]
2.2 (B) HA H+ + A- ; K1 =
[HA]
[H + ][B- ]
HB H+ + B- ; K2 =
[HB]
By mass balance,
[HA]initial = [HA]eq + [A-] = C1
[HB]initial = [HB]eq + [B-] = C2
By charge balance,
K [HA] K [HB]
[H+] = 1   2 
[H ] [H ]
[H ] = K1 [HA] + K2 [HB] = K1 {C1 – [A-]} + K2 {C2 – [B-[}
+ 2

If K1, K2 are very less then

n
[H+] = K1 C1  K 2 C 2  ....K n C n = K C i i for ‘n’ number of weak acids
i =1

2.3 (C) pH = pKa1 = 2.34.

pH = pKa2 = 9.6.
pKa1 + pKa 2
pH = = 5.97.
2

2.4 (C) In horizontal part of titration curve it is acting as a buffer when pH = pKa.

2.5 (D) Mg(aq) + 2HCl(aq)  MgCl2 (aq) + H2

1.458
24.3
Millimoles of HCl = 3  80 = 240 mM
Moles of HCl after reaction = 240 – 60  2 = 120
120
New Molarity = = 1.5 M
80
pH = - log[H+] = - log 1.5 = - 0.176
Change is pH = - 0.176 – (- 0.477) = 0.3

2.6 (D)

2.7 (A) pH of NaHCO3 solution = 9

Now H+ + HCO3 -   H2CO3
 no. of mmole of HCl remaining = 1 – 0.1 = 0.9 mmole
 pH = - log (9  10-3) = - 2 log 3 + 3
2.8 (A) In pure water: C6H5COOAg C6H5COO- + Ag+
(s – x) s
C6H5COO- + H2O C6H5COOH + OH-
(s – x) x x
s (s – x) = 2.5  10-13 ..………. (1)
2 14
x 10
 ..………. (2)
(s  x) (6.46 105 )
Calculate s.
In buffer: C6H5COOAg C6H5COO- + Ag+
(s’ – x’) s’
C6H5COO- + H+ C6H5COOH
-13
S’ (s’ – x’) = 2.5  10 ..………. (3)
3.19
(s'  x') 10
= 6.46  10-5..………. (4) solve for s’.
x'
s'
Calculate .
s

pK a1 + pK a 2 2.28  9.2
2.9 (B) pH = = = 5.74
2 2

[In  ]
2.10 (A) pH = pK1 + log
[HIn]
5
5 = pK1 + log
25
 pK1 = 4.523
 K1 = 3  10-5
10
pH = 4.523 + log = 4.523 – 0.954 = 3.56
90

h Kω 1014 1
2.11 (A)  Kh   7 2
  h  0.25
1 h Ka Kb (3x10 ) 3

2.12 (D)

2.13 (B) Zn [Hg(NCS)4] Zn+2 + [Hg(NCS)4]2-

 KSP = S2
 S= 22 108 = 4.69  10-4 mol/L

2.14 (B) Indicator is weak acid HIN H+ + In-

given it shows colour at half way of ionization
 [H  ][In  ]
Ka = so pKa = pKa = pH = 5.45
[HIn]
but for CH3COOh and CH3 COONa buffer
[Salt]
pH = pKa + log
[Acid]
[Salt] [Salt] 5
5.45 = 4.75 + log  =
[Acid] [Acid] 1

2.15 (A) NaOH + HCl   NaCl + H2O

mm 100.01  0.01 100  0.01
0.001
conc. 0 1 1
200
HPh H+ + Ph-
[H + ][Ph - ]
Ka =
[HPh]
k w [Ph] 1014  [Ph] [Ph 2
 10-10 = = 
[OH - ]  [HPh] 0.01
[HPh] [HPh] 1
200
[Ph  ] 2
so -
 .
[Ph ]  [HPh] 3

2.16 (A) Initial [H+] = 0.1 (H+ from weak acid can neglect)
0.1 20
after neutralization of HCl concentration of CH3COOH = = 0.05
40
volume would double [H+] = KaC

[H+] = 1.8 105  0.05 = 9.48  10-4

pH = 3.03
change in pH unit = 3.03 – 1 = 2.03

 c  0.1 
2.17 (D) For buffer capacity of 0.1 we should have   = 10
 c  0.1 
where is concentration of weak acid or salt in the buffer solution
1.1
So, c + 0.1 = 10 c – 1 so 9c = 1.1 or c =
9
1.1
So, moles required for 90 solution =  90  10-3 moles = 11 m
9
moles.
 80
2.18 (D) 106 ml water contains 80 gm of Ca2+ = moles = 2 moles of Ca2+ = 2
40
 2 moles of H+ ions so 103 ml of H2O will have = 4  10-3 moles of H+
ions
so pH = 3 – log 4 = 3 – 0.6 = 2.4.

2.18 (A, B, C, D)
After dilution [H+] = 10-2  pH = 2
Let V litre solution of pH = 2 is added in original solution so that pH
remains fixed.
102 x  V x102
 [H+] =  102
10  V
This result is independent of volume taken.

2.20 (A, B)
KSP = 1.1 x 10-11 = (1.4 x 10-4)x + y xx  yy
so we have x + y = 3 (by comparing values)
x y .11011 110
so, x  y = 12
 4
1.4 1.4 1.4 10 1.96 1.4
Hence x = 1, y = 2 or y = 1, x = 2

2.21 (A, C, D)

2.22 (C, D)
[H+] = 1.8 105  0.1  1.34 103 M
to which the solution in (C & D) are ISOHYDRIC.

2.23 (A, C)
(pH)1 = pKa + log (y/x)
(pH)2 = pKa + log (x/y)
x y  x2 
(pH)2 - (pH)1 = log   - log   = 1  log  2  = 1
y x y 
x2 x
so = 10  = 3.162
y2 y
x y
(pH)2 + (pH)1 = 2pKa + log   + log   = 2 pKa = 9.5
y x
9.5
so, pKa = = 4.75
2

2.24 (D) BaSO4 (s) Ba2+ + SO4 2-

s s + 0.1 KSP = (s) (s + 0.1)
s < 10-9
2.25 (A) All are strong ( α = 1) (leavelling effect).

2.26 (A)

2.27 (B) CN- is more basic than F- Ka (HCN) < Ka (HF)

CN- is more basic than CH3COO- Ka (HCN) < Ka (CH3 COOH)

2.28 (B) Ampholyte ion can undergo hydrolysis as well as ionization.

2.29 (A)

1014
2.30 (B) (a) False, [OH-] = at 25°C
[H  ]
K
= W+ at any other temperature
[H ]
(b) False,  G° > 0 then only in standard state reaction will not
proceed in forward direction.

2.31 (C) (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
Cα 2
Ka =
(1  α)
ka
When α << 1 the α =
C
as C increases  α decreases
as C is tending to zero  α will be unity
(c) At 1/4th neutralisation
CH3COOH + NaOH   CH3COONa + H2O
 3  1
 0.1   0.1 
 4  4
[CH 3COO- ] 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

149
2.32 (B) Moles of AgIO3 precipitated = millimoles
150
 149
Mass of AgIO3 precipitated = 285 x x 10-3 = 0.283 g
150

(10  x) (3.0  x) (6.66 x103 ) (2)

2.33 (C) KSP = [Ag +
][IO3-] =   5.3 x108
500 500 25000

149
1
unprecipitated Ag  150 x 100 = 0.666%
2.34 (C) % unprecipitated = x 100 =
Total taken Ag  1

2.35 (D)

2.36 (C)  Ka = Kb

PK a1  PK a 2
2.37 (C)  PH =
2

2.38 (A) 2.39 (A) 2.40 (A) 2.41 (D) 2.42 (A)

2.43 (A – p, q); (B – p, q) ; (C – q, r) ; (D – q, r)

2.44 (A – q), (B – p), (C – s), (D – r)

2.45 (A – q), (B – r), (C – s), (D – p)

(A) acidic buffer will form, (B ) both are salt of SASB,
(C) weak base NH4OH will form, (D) remain strong acid solution

2.46 (A – r), (B – s), (C – p), (D – q)

(A) diprotic weak acid, H+ only comes from first ionization (K1)
(B) HCrO4 – is amphiprotic anion.
(C) (NH4)2 CrO4 it is salt of weak base and weak acid.
(D) Hydolysis of CrO4 2– (polyvalent anion), but only first hydrolysis is
apprecitable.

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

1 1
2.48 At isoelectric point pH = [pKa1 + pKa2] = [2.3 + 9.7] = 6
2 2
[H+] = 5 103 M  0.2 = 10 105 = 10-2
pH = - log [H+] = 2

2.49 Dissolved [Zn(OH)2] = [Zn+2]aq + [Zn(OH+)2]aq + [Zn(OH2)aq + [Zn(OH)3 -] +

[Zn)OH)4]2-
Now, [Zn(OH)2]aq = 10-6 M in saturated solution.
 106 107 10 13
so, [Zn(OH]+ = =
[OH - ] [OH - ]
10 17
Similarly, [Zn+2] = , [Zn(OH)3] = 10-3 [OH-],
[OH - ]2
[Zn(OH)42-] = K5 [Zn(OH)3 – ] [OH-] = (10-2 M-1) [OH-]2
10 17 10 13
Dissolved Zn(OH)2 = + + 10-6 + 10-3  [OH-] + 10-2 [OH-]2
[OH - ]2 [OH - ]
1017 1013
= + + 10-6 + 10-3  10-8 + 10-18 = 10-1 + 10-5 + 10-6 + 10-
10 16 108
11
= 10-1 – log Zn(OH)2 (aq) = 1

(N1V1 ) - (N 2 V2  N3 V3 ) 200  0.2  2  0.6 100  0.2  2 100

2.50 [H-] = =
V1 + V2 + V3 + 700 -100) 200  100  100  700 100
80  60  40 20
=   2 102
1000 1000
pOH = 1.7
pH = 12.3 so pH  101 = 123

2.51 Let initial conc. Of HA & NaOH be C1 & C2 mol/L and initial volume of HA =
V1mL
10C 2
 5.0 = pKa + log …….. (1)
(C1V1 10C 2
10C2
6.0 = pKa + log …….. (2)
(C1V1  20C 2
from these we get
C1V1 = 22.5 C2
10C 2
 5.0 = pKa + log = pKa + log (0.8)
(C1V1 10C 2
 pKa = 5.1  Answer is 51

2.52 KSP = S2
 S 10-4 mol/L
Hence in mmol/10L it is 1.
Now C2O42- + H2O HC2O4 – + OH–
[OH-] = 109 x104  1013 M
1
 [H+] = x107 M  10 x107 M
10
1 1
 Ph = 7 + log 10 = 7 + = 7.5  10PH = 75
2 2

2.53 Mg(OH)2 Mg+2 + 2OH-

 x 2x + 3y KSP of Mg(OH)2 > KSP of Al(OH)3
Al(OH)3 Al3+ + 3OH-
y 3y + 2x so x >> y
2x + 3y 2x
 4  10-12 = [Mg2+] [OH-]2
= x  (2x)2
x = 10-4
1  10-33 = [Al3+] [OH-]3
1  10-33 = (y) (2x)3
1  10-33 = y  (10-4  2)3
1021 x
y= so = 8  1017
8 y
8  1017  10-16 = 80

2.54 T  N3 T+ + PO43-

(S + 1.5  10-2) S
T3  PO4 3T  + + PO43-
1.5  10-2 + S) 5  10-3
Or T  N3
S (S + 1.5  10-2) = 5.6875  10-4  S2 + 0.015 S – 5.6875  10-4 = 0
 0.15  (0.015)2  22.75 104
 S= = 1.75  10-2 mol/L Ans. 175.
2

2.55 Let initial volume o NaOH = VmL

 volume of HCl added is also is also VmL and hence final total volume =
2VmL
In the first case when 0.1NHl is titrated with 0.1N NaOh using MeOH
indicator, the equivalence point is pH = 7.0 but titration ends at pH = 4.0.
 there are residual H+ at the end point and the error is due to H+.
and residual [H+] = 10-4  2V meq. = error
104  2V
 % error = 100  0.2%
0.1 V
This error is small hence titration can be performed and result can be taken to
be accurate.
But if 0.01 NHCl is titrated with 0.01N NaOH using MeOH as indicator then
this error will be equal to
104  2V
100  0.2%
0.1 V
Since this is large error hence MeOH cannot be used in this titration.
However, if HPh is used in the above case then the error will be due to [OH-],
which can be calculated as
Total meq. Of OH- added = 10-2V
and residual OH- at end pt. = 10-5  2 V meq.
 105  2V
 % error = 100
102  V
= 0.2%
 HPh can be used with the same accuracy as found in the first case.
 DPP-3
Solution & Collegative Properties
SECTION - I : STRAIGHT OBJECTIVE TYPE
3.1 Three solutions are prepared by adding 'w' gm of 'A' into 1kg of water, gm of '13' into
another 1 kg of water and 'w' gm of 'C' in another 1 kg of water (A, B, C are non
electrolytic). Dry air is passed from these solutions in sequence (A   B   C).
The loss in weight of solution A was found to be 2 gm while solution B gained 0.5 gm
and solution C lost 1 gm. Then the relation between molar masses of A, B and C is :

1 1 1
(A) MA: MB : Mc = 4 : 3 : 5 (B) MA : MB: Mc = : :
4 3 5
(C) Mc > MA > MB (D) MB > MA > Mc

3.2 How many mili moles of sucrose should be dissolved in 500 gms of water so as to get
a solution which has a difference of 103.57°C between boiling point and freezing
point.
(K1 = 1.86 K Kg mol-', Kb = 0.52 K Kg mo1-1)
(A) 500 mmoles (B) 900 mmoles (C)750 mmoles (D) 650 mmoles

3.3 Barium ions, CN– and CO2+ form an ionic complex, If this complex is 75% ionised in
aqueous solution with Vent Hoff factor (i) equal to four and paramagnetic moment is found to
be 1.73 BM (due to spin only) then the hybridisation state of Co (II) in the complex will be :
(A) sp3d (B) d2sp (C) sp3d2 (D) dsp3

3.4 Select the correct statement:

(A) The semipermeable membrane is the cause of osmotic pressure.
(B) Osmosis results from decrease in entropy
(C) Osmotic pressure depends on temperature and concentration but is independent of the
nature of the membrane.
(D) The passage of solvent molecules occur only in one direction through a
semipermeable membrane.

3.5 The incorrect statement is

(A) Vapour pressure of a liquid always increases by increasing temperature.
(B) Vapour pressure only depends on temperature and not on the nature of substance.
(C) Vapour pressure does not depend on the quantity of the liquid taken and the surface
area of the liquid.
(D) Vapour pressure is not a colligative property & is independent of the concentration
of the liquid.

3.6 The molar heat of vapourization of toluene is AHv. If its vapour pressure at 315 K is 60
torr & that at 356K is 300 torr then AHv = ? (tog 2 = 0.3)
(A) 37.5 kJ/mole (B) 3.75 kJ/mole (C) 37.5 J/mol (0) 3.75 J/mole
3.7 Relative decrease in vapour pressure of an aqueous solution containing 2 moles
[Cu(NH3)3CI) CI in 3 moles H20 is 0.50. On reaction with AgNO3, this solution will
form(assuming no change in degree of ionisation of substance on adding AgNO3)
(A) 1 molAgCl (B) 0.25 molAgCl (C) 0.5 molAgCl (0) 0.40 molAgCl

3.8 Which of the following has been arranged in order of decreasing freezing point?
(A) 0.05 M KNO3 > 0.04 M CaCl2 > 0.140 M sugar > 0.075 M CuSO4
(B) 0.04 M BaCl2 > 0.140 M sucrose > 0.075 M CuSO4 > 0.05 M KNO3
(C) 0.075 M CuSO4 > 0.140 M sucrose > 0.04 M BaCl2 > 0.05 M KNO3
(D) 0.075 M CuSO4> 0.05 M NaNO3> 0.140 M sucrose > 0.04 M BaCl2

3.9 A solution of x moles of sucrose in 100 grams of water freezes at -0.2°C. As ice
separated the freezing point goes down to 0.25°C. How many grams of ice would have
separated?
(A) 18 grams (B) 20 grams (C) 25 grams (D) 23 grams

3.10 An ideal mixture of liquids A and B with 2 moles of A and 2 moles of B has a
total vapour pressure of 1 atm at a certain temperature. Another mixture with 1
mole of A and 3 moles of B has a vapour pressure greater than 1 atm. But if 4
moles of C are added to the second mixture, the vapour pressure comes down to 1
atm. Vapour pressure of C, Pc° = 0.8 atm. Calculate the vapour pressures of
pure A and pure B.
(A) PA° = 1.4 atm, PB° = 0.7 atm (B) PA = 1.2 atm, PB° = 0.6 atm
(C) PA = 1.4 atm, PB° = 0.6 atm (D) PA° = 0.6 atm, PBC) = 1.4 atm

3.11 A sample of air is saturated with benzene (vapor pressure = 100 mm Hg at

298 K) at 298K, 750mm Hg pressure. If it is isothermally compressed to one
third of its initial volume, the final pressure of the system is
(A) 2250 torr (B) 2150 torr (C) 2050 torr (D) 1950 torr

3.12 Available solutions are 1L of 0.1 M NaCI and 2L of 0.2 M CaCl2. Using only
these two solutions what maximum volume of a solution can be prepared
having [Cl–] = 0.34 M exactly. Both electrolytes are strong
(A) 2.5 L (B) 2.4 L (C) 2.3 L (D) None of these

3.13 Calculate the osmotic pressure of the solution prepared in the above
questionT = 300 K, (R = 0.082 L atm mol-1K-1)
(A) 10.8 atm (B) 12.8 atm (C) 5.6 atm (D) None of these

3.14 Consider equivocal aqueous solutions of NaHSO4 and NaCI with ATb and Arb
T
as their respective boiling point elevations. The value of lim b' will be :
x 0 T
b

(A) 1 (B) 1.5 (C) 3.5 (D) 3

3.15 A solute'S' undergoes a reversible trimerization when dissolved in a certain
solvent. The boiling point elevation of its 0.1 molal solution was found to be
identical to the boiling point elevation in case of a 0.08 molal solution of a
solute which neither undergoes association nor dissociation. To what percent
had the solute 'S' undergone trimerization?
(A) 30% (B) 40% (C) 50% (D) 60%

3.16 The vapor pressures of benzene, toluene and a xylene are 75 Torr, 22 Torr
and 10 Torr at 20°C. Which of the following is not a possible value of the vapor
pressure of an equimolar binary/ternary solution of these at 20°C ? Assume all
form ideal solution with each other.
1 2 1
(A) 48 (B) 16 (C) 35 (D) 53
2 3 2

3.17 3.24 g of Hg(NO3)2 (molar mass = 324) dissolved in 1000 g of water

constitutes a solution having a freezing point of - 0.0558°C while 21.68 g of
HgC12 (molar mass = 271) in 2000 g of water constitutes a solution with a
K – Kg
freezing point of - 0.0744°C. The Kf for water is 1.86 . About the state
Mol
of ionization of these two solids in water it can be inferred that:

(A) Hg(NO3)2 and HgC12 both are completely ionized

(B) Hg(NO3)2 is fully ionized but HgC12 is fully unionized
(C) Hg(NO3)2 and HgC12 both are completely unionized
(D) Hg(NO3)2 is fully unionized but HgC12 is fully ionized
3.18 For a solution of 0.849 g of mercurous chloride in 50 g of HgC12(f) the
freezing point depression is 1.24°C. Kf for HgC12 is 34.3. What is the state of
mercurous chloride in HgC12 ? (Hg - 200, CI - 35.5)
(A) as Hg2Cl2 molecules (B) as HgCI molecules
-
(C) as Ng+ and Cl ions (D) as Hg22+ and Cl- ions
SECTION -1I : MULTIPLE CORRECT ANSWER TYPE
3.19 Dry air is slowly passed through three solutions of different concentrations, c,,
c2 and c3 ; each containing (non volatile) NaCI as solute and water as solvent, as
shown in the Fig. If the vessel 2 gains weight and the vessel 3 loses weight, then

(A) c1 > c2 (B)c1 < c2 (C)c1 < c3 (D) c2 >

3.20 In which of the following pairs of solutions will the values of the vent Hoff factor be
the same?
(A) 0.05 M K4 [Fe(CN)6] and 0.10 M FeSO4
(B) 0.10 M K4[Fe(CN)6J and 0.05 M FeSO4(NH4)2SO4. 6H20
(C) 0.20 M NaCI and 0.10 M BaCl2
(D) 0.05 M FeSO4 (NH4)2SO4 6H20 and 0.02 M KCI . MgC12. 6H20

3.21 Vapour pressure of solution containing 6g of a non-volatile solute in 180 g water is

20.0 Torr. If 1 mole water is further added vapour pressure increases by 0.02 Torr.
Which of the following is true ?
(A) The molecular weight of solute is 54g mol—1
(B) The vapour pressure of pure water is 20.22 Torr
(C) Addition of more water in the solution will further raise the vapour pressure of
solution
(D) The vapour pressure of pure water is 22.22 Torr

3.22 Two liquids Aand B form an ideal solution. The solution has a vapor pressure of 700
Torr at 80°C. It is distilled till 2/3°' of the solution is collected as condensate. The
composition of the condensate is x'A= 0.75 and that of the residue is x"A= 0.30. If the
vapor pressure of the residue at 80°C is 600 Tom, which of the following is/ are true?
(A) Tile composition of the original liquid was xA = 0.6.
(B) The composition of the original liquid was xA = 0.4.
2500
(C) PA° = Torr.
3
(D) PB° = 500 Torr.

3.23 For chloroform and acetone or for a solution of chloroform and acetone if p,
(observed (actual)) is compared with p s (Theoretical (Raoult)) then
which of the following is /are true ?
(A) ps(actual) < ps(Raoult)
(B) limit
X 
chloroform
0
P0
acetone 
 Ps  actual   0

(C) limit
X acelone  0
P0
chloroform 
 Ps  actual   0

(D) P 0 acetone >P 0chloroformnear room temperature

SECTION - Ill: ASSERTION AND REASON TYPE

3.24 Statement-1 : Perfectly ideal solution is not possible with respect to binary solution
of two liquids.
Statement-2 : No two substances can have exactly the same nature of intermolecular
forces & also of the same magnitude.
 (A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation
for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct
explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

3.25 Statement-1 : When a cell is placed in hypertonic solution, it shrinks.

Statement-2 : Reverse osmosis is used for desalination of water.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for
Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct
explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

3.26 Statement-1 : The difference in the boiling points of equimolar solution of HCI and
HF decreases as their molarity is decreased.
Statement-2 : The extent of dissociation decreases steadily with increasing
dilution.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for
Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct
explanation for Statement-1
(C) Statement -1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

327 Statement-1 : The molar mass obtained for benzoic acid in benzene is found to be
nearly Statement-2 : Benzoic acid has the formula HOOC

(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for

Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct
explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

3.28 Statement-1 : When 'a' mL of a 0.1 molal urea solution is mixed with another 'b'
mL of 0.1 molal glucose solution, the boiling point of the solution is no different from
the boiling points of the samples prior to mixing but if 'a' mL of 0.1 molal urea is mixed
with 'b' mL of 0.1 molal HF the boiling point of the mixture is different from the boiling
points of the separate samples .
.Statement-2 : HF is an electrolyte (weak) whereas glucose is a non electrolyte.
 (A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for
Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct
explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

SECTION - IV : TRUE AND FALSE TYPE

3.29 The lowering of vapour pressure of a solvent is equal to mole fraction of the solute.

NormalColligative Property
3.30 Van'sHoff factor =
ObservedColligativeProperty
3.31 0.1 M aqueous NaCI & 0.1 M aqueous sugar solutions are isotonic

3.32 Vapour pressure of a solvent decreases with decreasing temperature.

3.33 Vapour pressure is a colligative property.

3.34 Freezing point of a solution is always lower than that of the pure solvent.

3.35 Acetic acid undergoes association in benzene. Themolar mass of acetic acid,
determined by elevation of boiling point is always higher than its normal molar mass.

3.36 A plant cell swells when placed in a hypertonic solution.

3.37 Osmotic pressure measurements can be used for determination of molar mass of
polymers.

SECTION – V : COMPREHENSION TYPE

Comprehesion # 1
IDEAL SOLUTION FIXED TEMPERATURE
Consider two liquids ‘B’ and ‘C’ that form an ideal solutlion. We hold the temperature
fixed at some value T that is above the freezing points of ‘B’ and ‘C’ .We shall plot the
system’s pressure P and against XB’ the overall mole fraction of B in the system :
.
nB.total nB  nBv
xB   v
ntotal nB  nB  nc  nB
Where nB and nBv are the number of moles of B in the liquid and vapor phases,
respectively. For a close system xB, is fixed, although nB and nBv may vary.
Let the system be enclosed in a cylinder fitted with a piston and immersed in a
constant-temperature bath.To see what the P-versus-xB phase diagram looks
 like, let us initially set the external pressure on the piston high enough for the
system to be entirely liquid (point A in figure) As the pressure is lowered below that
at A, the system eventually reaches a pressure where the liquid just begins to
vaporizes (point D). At point D, the liquid has composition x B where x B at D is
equal to the overall mole fraction xB since only an infinitesimal amount of liquid has
vapourized. What is the composition of the first vapour that comes off ? Raoult's
law, PB  x Bv PB0 relates the vapour-phase mole fractions to the liquid composition
as follows:

xB pB0 x  p0
xvB  and xCv  C c ………….(i)
P P
Where PB0 and PC0 are the vapour pressures of pure 'B' and pure 'C' at T,
where the system's pressure P equals the sum PB + Pc of the partial pressures,
n
where x B   B  , and the vapor is assumed ideal.
 nB  nC 

x Bv xB pB*
. = ideal solution ……………(2)
x cv x C p*C

Let B be the more volatile component, meaning that PB0 >PC0 Above equation
then shows that x vB / xcv  x B / xC . The vapor above an ideal solution is richer than
the liquid in the more volatile component. Equations (1) and (2) apply at any
pressure where liquid -vapor equilibrium exists, not just at point D.
Now let us isothermally lower the pressure below point D, causing more liquid to
vaporize. Eventually, WE reach point F in figure, where the last drop of liquid
vaporizes. Below F, we have only vapor. For any point or the line between D and
F liquid and vapor phases coexist in equilibrium.
3.38 If the above process is repeated for all other compositions of mixture of C and
B. If all the points where vapours start converting into liquid are connected and
all the points where vapours get completely converted into liquid are connected
then obtained graph will look like.

3.39 The equation of the curve obtained by connecting all those points where the
vapors of above mixture (all mixtures of different composition are taken) just
start forming will be
(A) P =PC0  (P 0C  P 0C ) X  B (B) P  P 0B  (P 0B  P 0C ) X B
PB0PC0 PB0PC0
(C) P = (D) P=
 
XB0 PC0 – PB0 +PB0  
XB PC0 – PB0 +PB0

3.40 Two liquids A and B have the same molecular weight and form an ideal solution.
The solution has a vapor pressure of 700 Torrs at 80°C. It is distilled till 2/3rd of the
solution (2/3rd moles out of total moles) is collected as condensate.The
composition of the condensate is x'A = 0.75 and that of the residue is X" A= 0.30. If
the vapor pressure of the residue at 80°C is 600 Torrs, find the original
composition of the liquid.
(A) XA = 0.5 (B) XB = 0.6 (C) XA = 0.6 (D) X B = 0.3

Comperhension # 2
The pressure of two pure liquid A and B which form an ideal solution are 400 mm
Hg and 800 mm Hg respectively at temp T. A liquid containing 3 : 1 molar
composition of A and B present in a cylinder closed by a piston on which
pressure can be varied. The solution is slowly vaporised at temp T by
 decreasing the applied pressure starting with a pressure of 760 mm Hg. A
pressure gauge (in mm) Hg is connected which given the reading of pressure
applied.

3.41 The reading of pressure Gauge at which only liquid phase exists.
(A) 499 (B) 399 (C) 299 (D) None

3.42 The reading of pressure Gauge at bubble point is

(A) 500 (B) 600 (C) 700 (D) None

3.43 The reading of pressure Gauge at which only vapour phase exists is
(A) 501 (B) 457.14 (C) 425 (D) 525

Comprehension # 3
Colligative property measurement is one of the techniques used in the
measurement of chemical quantities with reasonable accuracy.

If a 40.65 gm sample of K2SO4 and BaSO4 is dissolved in 900 gm of pure water to

form a solution 'A' at 57°C, its vapour pressure is found to be 39.6 torr while vapour
pressure of pure water at 57°C is 40 torr. Density of solution A is 1.24 gm/ml.

In a different experiment when small amount of pure BaSO4 is mixed with water at
57°C it gives the osmotic rise of 4.05 x 10-5 atm. (R = 0.082 Lt.-atm/mol-K ; K = 39,
Ba = 137, S = 32, 0 = 16)

3.44 Percentage of K2SO4 in the sample is :

.(A) 65.75% (B) 71.34% (C) 60.35% (D) 78.74%

3.45 Solubility product of BaSO4 in water at 57°C is :

.(A) 5 x 10-15 (B) 3.125 x 10-13 (C) 5.625 x 1043 (D) 2.25x 10-12

3.46 Concentration of Ba2+ ions in solution 'A' is :

.(A) 3.5 x 10-" M (B) 4.7 x 10-15 M (C) 2.3 x 10431111 (D) 3.9x 10-12 M

3.47 Boiling point of solution A is (Kb water = 0.54 K-kg/mol) :

(A) 0.3K (B) 0.1K (C) 0.04K (D) 0.05 K

Comprehension # 4

A system of greater disorder of molecules is more probable. The disorder of

molecules is reflected by the entropy of the system. A liquid vaporizes to form
a more disordered gas. When a solulte is present , there is additional
contribution to the entropy of the liquid due to increase randomness. As the
entropy of solution is higher than that of pure liquid, there is weaker tendency
 to form the gas. Thus , a solute (non volatile) lowers the vapour pressure of a
liquid, and hence a higher booing point of the solution
Similarly, the greater randomness of the solution opposes the tendency to
freeze. In consequence, a lower the temperature must be reached for achieving the
equilibrium between the solid (frozen solvent) and the solution . Elevation of B.Pt.
 Tb  and depression of F.Pt.  Tf  of a solution are the colligative properties
which depend only on the concentration of particles of the solute, not their
identity.For dilute solutions, Tb and Tf are proportional to the molality of the
solute in the solution.

2
RTb0 M
ΔTb =K bm Kb = Ebullioscopic constant =
1000ΔHvap
2
RTf0
And Tf  K f m Kf = Cryoscopic constant =
1000ΔHfus
(M = molecular mass of the solvent)

The vaues of Kb and Kf do depend on the properties of the solvent. For

ΔHvap
liquids, is almost constant .
Tb0
[Troutan’s Rule , this constant for most of the Unassociated liquids (not
having any strong bonding like Hydrogen bonding in the liquid state) is equal
to 90J/mol. ]
For solutes undergoing change of molecular state is solution (ionization or
association), the observed T values differ from the calculate ones using the
above relations. In such situations, the relationships are modified as
ΔTb =iK bm; ΔTf =iK f m
Where i = Van’t –Hoff factor, greater than unity for ionization and smaller than
unity for association of the solute molecules.

3.48 Depression of freezing point of which of the following solutions does represent
the cryoscopic constant of water?
(A) 6% by mass of urea is aqueous solution
(B) 100 g of aqueous solution containing 18 g of glucose
(C) 59 g of aqueous solution containing 9 g of glucose
(D) 1 M KCl solution in water.

3.49 Dissolution of a non-volatile solute into a liquid leads to the –

(A) decrease of entropy
(B) increase in tendency of the liquid to freeze
(C) increases in tendency to pass into the vapour phase.
(D) decrease in tendency of the liquid to freeze
3.50 To aqueous solution of Nal, increasing amounts of solid HgI2 is added. The vapor
pressure of the solution
(A) decreases to a constant value
(B) increases to a constant value
(C) increases first and then decreases
(D) remains constant because HgI2 is sparingly soluble in water.

3.51 A liquid possessing which of the following characteristics will be most suitable for
determining the molecular mass of a compound by cryoscopic measurements?
(A) That having low freezing point and small enthalpy of freezing
(B) That having high freezing point and small enthalpy of freezing
(C) That having high freezing point and small enthalpy of vaporization
(D) That having large surface tension

3.52 A mixture of two immiscible liquids at a constant pressure of 1 atm boils at a

temperature
(A) equal to the normal boiling point of more volatile liquid.
(B) equal to the mean of the normal boiling points of the two liquids.
(C) greater than the normal boiling point of either of the liquid.
(D) smaller than the normal boiling point of either of the liquid.

.SECTION - VI : MATRIX - MATCH TYPE

3.53 Column I Column II

(A) Acetone + CHCI 3 (p) ASnu. > 0
(B) Ethanol + Water (q) > 0
(C) C2H5Br + C2H5I (r) AH m < 0 ,
(D) Acetone + Benzene (s) Maximum boiling azeotropes
(t) Minimum boiling azeotropes

3.54 Column —1 Column — II

Assuming all the solutes are non volatile and all solutions are ideal.
(A) 10 ml 0.1 M NaOH aqueous (p) Osmotic pressure of solution
solution is added to 10 ml 0.1 M increases
HCI aqueous solution
(B) 10 ml 0,1 M NaOH aqueous (q) Vapour pressure of solution
solution is added to 10 ml 0.1M increases
CH3 COOH aqueous solution
(C) 10 ml 0.1 M HCI aqueous solution (r) Boiling point of solution increases
is added to 10 ml 0.1 M NH3
aqueous solution
(D) 10 ml 0.1 M HCI aqueous solution (s) Freezing point of solution increases
to 10 ml 0.1 M KOH aqueous solution
3.55 For a binary liquid solution of A and B. p 0A = pure vapour pressure of A. p 0B = pure
vapour pressure of B. XA = mole fraction of A in liquid phase. YA = mole fraction of
A
in vapour phase.
Column —I Column—II

(A) p2 > pa [Ideal liquid solution] (p) XA YA

(B) Azeotropic mixture (q) XA < YA
(C) Equimolar ideal mixture of
A & B with PA0 < PB0 (r) XB < YB
(D) Equimolar ideal mixture of A & B
with PA0  PB0 (S) YB > YA
SECTION - VII : SUBJECTIVE ANSWER TYPE
SHORT SUBJECTIVE

3.56 A solution of A and B with 30 mole percent of A is in equilibrium INN limp= which
contains 60 mole percent of A. Assuming ideality of the solution and its vapour
calcutde lhealloolvapour pressure of pure A to that of pure B. (Report your
answer as ratio x 2)

3.57 0.0125 mol of sucrose is dissolved in 100 gm of water and it undergopmealliavalsion

according to following equation
C12H22011 + H20   C61-11206+ C6H1206

1
If elevation in boiling point of solution is 0.104°C calculate mol
10
percentage of sugar inverted (Kb, H20 = 0.5 2).

.3.58 25 ml of FeC2O4 dissolved in 186 gm of water calculate depression inflecting point if

10 mid of same FeC2O4 titrated with 30 ml of 0.4 M KMn04 in acidic medium (kf for H20
= 1.86i,Assme100% ionisation of FeC204).

3.59

CD : Fixed wall, EF : SPM, Fixed wall : allows the pressure transfer but no mass
transfer.
If 16 gm Helium present in ABCD chamber calculate the length of this chamber in
cm if no osmosis takes place through SPM EF. Assume 75% ionisation of K
4Fe(CN)6.
3.60 In 103 Litre sample of hard water CaS04 and MgS04 present If elevation in Boiling
point is 0.000052°C.Calculate the degree of Hardness of hard water. (Kb for H20 =
0.52)

LONG SUBJECTIVE
3.61 The vapour pressure of fluorobenzene at t°C is given by the equation
1250
log p (mm Hg) = 7.0 
t  220
Calculate the boiling point of the liquid in °C if the external (applied) pressure is
5.26% more than required for normal boiling point. (log 2 = 0.3)

3.62 Two liquids A and B are miscible over the whole range of composition and may be
treated as ideal (obeying Raoult's law.) At 350 K the vapour pressure of pure A is
24.0 kPa and of pure B is 12.0 kPa. A mixture of 60% A and 40% B is distilled at this
temperature; what is the pressure in a closed distillation apparatus from which air is
excluded ? A small amount of the distillate is collected and and redistilled at 350 K;
what is the composition of the second distillate ?

3.63 A saturated solution of a sparingly soluble salt MCl2 has a vapour pressure of
31.96 tor while pure water has a vapour pressure of 32.0 torr at the same
temperature. Calculate the solubility product of MCl2.

3.64 An ideal solution was prepared by dissolving some amount of can sugar (non-
volatile) in 0.9 moles of water. The solution was then cooled just below its freezing
temperature (271 K) where some ice get separated out. The remaining aqueous
solution registered a vapour pressure of 700 torr at 373 K. Calculate the mass of ice
separated out, if the the molar heat of fusion water is 6 kJ.

3.65 If osmotic pressure of 1 M aqueous solution of H2SO4 at 500 K is 90.2 atm. Calculate Ka2
of H2SO4. Give your answer after multiplying 1000 with Ka2. (Assuming ideal
solution).
(Given : Ka12 of H2 SO4 is  , R = 0.082 It atm/mol-K).

3.66 100 ml of 0.1 M solution of a weak acid HA has molar conductivity 5 S cm2 mol-1.
Calculate osmotic pressure of resulting solution obtained after dilution of original
solution upto 1 litre at 500 K assuming ideal solution.
( Given : λ m (H+ ) = 450 S cm2mo1-1, λ m (A  ) = 50 S cm2mol-1, R = 0.08 It - atm / mole
- K, 10 = 3.2 ).
Report your answer as X where X = Osmotic pressure (in atm) x 104.
3.67 Assume liquefied petroleum gas (LPG) is a 50-500y mole) mixture of n-pentane
and n-butane. Calculate the calorific value ( in kJ/mol ) of gas available fro_m a
newly filled cylinder. Will the calorific value increase, decrease or remain the
same during use?
n-butane,C4H10 n-pentane, C5H,2
Vapour pressure 1800 Torr 600 Torr
Calorific value 2800 kJ/mol 3600 kJ/mol
 3. SOLUTION & COLLIGATIVE PROPERTIES

3.1 (C) The loss in weight should be proportional to vapour pressure above that
solution:
So, PSA  2gm
PSB  1.5gm
PSC  2.5gm
So, maximum vapour pressure is above C solution hence, it is having
minimum lower and hence minimum mole fraction (hence minimum
number of moles of solute) So max, molar mass of substance.

3.2 (C) Boiling point of solution = boiling point of pure solvent +  Tb = 100 + 
Tb
Freezing point of solution = freezing point of pure solvent -  Tf = 0 -  Tf
Difference in temperature (given) 100 +  Tb – (-  Tf)
103.57 = 100 +  Tb +  Tf = 100 + molality  Kb + molality  Kf
= 100 + molality (0.52 + 1.86)
103.57 100 3.75
 Molality =   1.5 m
2.38 2.38
moles×1000 moles×1000
and molality = ; 1.5 =
Wgm(solvent) 500
1.5×500
 Moles of solute = = 0.75 moles
1000
Ans. 750 mmoles

3.3 (D) 3.4 (C) 3.5 (B)

3.6 (A) [Apply Clausicu – Clapeyron equation].

P 2 1
3.7 (C) X solute  i  
P 5 2
1
so, i = 1.25  Hence degree of dissociation =
4
1 1
so, moles of Cl- ions 2  = moles
4 2
1
so, moles of AgCl ppt = moles
2

3.8 (A) Higher freezing point  lesser  Tf

 lesser molality
 lesser number of particles
 x 1000 0.2
3.9 (B) (molality)i = 10x  0.2 
100 Kf
x 1000 0.25
(molality)f = = 10x = 0.2 
W Kf
0.2 W
so   so w = 80 gm
0.25 100
Hence ice separated = 20 gm

PA0 PB0
3.10 (D)  = 1 atm  PA° + PB° = 2 atm
2 2
p 0A 3PB0
 > 1 atm  PA° + 3PB° > 4 atm
4 4
PA0 3PB0 4P 0
&  + C = 1 atm  PA° + 3PB° + 4P C° = 8 atm
8 8 8
So PA° + 3PB° = (8 – 4  0.8 ) atm = 4.8 atm
Hence PB° = 1.4 atm
PA° = 0.6 atm

3.11 (C) Pressure of air = 750 – 100 = 650 mm of Hg

on compressing Pf = 650  3 mm of Hg = 1950 mm of Hg
so PT = (1950 + 100) = 2050 mm of Hg

3.12 (A) Let volumes taken to be ‘x’ & ‘y’ litres,

0.1x  0.4y
so = 0.34 & Vg = (x + y) (to be maximised)
xy
so y = 4x so for maximum volume
1
y = 2L & x = L.
2

3.13 (B) π = CRT

0.1 0.5 0.2  2
C = (0.34 +  ) = 0.34 + 0.02 + 0.16 = 0.52
2.5 2.5
so π = 0.52  0.082  300 atm = 12.792 atm

3.14 (B) As m  0, NaHSO4 will generate three particles while NaCl will
generate only two particles.

3.15 (A) 3S S3
α 2α
1- α  i=1-
3 3
 2α 
Now 0.1  1   = 0.08
 3 
 α = 0.3. hence 30% trimerization.
 1
3.16 (D) PT = (75 + 22) = 48.5 torr
2
1
PT = (75 + 10) = 42.5 torr
2
1
PT = (22 + 10) = 16 torr
2
1 2
PT = (75 + 22 + 10) = 35 torr
3 3

3.24
3.17 (B) 0.0558 = i  1.86  i = 3 (100% dissociated)
324
21.68 1000
0.0744 = i =   1.86  i  1 (almost undissociated)
271 2000

 0.849 
 
3.18 (A) 1.24 = 34.3  M   M = 469.68
 0.050 
 

3.19 (B, D)

3.20 (B, D)
Number of particles from K4 [Fe(CN)6] = 5
Number of particles from FeSO4 (NH4)2 SO4 . 6H2O = 5
Number of particles from KCl. MgCl2. 8H2O = 5

3.21 (A, B, C)
P  20 6 18 6 1
   
20 m 180 m 10
P  20.02 6 18 6 1
   
20.02 m 198 m 11
calculation gives m 54 gm/mole
p = 20.22 torr
& on dilution  P decreases (lowering) so net pressure increases.

3.22 (A, C, D)
xA PA° + xB PB° = 700 … (i)
xA“ PA ° + xB“ PB° = 0.30 PA° + 0.70 PB° = 600 … (ii)
if moles of A & B initially are x & y then
2 1
x = 0.75  (x + y) + 0.30  (x + y)
3 3
x y
& xA = or xB =
x+y x+y
solving gives
 2500
xA = 0.6, xB = 0.4, PA° = torr & PB° =
3
500 torr

3.23 (A, B, C, D)
Acetone is more volatile than chloroform due to greater molar mass of
chloroform and both forms solution which shows negative deviation.
Hence the results follow.

3.24 (A) S-1 is true, S-2 is true & S-2 is the correct explanation of the S-1.

3.25 (B) ‘S-1’ is correct because fluids present inside the cell come out due to
higher vapour pressure inside the cell than outside the cell.
‘S-2’ is correct because in reverse osmosis, solvent from saline water
enters the pure solvent through semi-permeable memberane.

3.26 (C) Extent of dissociated increases steadily with increasing dilution.

3.27 (C) The benzoic acids forms a dimer due to H-bonding as

O --- H - O

C C

O- H--- O
--

3.28 (A) As degree of dissociation of HF gets changed on dilution.

3.29 False Relative lowering = Xsolute

observed colligative properly

3.30 False i=
normal colligative properly

3.31 False NaCl is electrolyte while sugar is not

3.32 True

P
3.33 False is a Colligative property.
P

3.34 True

3.35 True

3.36 False it shrinks

3.37 True

3.38 (B) When liquid just starts forming vapours we have Roult’s law valid with Xb
& Xc as mole fraction in liquid state so equation of curve obtained by
collecting such points will be
P = X B PB + X C PC0 = X B PB + 1- X B  PC0 + PC0 + (PB  PC ) X B = PC +
(PB  PC ) XB
The second curve will not be a straight line having equation
P - P 
P =   B C
X B (PC  PB )  PB

3.39 (A) Form solution of above question

3.40 (C) If initially liquid there are x moles of A and y moles of B then XA =
x y
, XB 
x+y (x + y)
we have 700 = XA PA° + XB PB° ……….. (1)
600 = XA “PA° + XB” PB° ……….. (2)
1 3 2 3
Also x = (x + y)  + (x + y) 
3 10 3 4
x
Which gives = 0.6
x+y

Sol. (3.41 to 3.43)

xA = 0.75 xB = 0.05 above 500 mm Hg only liquid phase
exists.
Pbubble point = xA PA + xB PB P cqycqfyr fcUnq = xA PA + xB PB
= 0.75  400 + 0.25  800 = 500 mm.
yA = 0.75, yB = 0.5
At dew point
1 y y 1 0.75 0.25 1.5  0.25
= A0  B0  =  
PT PA PB PT 400 800 800
800
 PT = = 457.14 mm Hg
1.75
Below dew point only vapour phase exists.

3.41 (D) 3.42. (A) 3.43 (C)

3.44 (B) 3.45. (C) 3.46 (D)

3.47 (A)
3.48 (C) Cryoscopic constant Kf =  Tf of solution having unit molality of normal
solutes
9 1000
Molality of glucose solution in (c) = 1
(59  9) 180

3.49 (D) Since the solution has greater entropy (disorder) than the pure liquid, so
former has lesser tendency to freeze i.e., the temperature has to be
lowered to freeze the solution.

3.50 (B) 2Na+ (aq) + 2I- (aq) + HgI2(s) 

 2Na+ (aq) + HgI42- (aq)
The number of mole particle decreases from 4 (2Na+ + 2I-) to 3 (2Na+ +
HgI42-). Hence, the Colligative property will decrease or, the vapour
pressure will increase to a constant value until NaI is completely
consumed.

RTf02 M
3.51 (B) Kf = would be larger for larger value of T°f and smaller value
1000H fus
of the enthalpy of fusion of the solid solvent.

3.52. (D) The vapour pressure of a mixture of two immiscible liquids is the sum o
their vapour pressure in the pure states, independent of their relative
amounts. Hence, B.Pt. of the mixture will be less than that of either of the
liquids, remaining constant throughout.

3.53. (A – p, s, r), (B – p, q, t), (C – p), (D – p, q, t)

(A) Acetone + CHCl3 - ve deviation from Raoult’s law  S > 0
H < 0 V < 0
Maximum Boiling Azeotropes.
(B) Ethanol + Water + ve Deviation from Raoult’s law  S > 0
H > 0 V > 0 Minimum Boiling Azeotropes
(C) C2H5Br + C2H5l Ideal solution no Azeotropes
H = 0 V = 0
Acetone + Benzene
H > 0 V > 0 S > 0
Minimum Boiling Azeotropes

3.54. (A – q, s), ; (B – q, s), (C – q, s), (D – q, s)

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

(A) PA0 > PB0 means A is more volatile than B and therefore A will be richer in
PA0
vapour phase. [or YA = XA ]
PT
(B) For Azeotropes, composition of vapour phase and liquid phase is same
(C) For PA0 < PB0 , < XB < YB and YB > YA for an equimolar ratio.
 (D) For PA0 = PB0 , XA = YA for an equimolar ratio.

3.56 In solution, xA = 0.3 ; xB = 0.7

In vapour phase, x’A = 0.6 ; x’B = 0.4
P
xA’ = A = 0.6
P
PA P0 x
= 0 A A0
PA  PB PA x A  PB x B
0.3PA0
0.6 = … (1)
0.3PA0  0.7PB0
PB PB
x’B =   0.4
P PA  PB
0.7 PB0
  0.4 … (2)
0.3PA0  0.7PB0
Dividing (1) by (2)
0.3PA0 0.6

0.7 PB0 0.4
PA0 0.6  0.7 7
    3.5
PB0 0.4  0.3 2

3.57 C12H22O11 + H2O   C6H12O6 + C6H12O6

mol 0.0125 0 0
0.0125 – x x x
 Tb = m1Kb + m2Kb + m3Kb
0.104
m1 + m2 + m3 = = 0.2
0.52
0.125  x  x  x
100  0.2
100
x = 0.0075
0.0075
mol % =  100 = 60
0.0125
1 60
th of mol% = = 6.
10 10

3.58 x FeC2 O4 = x KMnO4  Fe +2 + C 2 O 4 -2

a FeC 2 O 4 
MV
x Fe+2  x C O -2  x KMnO4 n FeC2O4 =
2 4
1000
0.4  5  30 M 10
1  n+2  n= 0.02 =
1000 1000
2 10
n= = 0.02 M=2
1000
 25  2 1000 100
TF = mKfi =   1.86  2 = 1
1000 186 100

3.59 π = MRTi i = 1 + (y – 1) α
π = 2  0.0821  300  4 i = 1 + (5 – 10)0.75
For He PV = nRT i=1+3
π V = nRT i=4

16
2  0.0821  300  4  100    10-3 =  0.0821  300
4
4 40
 = 1
 5
8 10 8

3.60 Tb  T1  T2

Tb = 0.0000104 = (m1ii1 + m2i2)  kb
CaSO4 MgSO4
i = i1 i’ = i2
n = n1 n’ = n2
(n1  n 2 )  0.52  2
0.000052 =  1000
106
n1 + n2 = 0.05
for degree of Hardness
n CaSO4 + n MgSO4 = n CaCO3
n CaCO3 = 0.05
mCaCO3 = 0.05  106 = 5 ppm

3.61 1.0526  760 = Pext

Pext = 799.976 800 Torr
1250
 log 800 = 7 -
t  220
1250
 2.9 = 7 -  t = 84.878°C Ans. 85
t  220

6 42 16 12 192
3.62 PT =  24  12    19.2 = kPa
10 10 10 10
6 144
PA‘ = XA PA =  24  14.4  XA‘  19.2
10 10
144
so XA‘ = = 75% XB‘ = 25%
192
3 1
so PT =  24  12 18  3  21k Pa
4 4
 3
& PA =  24 = 18 = XA” (21)
4
18 6
so XA” =  = 85.7% of A
21 7

p0  p
3.63 = x2
p0
0.04
= 0.00125 = mole fraction of solute.
32
The salt is dissociated in solution
MCl2 (s) M2+ + 2Cl-
On dissociation, the salt produces 3 ions.
0.00125
 Mole fraction of undissociated salt = = 0.00042 moles
3
Mole fraction of water = 0.99958 moles
Mass of solvent = 0.9996  18 = 17.993 g
0.00042 100
Solubility of the salt = = 0.02334 mol. Lit-1 = s
17.993
KSP = s  (2s)2 = 4s3
= 4  (2.334  10-2)3 = 5.08  10-5

RTf2
3.64 Kf = M (M = mol. Wt. Tf = normal freezing ap)
H fusion
8.314  (273)2 18
Kf =
1000  6 103
 Kf  1.86 K. Kg mol-1
Now Tf = Kf  m (m = molality)
Tf (273  271)
 m= = = 1.07 moles / Kg
Kf 1.86
moles of solutes
But m =
weight of solvent (in Kg)
 0.9 18  -2
n = moles of solute = 1.075    = 1.74  10
 1000 
760  700
Also Xsolute = - 0.079 (where X = mole fraction)
760
1.74 102
 Total moles (N) = = 0.22
0.079
Moles of solvent (H2O) = 0.2026
 Mass of ice separated out = (0.9 – 0.2026)  18 = 12 gm
3.65  H+
H2SO4  + HSO4- ; HSO4- H+ +
SO42-
1 1 1
 1 1 1  x 1+x
x

Total concentration, CT = (1 + x) + (1 – x) + x = 2 + x.
π = CTRT  90.2 = (2 + x)  0.082  500  x = 0.2.
+ 2-
 [H ] = 1.2 M, [HSO4 ] = 0.2 M, [HSO4-] = 1 – 0.2 = 0.8.
[H + ][SO 24  ] 1.2  0.2
 Ka2 = = = 0.3.
[ HSO 4 ] 0.8

m 5 1
3.66 For original solution, α = 
=  .
m 5000 100
For dilution, C1V1 = C2V2  100  0.1 = 100  C2.  C2 = 0.01 M.
+
For weak acid, HA H + A-
C
C (1 - α ) Cα Cα
Ka = C1 α 12 = C2 α 22
2
 1  2
0.1    = 0.01 α 2
 100 
α 2 = 0.032.
Osmotic pressure = i  C RT = (1 + α 2)  0.01  0.08  500. = 0.4128 atm.

3.67 Fist of all we will mole fractions in liquid mixture, let wt of this mixture is 100
gram.
50
So moles of pentane =
72
50
Moles of Butane =
58
50
So Xpentane = 72 = 0.446
50 50

72 58
 XButane = 0.554
Now Total Pr. = 0.446  521 + 0.554  1823
= 232.37 + 1009.3
= 1241.76
Now we will find mole fractions in vapour phase
X P ° 0.446  521
 Ypentane = A A = = 0.187
PT 1241.67
So YButane = 0.813
So Calorific value will be
= YButane  (2856) + YPentane  (3514) = 0.813  2856 + 0.187  3514 =
2978.6 KJ/mol.
 DPP-4
Chemical Kinetics & Radioactivity
SECTION - I : STRAIGHT OBJECTIVE TYPE
4.1 What is order with respect to A, B, C respectively
[A] [B] [C] rate (MFsec.)
0.2 0.1 0.02 8.08 x 10-3
0.1 0.2 0.02 2.01 x 104
0.1 1.8 0.18 6.03 x 10-3
0.2 0.1 0.08 6.464 x 10-2

(A) –1, 1, 3/2 (B) –1, 1, ½ (C) 1, 3F2,–1 (D) 1,–1,. 3F2

4.2 N20 5 ---* 2NO 2 + 0 2

When N205 decompose, its t12 does not change with its changing pressure during the
reaction, so which one is the correct representation for "pressure of 2NO2" vs lime°
during the reaction when initial N205 is equals to Po.

4.3 In a hypothetical reaction

A(aq) 2B(aq) + C(aq) (1st order decomposition)
'A' is optically active (dextro-rototory) while 'B' and 'C' are optically inactive but 'B' takes part
in a titration reaction (fast reaction) with H202. Hence the progress of reaction can be
monitored by measuring rotation of plane of plane polarised light or by measuring
volume of H202 consumed in titration.
In an experiment the optical rotation was found to be 0 = 30° at t = 20 min and 8 =15° at t=
50 min. from start of the reaction. If the progress would have been monitored by titration
method, volume of H202 consumed at t = 30 min. (from start) is 30 ml then volume of H202
consumed at t = 90 min will be:
(A) 60 ml (B) 45 ml (C) 52.5 ml (D) 90 ml
44 The elementary reaction A + B  products has k = 2 x 10-5 M-1 S-1 at a
temperature of 27°C. Several experimental runs are carried out using stoichiometric
proportion. The reaction has a temperature coefficient value of 2.0. At what temperature
should the reaction be carried out if inspite of halving the concentrations,
n 6
the rate of reaction is desired to be 50% higher than a previous run. (Given =
n 2
2.585).
(A) 47 °C (B) 53 °C (C) 57 °C (D) 37 °C

4.5 At a certain temperature, the first order rate constant k1 is found to be smaller than
the second order rate constant k2. If the energy of activation E1 of the first order reaction
is greater than energy of activation E2 of the second order reaction, then with increase in
temperature.
(A) k1 will increase faster than k2, but always will remain less than k2.
(B) k2 will increase faster than k1
(C) k1 will increase faster than k2 and becomes equal to k2.
(D) k1 will increase faster k2 and becomes greater than k2.

4.6 For the system A2(g) + B2(g) 2AB(g), AH = – 80 KJ/ mole

If the activation energy for the forward step is 100 kcal /mole. What is the ratio of
temperature at which the forward and backward reaction shows the same %
change of rate constant per degree rise of temperature ? (1 cal = 4.2 J)
.(A) 0.72 (B) 0.84 (C) 0.42 (D) 1

47.
All reactions are of Ist order
At time t = ti (ti > 0)
[B ]
  . Therefore at
[C ]
time t = t2 (where t2 > ti)
[C]
 β which of the following is correct.
[D]
(A) a > 13 (B) a = 13 (C) a13 =0.4 (D) a + 8 = 0.4

4.8 In the formation of HBr from H2 & Br2 , following mechanism is observed.
(A) Br 2 2 Br • Equilibrium step

(B) H 2 + Br   HBr + H• Slow step
(C) H• + Br2   HBr + Br• Fast step
Calculate the rate of reaction, it concentration of hydrogen is twice that of bromine and
the rate constant is equal to one rutherford. If conc. of bromine is 1 M.
(A) 2 x 106 dps (B) 10 X 109 dps (C) 20.2 X 1010 dps (D) 4 x 102 dps
4.9 For a two step reaction
K1
K3
A R+B R + C  Products
K2
(where, R is a reactive intermediate whose concentration in maintained at some low
steady state throughout the reaction). If the concentration of C is very high then the
order of reaction will be.
1
(A) 1 (B) 2 (C) 0 (D)
2
4.10 A graph between log t112 and log a (abscissa) a being the initial concentration of
A in the reaction For reaction A  4 Product, is the rate law is

– d[A] – d[A] – d[A] – d[A]

. (A) =K (B) =K[A] (C) =K[A]2 (D) =K[A]3
dt dt dt dt

4.11 The reaction A (g) + B (g) C (g) + D (g) is elementry 2nd order reaction. When
started with equimolar amounts of A and B, at equilibrium, it is found that the
concentration of A is twice that of C. Specific rate for forward reaction is 2 x 10-3 mol –-1
Lsec-1. The specific rate constant for backward reaction is :
(A) 5.0 x 10-4 M-1 see (B) 8 x 10-3 M-1 sec-1
(C) 1.5 x 1021A-4 sec-1 (D) none of these.

4.12 For the reaction R – X + OH- ROH + X- The Rate is given of

Rate = 5.0x 10-5[R – X [OH-] + 0.20x 10-5[R – X] what percentage R – X Reaction by
SN2 mechanism when [OH-–] = 1.0x 10-2 M
(A) 96.1 % (B) 3.9 % (C) 80 % (D) 20%

4.13 For a 1st order reaction (gaseous) (cont. V, T)

a A 
 4 (b 1) B + 1 C (with b > a) the pressure of the system
b 
rose by 50  –1 % in a time of 10 min. The half life of the reaction is therefore.
a 
(A) 10 min (B) 20 min (C) 30 min (D) 40 min.
4.14 For a certain reaction the variation of the rate constant with temperature is given by
the equation
(ln3)t
In Ft = In For + (t  0°C)
10
The value of tile temperature coefficient of the reaction is
(A) 0.1 (B) 1.0 (C) 10 (D) 3

4.15 The high temperature (  1200K) decomposition of CH3COOH) occurs as follows

as per simultaneous 1St order reactions.
k1
CH3COOH   CH4 + CO2
k2
CH3COOH   CH2C0 + H20
What would be the % of CH4 by mole in the product mixture (excluding CH3COOH)?
50k1 100k1
(A) (B)
k1+k 2  k1+k 2 
200k1
(C) (D) it depends on time
k1+k 2 

4.16 A reaction takes place in three steps ; the rate constants are Br k2 and k3.The
kk
overall rate constant K  1 3 . If energies of activation are 40 , 30 and 20 kJ, the
k2
overall energy of activation is (assumming 'A' to be constant for all )
(A) 10 (B) 15 (C) 30 (0) 60

417 The inversion of cane sugar proceeds with half life of 600 minute at pH = 5 for any
concentration of sugar, However at pH = 6, the half life changes to 60 minute, The
rate law expression for sugar inversion can be written as
(A) r = k [sugar]2 [H+]° (B) r = k [sugar]' [Hl°
2 + 1
(C) r = k [sugar] [H ] (D) r = k[sugar]°[H+]-1

4.18 Some graph are sketch for the reaction A  B (assuming different orders).Where
' α' represent the degree of dissociation.
.

The order of reaction is respectively.

. (A) 0, 1, 2 (B) 1, 0, 2 (C) 2, 0, 1 (D) 1, 2, 0
4.19 Compounds A and B react with a common reagent with first order kinetics in both
cases. If 99% of A must react before 1% of B has reacted. What is the minimum
ratio for their respective rate constants?
(A) 916 (B) 229 (C) 500 (D) 458

4.20 The activity per ml of a solution of radioactive substance is x. How much water be
added to 200 ml of this solution so that the acitivity falls to x/20 per ml after 4 half-
lives ?
(A) 100 ml (B) 150 ml (C) 80 ml (D) 50 ml.

4.21 A hypothetical reaction :

A2 + B2   2AB Follows mechanism as given below :
KC
A2 A + A (fast) (Kc – is equilibrium constant)

K
A + B2  1
 AB + B…………..(slow) (k1- rate constant)
K2
A+B AB (fast) (k2 ,k3 - are rate constant)
K3
The order of overall reaction is :
(A) 2.5 (B) 1 (C) 3/2 (D) Zero

4.22 For the decomposition of H202(aq) it was found that VO2 (t =15 min.) was 100 mL
(at 0°C and 1 atm) while VO2 (maximum) was 200 mL (at 0°C and 2 atm). If the
(cM)
same reaction had been followed by the titration method and if VKMnO 4
(t = 0) had
(cM)
been 40 mL, what would VKMnO 4
(t = 15 min) have been ?
(A) 30 mL (B) 25 mL (C) 20 mL (D) 15 mL

4.23 The high temperature (z, 1200K) decomposition of CH3COOH(g) occurs as follows
as per simultaneous 1St order reactions.
k1
CH3COOH   CH4 + CO2
k2
CH3COOH   CH2CO + H20
What would be the % of CH4 by mole in the product mixture (excluding CH3COOH)?
50k1 100k1
(A) (B)
(k1  k2 ) (k1  k2 )
200k1
(C) (D) it depends on time
(k1  k2 )
K1 K2
4.24 For the system A B, A C which was started with only
K–1 K–2
A the equilibrium concentration [A]eq is correctly related to [B]eq and [C]eq. as:
 k –1[B]eq +k –2 [C]eq k –1[B]eq – k –2 [C]eq
(A) (B)
 k1+k 2  k1 – k 2 
k –1[B]eq +k –2 [C]eq k –1[B]eq – k –2 [C]eq
(C) (D)
 k1 – k 2   k1+ k 2 
4.25 A certain reaction A -3 B follows the given concentration (Molarity)-time graph. Which of the
following statement is true?

(A) The reaction is second order with respect to A

(B) The rate for this reaction at 40 second will be approximately 3.5 × 10–3 Ms–1
(C) The rate for this reaction at 80 second will be 1.75 x 10-3 M s–1
(D) The [B] will be 0.25 Matt = 60 second

4.26 The activation energies of two reactions are Ea and Ea’ with Ea > Ea’ If temperature of
the reacting systems is increased from T1 to T2, predict which of the following
alternatives

k1 k 2 k k k k k k
.(A) = (B) 1  2 (C) 1  2 (D) 1  2 2
k1 k 2 k1 k 2 k1 k 2 k1 k2
4.27 A simple mechanism for enzyme-catalyzed reaction is given by the following of
equations

E + S ES
(enzyme) (reactant) (intermediate-1)
ES EP
(intermediate-1) (intermediate -2)
EP E + P
(intermediate-2) (enzyme) (product)

This is known as the Michaleis-mechanism. The potential energy diagram is

shown in the figure. Which of the following sets of identifications is correct ?
(Assume that the temperature and pressure are constant).
(1) (2) (3) (4)
(A) E+P EP ES E+S
(B) ES Activated complex EP Activated complex
(C) EP Activated complex ES Activated complex
 (D) E + S ES EP E+S

SECTION - II: MULTIPLE CORRECT ANSWER TYPE

-1 -1
K1(time ) K 2 (time )
4.28 For the consectutive reaction A   B   C following curves were
obtained depending upon the relative values of k1 & K2

Now which of the following is the correct match?

(A) figure 1 — (k1 < k2) (B) figure 2 — (k1 < k2)
(C) figure 2 — (k1 » k2) (D) figure 1— (k1 » k2)

429 Which is correct graph:

(A) (B)
(B) (D)

4.30 For a certain reaction A   products, the t1/2 as a function of [A]0 is given as
below :
Which of the following is true :
1
(A) The order is (B) t112 would be 100 10 min for [A]0 = 1M
2
(C) The order is 1 (D) t112 would be 100 min for [A]0 = 1 M

4.31 Decomposition of 3 A(g)   2 B(g) + 2C(g) follows first order kinetics.

Initially only A is present in the container. Pressure developed after 20 min. and
infinite time are 3.5 and 4 atm respectively. Which of the following is true.
(A) t50 = 20 min (B) tams = 40 min (C) t99% = 64/3 min (D) t8, 5% = 60 min

4.32 The reaction 2N0 + Br2   2N0Br follows the mechanism :

Fast
(1) N0 + Br 2 N0Br 2
Slow
(2) N0Br2 + N0   2N0Br
Which of the following islare true regarding this :
(A) The order of the reaction with respect to N0 is two
(B) The molecularly of the steps (1) and (2) are two each.
(C) The molecularly of the overall reaction is three.
(D) The overall order of the reaction is three.
4.33 In the following gaseous phase first order reaction
A(g)   2B(g) + C(g)
initial pressure was found to be 400 mm of Hg and it changed to 1000 mm of Hg
after 20 min. Then :
(A) Half life for A is 10 min
(B) Rate constant is 0.0693 min-1
(C)
Partial pressure of C at 30 min is 350 mm of Hg
(D) Total pressure after 30 min is 1150 mm of Hg
4.34 The polarimeter readings in an experiment to measure the rate of inversion of cane
suger (1st order reaction) were as follows
time (min) : 0 30 co
angle (degree) : 30 20 -15
Identify the true statement (s) log 2 = 0.3, log 3 = 0.48, log 7 = 0.84 , loge 10 = 2.3
(A) The half life of the reaction is 75 min
(B) The solution is optically inactive at 120 min.
(C) The equimolar mixture of the products is dextrorotatory
(D) The angle would be 7.5° at half time

4.35 Identify the true statement(s)

(A) A catalyst is chemically unchanged at the end of a reaction
(B) A catalyst may appear in the kinetic rate equation of the reaction
(C) A catalyst will not affect the composition of an equilibrium mixture
(D) A catalyst cannot cause a non-spontaneous (  G > 0) reaction to proceed

4.36 The half – period T for the decomposition of ammonia on tungsten wire, was
measured for different initial pressure P of ammonia at 25°C. Then
P (mm Hg) 11 21 48 73 120
T (sec) 48 92 210 320 525
(A) Zero order reaction
(B) First order reaction
(C) rate constant for reaction is 0.114 seconds
(D) rate constant for reaction is 1.14 seconds.

4.37 The substance undergoes first order decomposition. The decomposition follows two
parallel first orde reactions as :

.
K1
K1 = 10–2 Sec–1 and K2 = 4 × 10–2 Sec–1

K2

If the corresponding activation energies of parallel reaction are 100 and 120 kJ mol-1
then the net activation energy of A is / are :
(A) 120 KJ mol-1 (B) 116 KJ mol-1 (C) 100 KJ mot' (D) 150 KJ mot'

4.38 A certain reaction obeys the rate equation (in the integrated form) [Co -") - Co' - = (n -
1) kt where C, is the initial concentration and C is the concentration after time, t.
(A) the unit of k for n = 1 is sec-1 (B) the unit of k for n = 2 is litre mo1-1 sec1
(C) the unit of k for n = 3 is mol litre sec1 (D) the unit of k for n = 3 is litre mol-2 sec1

.
4.39 The ozone layer in the earth's upper atmosphere is important in shielding the earth
from very harmful ultraviolet radiation. The ozone, 03, decomposes according to the
 equation 203(g) -› 302(g). The mechanism of the reaction is thought to proceed through
an initial fast, reversible step and then a slow second step.
Step 1: Fast, reversible 03(g) 02(g) +0(g)
Step 2 : Slow 03 (g) + 0(g)  202(g)
The which of the following is correct ?
(A) Step 2 is rate determining step
d
(B) the rate expression for step 2 is -- [O3 ] = k[03][0]
dt
(C) For Step 1 , molecularity is 1
(D) For Step 2 , molecularity is 2

4.40. Consider the following case of COMPETING 1ST ORDER REACTIONS

\.
After the start of the reaction at t = 0 with only A, the [C] is equal to the [D] at all times. The
time in which all three concentrations will be equal is given by
1 1 1 1
(A) t = n3 (B) t  n 3 (C) t  n 2 (D) t  n 2
2k1 2k2 3 k1 3k 2
.4.41 Rate of a chemical reaction 2A (g)   B (g) is defined as
1 dnB
'rB ' 
V dt
Where nB = number of moles of B formed and CB = concentration of B then which of the
following relation is correct.
dCB CB dv
(A) rB = + (If volume V is not constant)
dt v dt
dCB
(B) rB = (If volume V is constant)
dt

dCB CB dv
(C) rB =  (If volume V is not constant)
dt v dt
dCB CB dv
(D) rB = –  (If volume V is not constant)
dt v dt

SECTION - III : ASSERTION AND REASON TYPE

4.42 Statement-1 : If the activation energy of reaction is zero temperature will have no
effect on the rate constant.
Statement-2 : Lower the activation energy fasten is the reaction.
 (A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for
Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for
Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

4.43 Statement-1 : If the order of reaction is zero than degree of dissociation will be
independent upon initial concentration.
kt
Statement-2 : The degree of dissociation of Zero order reaction is given by  =
c0
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for
Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for
Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

4.44 Statement-1 : For a reaction A(g)  B(g)

—re =2.5 PA at 400K
—re =2.5 PA at 600K
activation energy is 4135 J/mol.
Statement-2 : Since for any reaction, values of rate constant at two different temp is
same therefore activation energy of the reaction is zero.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for
Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for
Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

4.45 Statement-1 : For A+ 2B   C (rate = K [A]1[B]°), the half life time of reaction
is only defined when conch of A and B are in stoichometric ratio
Statement-2 : For above given order half life of reaction is directly proportional to
conch of A and not to conch of B due to its zero order.
(A) Statement-1 is True, Statement-1 is True; Statement-1 is a correct explanation
for Statement-1.
(B) Statement-1 is True, Statement-1 is True; Statement-1 is NOT a correct
explanation for Statement-2.
(C) Statement-1 is True, Statement-1 is False.
(D) Statement-1 is False, Statement-1 is True.
 SECTION - IV: TRUE AND FALSE TYPE

d[A]
4.46 The rate of the reaction A  B having the rate law – = k [A] [B] when plotted
dt
against time will exhibita maximum at some time.

4.47 A catalyst in a chemical reaction increases the forward Ea and decreases the
backward Ea

4.48 A catalyst in a chemical reaction decreases both forward and backward Ea

4.49 For a first-order reaction, the time required to reduce successively the
concentration of reactant by a constant fraction is always same.

4.50 As a first order reaction proceeds at a constant temperature, the ode rewislis
constant

4.51 Generally the rate of reaction decreases with decrease in temperature.

4.52  B + C, must be r = k [A]2

The rate law of the elementary reacton; 2A 

4.53 Generally the rate of reaction depends upon the surface area of the solid reactants

4.54 Zero order reaction is uniform rate reaction but it can not be elementry reaction (single
step reaction)

4.55 Molecularly of a reaction may includes the number of product melecules taking part in the
reaction.

4.56 Larger the value of Ea , greater is the effect on the value of k for a given temperature
change.

4.57 At lower temperature, increase in temperature cause more change in the value of k than
at higher temperature.

4.58 If concentration of catalyst appear in rate law (rate = k [catalyst]1[reactant]1) then it may
becomes pseudo first order reaction during the reaction.

SECTION - V : COMPREHENSION TYPE

Comprehension # 1
Consider the inter conversion of nitrosotnacetoamine into nitrogen phorone and
water.
 The reaction is 1st order in each direction, with an equilibrium constant of 104, the activation
energy for the forward reaction is 11usactivation energy for the forward reaction is 57.45 kJ / mol.
Assuming arrehemus preexponetial factor of 1012 S–-1

4.59 What is the expected forward constant at 300K , it we initiate this reaction
starting with only reactant
(A) 102 (B) 106 (C) 106 (D)104

4.60 If the change in entropy of the reaction is 0.07 KJ. K-1 mol-1 at 1 atm pressure.
Calculate up to which temperature the reaction would not be spontaneous. (For
forward reaction)
(A) T < 285.7 K (B) T > 250 K (C) T < 340.2 K (D) T > 200 K

4. 61 Calculate Kp of the reaction at 300 K

(A) 2.4 x 104 atm-1 (B) 104atm (C) 24.6 x 104atm (D) 2.82x102 atm1

Comprehension # 2
.REACTIONS TENDING TO EQUILIBRIUM
Not all chemical reactions proceed to a stage at which the concentrations of the
reactants become vanishingly small. Here we consider the kinetics of such
reactions.
Let a reaction be represented in general terms by the scheme
K1
A B
K2
where k., and k_., represent the rate constants for the forwards and reverse
reactions, respectively. The equilibrium constant for this reaction may be written
as
K = [B] /[A] = K1/K–1 --(1)
where the subscript 00 refers to a time t, sufficiently long to establish equilibrium at
the given temperature. The initial concentration of species A is [A]O, and that of B
is [B]O . After a time t, let the concentration of species A be [A/t and that of B be
[Bat. The total rate of change of [At is given by
d[A]t/dt= - K1[A]t + k-1[B]t
 If, as is usual, [B]O is initially zero, it follows from a mass balance that at any time t,
[Bat = [A]0 - [A]t, whence
d[A]t/dt = –K1[A]t + k-1([A]O - [A]t)
or d[A]t/dt = – (K1 + k-1)

k1
4.62 For the reaction A C (having both 1ts order reactions),
K2
the concentration as a function of time are given for a certain experimental run
along with a tangent to the graph at the origin. The ratio of the magnitude of the
slopes of the graph of [A/ and [C/ at the origin would be :

3 4
(A) 1 (B) (C) (D) None of these.
4 3

4.63 At what time is the rate of change of concentration of A equal to rate of change
of concentration of C in magnitude ?
(A) t = 0 only (B) t  t equilibriumonly (C) t = 10 only (D) at all time

4.64 What is the Cc of the reaction 2C 2A?

2 3
(A) (B) (C) 1 (D) None of these
3 2

Comprehension # 3
PSEUDO - MOLECULAR REACTIONS
There are many reactions which obey a first order rate equation although it reality
they are bi- or ter-molecular. As an example of these may be taken the decomposition
of Carbonyl sulfide in water, namely,
COS + H20   002 + H2S
According to the law of mass action this reaction should be second order with the rate
dependent on the concentration of both the carbonyl sulfide and the water. Actually
however, the rate is found to be first order with respect to the carbonyl sulfide and
independent of the water Reactions exhibiting such behaviour are said to be pseudo-
molecular.
The pseudo-unimoecuar nature of this reaction is explainable by the fact that water is
present in such excess that its concentration remains practically constant during the
course of the reaction. Under these condition b x = b, and the rate equation
becomes
dx
 k2 (a  x )b
dt
On integration this leads to
2.303 a
k  bk 2  log10
t ax
 which is the equation for a first order reaction. It is evident, however, that the now
constant k is not independent of the concentration, as is the case with true first order
constants, but may vary with b if the latter is changed appreciably, When such is the
case, the true constant k2 can be obtained from k by dividing the latter by b.
pseudo-molecular reactions are encountered whenever one or more of the
reactants remain constants during the course of an experiment. This is the case
with reactions conducted in solvents which are themselves one of the reactants, as
in the decomposition of carbonyl sulfide in water, or in the esterification of acetic
anhydride in alcohol
(CH3C0)20 + 2C2H5OH   2CH3C00C2H5 + H20
Again, this is also true of reactions subject to catalysis, in which case the
concentration of the catalyst does not change. The decomposition of diacetone
alcohol to acetone in aqueous solution is catalysed by hydroxyl ions, with the
rate proportional to the concentration of the alcohol and that of the base. Since
the concentration of the base does not change within any one experiment,
however, the rate equation reduces to one of first order with respect to the
alcohol. But the rate constant k obtained for various concentrations of base are
not identical, as may be seen from table. To obtain from these the true second
order velocity constant, the k's must be divided by the hydroxyl ion
concentration. When this is done excellent k2 values result, as column 3
indicates.

Table : Decomposition of diacetone alcohol in water at 25°C (Catalyst : NaOH)

4.65 Which of k or k2 is dependent on concentration ?

(A) only k (B) only k2 (C) both k and k2 (d) neither k nor k2

4.66 By what factor does the rate of reaction of diacetone alcohol in water solution
change if p0H is increased by 2 units other things remaining same ?
(A) increases 100 times (B) decreases 100 times
(C) increases 2 times (D) decreases 2 times

4.67 For the reaction A + B  C ; r = k [A] [B] with [A]0 = 0.001 M and [B]0 = 10 M, the
time in which the conc. of A becomes 0.005 M will be nearly
0.693 0.693 6.93 693
(A) (B) (C) (D)
10k k k k
Comprehension # 4

From the following data answer the questions :

Reaction : A + B  P

4.68 The order w. r.t A is

(A) 1 (B) 2 (C) 3 (D) -1.

4.69 The value of rate constant at 300 K is (M-2 sec-1)

(A) 2.667 n 108 (B) 2.667 x 105 (C) 2.667 x 105 D) 2.667 X 109

4.70 The energy of activation for reaction (KJ/mol) is

(A) 20.83 (B) 13.83 (C) 15.23 (D) 10.23

Comperhension # 5

The rate law expressed the relationship of the rate of a reaction to the rate
constant and the concentration of the reactants raised to some powers for the
general reaction
aA + bB   cC + dD
Rate law takes the form
r = k [A]X [B]y
where x and y are number that must be determined experimentally k is the rate
constant and [A] and [B] are concentration of A & B respectively.
4.71 Gaseous reaction A   B + C follows first order kinetics concentration of A
changes from 1M to 0.25M in 138.6 min. Find the rate of reaction when conc. of
A is 0.1 M.
(A) 10-2M min1 (B) 10-3 M min-1 (C) 10-4M min–1 (D) 10-5M min–1

4.72 The initial rate of zero order reaction of the gaseous equation A (g)   2B
-2 1
(g) is 10 M min if the initial conc. of A is 0.1 M what would be conc. of B after
60 sec.
(A) 0.09 M (B) 0.01 M (C) 0.02 M (D) 0.03 M
 4.73 The variation of concentration of 'A'
with time in two experiments starting
with two different initial concentration
of 'A' is given by the following
graph.The reaction is represented by
A (aq)   B(aq) what is rate of
reaction 1.5M (M/min) when conc. of A
in aqueous solution was 1.8 M.

(A) 0.072 M min -1 (B) 0.1296 M min–1

(C) 0.036 M min -1 (D) 1 M min-1

Comprehension # 6 K1 2B
k1 1
For a hypotherical elementary reaction A where 
k1 2
K2 2B
.Initially only 2 moles of A are present.

4.74 The total number of moles of A, B and C at the end of 50% reaction are:
(A) 2 (B) 3 (C) 5 (D) None

4.75 Number of moles of B are :

(A) 2 (B) 1 (C) 0.666 (D) 0.333

4.76 The sum of mole of (B) and (C) is :

(A) 2 (B) 3 (C) 1 (D) 4

SECTION - VI : MATRIX - MATCH TYPE

4.77 For A + B   C in column - II the graphs given can be from any of these
four types.
dA
(a)  Vs time (x axis) (b) t1/12 Vs initial conc. (x axis)
dt
 C  Ct 
(c)  0  Vs time (x axis) (d) Conc. Vs time (x axis)
 Ct 
Match the graphs in Column—I I for the given order of reactions in Column – I
 .Column – I Column – II

(A) 1st order

.(B) Zero order

.(C) Second order

. (D) Pseudo first order

4.78 Match the following :

Coloumn – I Coloumn – II
(A) A + B   C + D (p) Unit of rate constant possess concentration unit
r = k1[A] [B]
(B) A + B   C +D (q) Rate constant for the reaction of both the reactants are
r = k2 [A] [B]° equal
(C) A + B   C + D (r) Rate of consumption of at least one of the reactants is
r = k3 [A]° [B]° is equal to rate of production of at least one of the
products
(D) 2A + B r  2C +3D (s) If both reactants are taken in stoichiometric ratio, half
k3 [A]° [B]° life for both reactants are equal.

479 Match the following:

Column – I Column – II
st
1 order
.(A)2N205 (g)   4NO2(g) + 02(g) (p) All the gaseous products are
paramagnetic in nature
 st
1 order
(B) 2H202 (aq)   2H20(aq)+02(g) (q) Hybridisation of reactant involves only

s & p orbitals
Zero order
.(C) 2NH3(g)  N2 (g) + 3H2(g) (r) As the reaction proceeds half life or
reactant changes with time
Zero order
(C) .2Cl207(g)  4C102 (g) + 302(g)(s) rate of production of, gases decreases
with increases in concentration of
products.

4.80 Match the following

Column I Column II
(A) If the activation energy is 65 kJ then how much time (p)5
faster a reaction proceed at 25°C than at 0°C
(B) Rate constant of a first - order reaction is 0.0693 min-1 . (q)11
-1 -1
If we start with 20 mol L , it is reduced to 2.5 mol L
in how many minutes
(C) Half - lives of first - order and zeroth order reactions are same. (r)30
Ratio of rates at the start of reaction is how many times of 0.693.
(D)The half-life periods are given , (s)1/4
[A]0 (M) 0.0677 0.136 0.272 (t)2
t1,2 (sec) 240 480 960 (u)1
order of the reaction is (v) 0

SECTION - VII : SUBJECTIVE ANSWER TYPE

SHORT SUBJECTIVE :
4.81 Reaction A   B carried inside a container concentration varies as At = a + bt. Rate
of reaction can be expressed in term of pressure at temp T = 300 K take b = 4, R=
1
atm mol–1k–1
12

4.82 If dt= k [H+]n and rate becomes 100 times when pH changes from 2 to 1. Find the
order of reaction.

1
4.83 The graph between log k and A [K is rate constant (sec-') and T the temperature.
T
 1 
(K)] is a straight line with OX = 5 and θ = tan-1   .Calculate the value of Ea is
 2.303 
cal.

4.84 For the reaction A  products, the following data is given for a particular run.
time (min.) : 0 5 15 35
1
(M–1 ) : 1 2 4 8
A
Determine the order of the reaction.
LONG SUBJECTIVE :

4.85 The rate constant of 1st order decomposition reaction of an organic compound (X)
into another organic compound Y and an inorganic compound (gas) (Z) may be given

1.25×10 4
Iog1ok (sec-1) = 12.37 –
T  inkelvin 
Find the activation energy and rate constant at 750 K and indicate your answer as
the product of Ea (in Joules moll and rate constant (in unit sec-1) and fill the answer as
a neares whole number.
Take R = 8.3 JK-1mo1-1, {antismog (-4.3) = 5 x 10-5}

4.86 Find out the percentage of the reactant molecules crossing over the energy barrier
at 325 K, given that  H325 = 0.12 kcal, Ea(b) + 0.02 kcal.

4.87 For the same first-order reaction, A   B + C, occurring in solution phase, now
let us assume that the reagent reacts with all the species A, B and C. The 'n' factor
of A, B and C with the regent is α,β and  respectively and that of the reagent with A,
B and C is a, b, and c.

. Calculate the expression of rate constant.

4.88 Decomposition of H202 (1st order)

1
 H2O(  ) +
H2O(aq)  O2(g)
2
Can be monitored by titration method by pressure measurement..If
Time (min) t=0 30 
Pressure (mm of Hg) 200 375 400
While when progress of same reaction was monitored by titration mnanit volume of
titrant consumed after 10 min was found to be 20 ml. Then complete the following Win.
Time (min) t=0 10 30
Pressure (mm of Hg) 200 (b) (c)
Volume of KMn04 (a) 20 (d)
consumed (m1)
 4. CHEMICAL KINETICS & RADIOACTIVITY

y
1
4.1 (D) From first two given data (2) x    4
 2
x z
If rate = K[A] [B]y [C]

From sec. and third data (9)y (9)z = 3

From first and forth data 2y + 2z = 1 … (2)
From first and forth data 4z = 8 = 23
2z = 3
So z = 3/2, y = -1, x = 1

4.2 (C)

4.3 (B)As only A is optically active. So conc. of A at t = 20 min  30°

While concentration of A at t = 50 min  mc 15°
So conc. has decreased to half of its value in 30 min, so t1/2 = 30 min.
So volume consumed of H2O2 at t = 30 min = t1/2 , is according to 50% production of B. at t =
90 min. production of B = 87.5% (Three half lives)

 30   30 
So volume consumed = (30 ml) +  ml     ml = 52.5 ml ans.
 2   4 

4.4 (B) r2 = k2 [A]21 [B]21 for a certain run

r1 = k1 [A]11 [B]11 for a previous run
r2 k 2 [A]2 [B]2

r1 k1 [A]1 [B]1
Substituting the given information
 t 2  27 
 10 
  1 1
1.5 = 2 1.5  2  
2 2
t 2 27
t 2  27 t 2  27 n6
 62 10
 n2  n6  
10 10 n2
t 2  27
 2.585  t2 = 52.85°C
10
53°C

d (Ink) E a
4.5 (A) 
dT RT 2
As Ea increases rate of increase in K also increases so k1 will increase faster than k2 but
always will remain less than k2.

4.6 (B) Eaf – Eab =  H

 Eab – Eaf -  H = 420 + 80 = 5000 kj/mjol
 d (In f ) E af d (In b ) E ab
Now,  & 
dT RTf 2 dT RTb 2
Eaf E ab

Tf 2 Tb 2
Tf E af 420
    0.84
Tb Tab 500

[B] 3k1 3
4.7 (C)   α
[C] 8k1 8
[C] 8k1 8
  β
[D] 7.5k 2 7.5
 α β = 0.4

4.8 (A) 1 - Rutherford = 106 dps

d[R]
 at steady state 0
dt
d[R]
= k1[A] – k2 [R] [B] – k2 [R] [C] = 0
dt
k1[A] = [k2 (B) + k2 (C)] [R] = 0
k1[A] k [A]
[R] = = 1
k 2 (B)  k 2 (C) k 2 [B]  [C]
k1 [A] k1[A]
Rate = k2  [C] =
k 2 [B]  [C] [B]
  [1]
[C]
Rate = k1 [A] C 
[B]
So order = Ist 0
[C]
4.10 (C) t1/2 = Ka(1 – n) , n being order k = Rate constant
log t1/2 = log K + (1 – n) log a
1–n=-1
n=2

4.11 (B) A(g) + B(g) (C)g + D(g) a – x 2x x = a/3

a–x a–x x x
2
a
1
 keq = 9 2 =
4a 4
9
1 2 103
keq = =
4 kb
keq = 8  10-3
4.12 (D) Rate (SN2) = 5.0  10-5  10-2 [R - X] = 5.0  10-7 [R - X]
Rate (SN1) = 0.20  10-5[R - X]
5 107 [R  X]100
% of SN2 =  20
5 107 [R  X]  0.20 10 5 [R  X]

4.13 (A) aA 
 (b – 1) + C
t = 0 P0 0 0
(b 1)x x
t = t P0 - x
a a
b b 1
Total pressure P0 – x + x = P0 +   1 P0
a a 2
b  b P
P0 +  1 x  P0   1 0
a  a  2
p
x = P0 + 0
2
1 p
k= n 0
t p0 /2
1
k= n 2
t
In1
t= = 10 min.
k

kt
4.14 (D) = (TC)t-0/10
k0
t
Taking log gives loge kt – loge k0 = loge (TC)
10
 In (TC) 
 In kt = In k0 +  t
 10 
 In (TC)  In 3
Comparision indicates   =
 10  10
 TC = 3

n CH4  n CO2 k1
4.15 (A) 
n CH2CO  n H2O k2
n CH4  n CO2 k1
 
n CH4  n CO2  n CH 2CO  n H2O k1  k 2
2n CH4 k1
 
n total (k1  k 2 )
n CH4 k1
 
n total 2(k1  k 2 )
 n CH4 50 k1
 100 
n total (k1  k 2 )

k1 k 3
4.16 (C) K=
k2
  n K  n K1 +  n K3 -  n K2
E
But n K = - + n A
RT
E E E E
 - + n A = - 1 + n A - 3 + n A + 2 - n A
RT RT RT RT
or ETotal = E1 + E3 – E2 = 40 + 20 – 30 = 30 KJ.

4.17 (B) At pH = 5 the t1/2  [sugar]° or the reaction is first order w.r.t. sugar because
t1/2 remains same forany conc. of sugar.
so rate = k [sugar]1 [H+]0 [n = order w.r.t. H+ ion]
1
Also t1/2 for [H+]  n -1
 Col-n
[C0 ]
-5 1-n
 600  [10 ]
60  [10-6]1-n
or 10 = (10)1-n or 1 - n = 1
n=0

4.18 (B) (A) α = 1 – e–kt

t = 0, α = 1  I s t order
kt
(B) α = for Zero order
C0
α is direct ly proport ional to ‘t ’ so 0°
C0 kt
(C) α =
C0 kt  1
1 1 1
1  for IInd order.
α (C0 k) t

4.19 (D) The fraction of A and B remaining at any time t, are

1 1 100
kA = In 100 and kB = In
t t 99
kA n100
 =  458
kB 100 
n 
 99 

n
1
4.20 (D) N = N0  
2
 4
 xv  1
   (x)  200  
 20  2
V = 250 ml.
So added volume of water = 50 ml.

4.21 (C) Rate is governed by slowest step

K1
A + B2   AB + B
KC
From A2 …… (i)
[A]2
kC = …… (ii)
[B2 ]
[A] = k c [A2]1/2
1 3
r = k1 k c [A2]1/2 [B2] order is =  1
2 2

1 3
4.22 (A) th reaction has completed upto 15 min. Hence VKMnO4 will be x 40  30
4 4
mL

n CH4  n CO2 k1
4.23 (A) 
n CH2CO  n H2O k2
n CH4  n CO2 k1
 
n CH4  n CO2  n CH 2CO  n H2O k1  k 2
2n CH4 k1
 
n total (k1  k 2 )
n CH4 k1
 
n total 2(k1  k 2 )
n CH4 50 k1
 100 
n total (k1  k 2 )

4.24 (A)

4.25 (B) Rate is slope of curve

y  y 0.35
at 20 sec 2 1  (approve) = 7  10-3M sec-1
x 2  x1 50
at 40 sec rate become half because of first order
r40 sec = 3.5  10-3 M sec-1
r60 sec = 1.75  10-3 M sec-1
1.75
r80 sec = 103
2
A   B
 t=0 0.4
t = 60 0.4 – x x
= 0.05
50 x = 0.35

4.26 (C) Ea > Ea’ T1  T2

1 d(Ink) Ea 1 d(Ink) Ea
 , 
K1 dT RT12 K 2 dT RT22
1 d(Ink) Ea' 1 d(Ink) Ea
 
K1' dT RT12 ' K '2 dT RT22
k2 k2 k1 k 2
 <  <
k1 k1 k1 k 2

4.27 (D)

4.28 (B, D)

1
4.29 (A, B, C) (A) tx%  for sec. order
a
(B) rate = kC t = kC 0 e -k t
 dc 
n    n (rate) = InkC0 – kt
 dt 
So straight line
(C) k = Ae-Ea/RT
rate = k(conc.)n = Ae-Ea/RT (conc.)n
- Ea
 n (rate) = -
R

t 0.75
(D) = ratio of time is constant with initial conc.
t 0.5

4.30 (A, B) 100  (0.1)1-n

50  (0.025)1-n
divide 2 = 41-n
log 2
 log2 = (1 – n)log4  1-=
log 4
log 2 log 2 1 1
 n =1- =1- =1- =
log 4 log 2 2 2
1/2
100  (0.1)
t1/2  (1)1/2
1/ 2
t  1 
divide 1/2 =  
100  0.1 
 t1/2 = 100 10 min.

4.31 (A, B, D) 3A(g)  2 B(g) + 2C (g)

t = 0 P0
2x 2x
t = 20 P0 – x
3 3
2P0 2P0
t= 
3 3
4P0
 4
3
P0 = 3 atm.
x
P0 +  3.5  t50% = 20 is the half life.
3
t75% = 2  20 = 40 min
t78.5% = 3  t50% 3  20 = 60 min
2 2 400
t99% =  t 99.9% 10  t 50% 
3 3 3

4.33 (A, B, C, D) A(g)   2B (g) + C(g)

t=0 400 0 0
t = 20 min 400 – p 2p p
given 400 – p + 2p + p = 1000
400 + 2p = 1000
p = 300 mm
1 400 1
k= In = n4
20 400  300 20
In 2
k= min-1
10
t1/2 = 10 min
After 30 min Partial Pressure of A is 50 mm
After 30 min Partial Pressure of B is 700 mm
After 30 min Partial Pressure of C is 350 mm
After 30 min total Pressure become 1150 mm

0 30 
4.34 (A, B, D)
30 20 15
1 30  (15) 1 45
k= 2.3 log  2.3log
30 20  (15) 30 35
 t1/2 = 75 min
1 45
k= 2.3 log
t 0  (15)
t = 120 min
 30  (15)
= 2 at half time
x  ( 15)
45 45
 2  x + 15 =  x = 22.5 – 15 = 7.5°
x 15 2

4.35 (A, B, C, D)

log t ' 1/2  log t "1/2

4.36 (A, C) t1/2  (a)1 – n or (1 – n) =
log a '  log a "
n 1
1 21  49  P
t1/2     n=0 for zero order t1/2 = K
P n -1 11  92  2K
P
=
2t1/2
11
K=  0.114sec.
2  48

k1E1  k 2 E 2 102 100  120  4 102

4.37 (B) E=  2 2
 116 KJ mol-1
k1  k 2 10  4 10

1 n
 mol 
4.38 (A, B, D) Unit of k =    s-1 for n = 1 is sec-1, n = 2 is litre mol-1 sect-1, n = 3 is litre2
 litre 
mol-2 sec-1

4.39 (A, B, C, D)

d
Slow step is rate determining step, from slow step – [O3 ]  k[O3 ][O]
dt
Molecularity for step 1 is 1 and for step 2 is 2 as shown in above given reaction.

4.40 (A,B) k1 = k2
2
 rd A has reacted for [A] = [C] = [D]
3
1 [A]0
 k1 + k2 = In
t 1
[A]
3 0
1 1 1
 t= In 3 = In 3 = In 3
k1 + k 2 2k1 2k 2

dCB 1 dn B 1 d(CB V)
4.41 (A, B) rB = = =
dt V dt V dt
 V dCB CB dV dCB CB dV
=    .
V dt V dt dt V dt

4.42 (B) According to arrhenius equation K = Ae-Ea/RT when Ea = 0, K = A.

kt
4.43 (D) For zero order reactions α  They depend upon initial concentration.
c0

4.44 (B) – rA = [2.5 R (400)] CA (at 400 K)

– rA = [2.5 R (600)]CA (at 600 K)
4 Ea  1 1 
log   = 
 6  2.303R  400 600 
Ea = 4135
So Assertion and Reason both are correct and reason is not the correct
explanation.
4.45 (C)

4.46 True Because rate = 0 at t = 0 and t = 

4.47 False It decreases both by equal amount.

4.48 True It decreases both by equal amount.

4.49 True Such as t 1/2 is constant for 1st order reaction

4.50 False Rate of Is' order always decreases with time.

4.51 True 4.52 True 4.53 True 4.54 True 4.55 False

4.56 True 4.57 True 4.58 Tr ue

Ea 57450
4.59 (B) log K b = log A -  log K b = 12 -
2.303RT 2.303  8.314  300
Log K b = 2
K b = A ntilog 2
K b = 10 2
K KF
K c = F  10 4 =  K F = 10 6
Kb 102

4.60 (A)  G =  HD - T  S
 G = 20 – T x 0.07
For non-spontaneous process  G > 0
hence 0 < 20 - T x 0.07
 20
T<  T < 285.7 K
0.07

4.61 (C) Kp = Kc(RT )  n = 10 4 (0.082 x 300) 1 = 24.6 x 10 4

dA
4.62 (A) - = k f [A] – k b [C ] at any time
dt
And slope between conc and time is known as rate and they always
equal at any time.

4.63 (D) Arrhenius equation k = Ae-Ea/RT

Ea
or log10 k = log A - … (i)
2.303RT
Comparing the given equation with equation (i),
Ea 1.25 104 (k)
=
2.303RT T
 Ea = 2.303 x 1.25 x 104 x 8.3 = 238936.25 J mol-1
Rate constant at 750 C is
 1.25 x104  -1
k = antilog 12.37   = antilog (- 4.3) sec
 750 
-5 -1
= 5 x 10 sec
 Eak = 238936.25 x 5 x 10-5 = 11.95  12
Hence Ans. 12

Kf
4.64 (D) A Kb
C
kf [C] 0.4 2
KC = = =  from graph
kb [A] 0.6 3
2C 2A
2 2
 1  3 9
K’c =     
 KC   2  4

4.65 (A)

4.66. (B) If [OH-] is decreased by 100 times pOH increases by 2 units. Hence rate decreases
by 100 times.

4.67 (A) r  10k [A]

0.693 0.693
 10k =  t1/2 =
t1.2 10 k

4.68 (B) R = k [A]m [B]n

5  10-4 = k [2.5  10-4]m [3  10-5]" ...(i)
 4  10-3 = k [5  10-4]m [6  10-5]n … (ii)
1.6  10-2 = k [1  10-3]m [3  10-4]n ... (iii)
From it m= 2.
5 104
4.69 (A) K300 =  2.677 108
(2.5 104 )2 (3105 )

4.70 (B) K = A . e –Ea/RT

k E  1 1 
n 2  a  
k1 R  300 400 
Ea = 13.83

0.693
4.71 (B) r = k [A] =  0.1 = 10-3 M, t1/2 = 69.3 min.
69.3

4.72 (C) r = k1 [C]t = C0 – kt

= 0.1 – 10-2  1 = 0.09 M.
[B]t = 0.01  2 = 0.02 M

0.3 0.2
4.73 (A) r= M min-1 ; r2 =
5 5
m
r1 A 
=  1
r2  A2 
m
0.3  1.5  0.3
=    m = 1; = k(1.5)
0.2  1  5
1
k=
25
1
r=  1.8 = 0.072 Mmin-1.
25

4.74 (B) When 1 mole of A is present then 2 mole of B and C will forms after
completion of the reaction but when 50% is complete then the total mole = 1 +
2  1 = 3.

4.75 (C) Mole of B = 0.666.

4.76 (A)

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

4.78 (A - p, q, r, s), (B - q, r, s), (C - p, q, r, s), (D - p, r, s).

4.79 (A - p, q, s), (B - p, q, s), (C - q, r), (D - p, q, r).

4.80 (A - q), (B - r), (C - t), (D - v)

K2 E T -T  K2
(A) 2.303 log10 = a  2 1  = 11
K1 R  T2T1  K1
T2 = 298 K ; T1 = 273 K , Ea = 65000 J , R = 8.314 J/(mol K)
n
2.5 1  1  0.693
(B)     n=3  t=3   30
20 8  2  0.0693

a 0.693
(C) Zero order: t1/2 = I order: t1/2 =
2K K
1 0.693 K2
=   2  0.693
2K1 K2 K1
logt'1/2 - lott"1/2
(D) t1/2  (a)1-n or (1 – n) =
loga'- loga"
n 1
1 480  0.0577 
t1/2     n0
a n -1 240  0.136 

4.81 A   B
Ct = a + b t
p = (a + b t) RT
dp 1
= bRT = 4 4   300 100 atm sec-1
dt 12

dx
4.82 = k[H+]n
dt
r1 = k[10-2]n
r2 = k[10-1]n
r1 = k[10-2n] …… (i)
100 r1 = k (10-n) …… (ii) Divide: (i) / (ii)
1
 10  n  n = 2.
100

Ea
4.83 2.303 log K = -  2.303log A
RT
Ea 1
Thus, -  tan θ = -
2.303 R 2.303
 Ea = R = 2. Cal.

4.84 t: 0 5 15 35
 [A]: 1 0.5 0.25 0.125
IInd order of the reaction
Ans. 2

4.85 Arrhenius equation k = Ae-Ea/RT

Ea
or log10 k = log A - …… (i)
2.303RT
Conparing the given equation with equation (i),
Ea 1.25 x104 (K)

2.303RT T
 Ea = 2.303 x 1.25 x 104 x 8.3 = 238936.25 J mol-1
Rate constant at 750 K is
 1.25 x104 
k = antilog 12.37  = antilog (- 4. 3) sec-1
 750 
= 5 x 10-5 sec-1
 Eak = 238936.25 x 5 x 10-5 11.95  12
Hence Ans. 12

4.86 Given,  H = 0.12  103 cal;

Ea(b) = 0.02  103 cal (Ea can never be negative)
  H = Ea(f) – Ea(b)
 Ea(f) = 0.12  103 + 0.02  103 cal = 0.14  103 cal
E /RT
% of molecule crossing over the barrier = 100  e af 
= 1000  e – 140/2  325
= 100  0.8065 = 80.65%

4.87 A   B+C
V
V–x x x
α V  aV0 … (i)
α
 V  V0
a
α (V – x)  aV1
β x  bV2
γ x  CV3
α β γ
(V – x) + x + x  Vt
a b c
αV  γ α
 x  x     Vt
a b c a
 γ α
x      Vt  V0
b c a
 Vt  V0 aV0
x ; V=
β γ α α
   
b c a
av 0
α
1 av v t  v0
k = n 0 
t α β γ α 
   
b c a 

1  400  200  1  200  n2

4.88 k= In   n  
30 min  400  375  30 min  0.25  T1/2
n2
T1/2 = (30 min) 10 min
n8
So, we will have
Time (min rt = 0 10 30
Pressure (in mm of Hg) 200 300 375
Volume of KMnO4 40 2 5
Consumed (ml)

Ans. (a) 40, (b) 300, (c) 375, (d) 5

 DPP-5
Stiochimetry

SECTION - I : STRAIGHT OBJECTIVE TYPE

5.1 H2O2 acts as both oxidising as well as reducing agent its product is H20, when act
as oxidising agent and its product is 02 when act as of reducing agent. The
strength of '10\P means one liter of H202 solution on

decomposition at S.T.P. condition liberate 10 liters of oxygen gas

1
(H2O  H2O+ O2 ) 15 gm Mn04)2 sample containing inert impurity is completely
2
reacting with 100 ml of '11.2 V' H202, then what will be the % purity of Ba (Mn04)2 in
the sample ?
(Atomic mass Ba = 137, Mn = 55)
(A) 5% (B) 10% (C) 50% (D) none

5.2 1.2 gm of carbon is burnt completely in oxygen (limited supply) to produce CO

and C02. This mixture of gases is treated with solid 1205 (to know the amount of
CO produced), the liberated iodine required 120 ml of 0.1 M hypo solution for
complete titration. The % of carbon converted into CO is :
(A) 60% (B) 100% (C) 50% (D) 30%

5.3 Nitrogen (N), phosphorus (P) and Potassium (K) are the main nutrients in plant
fertilizers. According to an industry convention, the numbers on the label refer to the
mass % of N, P205 and K20 in that order calculate the N : P : K ratio of a 30 : 10 :
10, fertilizer in terms of moles of each element and express it as x : y : 1.
(A) 10 : 0.67 : 1 (B) 20 : 0.37 : 1 (C)0.37 : 10: 1 (D) 5 : 2 : 1

5.4 In what ratio should a 15% solution of acetic acid be mixed with a 3% solution of
the acid to prepare a 10% solution(all percentages are mass/mass percentages) :
(A) 7 : 3 , (B)5: 7 (C) 7 : 5 (D) 7 : 10

5.5 105 ml of pure water at 4°C saturated with NH3 gas yielded a solution of density 0.9
g/ml and containing 30% NH by mass. Find the valume of resulting NH3 solution.
(A) 66.67 ml (B) 166.67 ml (C) 133.33 ml (D) 266.67 ml

5.6 The equivalent mass of H3BO3 (M = Molar mass of H3BO3) in its reaction with
NaOH to from Na2B4O7 is equal to –
M M M
(A) M (B) (c) (D)
2 4 6
5.7 x gram of pure As2S3 is completely oxidised to respective highest oxidation states
by 50 ml of 0.1 M hot acidified KMnO4 then x mass of As2S3 taken is : (Molar mass
of As2S3 = 246)
(A) 22.4 g (B) 43.92 g (C) 64.23 g (D) None
5.8 The number of moles of ferrous oxalate oxidised by one mole of KMn04 is
5 2 3 5
(A) (B) (C) (D)
2 5 5 3

5.9 How many moles of KMnO4 are needed a mixture of 1 mole of each FeSO4 &
FeC2O4 in acidic medium
4 5 3 5
(A) (B) (C) (D)
5 4 4 3

5.10 In the reaction

Na2S203 + 4C12 + 5H20   Na2SO4 + H2S04 + 8HCI
the equivalent weight of Na2 S2 03 will be
.(A) M/4 (13) M/8 (C) M/1 (D) W/2
(M= molecular weight of Na2S203)
5.11 Which of the following equations is a balanced one-
( A) 5Bi03 + 22H+ + 2Mn2  5Bi03+ + 7H20 + 2MnO–4
(B) 5BiO3 + 14H+ + Mn2 + -> 5Bi03+ + 7H20 + 2MnO4–4
(C) 26103 + 4H+ + 2Mn2+ --> 6Bi3+ + 2H20 + MnO4–4
(D) 6BiO3 + 12H+ + 2Mn2+ 6Bi3+ + 6H20 + 2MnO4 4–

5.12 The following equations are balanced atomwise and chargewise.

(i) Cr2O72- + 8H+ + 2H202   2Cr3+ + 7H20 + 202
2-
(ii) Cr207 + 8H+ + 5H202   2Cr3+ + 9H20 + 402
2-
(iii) Cr2 0 7 + 8H+ + 7H 20 2   2Cr+ + 11H 2 0 + 50 2
The precise equationlequations representing the oxidation of H202 is/are
(A) (i) only (B) (ii) only (C) (iii) only (D) all the three

5.13 An excess of NaOH was added to 100 mL of a ferric chloride solution. This
caused the precipitation of 1,425 g of Fe(OH)3. Calculate the normality of the
ferric chloride solution
(A) 0.20 N (B) 0.50 N (C) 0.25 N (D) 0.40 N

5.14 In the reaction Cr05 + H2SO4  Cr2(S04)3 + H20 + 02 one mole of CrO5 will liberate
how many moles of 02
(A) 5/2 (B) 5/4 (C) 9/2 (D) none of these

5.15 0.4g of a polybasic acid HnA (all the hydrogens are acidic) requires 0.5g of NaOH
for complete neutralization. The number of replaceable hydrogen atoms in the acid and
the molecular weight of 'A' would be : (Molecular weight of the acid is 96 gms.)
(A) 1, 95 (B) 2, 94 (C) 3, 93 (D) 4,92
5.16 A solution of Na2S2O3 is standardized iodimetrically against 0.1262 g of Mr% This
process requires 45 mL of the Na2 S203 solution. What is the strength of the Na2S2O3?
(A) 0.2M (B) 0.1 M (C) 0.05M (D) 0.1 N

.5.17 25.0 g of FeSO4.7H20 was dissolved in water containing dilute H2S04, and the
volume was made up to 1.0 L. 25.0 mL of this solution required 20 mL of an N/10
KMnO4 solution for complete oxidation. The percentage of FeSO4. 7H20 in the acid
solution is
(A) 78% (B) 98% (C) 89% (D) 79%

5.18 1.0 mol of Fe reacts completely with 0.65 mol of 02 to give a mixture of only Fe0 and
Fe2O3. The mole ratio of ferrous oxide to ferric oxide is
(A) 2 : 2 (B) 4:2 (C) 1:2 (D) 2: 7

5.19 25 mL of a solution containing HCf and H2S04 required 10 mL of a 1 N NaOH

solution for neutralization. 20 mL of the same acid mixture on being treated with an
excess of AgNO3 gives 0.1425 g of AgCf. The normality of the HC and the normality
of the H2S04 are respectively
(A) 0.40 N and 0.05 N (B) 0.05 N and 0.25 N
(C) 0.50 N and 0.25 N (D) 0.40 N and 0.5 N

5.20 If 10 gm of V205 is dissolved in acid and is reduced to V2+ by zinc metal, how many
mole of I2 could be reduced by the resulting solution if it is further oxidised to V02+
ions ?
[Assume no change in state of Zn2+ions] (V = 51, 0 = 16, I = 127) :
(A) 0.11 mole of 12 (B) 0.22 mole of 12 (C) 0.055 mole of 12 (D) 0.44 mole of 12

5.21 0.70 g of mixture (NH4)2 S04 was boiled with 100 mL of 0.2 N Na0H solution till all the
NH3(g) evolved andget dissolved in solution itself.The remaining solution was diluted to
250 mL. 25 mL of this solution was neutralized using 10 mL of a 0.1 N H2SO4 solution.
The percentage purity of the (NH4)2 SO sample is
(A) 94.3 (B) 50.8 (C) 47.4 (D) 79.8

5.22 A mixed solution of potassium hydroxide and sodium carbonate required 15 mL. of
an N/20 HCI solution when titrated with phenolphthalein as an indicator. But the
same amount of the solution when titrated with methyl orange as an indicator
required 25 mL of the same acid. The amount of KOH present in the solution is
(A) 0.014g (B) 0.14g (C) 0.028g (D) 1,4 g

5.23 The percentage of copper in a copper(II) salt can be determined by using a

thiosulphate titration. 0.305 gm of a copper(II) salt was dissolved in water and added
 to, an excess of potassium iodide solution liberating iodine according to the following
equation
2Cu2 (aq) + 4I– (aq) 2CuI(s) + I2(aq)
The iodine liberated required 24.5cm3 of a 0.100 mole dm-3 solution of sodium
thiosulphate
2S2032- (aq) + I2(aq)   2I– (aq) + S4062- (aq)
the percentage of copper, by mass in the copper (ll) salt is. [Atomic mass of
copper = 63.5]
(A) 64.2 (B) 51.0 (C) 48.4 (D) 25.5

.SECTION - II : MULTIPLE CORRECT ANSWER TYPE

5.24 Which of the following samples of reducing agents is /are chemically equivalent to
25 ml of 0.2 N KMnO4 to be reduced to Mn2+ and water.
(A) 25 ml of 0.2 M FeSO4 to be oxidized to Fe3+
(B) 50 ml of 0.1 M H3AsO3 to be oxidized to H3As04
(C) 25 ml of 0.1 M H202 to be oxidized to H+ and 02
(D) 25 ml of 0.1 M SnCl2 to be oxidized to S04+

5.25 There are two sample of CI having polarity 1M and 0.25 M. Find volume of these
sample taken in order to prepare 0.75 M HCI solution. (Assume no water is used)
(A) 20 ml, 10 ml (B) 100 ml, 50 ml (C) 40 ml, 20 ml (D) 50 ml, 25 ml

5.26 Chloride of an element is given by the formula MCI, and it is 100% ionised in
0.01 M aqueous solution.Then
(A) if [CI-] = 0,03 M then the value of x is 3.
(B) if [CI]- = 0.05 M then the value of x is 5
(C) [Mx+] = 0.01 M, irrespective of [CI-]
(D) [MX+] depends on [Al-]

5.27 If 100 ml of 1M H2SO4 solution is mixed with 100 ml of 98%(wlw) H2SO4 solution (d
= 0.1 gmlml) then :
(A) concentration of solution remains same
(B) volume of solution become 200 ml
(C) mass of H2SO4 in the solution is 98 gm
(D) mass of H2SO4 in the solution is 19.6 gm

5.28 3 moles of the gas C2 H6is mixed with 60 gm of this gas and 2.4 x 1024 molecules of
the gas is removed. The left over gas is combusted in the presence of excess
oxygen then :
(NA = 6 x 1023) (Density of water = 1 gm/ml)
 (A) 2 Moles of C2I-16 left for combustion
(B) Volume of C02 at S.T.P. produced after combustion 44.8 litre.
(C) Volume of water produced is 54 ml
(D) None

5.29 Which of the following contains the same number of molecules?

(A) 1g of 02, 2g of S02
(B) 1g of C02, 1g of N20
(C) 112 ml of 02 at STP, 224 ml of He at 0.5 atm and 273K
(D) 1 g of oxygen, 1g of ozone

5.30 A 200 ml mixture of CO and CO, is passed through a tube containing red hot
charcoal. The volume becomes 260 ml. The volumes are measured under the
same conditions of temperature and pressure. Amongst the following, select the
correct statement(s).
(A) Mole percent of CO2 in the mixture is 60.
(B) Mole fraction of CO in the mixture is 0.40
(C) The mixture contains 40 ml of CO2
(D) The mixture contains 40 ml of CO

5.31 Choose the correct statement :

(A) 2 mole of MnO4 - ion can oxidised 5 moles of Fe2 ion in acidic medium
(B) 2 mole of Cr2O,2- ion can oxidised 6 moles of Fe2 ion in acidic medium
(C) 2 mole of Cu2 S can be oxidised by 2.6 moles of MnO4 ion in acidic
medium
(D) 2 mole of Cu2S can be oxidised by 2.33 moles of Cr 2O, 2- ion in acidic
medium

5.32 0.1 M solution of KI reacts with excess of H2SO4 and and KIO3 solutions,
according to equation
51- + I03– + 6H+   3I2 + 3H 20 ; which of the following statement is correct
(A) 200 ml of the KI soluition react with 0.004 mole KIO 3
(B) 200 ml of the KI solution reacts with 0.006 mole of H2SO4
(C) 0.5 litre of the KI solution produced 0.005 mole of I2
 Molecular Weight 
(D) Equivalent weight of KI0 3 is equal to  
 5 

SECTION - III : ASSERTION AND REASON TYPE

5.33 KIO3 reacts with KI to liberate iodine and liberated Iodine is titrated with standard
hypo solution, The reactions are
 (i) I03– + I–   I2 (valency factor = 5/3)
(ii) I2 + S2032–   S4062– + I– (valency factor = 2)
meq of hypo = meq of I2 = meq of I03– + meq of I–
 I0 3– react with I–  meq of I03– = meq of I–
Statement-1 : meq of hypo = 2 x meq of I03–
Statement-2 : valency factor of I2 in both the equation are different therefore we
cannot equate milliequivalents in sequence
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct
explanation for Statement-2.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct
explanation for Statement-2.
(C) Statement-2 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

5.34 Statement-1 : One mole of SO2 cotains double the number of molecules present
in one mole of 02.
Statement-2 : Molecular weight of SO2 is double to that of 02.
(A) Statement-2 is True, Statement-2 is True; Statement-2 is a correct
explanation for Statement-2.
(B) Statement-2 is True, Statement-2 is True; Statement-2 is NOT a correct
explanation for Statement-2.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-2 is False, Statement-2 is True

5.35 Statement-1 : The ratio by volume of gaseous reactants and products is in

agreement with their molar ratio.
Statement-2 : Volume of a gas is inversely proportional to the number of moles
of a gas.
(A) Statement-2 is True, Statement-2 is True; Statement-2 is a correct
explanation for Statement-2.
(B) Statement-2 is True, Statement-2 is True; Statement-2 is NOT a correct
explanation for Statement-2.
(C) . Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

5.36 Statement-2 : In the titration of Na2CO3 with HCI using methyl orange indicator,
the volume required at the equivalence point is twice that of the acid required
using phenolphthalein indicator.
Statement-2 : Two mole of HCI are required for the complete neutralization of
one mole of Na2CO3.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct
explanation for Statement-2.
(B) Statement-2 is True, Statement-2 is True; Statement-2 is NOT a correct
 explanation for Statement-2.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

SECTION - IV : TRUE AND FALSE TYPE

5.37 The reaction 2H 20 2 --> 2H20 + 02 is not an example of a redox reaction.

5.38 In a reaction H2Mo04 is changed to MoO2+. In this case, H2MoO4 acts as a

reducing agent.

5.39 The equivalent mass of K2Cr2O7 in acidic medium is molar mass divided by
two.

5.40 In 3N HCI solution, iodate can oxidise I2 according to the reaction

I03– + 212 + 10C1- + 6W   5ICI2– + 3H20

5.41 The equivalent mass of a substance can be calculated without considering the
reaction it undergoes.

SECTION - V : COMPREHENSION TYPE

Comprehension # 1

632 g of sodium thiosulphate (Na2S2O3) reacts with copper sulphate to form cupric
thiosulphate which is reduced by sodium thiosulphate to give cuprous compound
which is dissolved in excess of sodium thiosulphate to form a complex compound
sodium cuprothiosulphate ( Na4[Cu6(S2O3)5] ).

 CuS 2 O 3 + Na 2 SO 4
C uSO 4 + Na 2 S 2 O 3 

2CuS 2O 3 + Na 2 S 2O 3  Cu2S 2O 3 + Na2 S4 O 6

3Cu2 S2O3 + 2Na2S2O3   Na 4[Cu6(S2O 3) 5]
Sodium cuprothiosulphaté

In this process, 0.2 mole of sodium cuprothiosulphate is formed. (O = 16, Na = 23, S

= 32)

5.42 The average oxidation states of sulphur in Na2S2O3 and Na2S4O6 are respectively.
(A) + 5 & + 2 (B) + 2 & +2.5 (C) + 5 &2.5 (D) + 2 & + 4

5.43 Moles of sodium thiosulphate reacted and unreacted after the reaction are
respecticvely.
(A) 3 & 2 (B) 2 & 3 (C) 2.2 & 1.8 (D) 1.8 & 2.2
5.44 If instead of given amount of sodium thiosulphate, 2 moles of sodium thiosulphate along
with 3 moles of Cu SO4 were taken initially. Then moles of sodium cuprothiosulphate
formed is
(A) 0 (B) 1 (C) 1.5 (D) 2

Comprehension it 2

We know that balancing of a chemical equation is entirely based on law of

conservation of mass. However the concept of Principle of Atom Conservation
(POAC) can also be related to law of conservation of mass in a chemical reaction.
So, POAC can also act as a technique for balancing a chemical equation. For
example, for a reaction
2AB3   AB + C 2

nABC3 nAB nC2

0n applying POAC for, B & C and relating the 3 equations, we get : = =
2 2 3
( nx : number of moles of X)
Thus, the coefficients of ABC3 , AB & C2 in the balanced chemical equation will be
2,2 & 3 respectively and the balanced chemical equation can be represented as
ABC 3   AB + 3C 2
Now answer the following questions :

5.45 Which of the following relation is correct regarding the numerical coefficients p, q, r
in the balanced chemical equation :
pA + qB2   rA2B5
(A) 2p = r (B) q = 1.25 p (C) r = 2q (D) q = 0.8p

5.46 If the weight ratio of C and 02 present is 1 : 2 and both of reactants completely
consume and form C0 and C02 and we will obtain a gasous mixture of C0 and CO2.
What would be the weight ratio of C0 and C02 in mixture.
(A) 11 : 7 (B) 7 : 11 (C) 1 : 1 (D) 1 : 2

5.47 If the atomic masses of X and Y are 10 & 30 respectivetly, then the mass of XY3
formed when 120g of Y2 reacts completely with X is :
Reaction X + Y2  XY3
(A) 133.3 g (B) 200 g (C) 266.6 g (D) 400 g

Comprehension # 3
Oleum is considered as a solution of S03 in H2S04 , which is obtained by passing 803 in
solution of H2SO4. When 100 g sample of oleum is diluted with desired weight of H20
then the total mass of H2SO4 obtained after dilution is known as % labelling in oleum.
For example, a oleum bottle labelled as '109% H2SO4 means the 109g total mass of
pure H2SO4 will be formed when 100 g of oleum is diluted by 9 g of Hp which combines
with all the free 803 to form H2SO4 as
S03 + H20   + H2 SO 4.
5.48 What is the % of free S03 in an oleum that is labelled as '104.5% H2SO4’?
(A) 10 (B) 20 (C) 40 (D) Noneof these

5.49 If excess water is added into a 100 g bottle sample labelled as '' 112% H2SO4 ''
and is reacted with 5.3 g Na2CO3, then find the volume of C02 evolved at 1 atm
pressure and 300 k temperature after the completion of the reaction : [R = 0.0821
L atom mol–1 K–1]
H2SO4 + Na2CO3   Na2SO4 + H20 + CO2

(A) 2.46 L (B) 24.6 L (C) 1.23L (D) 123

5.50 1 g of oleum sample is diluted with water.The solution required 54 ml of 0.4 N

NaOH for compete neutralization.The % of free S03 in the sample is :
(A) 74 (B) 26 (C) 20 (D) None of these

Comprehension # 4
Volumetric analysis is based on the principle of equivalence a that minloces lead in the
ratio of their equivalents. At the equivalence point of the reaction, involving the
reactahts A and B :

Number of gram equivalents of A = Number of gram equivalents of B..

If VA ml of solution A having normality NA react just completely with VB ml of solution B
having normality NB then
NA VA NB VB
= ;NA VA =NB VB ……………………(i)
1000 1000

Equation(1), called normality equation is very useful in numerical of volumetric

analysis. Equivalent masses of different substances :
Basically the equivalent mass of a substance is defined as the pads by seam
ctituhich combine with or displace 1.0078 parts (  1part) by mass of hydrogen, 8
parts by mansetaisiosaid 35.5 parts by mass of chlorine.

Mass of a substance expressed in gram equal to its equivalent man is' gam equivalent
mass. Equivalent mass of a substance is not constant but depends upon the maw i malice
the substance participates.
Equivalent mass of an acid in acid-base reaction is its mass in
grannehidicodoinisooleaf replaceable Fi ions (= 1.0078 g  1g).0n the other hand,
equivalent mass of a bagels istolonellfacontairis 1 mole of replaceable 0H– ions.
1 g equivalent mass each of an acid and base an ionclinegins saint and 1 mole of
water ( = 18 g).
Equivalent mass of an oxidising agent is its mass which gains 1 mole at
ellecismitcan be obtained by dividing the molecular mass or formula mass by the
total decrease in aididditaiiilberef one or more elements per molecule.
0n the other hand, equivalent mass of a reducing agent is the mass of the substance
which loses 1 mole of electorns. It can be calculated by dividing the molecular or formula
 mass of the subtance by the total increase in oxidation number of one or more elements per
molecular or formula mass.

5.51 When 5.00 g of a metal is strongly heated, 9.44 g of its oxide is obtained. The
equivalent mass of the metal is
(A) 2.22 g (B) 5.00 g (C) 9.00 g (D) 4.44 g

5.52 How many gram of phosphoric acid (H3PO4) would be required to neutralize 58 g of
magnesium hydroxide?
(A) 65.3 g (B) 70.2 g (C) 85.0 g (D) 112.0 g

5.53 Which of the following solutions, when mixed with 100 ml of 0.05 M NaOH, will give
a neutral solution?
(A) 100 ml of 0.1 M H2SO4 (B) 50 ml of 0.05 M H2SO4
(C) 100 ml of 0.05 M CH3 COOH (D) None of these

5.54 100 ml of 0.1 M H3 P02 is titrated with 0.1 M NaOH. The volume of NaOH needed will
be
(A) 300 ml (B) 200 ml (C) 100 ml (D) None of these

5.55 9.8 g of an acid on treatment with excess of an alkali forms salt along with 3.6 g
of water. What is the equivalent mass of the acid?
(A) 98.0 g (B) 49.0 g (C) 24.5 g (D) 73.5 g

Comprehension #5

Molality : It is defined as the moles of the solute present in 1kg of the solvent. It is
denoted by 'm'.

Number of moles of solute

Molality (m) =
Number of kilo-gram of the solvent
Let W A grams of the solute of molecular mass mA be present in W B grams of the solvent,
then
wA
Molality (m) = ×1000
mA ×w B
Relation between mole fraction and Molality :

n N
XA = and XB =
N+n N+n

X A n Molesof solute w A ×mB

= = =
XB N Molesof solute w B ×mA
X A  1000 w A ×1000 XA  1000
=  m or =m
XB  mB w B ×mA (1–X A )mB
 -
5.56 If the ratio of the mole fraction of a solute is changed from 3 to -2 in the 800 g of
solvent then the ratio of

molality will be :
(A) 1 : 3 (B) 3 : 1 (C)4 : 3 (D) 1 : 2

5.57 The mole fraction of the solute in the 12 molal solution of Na2CO3 is :
(A) 0.822 (B) 0.177 (C) 1.77 (D) 0.0177

5.58 What is the quantity of water that should be added to 16 gm, methanol to make the
mole fraction of methanol as 0.25 –
(A) 27 gm. (B) 12 gm. (C) 18 gm. (D) 36 gm.

5.59 A 300 gm, 30% (wlw) NaOH solution is mixed with 500 gm 40% (wow) NaOH
solution. What is % (wlw) NaOH. if density of final solution is 2 gm/ml.
(A) 72.5 (B) 65 (C) 62.5 (D) None

5.60 What is the molality of final solution obtained in the above problem
(A) 1.422 (B) 14.22 (C) 15.22 (D) None
SECION – VI : MATRIX – MATCH TYPE
5.61 Coloumn – I Coloumn – II
(Reactions) (Information conveyed by the
reactions)
(A) Complete reaction of Cuprous (p) Gases evolved do not have their
Sulphide with acidified Potassium constituent elements in their
permanganate solution producing maximum possible oxidation states
a gas which turns lime water milky.
(B) Reaction of Hydrochloric acid with (q) Greater than one mole of oxidising
Potassium dichromate solution agent is consumed for every mole of
Producing a gas necessary for reducing agent.
The manufacture of Bleaching
Powder
(C) Reaction of Iron pyrites (FeS2)with (r) The element in oxidant, which
Oxygen gas producing a gas having undergoes change in oxidation
Bent shape number, is in its maximum possible
Oxidation state.
(D) Complete reaction of Ferrous oxalate (s) Moles of reductant consumed is
with acidified Potassium dichromate greater ten times the moles of
solution producing a gas isoelectronic oxidant consumed.
a gas isoelectronic and isostrural with
nitrous oxide.
5.62 Match the coloumn
Coloumn- I Column- II
(A) CaCO3 + H3PO4  Ca3(PO4)2 + CO2 (p) 1 mole of oxidising agent gains more
+ H2O electrons than lost by 1 mole of reducing
Agent.
(B) MnO2+ HCl  MnCl2 + Cl2 + H2O (q) No change in oxidation number of any
element takes place.
(C) Na2CrO4+ H2SO4  Na2Cr2O7 (r) All elements (except oxygen) are in
+ Na2SO4 their maximum oxidation states on
the reactant side.
(D) H2O + F2  HF + O2 (s) Number of moles of oxidising agent
Consumed is less than number of
Moles of reducing agent.

5.63 [H =1, C = 12, O = 16, Na = 23 , P= 31, S = 32]

Coloumn – I Coloumn – II
(A) 4.1 g H2SO3 (p) 200 ml of 0.5 N NaOH is used for
complete neutralization
(B) 4.9 g H3PO4 (q) 200 millimoles of oxygen atoms
(C) 4.5 g oxalic acid (H2C2O4) (r) Central atom has its highest
oxidation number
(D) 5.3 g Na2CO3 (s) May react with an oxidising agent
(t) Shape around central atom is regular
5.64 Match the reacting mixture in coloumn-I with the reagent in coloumn – Il
Column – I Coloumn – I
(A) H2C2O4 + NaHC2O 4 (p) NaOH
(B) naHPO4 + NaNO2 (q) HCl
(C) Fe2(SO4)3 + FeC2O 4 (r) KMnO4
(D) FeO + Fe2O3 (s) Zinc dust

5.65 Match the following

Coloumn – I Coloumn – II
(A) 4.5 m solution of CaCO3 density (p) mole fraction of solute is 0.2
1.45 gm/ml
(B) 3M 100 ml H2SO4 mixed with 1M (q) mass of the solute is 360 gm
300 ml H2SO4 solution
(C) 14.5 m solution of Ca (r) molarity = 4.5
(D) in 4 M 2 litre solution of NaOH, (s) molarity 1.5
40 gm NaOH is added.
(E) 5m (molal) NaOH solutlion (t) 16.66% (w/w) of NaOH in solution
 SECTION - VII : SUBJECTIVE ANSWER TYPE
SHORT SUBJECTIVE

5.66 Polychlorinated biphenyls, PCBs, known to be dangerous enviromental pollutants,

are a group of compounds with the general empirical formula C12HmCl10-m, where m is
an integer. What is the value of m, if percentage of carbon atom in the compound is
40 ?

5.67 50 ml of water sample, containing temporary hardness only, required 0.1 ml of

M/50 HCI for complete neutralisation. Calculate the temporary hardness of water
in ppm.

5.68 A mixture contains 61.2% Ba0, 28% Ca0 and 10.8% (silica) impurities. What
volume in nit. of 3.00 M HCI would be required to react completely with 1 g of the
mixture ?

LONG SUBJECTIVE:

5.69 2.6 gms of an element X is reacted with an aqueous solution containing NaOH and
NaNO3 to yield Na2XO2 and NH 3. NH3 thus liberated is absorbed in 100 mL of
0.11 M H2 SO4. The excess acid required 48 mL of O.25M NaOH for complete
neutralisation. Find the atomic weight of X.

5.70 Pure Na2C2O4 plus KHC2O4.H2C2O4 (three replaceable protons, KH3A2) are mixed
in such a proportion that each gram, of the mixture will react with equal volumes of
0.100 M KMn04 and 0.100 M NaOH. What is the proportion ?

5.71 Calculate the amount (in milligrams) of SeO3-2 in solution on the basic of
following data 20 mL of M/60 solution of KBrO3 was added to a definite volume of
SeO3–2 solution.The bromine evolved was removed by boiling and excess of
KBrO3 was back titrated with 5.1 mL of M/25 solution of NaAsO2. The reactions
are given below. (Atomic mass of K = 39, Br = 80, As = 75, Na = 23, 0 = 16, Se
= 79)
(a) SeO 3 2 + BrO 3 - + H+  SeO42+ Br2 + H20
(b) Br O 3 + As O 2 + H 2 0   B r + As O 4 - 3 +

5.72 An important oxidation-reduction reaction used to determine very small amounts

of 03 and other oxidants in polluted air involves oxidation of iodide ion :
 20H – + I 2 + 0 2
2I – +0 3 +H 2 0 
The solution is acidified and the 12 is titrated with sodium thiosulphate solution
using starch indicator. One litre of a mixture of 03 and 02 at STP was allowed to
react with an excess of acidified solution of KI and I2 liberated required 40 mL of
M/10 sodium thiosulphate solution. What is the (mole or volume percentage of
ozone x 100) in the mixture ?
5.73 A sample consisting of cholate-brown powder of Pb02 is allowed to react with excess
of KID and iodine liberated is reacted with N2R4 in another container The volume of gas
liberated from this second container at STP was measured out to be 1.12 litre. Find out
volume of decimolar Na0R required to dissolve PbO2 completely.(Assume all reactions
are 100% complete).

5.74 Calcium phosphide (Ca3 P2) formed by reacting calcium orthophosphate (Ca (PO4)2) with
magnesium was hydrolysed by water. The evolved phosphine (PH3) was burnt in air to yield
phosphorus pentoxide (P2 Os). Row many grams of magnesium metaphosphate would be
obtained, if 19.2 g of magnesium were used for reducing calcium phosphide. (At. wt. Mg =
24, P = 31)
Ca, (P04)2 + Mg   Ca3P2 + Mg0
Ca3P2 + H20   Ca(0H)2 + PH2
PH3 + 02   P 2 O 5 + PH 3
MgO + P 2 0 5   Mg(PO 3 ) 2

magnesium metaphosphate

5.75 A sample of Fee (S04)3 and FeC2O4 was dissolved in dial. H2SO4. The complete oxidation
of reaction mixture required 40 ml of N/16 KMn04. After the oxidation, the reaction mixture
was reduced by Zn and dil. H2SO4. 0n again oxidation by same KMnO4, 60 ml were
required Calculate the ratio of millimoles of Fe2(SO4)3 & FeC2O4. (mol.wt.Fe2(SO4), = 400)

5.76 Based on the following information, determine value of x and y :

(CH3)x AlCly (0.643g)   xCH4(g) (0.22 g) + yCl- + Al3+ 
 AgCI (s) (0.996g).

5.77 If 100 ml of 0.2 M Na2SO4 (d = 1.5 gm/mI) is mixed with 1 M Na3PO4 having 100 g of solvent
R20 (density of solution = 1.164 g/ml). then calculate final polarity of Na+ ions in the solution.
Density of resultant solution is 1.2 g/mI.

5.78 An element X react with hydrogen leading to formation of a class of compounds that is
analogous to hydrocarbons. 5 g of X forms 5.628 g of a mixture of two compounds of X,
XH4 and X2H6 in the molar ratio of 2:1. Determine molar mass of X.

5.79 The mineral Argyrodite is a stoichiometirc compound that contain silver, sulphur (– 2)
and an unknown element Y (+4). The mass-ratio of silver and Y in the compound is,
m (Age) : m (Y) = 11.88.
Y forms a reddish brown lower sulphide on heating the mineral in stream of H2 (g), in
which Y is in +2 state. The residue are Ag2S and R2S. To convert 10 g Argyrodite
completely, 0.295 L of R2 (g) measured at 400 K and 1.0 atmosphere is required.
Determine molar mass of Y and empirical formula of mineral.

5.80 Urnaium is isolated from its ore by dissolving it as U02(N03)4 and separating it as solid
UO2(C204).x H2O.A 1.0 g sample of ore on treatment with nitric acid yielded 1.48 g
U02(N03)4 which on further treatment with 0.4 g Na2C2O4 yielded 1.23 g UO2(C204).x H2O.
Determine weight percentage of uranium in the original sample and x.
5.81 A mother cell disintegrate into sixty identical cells and each daughter cell further
disintegrate into 24 smaller cells. The smallest cells are uniform cylindrical in shape
with diameter of 120Å and each cell is 6000 Å long. Determine molar mass of the
mother cell if density of the smallest cell is 1.12 g/cm3.

5.82 A chloride mixture is prepared by grinding together pure BaCI2.2H2O, KCl and NCI. What
is the smallest and largest volume of 0.15 M AgNO3 solution that may be used for
complete precipitation of chloride from a 0.3 g sample of the mixture which may contain
any one or all of the constituents?
 5. STIOCHIMETRY

11.2
5.1 (C) N=
5.6
Milli equivalents Ba(MnO4)2 reacted  equivalents of H2O2 reacted
 2  100  200 m eqn  0.2 eqn
0.2
Moles of Ba(MnO4)2   0.02
10
 wt. of Ba(MnO4)2 = 0.02  375.
375 0.02
% purity of Ba(MnO4)2 =  100 = 50%
15

5.2 (D) C + O2  CO
 + CO2
t=0 0.1 - -
t 0 x (0.1 – x)
5CO + I2O5  5CO2 +
 I2
t=0 x
x/5

1 1
moles of I2 liberated = moles of hypo consumed = x 120 x 10-3 x 0.1 = 60
2 2
x 10-4
So x = 5 x 60 x 10-4 = 0.03 moles
So % of C forming C0 = 30%.

5.3 (A) 5.4 (C) 5.5 (B)

5.6 (A) H3BO3 is a mono basic acid

M
So = equivalent mass
1

5.7 (B) 5As2S3 + 28KMn04 + H+   10H3AsO4 + 28Mn2+ + SO42-

mmoles of KMn04 = 50 x 0.1 = 5
28 mmoles of KMnO4   5 Moles of As2S3
1 mmoles of KMnO4   5/28 moles of As2S3
5
Mass of As2S3 = x = 246 x g = 43.92 g
28

5.8 (D) Equivalents of FeC2O4 = equivalents of KMnO4

x (mole) x 3 = 1  5
5
x=
3
5.9 (A) Equivalents of KMnO4 = equivalent of FeSO4 + equivalent of FeC2O4
x  5 =1  1+1  3
4
x= mole
5

+2 +6
5.10 (B) Na2 s 2O3   Na2 s O4
see the total change in oxidation number = 4  2 = 8
mol.wt. M
 E Na 2S2O3 = =
V.f 8

Reduction

5.11. (B)  Bi3+ + MnO 4

BiO3- + Mn2+ 

Oxidation

(i) 2e + 6H+ + BiO3- 

 Bi3+ + 3H2O
(ii) 4H2O + Mn2+   MnO4- + 8H+ + 5e
(i)  5 + (ii)  2 we get
14 H+ + 5 BiO3- + 5Mn2+  5Bi3+ + 2MnO 4 + 7H2O
is the correct balanced reaction.

5.12 (A)

5.13 (D) 3 NaOH + FeCl3   Fe(OH)3 + 3NaCl

m.e. of NaOH = me.e of Fe(OH)3
W  mol.wt. 
100  N = 1000  E Fe(OH)3  
E  3 
1.42510  3
N= = 0.3999 = 0.4 N
107

5.14 (D) The balance reaction is

4CrO5 + 2H2SO4   2 Cr2 (SO4)3 + 2H2O + O2
1
 1 mole CrO5 can liberate only mole O2
4

5.15 (C) Eq of Acid = eq of base

0.4 0.5
n 
96 40
1 96 96
n=   3
80 0.4 32
 wt of A = 96 – 3 = 93.
 2+ +5 + 2.5
5.16 (D)  Br - + Na 2 S4 O6
Na 2 S 2 O3 + K B rO3 
v.f = 1 v. = 6
by m.e. of Na2S2O3 = m.e. of KBrO3
molarity of Na2S2O3 = 0.1 M

5.17 (C) M.e. of FeSO4  7H2 O in 25 ml = m.e. of KMnO4 used = 2 m.e.

M.e. of FeSO4  7H2 O in 1000 ml = 80 m.e.
80 1
mass of FeSO4  7H2O in solution =  2787   22.24gm
1 1000
22.24
% of FeSO 4  7H 2 O =  100 = 88.96 89%
25

5.18 (B) Let moles of FeO and Fe2 O3 in the mixture is a and b respectively, then by
POAC we get following two equation.
a + 3b = 0.65  2 = 1.3 ...(i)
a + 2b = 1 ...(ii)
by solving (i) & (ii) we get a : b = 4 : 3

5.19 (B) Let normality of HC  is N1 and H2SO4 is N2.

 M.e. of HC  + M.e. of H2SO4 = M.e of NaOH
25  N1 + 25  N2 = 10  1 ... (1)
N 1 + N 2 = 0.4 ... (1)
BY POAC
Moles of C  = moles of AgC 
20  N1 0.1435
 103
1000 143.05
N1 = 0.05 N
N2 = 0.35 N

5.20 (A) 6e- + 10H+ + V2 O5   2V2+ + 5 H2 O

Zn   Zn2+ + 2e - 3  3
V2O5 + 3 Zn + 10 H+   3 Zn2+ + 2V2+ + 5H2O … (1)
2+ 2+ + -
Now H2 O + V   VO + 2H + 2e
-
2e + I 2   2r -
V2+ + I2 + H2O  21- + VO2+ + 2H+
so we have 12 moles of V2O5 will reduce 2 moles of iodine
 10 
so    2 moles of will be reduced by given amount of V2O5 = 0.11 moles of
 102  80 
12

5.21 (A) M.e. of NH3 = 10

m.e. of NH3 = 10
 m.mole of (NH4)2SO4= 5
wt. of (NH4)2 SO4 = 5
5
wt. of (NH4)2 SO4 =  132 = 0.66 gm
1000
0.66
% of (NH4)2 S04 =  100 = 94.28 %
0.7

5.22 (A) K0H + Na 2 aO 3

a M.e. b.M.e.
b 1
a + = 15 
2 20
2a + b= 1.5 … (i) (in presence of phenolphthalein)
1
a + b = 25  = 1.25 … (ii) (in presence of Methyl orange)
20
by solving (i) & (ii) a = 0.25 m.e
0.25
mass of K0H =  56 = 0. 014 gm
1000

5.23 (B) From given reactions

mmoles of hypo = mmoles of iodine  2
= mmoles of Cu2+ ions
= 24.5  0.1 mmoles
So mass of copper = 24.5  0.1  10-3  63.5 gm
24.5  0.110 3  63.5
So % of copper = 100% 51.0 %
0.305

5.24 (A, D)

5.25 (A, B, C, D)

V1 ×1+ V2 ×0.25
Final molarity =
(V1 + V2 )
0.75 (V1 + V2) = V1 + V2 × 0.25
0.75 V1 + 0.75 V2 = V1 + V2 X 0.25
0.5 V2 = 0.25 V1
V1
2
V2

5.26 (A,B,C) MClx

In each mole of MClx there are x moles of Cl-
 [Cl - ] = x  0.01
conc. of [M x+ ] = 0.01
5.27 (A,B,D)
10  d  x
(A) Molarity of second solution is = 1M
M
(B) Volume = 100 + 100 = 200 ml
200 1
(D) Mass of H2S04 =  98 = 19.6 gm.
1000

28 (B,C) Moles of C2 H6 = 3
60
moles of C2H6 mixed = =2
30
total mole of C2H6 = 5
2.4 1024
moles removed = 4
6 1023
 moles of C2 H6 left =1
Now, C2 H6 + 7/2 O2   2CO2 + 3H2O
Clearly 3 moles of H2O or 54 gm H2O will be formed
volume of H2O = 54 ml
Ans. 54

5.29 (A,B,C) For same number of molecules, number of moles should be same.

5.30 (A,B,D) When mixture is passed through hot graphite the following reaction will
occur.
CO2 (g) + C(s)  2CO (g)
x ml 2x ml will formed
 Total volume of mixture = 160
100 - x + 2x = 160
x = 60 ml
volume of CO = 100 - x = 40 ml

5.31 (A,B,C,D)
Use equivalent of oxidising agent = equivalents of reducing agent.

5.32 (A,D) 5I - + IO 3 - + 6H +  3I 2 + 3H 2 O

moles of KI used
5
moles of KIO3 used
Valency factor of KIO3 = 5
mol. wt.
 EKIO3 =
5

5.33 (A)

5.34 (D) One mole of SOI2 and O2 have same number of molecule.
5.35 (C) V α n at same temperature and Pressure.

5.36 (B)

5.37 False It is a disproportionation reaction.

5.38 False H2MoO4 reduces itself therefore oxidise others and act as oxidising agent.

mol. wt.
5.39 False It is
6

5.40 True

5.41 False For calculation of valency factor reactant product should be known.

5.42 (B)

5.43 (C) Moles of Na2S2O3 used = 0.4 + 0.6 + 1.2 = 2.2

632
Moles of Na2S2O3 left unreacted = - 2.2 = 1.8
158

5.44 (A) No moles of Na2S2O3 would remain in step (i) so further reaction will stop
because Na2S2O3 is required in excess.

Sol. (5.45 to 5.47)

On applying POAC for A & B respectively, we get

1 x nA = 2x n A2B5 … (1)
2 x n B2 = 5  n A2B5 … (2)

n A n B2 n A2 B5
By (1) & (2), = =
4 5 2
 Balanced equation: 4A + 5B2  2A2B5
 q = 1.25
on applying POAC for X and Y respectively , we get
1 x nx = 1 x n XY3 … (3)
2 x n Y2 = 3 x n XY3 … (4)
by (3) & (4) , n Y2 = 1.5 x nx
from (3) and (4)
n x n Y2 n XY3
 
2 3 2
 Balanced equation: 2X + 3Y2  2XY3
 120 4
n Y2   n XY 
60 3
3
4
=2  mXY3  x100 133.3g
3
(2) C + O2  CO + CO2
W 2W x gm y gm
POAC for C POAC for O
w x y 2w x y
  2   2
12 28 44 32 28 44
w x y w x y
  … (1)   …. (2)
3 7 11 4 14 11
3y 3x 4x 4y
So now   
11 7 14 11
3y 3x y
 
7 7 11
x y x
 ,  7:11
7 11 y

5.45 (B) 5.46 (B) 5.47 (A)

5.48 (B) SO3 + H2O   H2SO4. ;

18 g water combines with 80 g SO3
 4.5 g of H2O combines with 20 g of SO3
 100 g of oleum contains 20 g of SO3
or 20% free SO3

5.49 (C) H2SO4 + Na2 CO3   Na2SO4 + H2O + CO2

Moles of CO2 formed = moles of Na2CO3 reacted (it is limiting reagent) =
5.3
= 0.05
106
volume of CO2 formed at 1 atm pressure and 300 K = 0.05  24.63 = 1.23 L.

5.50 (B) Equivalent of H2SO4 + equivalent of SO3 = equivalent of NaOH

x (1  x)  2
2  54  0.4 103
98 80
x = 0.74
1 0.74
% of free SO3 = 100  26%
1

5.51 (C) Mass of oxygen in oxide = 9.44 - 5 = 4.44

Eq. wt. of metal = mass of metal which combine with 8 gm of oxygen
5
=  8 = 9.00 gm
4.44
 W W
5.52 (A)    
 E H3PO4  E  Mg(OH)2
W 58
3   2
98 58
W = 65.33 gm

5.53 (B) Equilise the m.e. of NaOH by m.e. of acid.

5.54 (C) M.e. of H3PO2 = m.e. of NaOH

100  0.1  1 = V  0.1
V = 100 ml
H3PO2 is monbasic acid

5.55 (B) Number of moles of water produced = 0.2 moles

 0.2 equivalent of acid should be reacted
Wacid
 0.2  Eacid = 49
E acid

x A 1000
5.56 (D) Use formula and get answer.
(1  x A )xmA

5.57 (B) m Na 2CO3 = 12

n Na 2CO3 12
1000
n N2O   55.55
18
12
x Na 2CO3   0.177
12  55.55

5.58 (A) Let wg water is added to 16 g CH3 OH

16 1000 500
Molality = 
W  32 W
500 x 1000 0.25 1000
= A  W = 27 gm
W (1  x A )m B 0.75 18

300  0.3  500  0.4

5.59 (A) % (w/v) volume of NaOH = 100  72.5
800
2

300  0.3  500  0.4

5.60 (B) Mole of solute =  72.5
40
Mass of solvent = 800 - 290 = 510
 7.25
Molality = 1000 14.22.
510

5.61 (A - p, q, r), (B - p, r, s), (C - p, q), (D – r).

(A) 5Cu 2 S + 8 KMnO 4   Cu2+ + SO2 + Mn2 +
vf = 8 vf = 5
(B) K2 Cr 2 O 7 + 14HCl   2KCl + 2 CrCl3 + 3Cl2+ 7H2O
(C) 4FeS2 + 11O2   2Fe2O3 + 8SO2
(D) 6FeC 2 O4 + 3K2 Cr 2 O 7   Cr3 + + Fe3 + + CO2
Vf =3 Vf = 6

5.62 (A - q, r), (B - p, s), (C - q, r), (D - r).

5.63 (A - p, s), (B - q, r, t) ; (C - p, q, s, t), (D – r, t)

4.1
(A) 4.1 gm = mole H 2 SO 3 = 50 m mole
82
2NaOH + H2SO3   Na2 SO3 + 2H2O
m mole of NaOH requires = 2  m mole of H2SO3
= 100
= m mole of NaOH present (200 ml  0.5 N)
Highest O.N. of S = + 6
4.9
(B) 4.9 gm = mole = 50 m mole of H3 PO4 = 200 m mole ‘O’ atom
98
Highest O.N. of P = + 5
4.5
(C) 4.5 gm = = 50 m mole of H2 C2 O 4 (di basic acid)
90
m mole of NaOH requires = 2  50 = 100
Highest O.N. of C = + 4

1
(D) 5.3 gm = mole Na2 CO3 It do not react with NaOH and m mole of O atom =
20
1
 3 = 150
20

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

5.65 (A - r); (B - s); (C - p); (D - q, r, (E - t)

(A) 4.5 , H2 S O 4 means
4.5 moles of CaCO3 is present in 1000 g solvent.
mass of solute = 4.5  100 = 450 g
mass of solution = 1000 ml
Hence molarity = 4.5 M
 3100  1 300 3
(B) Resultant molarity =  1.5M
400 2
14.5
(C) mole fraction =  0.2
14.5  55.5
(D) moles of NaOH in 2 ltr = 4  2 = 8 mole
40
moles of NaOH added = = 1 mole
40
9
 Molarit = = 4.5 M
2
mass of NaOH = 9  40 = 360 g
5  40
(E) % (w/w) NaOH = 100 16.66%
5  40  1000

144
5.66 % of carbon = 100  40
144  m  36.5(10  m)
On solving

5.67 M1 V1 = M2 V2
1
50  M1 =  0.1
50
1
M 1 (HCO 3 -) =
25 103
1 1
mmole of HCO 3 - = 3
 50 =
25 10 500
1
mmole of Ca 2+ =
1000
1
mmole of CaCO 3 =
1000
1
weight of CaCO 3 =  10 -3  100 = 10 -4
1000
hardness = [weight of CaCO3 / weight of water]  10 6
104
= 106  2 ppm.
50

1 61.2
5.68 wt of BaO =  0.004
100
0.612
mole = = 0.004
100
0.28
wt of CaO = = 0.005 mol.
56
BaO + 2HCl   BaCl2 + H 2 O
0.004 0.004  2
 CaO + 2HCl   C aCl2 + H 2 O

0.005 2 0.005
Number of moles of HCl required = 0.008 + 0.018
MV L = 0.018
V
3  mL  0.018
1000
V = 9 mL.

NaOH 100ml,0.11MH 2SO 4 Excess

5.69 X 
NaNO3
 Na 2 XO 2 + NH3   (NH 4 )2 SO4 + H 2 SO 4 
req
 48
ml of 0.25M NaOH (excess)
Now, Reactions involved for part (i)
X   XO 2 -2 NJO 3 -   NH 3
On balancing above equation in basic medium we get
4X + NO3 - + 7OH -   4XO 2 -2 + NH 3 + 2H 2 O … (1)
2NH 3 + H 2 SO 4   (NH 4 ) 2 SO 4 … (2)
(5mM) reacted
H 2 SO 4 + 2NaOH   Na 2 SO 4 + 2H2 O … (3) (  Total
m moles of H 2 SO 4 = 11)
(excess) 48 0.25
6m moles) =12m moles

 m moles of X = 40
2.6
 40  10 -3 =  At. Wt. = 65 Ans.
At. wt.

5.70 Assume 10.0 mL titrant, so there is 1.00 mmol NaOH or KMnO4. The acidity is due of
KHC2O4. H2C2O4 (KH3A2)
1
mmol KH3A2 = mmol NaOH  (mmol KH3A2/mmol 0H-)
3
1
1.00 mmol NaOH  = 0.333 mmol KH3A
3
2
each mmol Na2C2O4 (Na2A) reacts with mmol KMnO4.
5
2 4
mmol KMnO4 = mmol Na2AX (mmol Mn04-/mmol Na2A) + mmol KH3A2  (mmol
5 5
MnO4-/mmol KH3A2)
2 4
1.00 mmol KMnO4 = mmol Na2A × + 0.33 mmol KH3A2×
5 5
mnol Na2 A = 1.8 A = 1.83 mmol
The ratio is 1.83 mmol Na2A/0.333 mmol KH3A2 = 5.5 0 mmol Na2A/mmol KH3A2
The weight ratio is
5.50 mmol Na 2 A×134 mg/mmol
 3.38 g Na 2 A/g KH3A 2
218kgKH3 A 2 /mmol
5.71 84 mg
5.72 2I  +O3 +H2O 
 2OH  +I2 +O2
I2 +2Na 2S2O3 
 Na 2S4O6  2NaI
From the above reaction :
2Na 2S2O3  I2  O3
40  0.1
mol of Na2S2O3 =  0.004
1000
mol of I2 = mol of O3 = 0.002
volume of O3 at STP = 0.002 × 22.4
= 0.0448 L present in 1 L mixture.
Percentage of O3 = 4.48 % (by volume )
Ans . 448

5.73 PbO2 + 4 KI   PbI2 + I2 + 2K2O

N2H4 + 2I2   N2 + 4HI
1.12
Moles of N2 liberated =  5 102 mole
22.4
so mole of I2 reacted = 5 × 10–2 × 2 = 10–1 mole
mole of PbO2 reacted = 10–1 mole
PbO2 + 2H2O   Pb(OH)4
Pb(OH)4 + 2NaOH   Na2[Pb(OH)6] or Na2PbO2
Mole of NaOH required = 10–1 × 2
1 2
V× 103  2 101 V= 3  2000 ml
10 10
5.74 Balance chemical equation are :
Ca3(PO4)2 + 8 Mg   Ca3P2 + 8MgO
Ca3P2 + 6H2O   3Ca(OH)2 + 2PH3
2PH3 + 4O2   P2O5 + 3H2O
MgO + P2O5   Mg(PO3)2
moles of magnesium used = 0.8 moles
moles of MgO formed = 0.8 moles
moles of Ca3P2 formed 0.1 moles
moles of PH3 formed = 0.2 moles
moles of P2O5 formed = 0.1 mole (limiting reagent)
moles of Mg(PO3)2 = 0.1 moles
mass of Mg(PO3)2 = 18.2 gram

5.75 Let the m. mole of Fe2(SO4)3 and FeC2O4 are a and b m. mole respectively.
m.e of FeC2O4 = m.e. of KMnO4
1
b×3 = 40× ……(i) (only FeC2O4 can oxidise )
16
After reduction we will get 2a + b moles of Fe2+ ion which will oxidise by KMnO4.
M.e. of Fe2+ = M.e. KMnO4
 1
(2a + b) × 1 = 60 × ……..(ii)
16
a : b = 7: 4
Ans 7 : 4

5.76 If M is molar mass of (CH3)x AlCly

0.64x
m  CH 4  = × 16 = 0.222.
M
0.643y
and m  AgCl  = × 143.5 = 0.996.
M
x 35.5x
dividing : = 2, Also M = 15x + 27 + 35.5y = 15x + 27 +  32.75x + 27.
y 2
5.77 Mass of Na2SO2 solution = 100 × 1.5 = 150 g
1164 g Na3PO4 solution has 164 gm of Na3PO4
100 g of H2O will have 16.4 g of Na3PO4
116.4
Vol of Na2PO4 solution taken =  100 ml
1.164

Final volume of solution 

150  116.4   222 ml
1.2
0.1  0.2  2  0.1  1  3 0.04  0.3 170
[ Na  ]     1.53M
0.222 0.222 111

5.78 Let mixture contain xg XH4 then (5.628 – x)gX2H6.

x x
 moles of XH4 = and, moles of X2H6 =
M+4 2(M + 4)
x
 5.628 – x =  2M+6 ………..(i)
2  M+4 
Mx 2Mx
Also + =5 ………..(ii)
M + 4 2 M + 4
Solving equation (i) and (ii) we geta M = 27.8.

5.79 Let formula unit of Argyrodite contain ‘a’ mol of silver and b mole of Y. Therefore,
moles of sulphide
a 
Per formula unit of mineral must be  +2b 
2 
Hence , Ag a YbS a  a
 +2b  +bH 2 
 Ag 2S+ bYS + bH 2S.
2  2

PV
Also, moles of H2 required = = 8.87×10 –3
RT
8.87  103
 moles of mineral present in its 10 g 
b
 8.87g×10-3 a 
 10 = [108a+bM  +2b  32].
b 2 
Solving, 1127b = 124a + b(M + 64) ………..(i)
Substituting ‘a’ in equation (i)
124×11.88b a
1127b = + b( M + 64)  M =72.6g mol –1and = 8.
108 b
Empirical formula = Ag8 YS6.

1.48
5.80 Mass of uranium in the sample  238  0.894 g .
394
Mass % of uranium in the sample = 89.4 g.
Now, UO2(NO3)2 + Na2C2O4 + xH2O   UO2(C2O4)xH2O  + 2NaNO3.
Here Na2C2O4 is the limiting reagent, therefore, m mol of UO2(C2O4).xH2O formed is
2.985.
1.23
 M (UO2 (C2 O4 )).xH 2 O =  1000  412  238  32  88  18x.
2.985
54
 x = = 3.
18

5.81 Volume of smallest cell = r2  =  (60 × 10–8 cm) = 6.785 × 10–17 cm3.
mass of one smallest cell = 7.6 × 10–17 g.
 Molar mass of mother cell = 7.6 × 10–17 × 24 × 60 × 6.023 × 1023 = 6.6 × 1010
amu.

5.82 Smallest volume of AgNO3 would be required when the entire mass is due to highest
molecular weight constituent.
Hence, for smallest volume, the wholemass should be of Bacl2.2H2O.
0.3
m mol of BaCl2.2H2O = × 1000 = 1.229 m mol.
244
m mol of AgNO3 required = 2 × 1.229 = 2.45.
2.458
Volume of AgNO3 required = = 16.38 mL (smallest).
0.15
Largest volume of AgNO3 would be required when entire mass is due to lowest
molecular weight constituent, i.e., NaCl.
0.3
m mol NaCl = 100  5.128 = m mol of AgNO3 required.
58.5
5.128
 Volume of AgNO3 required = = 34.18 mL (largest).
0.15
 DPP-6
Thermodynamics
SECTION – I : STRAIGHT OBJECTIVE TYPE

6.1 Consider the reaction at 300K

H2(9)+Cl2(9) 
 2HCI(g),  H° = — 185 KJ
If 3 mole of HE completely react with 3 mol of CI2 to form CI, AU° of the reaction
will be
(A) Zero (B) –185 KJ (C) 555 KJ (D) None

6.2 It has been observed that the ratio of the molar heat of vaporisation of liquid
and its normal boiling point is approximately same for most of the liquids
(called Triton's rule) Which of the following does not follow this rule
(A) C61-16 (B) C6H14 (C) CCI4 (D) NH3

6.3 A cyclic proces ABCD is shown in PV diagram for an ideal gas.

Which of the following diagram represents the same process

6.4 The change in free energy accompanied by the isothermal reversible

expansion of 1 mol of an ideal gas when it doubles its volume is  G1 The
change in free energy accompanied by sudden isothermal irreversible
doubling volume of 1 mole of the same gas is  G2 Ratio of  G1 and  G2
1 1
(A) 1 (B) (C) – 1 (D) 
2 2
6.5 The following curve represents the variation of Gibbs function 'G' with
pressure at constant temperature.
 Correct match of given plots with the physical state of a substance is
(A) c –solid, a – gas , b – liquid (B) c – gas , b liquid , a — solid
(C) a – liquid, b – solid, c – gas (D) c – gas, b – solid , a – liquid

6.6 Which of the following diagram correctly represents the variation of internal energy (U) of
gas under expansion at constant temperature.

(D) None of these

6.7 Which correctly represents the entropy (s) of an isolated system during a
process.
6.8 Which of the following represents positive work i.e. work of compression

6.9 Fora perfectly crystalline solid Cp m = aT3, where a is constant. If Cpm is 0.42 J/K-
mol at 10 K, molar entropy at 10 K is
(A) 0.42 J/K-mol (B) 0.14 J/K-mol (C) 4.2 J/K-mol (D) zero

6.10 One mole of an ideal monoatomic gas expands isothermally against

constant external pressure of 1 atm from initial volume of 1L to a state
where its final pressure becomes equal to external pressure. If initial
temperature of gas is 300 K then total entropy change of system in the
above process is :
[R = 0.082 L atm mol-1 K-1 = 8.3 J mo1-1K-1].
(A) 0 (B) R  n (24.6)
3
(C) R  n (2490) (D) R  n(24.6)
2

6.11 At 1000 K water vapour at 1 atm. has been found to be dissociated into H2 and 02
to the extent of 3 x 10-6 %.Calculate the free energy decrease of the system,
assuming ideal behaviour.
(A) –  G = 90,060 cal (B) –  G = 20 cal
(C) –  G = 480 cal (D) –  G = –45760 cal

6.12 In the reaction COCl2(g) C0(g) + CI2(g) at 550°, when the initial
pressure of CO & Cl2 are 250 and 280 mm of Hg respectively. The equilibrium
pressure is found to be 380 mm of Hg. Calculate the degree of dissociation of
COC12 at 1 atm. What will be the extent of dissociation, when N2 at a pressure of
0.4 atm is present and the total pressure is 1 atm.
 (A) 0.32 and no change
(B) 0.32 and 0.4
(C) 0.4 and 0.3
(D) In pressure of N2 dissociation cannot takes place

6.13 When 1 mole of an ideal gas at 20 atm pressure and 15 L volume expands
such that the final pressure becomes 10 atm and the final volume become 60 L.
Calculate entropy change for the process (Cpm = 30.96 J mole-1 K-1)
(A) 80.2 J.k-lmo1-1 (B) 62.42 kJ.k-1 mol-1
(C) 120 x 102 J1c1mol-1 (D) 27.22 J.k-1mor

6.14 An ideal gas is taken from the same initial pressure P1 to the same final
pressure P2 by three different processes. If it is known that point 1 corresponds
to a reversible adiabatic and point 2 corresponds to a single stage adiabatic then

(A) Point 3 may be a two stage adiabatic.

(B) the average K.E. of the gas is maximum at point 1
(C) Work done by surrounding in reaching point number '3' will be maximum
(D) If point4 and point 5 lie along a reversible isotherm then T5 < T1.

6.15 Which of the following graphs best illustrates the variation of entropy of a
substance with temp.
6.16 During winters, moisture condenses in the form of dew and can be seen on
plant leaves and grass. The entropy of the system in such cases decreases
as liquids possess lesser disorder as compared to gases. With reference to
the second law, which statement is correct, for the above process ?
(A) The randomness of the universe decreases
(B) The randomness of the surroundings decreases
(C) Increase is randomness of surroundings equals the decrease in
randomness of system
(D) The increase in randomness of the surroundings is greater as compared to
the decrease in randomness of the system.

6.17 A copper block of mass `m' at temperature 'T1' is kept in the open atmosphere
at temperature `T2' where T2 > T 1 . The variation of entropy of the copper block
with time is best illustrated by

6.28 For which process will AHD° and AG° be expected to be most similar.
(A) 2AI(s) + Al203(s) 
 2Fe(s) + Ai203(s)
(B) 2Na(s) + 2H20(I) 
 2NaOH(aq) + H2 (g)
(C) 2N02(g) 
 N204(9)
(D) 2H2 (9) + 02(9) 
 21120(g)

SECTION - II : MULTIPLE CORRECT ANSWER TYPE

6.19 One mole of an ideal diatomic gas(CV = 5 cal) was transformed from initial
25°C and 2 L to the state when temperature is 200°C and volume 10 L. Then for
this process(R = 2 calories/moIN) (take calories as unit of energy and kelvin for
temperature)
 (A)  H = 525
373
(B)  S = 5 In  2ln10
298
(C)  E = 525
(D)  G of the process can not be calculated using given information.

6.20 Which of the following statements) is/are false?

1
(A)  rS for CI2(g)  CI(g) is positive.
2
.(B)  E < 0 for combustion of CH4(g) in a sealed container with rigid adiabatic system.
(C)  G is always zero for a reversible process in a closed system.
(D)  G° for an ideal gas reaction is a function of pressure.
SECTION - III ASSERTION AND REASON TYPE

6.21 Statement-1 : Due to adiabatic free expansion temperature of real gas may
increase
Statement-2 : In adiabatic free expansion, temperature is always constant
irrespective of real or ideal gas
(A) Statement-1 is True, Statement-2 is. True; Statement-2 is a correct explanation for
Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct
explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

 dU 
6.22 Statement-2 : Under free expansion ,   is + ve when attractive forces
 dV T
are dominant between gas dB molecules [U, V, T respresent internal energy,
volume and temperature of gas respectively]
Statement-2 Internal energy is a state function.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation
for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a
correct explanation for Statement-1
(C) Statement-1 is True, Statement-2 is False
(D) Statement-1 is False, Statement-2 is True
6.23 Statement-1 : Diamond is thermodynamically less stable than its allotrope graphite
Statement-2 : Molar entropy of graphite is greater than that of diamond under similar
conditions.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for
Statement-1.
(B) Statement-2 is True, Statement-2 is True; Statement-2 is NOT a correct
explanation for Statement-2.
(C) Statement-2 is True, Statement-2 is False.
.(D) Statement-1 is False, Statement-2 is True.

6.24 Statement-1 : 'Diamonds are forever is generally quoted for diamond as rate of
conversion of diamond to graphite at room condition is nearly zero.
Statement-2 : At room condition, conversion of diamond into graphite is
spontaneons.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for
Statement-1.
(B) Statement-2 is True, Statement-2 is True; Statement-2 is NOT a correct explanation
for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-2 is False, Statement-2 is True.

6.25 Statement-1 : At low temperature, AH is the dominant factor for spontaneity of a

reaction.
Statement-2 : The opposing factor TAS remains very small, at low temperature.
(A) Statement-2 is True, Statement-2 is True; Statement-2 is a correct explanation for
Statement-1.
(B) Statement-2 is True, Statement-2 is True; Statement-2 is NOT a correct
explanation for Statement-2.
(C) Statement-2 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

6.26 Statement-2 : The amount of work done in the isothermal expansion is greater
than work done in the adiabatic system for same final volume.
Statement-2 : In the adiabatic expansion of a gas temperature and pressure both
decrease due to decrease in internal energy of the system.
 (A) Statement-1 is True, Statement-2 is True; Statement-1 is a correct explanation for
Statement-2.
(B) Statement-2 is True, Statement-2 is True; Statement-2 is NOT a correct
explanation for Statement-1.
(C) Statement-2 is True, Statement-2 is False.
(D) Statement-2 is False, Statement-2 is True.

6.27 Statement-2 : The heat absorbed during isothermal expansion of an ideal gas
against vacuum is zero.
Statemept-2 : In isothermal process, change in internal energy is always zero,
irrespective of ideal or real gas.
(A) Statement-2 is True, Statement-2 is True; Statement-2 is a correct explanation for
Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct
explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

6.28 statement : Heat of neutralization of CI and NaOH is same as that of H2S04 with
NaOH.
Statement-2 : HCI, H2S04 and NaOH are all strong electrolyte.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for
Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a_ correct
explanation for Statement-2.
(C) Statement-2 is True, Statement-2 is False.
.(D) Statement-1 is False, Statement-2 is True.

6.29 Statement-1 : A reaction which is spontaneous and accompanied by decrease of

randomness must exothermic.
Statement-2 : All exothermic reactions are accompanied by decrease of
randomness.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for
Statement-2.
(B) Statement-2 is True, Statement-2 is True; Statement-2 is NOT a correct
explanation for Statement-2.
 (C) Statement-2 is True, Statement-2 is False.
(D) Statement-2 is False, Statement-2 is True.

SECTION - IV : TRUE AND FALSE TYPE

6.30 Consider the following statements.
Si : Change in state function between two states is a definite quantity and
does not depend on path.
S2 : Intensive properties can't be algebraically added or subtracted.
S3 : Ratio of two extensive properties result into a parameter that dependson
amount of substance.
S4: Molar heat capacity is a path function.
The correct order of true / false of the above statements is
(A)FTFT (B) F F F T (C) TTFT (D) TTTF

6.31 Consider the following statements

S1 : Unit of molar entropy of a substance is SI system is Joule / Kelvin
S2 : Molar entropy of vapourisation of ice is – ve.
S3 : In adiabatic free expansion, heat involved is zero and therefore entropy
change mil be zero.
S4 : At absolute zero temperature, entropy of a perfectly crystalise substance
is zero.
(A)TFFT (B) TFTT (C) FFFT (D) FFTT
SECTION - V : COMPREHENSION TYPE
Comprehension # 1

Chemical reactions are invariably associated with transfer of energy miner in

form of heat or light. In the laboratory, heat changes in physical and chemical
processes are measured with an instrument called calorimeter. Heat change in
the process is calculated as :
q = ms  T s = specific heat J/K-gm
= C T C = heat capacity J/K
In Bomb calorimeter measurement are taking at constant volume.
So heat of reaction at constant volume :
q =  U (Internal energy change)
 Here heat is released by combustloin so sign of AU and heat should be
negative. In water colarimeter measurement are taking at constant
pressure.
So, qp =  H
qp = qv + P  V
 H =  U +  ngRT

6.32 Match the list-I and list-II and select the answer :
List-I (Unbalanced reaction) List-II
(a) CH 4 (g) + 0 2 (g) 
 CO2 (g) + H20 (t) (i)  H =  U
(b) C6H 6 (  ) + 0 2(g)  6CO2 (g) + 3H 20 (t) (ii)  H =  U – RT
(c) S(  ) + 02(g)   SO2 (g) (iii)  H =  U – 2RT
3
(d) .2 C 0 (g ) + 0 2 (g ) 
 2CO2(g) (iv)  H =  U – RT
2
.(A) (a) - (iii) (b) - (iv) (c) - (i) (d) - (ii)
.(B) (a ) - (i i) (b) - (iii) (c) - (i) (d) - (iv)
(C) (a) - (iii) (b) - (iv) (c) - (ii) (d) - (i)
(D) (a) - (ii) (b) - (i) (c) - (iii) (d) - (iv)

6.33 What volume of AT should be used for the calorimeter experiment when the
following graphical results are obtained ?

(A) 15°
(B) 35°
(C) 50°
(D) 30°

6.34 The heat capacity of a bomb calorimeter is 100 J/K. When 1 gm C7H16 (1) was
burnt in this calorimeter, the temperature increase by 5°C. The value of  H in
KJ/mole at 300 K temperature will be —
(A) — 50 (B) — 40.03 (C) — 59.97 (D) none

.Comprehension # 2
J.W. Gibbs and H.Von Helmoltz had given two equation and are known as Gibbs-
Helmholtz equation. One equation can be expressed in terms of change in free
energy (  G) and enthalpy (  HD) while other can be expressed in terms of
change in internal energy (  E) and work function (  W)
  G 
 G =  HD + T d   …………………………(1)
 dT P
 W 
W = E + T . d   ………………..(2)
 dT V
Where T is temperature equation (1) is obtained at constant pressure while
equation (B) is obtained at constant volume system. It is observed that for the
reaction.
N2(g) + 3H2(g) 
 2NH3(g)
Free energy change at 25°C is –33 kJ
while at 35°C is —28 kJ which are at a constant pressure.

6.35 What would be the difference between enthalpy change at 25°C and 35°C for a
given reaction :
(A) 4 kJ (B) 5 kJ (C) 3 kJ (D) zero

6.36 What would be the free energy change at 30°C –

(A) 30.5 kJ (B) 33 kJ (C) —28 kJ (D) —30.5 kJ

6.37 Internal energy change at 25°C is E1 while at 35°C is E2 then –

(A) E1 = E2 (B) E2 > E1 (C) E, > E2 (D) None

Comprehension # 3

Internal Energy (E, also denoted by U) :

Every system having some quantity of matter is associated with a definite

amount of energy, called internal energy
E= E Translational +ERotational + Evibrational + Ebounding+ …………
 E = EFinal + Einitial
 E = qv, heat supplied to a gas at constant volume, since all the heat
supplied goes to increase the internal energy of the gas .
It is an extensive property & a state function . It is exclusively a function
of temperature.
If  T = 0 ;  E = 0 as well.

The internal energy of a certain substance is given by the following equation :

u = 3 pv + 84
where u is given in kJ/kg, p is in kPa, and v is in m3/kg
A system composed of 3 kg of this substance expands from an initial pressure of
400 kPa and a volume of 0.2 m3 to a final pressure 100 kPa in a process in
which pressure and volume are related by pv2 = constant.

6.38 If the expansion is quasi-static, then the value of Q is :

(A) 80 kJ (B) 60 kJ (C) 40 kJ (D) 120 kJ
6.39 In another process the same system expands according to the same pressure-
volume relationship as in above question, and from the same initial state to the
same final state as in above question, but the heat transfer in this case is 30
kJ. Then the work transfer for this process is :
(A) – 80 kJ (B) –60 kJ (C) –90 kJ (D) –150 kJ

6.40 Explain the difference in work transfer in parts (a) and (b).

Comprehension # 4

The enthalpy in the process

HCI + nH2O 
 HCI in n moles of H20

where n is the number of moles of water, is called the integral heat of

solution. When n is large enough that continued addition of water does not
increase the heat of solution, one simply writes

HCI + aq 
 HCI (aq)

The enthalpy for this process is the limiting value for the integral heat of
solution. The enthalpy for the process

HCI in n moles of H2O + mH2O 

 HCI in (n + m) moles of H2O

is called the integral heat of dilution. These quantities are indicated in figure.
Another quantity of interest is the differential heat of solution, defined as the
slope of the enthalpy curve. The heats of solution depend on the composition of
the solution as shown in the figure.

.
6.41 Integral heat of solution for the following step is :
HCI + 5H20   HCI (5H20)
(A) –12 kJ (B) – 44 kJ (C) + 60 kJ (D) – 60 kJ

6.42 What is the enthalpy change for the reaction

HCI (aq)   HCl(aq)

(A) – 80 kJ/mole (B) – 60 kJ/mole

(C) – 70 kJ/mole (D)–20 kJ/mole

6.43 Approximate value of differential heat of that solution in which 1 mole of CI is

dissolved in 6 mole of water is:
(A) – 2.4 kJ (B) – 3.33 kJ (C) – 1.5 kJ (D) + 3.33 kJ

Comprehension # 5

A gaseous sample is generally allowed to do only expansion/compression type

of work against its surroundings. The work done in case of an irreversible
expansion (in the intermediate stages, of expansion/compression the states of
gases are not defined). The work done can be calculated using
dW = – Next dV
while in case of reversible process the work done can be calculated using
dw = –PdV where P is pressure of gas at some
intermediate stages. Like for an isothermal reversible process.
nRT
Since P = so
v
vf
nRT V 
W =  dw = –  .dv = – nrT ln  f 
vi
v  Vi 

S i n c e d w = – P d V s o m a g n i t u d e o f w o r k d o n e c a n also be
calculated by, calculating the area under the PV curve of the reversible
process in PV diagram.

6.44 An ideal gaseous sample at initial state i (P0V0T0) is allowed to expand to

volume 2V0 using two different process; in the first process the equation of
process is PV 2= K1 and in second process the equation of the process is PV =
K 2 .Then
(A) work done in first process will be greater than work in second process
(magnitude wise)
(B) The order of values of work done can not be compared unless we know
the value of K1 and K2.
(C) value of work done (magnitude) in second process is greater in above
expansion irrespective of the value of K1 and K2 .
(D) I st process is not possible
6.45 There are two samples of same gas initially under similar initial state.
Gases of both the samples are expanded. Ist sample using reversible
isothermal process and IInd sample using reversible adiabatic process till final
pressures of both the samples becomes half of initial pressure, then
(A) Final volume of Ist sample < final volume of lInd sample
(B) Final volume of IInd sample < final volume of lst sample
.(C) final volumes will be equal
(E) Information is insufficient

6.46 In the above problem

(A) work done by gas in Ist sample > work done by gas in IInd sample
(B) work done by gas in IInd sample > work done by gas in Ist sample
(C) work done by gas in Ist sample = work done by gas in IInd sample
(D) none of these

6.47 If four identical samples of an ideal gas initially at similar state (P0, Vo, T0) are
allowed to expand to double their volumes by four different processes..
I : by isothermal irreversible process
II : by reversible process having equation
P2 V = constant
III : by reversible adiabatic process
IV: by irreversible adiabatic expansion
against constant external pressure.
Then in the graph shown the final state is represented by four
different points then, the correct match can be :

(A) 1 – I , 2 - II, 3 — III, 4 - IV (B) 1 — II , 2 - I, 3 — IV, 4-III

(C) 2 –III, 3 - II, 4 – I, 1 - IV (D) 3 — II , I - I, 3 — IV, 4 – III

6.48
Two samples (initially under same
states) of an ideal gas are first allowed
to expand to double their volume
using irreversible isothermal
expansion against constant external
pressure, then samples are returned
back to their original volume first by
reversible adiabatic process and
second by reversible process having
equation PV2 = constant then

(A) final temperature of both samples will be equal

(B) final temperature of first sample will be greater than of second sample
 (C) final temperature of second sample will be greater than of first sample
(D) none of these

.Comperehension # 6

Spontaneity of any process can be predicted with the help of  Stotal. But this requires
calculation of changes in system as will as surroundings. If some criteria
(depending upon the system only) can be developed for checking spontaneity under
specific conditions, then that would be a more useful parameter. The criteria can be
derived from Clausius inequality.
T dS  q, > sign for rev. process
= sign for rev. process
or T dS > dB – W for an irr. Process
or T dSsys > dUsys + p dV [consider no non-PV work]

If U and V are constant,

T dSsys > 0

.or (dS)u v > 0 for spontaneous process

If V and T are constant
T dS > dU
or dB — T dS < 0
As temperature is constant, dU – d(TS) < 0 or d (U –TS)< 0
Another state function A(Helmholtz's function) = B – TS
A decrease in Helmholtz function (A) under constant volume and temperature is the
criteria of spontaneity of a process.

6.49 For a spontaneous process, if entropy and volume are constant, the internal
energy of system must
(A) increase (B) decrease (C) remain constant (D) be zero.

6.50 If a state function G is defined such as O = H – TS, then dO must decrease for
a spontaneous process (involving only PV work) occuring at
(A) Constant volume and temperature
(B) Constant pressure and temperature
(C) Constant volume and pressure
(D) Constnat entropy and volume

dq
6.51 For an irreversible cyclic process  is.
T
(A) equal to zero (B) greater than zero
(C) less than zero (D) eaual to chance in Oibb's energy.

Comprehension # 7
For a reversible reaction at constant temperature and at constant pressure the
equilibrium composition of reaction mixture corresponds to the lowest point on Gibbis
 energy Vs progress of reaction diagrams as shown. At equilibrium Gibbs energy of
reaction is equal to Zero.

6.52 The value of log10 keg is equal to Kg is the equilibrium constant]

ΔG° TΔS°–H°
(A) – (B) –
RT 2.303RT
ΔH°–TS° RT
(c) (D)
RT TS°– H°
6.53 Which diagram represents the large value of equilibrium constant for the
reversible reaction
 1
6.54 For a reaction M2 O(s) 
 2M(S) 
 2M(s) + O2(g) ,  H = 30 KJ/mol and
2
 S = 0.07 KJ/mol /K at latm. The reaction would not be spontaneous at
temperatures
(A) > 428 K (B) < 428 K (C) < 100 K (D) > 100 K

Comprehension # 8

The contributions of both heat (enthalpy) and randomness (entropy) shall be

considered to the overall spontaneity of a process. When deciding about the
spontaneity of a chemical reaction or other process, we define a quantity called the
Gibb's energy change (  G).

 G =  H – T S

where,  H = Enthalpy change ;  S = Entropy change;

T = Temperature in kelvin.

If  G < 0, Process is spontaneous ;  G = 0, Process is at equilibrium, AG > 0,

Process is non-spontaneous.

6.55 For the change H20 (s, 273 K, 2 atm)  H20 (  , 273K, 2 atom), choose
the correct option.
-
(A) AG = 0 (B) AG < 0 (C) AG > 0 (D) None

6.56 5 mol of liquid water is compressed from 1 bar to 10 bar at constant temperature.
Change in Gibb's energy
(  G) in Joule is t [Density of water = 1000 kg/m3].
(A) 18 (B) 225 (C) 450 (D) 900

6.57 Quick lime, Ca0 is produced by heating limestone, CaC03 to drive off C02 gas.
CaC03 (s)   CaO (s) + C02 (g), (  H°) = 180 KJ,  S° = 150 J/K.
Assuming that variation of enthalpy change and entropy change with temperature
to be negligible, choose the correct option :
(A) Decomposition of CaCO3 (s) is never spontaneous.
(B) Decomposition of CaCO3 (s)becomes spontaneous when temperature is less
than 900°C.
(C) Decomposition of CaC03 (s) becomes non-spontaneous when temperature is
greater than 1000°C
(D) Decomposition of CaCO3(s) becomes spontaneous whentemperature is greater than
927°C.

.SECTION - VI : MATRIX - MATCH TYPE

6.58 Column - I Column -11

 [Under adiabatic free expansion]
(A) An ideal gas (p) Temperature increases
(B) A real gas at inversion temperature (q) Temperature decreases
.(C) H2 gas at STP (r) Temperature remains constant
.(D) NH 3 gas at STP (s) Temperature first increases and
then Decreases

6.59 Column-I Coloumn – II

(For a definite amount of an ideal gas) (Enthalpy change I work done)

W>0 (s)W < 0

(p) AH>O

(p)  H = 0

(r) W > 0

(S) W < O

6.60 The feasibility of a chemical reaction can be explained based on  H,  S

and  G, so answer the following :
Column-I Coloumn –II
.(A) 203(g)   302(g) (p)  H = +ve,  S = –ve
(B) .30 2 (g)   20 3 (g) (q)  H = –ve,  S = +ve
Low temp.
.(C) NH 2COONH 4 (s)  (r)  G = +ve
2NH 3 (g) + CO 2 (g)
 (D) Ice H20(  ) at room (s)  H = –ve
temperature 25°C
(t)  G = —ve

6.61 Match the following :

Column- I Column – II
(A) For spontaneous reaction (p)  B.E.R –  B.E.P
(B) For endothermic reaction (q)  H =  E
(C) Bond dissociation energy (r)  G = — ve
(D) For solids and liquids in a (s)  HP >  HR
therrnochemical reaction

6.62 Match the following :

Column-I Column – II
(A)  H = qp (p)  H0f = 0
.(B) Kirchhoff’s equation (q) A definite quardity
.(C) H+(aq.) (r) Path function
(D)Spontaneous process (s)  G > 0
(t)  S° Total > 0
(u)  H 2 –  H 1 =  CP (T2 – T1)

6.63 Match the column.

Column-I Column-II
(A) Perfectly crystalline solid (p)  Hsys = 0
(B) Reversible cyclic process (q) lim S  0
T 0

(C)Irreversible cyclic process (r)  Ssurrounding = 0

(D) Any adiabatic process (s)  Usys = 0
(t) net heat change is zero

6.64 Based on data given below, match column-I and column-II

250k,1atm
3X (g)  X3 (g),  H = – 200 KJ/mol ;  S = – 300 J/K/mol

1atm,250k
X (t)  X (g),  Hvap = 10 KJ/mol

250K,1atm
X3(  )  X3 (  ),  H,vap = 80 KJ/mol

X3 (g, 250 K, 1 atm)   X3 (g, 500 K, 1 atom)  H =100 KJ/mol ;

 S = 100 J/K/mol ;  G = 60 kJ/ml Normal boiling point of X = 250 K,
Normal boiling point of X3 = 500 K,
 Enthalpy change and entropy change of cooling X. (1) to lower temperature
is negligible.
Column-I Column-II
(A) For 3X (  )   X3 (  ),  S in J/K/mol is (p) 40
250K,1atm
(B) For 3X (  )  X3 (  ),  H in KJ/mol is (q) – 150
250K,1atm
(C) For 3 X(  )  X3 (  ),  G in KJ/mol is (r) –240
250 K ,atm
(D) For X (  )  X (g),  S in J/Klmol is (s) – 65

SECTION - VII : SUBJECTIVE ANSWER TYPE

SHORT SUBJECTIVE:

6.65 Only N2, CO and CO2 gases remain after 0.72 gm of carbon is treated with
one litre of air at 27°C and 4.92 atm pressure. Assume air composition 02=
0%, N2 = 79% and CO2 = 1% (by volume). The heat evolved (in Kcal) under
constant pressure is :

Given : C + 02 
 CO2,  H = – 100 Kcal/mol
C + 02 
 CO,  H = – 25 Kcal/mol

7
6.66 A sample of an ideal gas (Poisson's ratio  = ) in a state X (44.8 lit, 1
5
atm, 273 K) is taken to a state (44.8 lit, 2 atm, 546 K). The entropy change
(in calories) is [Given In 2 = 0.7 and RT = 22.4 at 0°C temp.]

6.67 It is known that entropy of neutralisation of a strong acid and strong base is
– 13.68 kcal/mol. If enthalpy of neutralisation of N2H4 (hydrazine) with strong
acid is equal to –11.68 kcal/mol, then enthalpy of the reaction
N2H4 + H20 —> N2H5 (aq) + OH- (aq) in Kcal/mol is :

6.68 All of HgO (s) is 20 kcal/mol. The mass (in gm) of mercury, which can be
liberated if 800 cal of heat is given to excess Hg0 (s) is :

6.69 The magnitude of work done (in kcal) when 140 gm of Mg (s) is reacted
with excess of hydrochloric acid in an open vessel at 27°C is.

6.70 Heat supplied to the carnot engine is 37.3 kJ. How much useful work in kJ
can be done by engine which works between 10°C and 100°C.

6.71 For the synthesis of ammonia of 300 K :

N2 (g) + 3H2 (g)   2NH3(g)
Calculate the value of  G° in Kcal and give your answer in magnitude by
using the following data :
N2 H2 NH3
°
 H f (Kcallmole) 0 0 -10
 S° (Cal/K-mole) 40 30 45

6.72 If a monatomic ideal gas from state (5 atm, 1 It, 300K) is expanded to 5 It
volume by reversible adiabatic process and reversible Isothermal process
seperately. What is the value of 2(wisothermal–wadiabatic) in atmx lt.
(Given : (1/4)5I3 = 0.1, In 2 = 0.3).

6.73 A liquid in container is compresed from (2 atm, 1 It) to (10 atm, 0.5 It)
isothermally where it absorb 200 J heat and work done on the system is
500 J. Calculate the enthalpy change of process in KJ. (1 atm x 1
It = 100 J).

6.74 Calculate the pH at which the following conversion(reaction) will be at

equilibrium in basic medium
I2(s) I– (aq) + IO3–(aq)
when the equilibrium concentrations at 300 K are [I-] = 0.10 M and [IO3–] =
0.10 M
{Given that  Gf°(I–,aq) = – 50 kJlmole,  Gf°(I03-,aq) = –123.5 kJlmole,
 Gf°(H20,  ) = – 233 kJ/mole,
25
Gf°(OH-,aq) = - 150 kJlmole, Ideal gas constant = R = Jmole-1K-1,
3
log e = 2.3,

LONG SUBJECTIVE :

6.75 Reaction of gaseous fluorine (F2) with compound X yields a single product Y,
whose mass precent composition is 61.7%`F and 38.3% CI. Calculate  rH°
(in kJ/mol ) for the synthesis of Y using following information
2CIF3 (g) + 02 (g)  Cl2O (g) + 0F2 (g) H0 = 205.6 kJ
2CIF3 (g) + 202 (g)   CI20 (g) + 30F2 (g)  H° = 533.0 kJ
 fH° (0F2, g) = 24.7 kJlmol

6.76 The heat of combustion of ethene gas is 330 Kcal mol-1 calculate bond
C=C energy( in kcallmol) assuming that bond energy of C-H bond is
93.6 KCal mol-1
Given : AH°f fo C02(g) and H20 (  ) are – 94.2 and -61 Kcal mol-1 respectively.
Heat of atomisation of carbon and hydrogen are 150 and 51.5 Kcal mo1-1
respectively.

6.77 Calculate the enthalpy of formation of sulphuric acid (  ) from the following
data:
(a) S (s) + 02 (g)  S02(g);  H = – 71.0 kcal
1
(b) S02 (g) + 02 (  )  S0 3(g);  H = – 23.5 kcal
2
 (c) S03(g) + H20 (  )  H2S04(  );  H= – 31.2 kcal
1
(d) H2(g) + 02 (g)  H2O(  );  H = – 68.5 kcal
2

6.78 Calculate AH for the following homogeneous gaseous reaction

CH3COCH3 + 202  CH3COOH + C02 + H20
from the following data :
Bond energies : C — H = 99 kcal
C — C = 83 kcal
C  0 = 173 kcal
0  0 = 1 1 8 k c a l
C  0 = 8 4 k c a l
C — H =110 kcal

6.79 Calculate  G at 298 K for the following reaction if the reaction mixture
consists of 1 atm of N2,3 atm of H2 and 1 atm of NH3 kJ.
N2(g) + 3H2 (g) 2NH3(g);  G° = – 33.32 kJ.
What is the effect of increasing pressure on the reaction ?

6.80 Ka for acetic acid at 25.0°C is 1.754 x 10-5. As 50.0°C, Ka is 1.633×10-5.

What are  H° and  S° for the ionization of acetic acid ?

6.81 The standard enthalpy and entropy changes for the reaction in equilibrium for
the forward direction are given below :
CO(g) + H2O(g) C02(g) + H2O(g)
H°300K  – 41.16 kJ mo1-1 ;  S°300K = – 4.24 x 10-2 kJ mol–1
H°1200K  – 32.93 kJ mo1 -1 ; S° 1200K = – 2.96 x 10 –2 kJ mol–1
Calculate K P at each temperature and predict the direction of reaction at
300 K and 1200 K, when PCO  PCO2  PH2  1 atm at initial state.

6.82 1 mol of a liquid of molar volume 100 mL is kept in an adiabatic container

under a pressure of 1 bar. The pressure is steeply increased to 100 bar.
Under this constant pressure of 100 bar, the volume of the liquid decreases
by1mL.Calculate  U and  HD of the process.

6.83 The given reaction

2C0 + 0 2 
 2C02  H = – 560 kJ
2moles 1 mole

is carried and in one litre container, if the pressure in the container gets
changes from 70 atm to 40 atm as reaction gets completed. Calculate  U of
the reaction. [1L atm = 0.1 kJ]
6.84 The state of a mole of an ideal gas changed from state A(2p, v) through four
different processes and finally returns to initial state A reversibly as shown
below.

Calculate the total work done by the system and heat absorbed by the
system, in the cyclic process.
 6. THERMODYNAMICS
6.1 (D)  ng = 0,  H° =  U° = - 185 KJ
For 3 mole,  U° = 3x (- 185) = - 555KJ

6.2 (D) 6.3 (D) 6.4 (A) 6.5 (B)

6.6 (B) 6.7 (C) 6.8 (D)

6.9 (B) 0.42 = a(10)3  a = 0.42 × 10-3

10 10
C a 0.42
Sm =  p.m. dT =  aT 2  [103  0]   0.14J/K - mol
0
T 0
3 3

V  P   300R 
6.10 (B)  S = nR  n  f   Rn  i  = R  n   = R  n (24.6)
 Vi   Pf   1L×1atm 

1
6.11 (D) H2O(g) H2O + O2
2
1- α α α /2
1/ 2
α   α/ 2  P
KP = × = 11.62 × 10-11 (atm)1/2  G° = - RT In Kp =
(1  α) (1  α/ 2 )
- 45.76 kcal
6.12 (B) CoCl2 (g) CO(g) + Cl2 (g)
I.Pr - 250 280
Eq.pr x 250-x 280-x
x + 250 – x + 280 – x = 380
x = 150
Kp = 0.114
P ×P
Kp = CO Cl2
PCOCl2
α2  p
Kp =
1  α2
α 2 1
0.114 =
1  α2
In presence of N2 (constant pressure process)
α 2  0.6
Kp =
1  α2
α 2  0.6
0.114 =
1  α2
 0.115
α =
0.715
α = 0.4
α -increases from 0.32 to 0.4.

P1V1 P2 V2
6.13 (D) 
T1 T2
T2 6

T1 3
 T P
 S = 2.303 × n C p log10 2  R log10 1 
 T1 P2 
 6 20 
 S = 2.303 × 1 10.96log10  R log10 
 3 10 
 S = 27.22 J.K-1 mol-1

6.14 (D) Since work done on the system, is maximum in single stage
compression hence all other adiabatic points will fall between 1 and 2.

6.15 (C) At phase transitions, entropy increases at constant temperature and it

is ero at absolute zero.

6.15 (D) As dew formation is spontaneous process therefore entropy or

randomness of the universe will increase. As randomeness of system
has decreased but randomness of the surrounding will increase larger
so that change is positive.

6.17 (C) There is some finite value of entropy at t = 0. It increases constantly till
the temperature of the copper block and surroundings is equal. This
will be the equilibrium situation hence further change in entropy is
restriticted  S = 0 at equilibrium.

6.18 (A) All product and reactants are in solid state

So  S°  0
 G° =  H - T  S°
So  G°   H°

6.19 (A, B, D)
T   Tf 
 S = nCV In  f  + nR In  
 Ti   Ti 
 H = nCp  T
 E = nCV  T
 G =  H -  (TS)
6.20 (B, C, D) 6.21 (C) 6.22 (B) 6.23 (B)

6.24 (B) 6.25 (A) 6.26 (A) 6.27 (C)

6.28 (A) 6.29 (C) 6.30 (C) 6.31 (C)

6.32 (A)  H =  U +  ngRT for (a)  ng = - 2

3
(b)  ng = -
2
(c)  ng = 0
(d)  ng = - 1

6.33 (D) From combustion of fuel, the temp of calorimer raises and reaches to
maximum value and then it decreases due to heat loss to the
surrounding.
So,  T = Tmax – Tinitial = 50 – 20 = 30°

6.34 (C) C7H16 (  ) + 110  7CO2 (g) + 8H2 O (  )

q = C  T = 5 × 100 = 500 J
500
q
 V = = - 1 = - 50 KJ/mole (heat release).
n 100
8.31 300
 H =  U +  ngRT = - 50 – 4 × (  ng = - 4)
1000
= - 59.97 KJ/mole.

 G 
6.35 (D)  G1 =  H1 + T1 d  
 dt P
 G 
 G2  H2 + T2 d  
 dt P
 G 
 G2  G2 = (  H2 -  H1) + (T2 – T1) d  
 dt P
 G 2  G1 
(  H2 -  H1) = (  G2 -  G1) – (T1 – T2)   =0
 T2  T1 

 ΔG   G 2  G1    28  (33) 
6.36 (D) S = - d   = -     0.5 KJ/K
 dt  P  T2  T1   308  298 
 ΔG 
 G1 =  H1 + T1 d  
 dt  P
- 33 =  H1 + 298 x 0.5
 H1 = - 33 – 149 = - 182 KJ/mole
Now,  G =  H + T.d
  G = - 182 + 303 x 0.5 = - 30.5 KJ
This is average of  G at 25°C of 35°C.

6.37 (C)  H1 =  E1 +  ngRT

 H2 =  E2 +  ngRT2
So  E1 +  ngRT1 =  E2 +  ngRT2
(  E1 -  E2) =  ngR(T2 – T1)
But (  E1 -  E2) > 0
So (  E1 >  E2)

6.38 (A) u = 3 pv + 84
 u = u2 – u1 = 3 (p2v2 – p1v1)
  U = 3 (p2V2 – p1V1)
Now, p1V1 2 – p2V2 2
1/2 1/ 2
p  1
 V2 = V1  1  = 0.2   = 0.4
 p2   4
 U = 300 (1 x 0.4 – 4 x 0.2) KJ = - 120 KJ
For a quasi-static process
p V - p V (1x 0.4  4 x 0.2)100
W =  pdV = 2 2 1 1    40 KJ
1- n 2 1
 U = Q + W
Q = - 120 + 40 = - 80 KJ

6.39 (D) Since the end states are the same,  U would remain the same as in
(a).
W = U – Q
W = - 120 – 30 = - 150 KJ

6.40 The work in (b) is not equal to  pdV since the process is not quasi-static.

6.41 (D) 6.42 (C) 6.43 (A)

6.45 (C) Work done in isothermal process will be more than PV2 = const
process whatever the value of K1 and K2 is
2V0
K1 k 1
WI = -  dv = - 1   P0 V0
V0
2V0 2V0 2
2V0
W II = - K2 In = - 0.7 P0V0.
V0
|W II | > |W I |
6.45 (B)

Clearly (Vf)isothermal > (Vf)adiabatic

6.46 (A) Magnitude of work done in isothermal expansion process is more than
adiabatic expansion process.

6.47 (B) Work done is least incase of reversible adiabatic process. Work done
will be greatest in the process P2V = Constant

6.48 (C) Processes may be represented as

If initial temperature is same then temperature in 2nd case is more.

6.49 (B) 6.50 (B) 6.51 (C)

6.52 (B) 6.53 (C) 6.54 (B)

6.55 (B) H2O (s)   H2O (  ),

As P  , more H2O (  ) is formed.
At P = 1 atm,  G = 0.

6.56 (D)  G = V (P2 - P1) = 5 × 18 × 10-6 (101 - 1) × 105 Joule = 5 × 18 × 10-1 ×

102 = 900 Joule.

ΔH 180 103
6.57 (D) T=   1200 K.
ΔS 150
Temperature = 1200 - 273 = 927°C
For Δ G < 0, T > 927°C
6.58 (A - r), (B r), (C - p), (D - q).

6.59 (A – s, q), (B – r, p), (C – s, p), (D – s, p)

6.60 (A - q, t), (B – p, r), (C – r), (D – t)

6.61 (A – r), (b – s), (C – p, (D – q)

All the matching is obvious from the fact see the formula.

6.62 (A – q) , (B – u), (C – p), (D – t)

6.63 (A – q), (B – p, r, s, t), (C – p, s), (D – r, t).

(A) IIIrd law states lim S  0 for perfect solid.

x0

(B) In reversible cyclic process the every net energy change is zero.
(C) In irrcyclic process Δ Ssys = 0 but Δ Ssurrounding > 0 by IIrd law and all state
function are zero.
(D) In adiabatic process net heat change is zero so Δ Ssurrounding = 0.

6.64 (A – r), (B – q), (C – t), (D – p).

3X (  , 250K, 1 atm) x3 (  , 250K, 1 atm)

 H = 3 × 10 H = 0
310 103
 G = 0, S = 120 J/K S = 0
250

3X (g, 250K, 1 atm) X, (  , 500K, 1 atm)

 H = - 200 KJ/mol G = 0
 S = - 300 JK/mol  H = - 80 KJ/mol
80 103
 G = - 125 KJ/mol S = = - 160JK/mol
500
H 100J/mol/K
X3 (g 250, 1 atm)   X3 (g, 500K, 1 atm)
 S = + 100 J/mol/K
 G = 60 KJ/mol
Overall,  H = 3 × 10 – 200 + 100 - 80 + 0 = 30 – 200 + 100 – 80 = –150
KJ/mol.
 S = 20 – 300 + 100 –160 + 0 = – 240 J/mol/K.
 G = 0 + (- 125) + 0 + 0 = – 65 KJ/mol.

4.92 1
6.65 n=  0.2 mol.
24.6
n O2 = 0.2 × 0.2 =0.4 mol
 1
C + O2   CO
2
0.06 0.04mol, 0.01 0.06
1
CO + O2   CO 2
2
0.06 0.01 0.02
0.04
Heat evolved = 0.04 × 25 + 0.02 × 100 =1 + 2 = 3 Kcal.

T2 T
6.66  SX-Y = nCVIn + nRIn 2
T1 T1
44.8 1 5 546 5
=   R  In  2   2  In 2  10  0.7  7 cal.
22.4 2 273 2

6.67  Hion = 13.68 – 11.68 = 2 kcal/mol.

1
6.68  Hg (  ) +
HgO (s)  O2 , 20kcal/mol.
2
0.8
Mol of Hg (  ) = mol
20
0.8
Mass of Hg (  ) = × 200 = 8 gm.
20
6.69 Mg (s) + 2HCl (aq)   MgCl2 + x2  .
2  300
W = - Pext (V2 – V1) = -  nRT = - 5 ×   3 Kcal.
1000
6.70 T1 = 10 + 273 = 283 K ; T2 = 100 + 273 = 373 K
Work = heat × efficiency

 T -T  373  283
= 37.3 ×  2 1  = 37.3 ×  9 KJ
 T2  373

6.71  H°R = 2 ×  H° f (NH3 ) - 3 ×  H° f (H2 ) -  H° f (N2 ) = - 20 Kcal

 S°R = 2 × S° f (NH3 ) - 3 × S° (H 2 - S° N 2 = 2 × 45 – 3 × 30 – 40 = - Cal/K
300  ( 40)
 G° =  H° = - 20 - = - 20 + 12 = - 8 Kcal
1000

6.72 Adtabatic process: P2V2y = P1V1y

P2 × (4)y = 5 × (1)y
y
1
P2 = 5 ×   = 0.5
4
V2 V
Isothermal process : wIsothermal = - nRT In   PV In 2
V1 V1
 4
= - 5 × 1 In = - 5 × 0.6 = - 3
7
 9
Ans. = 2(W Isothermal – W adtabatic) = 2 ×   3    3
 2
6.73 Δ U = q + w = 200 + 500 = 700 J
Δ H = Δ U + (P2V2 – P1V1) × 100 + (10 × 0.5 – 2 × 1) × 100 = 1000 J = 1 KJ.

6.74 Balanced equation will be

3I2(s) + 6OH- 5I-(aq) + IO3- (aq) + 3H2O(  )
Δ G° = 5 × (-50) + (- 123.5)
+ 3 × (- 233)
- 0 – 6 × (-150)
= - 172.5 KJ/mol.
Δ G° = - 172.5 KJ mol-1
25
=-  300  2.3103 log K
3
log k = 30
105 10 1
1030 =
[OH - ]6
So [OH-] 10-6

6.75 Cl F
38.7 61.7
no. of moles  1.09  3.42
35.5 19
Simplest relative ratio 1 : 3
So, product Y is ClF3 & compound X is ClF
For the synthesis of Y reaction is F2(g) + CIF(g)  ClF3(g)
1/2Cl2O(g) + 3/2OF2(g)   ClF3(g) + O2(g) Δ H° = - 533.0/2 KJ  - 266.5 KJ
ClF(g) + 1/2O2(g)   1/2Cl2O(g) + 1/2OF2 Δ H° = 205.6/2 KJ  102.8 KJ
1
F2(g) + O 2 (g)  F2 O(g) ΔH  24.7 KJ
2

6.76 CH2 = CH2(g) + 3O2(g)   2CO2(g) + 2H2O(  )

 - 330 = [2 × (- 94.2) + 2 (- 61)] -  ΔH °f C 2 H 4 
 ΔH°f (C2H4) = 19.6 Kcal mol-1
 2C(s) + 2H2(g)  CH2 = CH2(g) ; Δ Hf = 19.6
 Δ H Reaction =  B.E (Reactants)   B.E (Products)
On substituting the value in above relation we get B.E(c = c) = 122 Kcal / mol
Ans.
6.77 From the above equations, we have to calculate  H for the equation
H2 (g) + S (s) + 2O2 (g)  H2SO4 (  );  H =?
Applying the inspection method,
[Eqn. (a) + Eqn. (b) + Eqn. (c) + Eqn. (d)]. We get,
1 1
S (s) + 2O2 (g) + SO2 (g) + O2 (g) + SO3 (g) + H2O(  ) + H2 (g) O2 (g) 
2 2
SO2(g) + SO3(g) + H2SO4 (  ) + H2O(  );
 H = (- 71.0 – 23.5 – 31.2 – 68.5) kcal or H2 (g) + S(s) + 2O2(g)  H2SO4
(  )  H = - 194.2 kcal.
Ans. – 194.2 kcal

6.78 We have,

H O H H O
|| || | | ||
H–C–C– C – H + 20 = 0  H – C – C – O – H + O C O
| | |
H H H
+ H – O H;  H =?
For reactants:
Bond energy of 6 moles of C – H bonds = 6 × 99 kcal
Bond energy of 2 moles of C – C bonds = 2 × 83 kcal
Bond energy of 1 moles of C H bonds = 6 × 99 kcal
Bond energy of 2 moles of O O bonds = 2 × 118 kcal
For products:
Energy of formation of 3 moles of C – H bonds = - 3 × 99 kcal
Energy of formation of 1 moles of C – C bonds = - 83 kcal
Energy of formation of 1 mole of C O bonds = - 173 kcal
Energy of formation of 1 moles of C – O bonds = - 84 kcal
Energy of formation of 1 moles of C – H bonds = - 110 kcal
Energy of formation of 2 moles of C O bonds = - 2 × 173 kcal
Energy of formation of 2 moles of C – H bonds = - 2 × 110 kcal
Adding up, we get  H of the required equation, i.e.,
 H = - 144 kcal.
Ans. – 144 kcal.

2
PNH 12
6.79 Q= 3
  3.7 102
PN2 PH3 2 1 33
Where Q is the reaction quotient.
  G =  G° + 2.303RT log Q
 G = (- 33.32) + 2.303 × 8.314 × 10-3 × 298 log (3.7 × 10-2)
 G = - 41.49 KJ.
 Thus, increasing the pressure of H2 from 1 atm (std. condition) to 3 atm, free
energy change,  G, becomes more negative, that is, from – 33.32 KJ to
– 41.49 KJ. Hence increase in pressure favours the forward reaction.
 K   H  1 1 
6.80 n  2     
 K1  R  T1 T2 
 1.633  H°  1 1 
n   =   
 1.754  R  298 323 
8.314  298  323  1.633 
so  H° = n  = - 2.285 KJ/mol
25 1.754 
Also,  G° = - RT n Keq = - 8.314 × 298 In (1.754 × 10-5)
= - 8.314 × 298 [-5 + log 1.754] × 2.303
= + 27.137 KJ/mole
 ΔG°  H° 
so,  S° = -   = 98.7 J/mole
 T 
Ans, - 2.29 KJ/mol, - 98.7 J/mol

6.81 Δ G°300 K = Δ H° - T Δ S°
= - 41160 + 300 × 4.24 × 10 = - 28440 = - RT In KP
28440
n Kp = 11.402
8.314  300
so Kp = 8.936 × 104
similar at 1200 K, Δ G° = - 32930 + [1200 × 29.6 = + 2590
J/mole
so, Kp = 0.77
Ans. At 300 K Δ G° = - 28.44 KJ, Kp = 8.94 × 104
At 1200 K Δ G° = + 2.59 KJ, Kp = 0.77

6.82 Δ U = 10 J and Δ H = 990 J

ΔU + ΔQ + Δ W
for adiabatic process ΔQ = O
 Δ Q = Δ W = - P Δ V = - 100 × 105 (-10-6) = 10 J
Δ H = Δ U + Δ (PV)
 Δ H = Δ U + P2V2 – P1V1
= 10 + 100 × 105 × 99 × 10-6 – 1 × 105 × 10 × 10-6
= 10 + 990 – 10 = 990 J

6.83 Δ H = Δ U + Δ (PV)
 so, Δ U = Δ H - Δ (PV) = - 560 – [40 – 70] (L atm) = (- 560 + 30
× 0.1) KJ = - 557 KJ
Ans. – 557 KJ

6.84 - pv, pv
State A to State B (Isobaric expansion)
Pressure is held constant at 2p and the gas is heated until the volume v
becomes 2v.
 W1 = - p  V = - 2p(2v – v) = - 2 pv (= area ABFE)
State B to State C (lsochoric process)
Volume is held constant at 2v and the gas is cooled until the pressure 2p
reaches p.
 W 2 = 0 (  V = 0)
State C to State D (lsochoric compression)
Pressure is held constant at p and the gas is further cooled until the volume 2v
becomes v.
 W 3 = - p (v – 2v) = pv (= area CDEF)
State D to State A (lsochoric process)
Volume is held constant at v and the gas is heated until the pressure p reaches
2p.
 W 2 = 0 (  V = 0)
Total work done by the gas = W = W1 + W2 + W3 + W 4
or W = - 2pv + 0 + pv + 0 = - pv (= area ABCD)
As the process is cyclic  E = 0
q = E - W = - W = p v
Where q is the heat absored in the cyclic process.
 DPP-7
Solid State
SECTION - E: STRAIGHT OBJECTIVE TYPE

7.1 Acrystal is made of particles A and B. A

forms FCC packing and B occupies all
the octahedral voids. If all the particles
along the plane as shown in figure are
removed, then, the formula of the crystal
would be:

(A) AB (B) A5B7

(C)A7B5 (D) None of these.

7.2 A crystal is made of particle X, Y & Z. X forms FCC packing, Y

occupies all octahedral voids of X and Z occupies all tetrahedral voids of
X, if all the pariticles along one body diagonal are removed then the
formula of the crystal would be –
(A) XYZ2 (B) X2YZ2
(C) X5Y4Z5 (D) X5Y4Z8

7.3 In a hypothetical solid C atoms are found to form cubical

close packed lattice. A atoms occupy all tetrahedral vioids
& B atoms occupy all octahedral voids. A and B atoms are
of appropriate size, so that there is no distortion in CCP
lattice of C atoms. Now if a plane as shown in the following
figure is cut.
Then the cross section of this plane will look like.

7.4 In hexagonal close packing of sphere in three dimensions.

(A) In one unit cell there are 12 octahedral voids and all are completely
inside the unit cell.
(B) In one unit cell there are six octahedral voids and all are completely
inside the unit cell.
 (C) In one unit cell there are six octahedral void and of which three are
completely inside the unit cell and other three are partially inside the unit
cell.
(D) In one unit cell there are 12 tetrahedral voids, all are completely
inside the unit cell.

7.5 Diamond has face-centred cubic lattice. There are two atoms at (0,0,0)
 1 1 1
and  , ,  coordinates.The ratio of the carbon-carbon bond distance to
4 4 4
the edge of the unit cell is
3 1 1
(A) (B) 4 ( c ) (D)
16 4 2

7.6 The following diagram shows arrangement of lattice point with a = b = c

and  =  =  = 90°.
Choose the correct options.
(A) The arrangement is SC with each lattice point
surrounded by 6 nearest neighbours.
(B) The arrangement is SC with each lattice point
surrounded by 8 nearest neighbours.
(C) The arrangement is FCC with each lattice point
surrounded by 12 nearest neighbours.
(D) The arrangement in BCC with each lattice
point surrounded by 8 nearest neighbours.

7.7 Consider a cube containing n unit cells of a cubic

system. A plane ABCD obtained by joining the mid
points of the edges on one of its identical faces had
atoms arranged as shown. Let p be the packing
fraction. Choose the correct option:

22 11
(A) n = 1, p = (B) n = 8 , p =
21 2 21
11 11 3
(C) n =8,p = (D) n = 1, p =
14 28

7.8 Spinel is an important class of oxides consisting of two types of metal

ions with the oxide ions arranged in CCP pattern. The normal spinel has
1/ 8 of the tetrahedral holes occupied by one type of metal ion and 1/2 of
the octahedral holes occupied by another type of metal ion. Such a spinel is
formed by Zn2+, A13* and 02-with Zn2+ in the tetrahedral holes. If CCP
arrangement of oxide ions remains undistorted in the presence of all the
cations, formula of spinel and fraction of the packing fraction of crystal are
 respectively :

(A) ZnAl204 , 77% (B) ZnAl2o4, 74%

(C) Zn2A104, 74% (D) Zn3Al2O6, 74%

7.9 What is the maximum number of layers of atoms in close packed planes
that will lie within two imaginary parallel planes having a distance
2
between them of 13 R (where R is the radius of atom) in the copper
3
crystal (FCC) ? Consider the atoms to be within the parallel planes if their
centres are on or within the two parallel planes.
(A) 5 (B) 6 (C) 7 (D) 8

7.10 A transition Metal M can exist in two oxidation states +2 and +3.It forms
an oxide whose experimental formula is given by MxO where x < 1. Then
the ratio of metal ions in +3 state to those in +2 state in oxide is given by :
1 x
(A) (B) 1+2X
1 x
x 2  x  1
(C) 1+ (D)
2 3x  2

7.11 Analysis show that nickel oxide consist of nickel ion with 96% ions having
d8 configuration and 4% having d7 configuration. Which amongst the
following best represents the formula of the oxide.
(A) Ni1.02O1.00 (B) Ni0.96O1.00
(C) Ni0.96O0.98 (D)Ni0.98O1.00

7.12 PCI5 molecule has

(A) three fold axis of symmetry (B) two fold axis of symmetry
.(C) both (D) none of these

7.13 Which of the following statements is correct about the conduction of

electricity in pure crystal of silicon at room temperature?

(A) The conduction is due to electrons present in fully occupied lowest

energy states.
(B) The conduction is due to only some electrons capable of leaving the
bonds at room temperature.
(C) The conduction is only due to the holes formed from the release of
electrons.
(D) The conduction is due to the movement of both the electrons released
and holes formed.
SECTION - II : MULTIPLE CORRECT ANSWER TYPE

 3 
7.14 In the fluorite structure if the radius ratio is   1 ,how many ions
 2 
 
does each cation touch '?
(A) 4 anions (B) 12 cations
(c) 8 anions (D) No cations

7.15 The co-ordination number of FCC structure for metals is 12, since
.(A)each atom touches 4 others in same layer, 3 in layer above and 3 in layer
below.
(B) each atom touches 4 others in same layer, 4 in layer above and 4 in layer
below.
(C) each atom touches 6 others in same layer, 3 in layer above and 3 in layer
below.
(D) each atom touches 3 others in same layer, 6 in layer above and 6 in layer
below.

7.16 In an FCC unit cell, atoms are numbered as shown below. The atoms not
touching each other are : (Atom numbered 3 is face centre of front face).

(A) 3 & 4 (B) 1 & 3 (C) 1 & 2 (D)2 & 4

7.17 Following three planes( P1, P2, P3) in an FCC unit cell are shown.
Consider the following statements and choose the correct option that follow :

(A) P1 contains no three dimensional voids.

(B) P2 contains only octahedral voids.
(C) P3 conatins both octahedral and tertahedral voids.
(D) All are true

7.18 In a AB unit cell (Rock salt type) assuming A+ forming FCC :

(A) The nearest neighbour of A+ is 6B- ion.
(B) The nearest neighbour of B- is 6A+ ion.
(C) The second neighbour of A+ is 12A+.
(D) The packing fraction of AB crystal is 0.79.
7.19 The Miller indices of the four planes shown in the figure below :

. (A) A - [1 1 0] ; B - [1 2 1] ; C - [5 4 10] ; D - [2 2 4].

(B) A - [1 2 1] ; B - [1 1 0] ; C - [2 2 4] ; D - [5 4 10].
(C) A - [1 2 1] ; B - [0 1 1] ; C - [4 4 2] ; D - [5 4 10].
(D) A- [0 1 1] ; B - [1 2 1] ; C - [4 4 2] ; D - [10 2 5].

7.20. The HCP and CCP structure for a given element would be expected to have :
(A) the same co-ordination number. (B) the same density.
(C) the same packing fraction. (D) all the above.

SECTION - III : ASSERTION AND REASON TYPE

7.21 Statement-1 : An important feature of Fluorite structures is that cations
being large in size occupy FCC
lattice points whereas anions occupy all the tetrahedral voids giving the
formula unit AB2 (A : cation, B : anion).
Statement-2 : There are 6 cations and 12 anions per FCC unit cell of the
Fluorite structure.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct
explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a
correct explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

7.22 Statement-1 : In NaCI crystal each Na ion is touching 6 CI– ions but these
CI- ions do not touch each other.
Statement--2 : The radius ratio roe rNa+ / rCl– is greater than 0.414,
required for exact fitting.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct
explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a
correct explanation for Statement-1.
 (C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

7.23 Statement-1 : In ZnS zinc blended structure Zn2+ form FCC while
alternate tetrahedral voids are occupied by S2-.
Statement-2 : Positions of Zn2+ and S2- in zinc blended structure are
similar.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct
explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a
correct explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

7.24 Statement-1 :The ratio of Zn2+and F– per unit cell of ZnS and CaF2 is 1 : 2.
Statement-2 : In ZnS, Zn2+ ions occupy alternate tetrahedral voids and in
CaF2, F– ions occupy all the tetrahedral voids of FCC unit cell.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct
explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a
correct explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

7.25 Statement-1 : Anion vacancies in alkali halides are produced by heating

the alkali halide crystal with alkali metal vapour.
Statemnt-2 : Electrons trapped in anion vacancies are referred to as F–
centres.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct
explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a
correct explanation for Statement-1
(C) Statement-1 is True, Statement-2 is False
(D) Statement-1 is False, Statement-2 is True
SECTION - IV : TRUE AND FALSE TYPE

7.26 One type of unit cells are possible for the crystallographic dimensions
as a = b  c and  =  =  = 90°.

7.27 Number of next neighbours of Cs+ ion in CsCI structure is 6 Cs ions.

7.28 A crystal has A ions at the cube corners and B ions at the edge centres.
The coordination numbers of A and B are respectively 6 and 2.
7.29 Distance between cation and its next neighbour in ZnS (zinc blander) is 1/4 of
the length of body diagonal.

 2 
7.30 In the configuration shown the size of the smallest circle is   1 times the
 3 
size of the biggest circles.

7.31 In the unit cell of HCP structure the three atoms shown in layer B are
completely inside the unit cell.

7.32 Six fold axis of symmetry is present in hexagonal close packing.

3 3 3
7.33 A rhombohedral unit cell is shown. Its volume is a Å , where side length is a
2
Å

SECTION - V : COMPREHENSION TYPE

Comprehension # 1
When an atom or an ion is missing from its normal lattice site, a lattice vacancy
(Schottky defect) is created. In stoichionetric ionic crystals, a vacancy of one on
has to be accompanied by the vacancy of the oppositely charged ion in order to
 maintain electrical neutrality.
In a Frenkel defect an ion leaves its position in the lattice and occupies an
interstitial void. This is the Frenkel defect commonly found along with the
Schottky defects and interstitial. In pure alkali halides, Frenkel defects are not
found since the ions cannot get into the interstitial sites. Frenkel defects are
found in silver halides because of the small size of the Age ion. Unlike Schottky
defects, Frenket defects do not change the densiy of the solids. In certain ionic
solids (e.g. AgBr) both Schottky and Frenkel defects occur.
The defects discussed above do not disturb the stoichiometry of the crystalline
material. There is large variety of Non-stoichiometric inorganic solids which
contain an excess or deficiency of one of the elements. Such solids showing
deviations from the ideal stoichiometric composition form an important group of
solid. For example in the vanadium oxide, VOx, x can be anywhere between 0.6
and 1.3. There are solids which are difficult to prepare in the stoichiometric
composition. Thus, the ideal composition in compounds such as Fe0 is difficult
to obtain (normally we get a composition of Fe° 96 0 but it may range from FeO93 0 to
Fe° 96O). Non-stoichiometric behaviour is mostcominonly found for transition
metal compounds though is also known for some Ianthanoids and actinoids.
Zinc oxide loses oxygen reversibly at high temperatures and turns yellow in
colour. The excess metal is accommodated interstitially, giving rise to electrons
trapped in the neighbourhood. the enhanced electrical conductivity of the non-
stoichiometric ZnO arises from these electrons.
Anion vacancies in alkali halides are produced by heating the alkali halide
crystals in an atmosphere of the alkali metal vapour. When the metal
atoms deposit on the surface they diffuse into the crystal and after
ionisation the alkali metal ion occupies cationic vacancy whereas electron
occupies anionic vacancy. Electrons trapped in anion vacancies are
referred to as F-centres ( from Farbe the German word for colour) that
gives rise to interesting colour in alkali halides. Thus, the excess of
potassium in KCI makes the crystal appear violet and the excess of
lithium in LiCI makes it pink.
7.34 The type of semicondution shown by crystal capable of showing
Schottky defect, will be.
(A) p - type (B) n - type (C) both (D) None
7.35 Which of the following is most appropriate crystal to show Freckle
defect.
(A) CsCI (B) NaCI (C) AgBr (D) CaCl2

7.36 In the crystal of Fe0.93O, the percentage of Fe(III) will be

(A) 15% (B) 85% (C) 30% (D) 78%

Comprehension # 2
In hexagonal systems of crystals, a frequently
encountered arrangement of atoms is described as a
hexagonal prism. Here, the top and bottom of the cell are
regular hexagons and three atoms are sandwiched in
 between them. A space-filling model of this structure,
called hexagonal close-packed (HCP), is constituted of
a sphere on a flat surface surrounded in the same
plane by six identical spheres as closely as possible.

There spheres are then placed cver the first layer so that they touch each
otherand represent the second layer. Each one of these three spheres
touches three spheres of the bottom layer. Finally, the second layer is
covered with third layer that is identical to the bottom layer in relative
position.

1 1
Total number of atoms per unit = (corners atoms) + (face-atoms) +
6 2
3 (body centered atoms).
1 1
=  12   2 + 3 = 2 + 1 + 3 = 6.
6 2

7.37 If in place of above HCP, close packing of sphere is changed such that 4
body centered atoms are arranged in middle layer, 4 atoms above the
middle layer and 4 below the middle layer, what will be the co-ordination
number of new closed packed arrangement ?
(A) 12 (B) 13
(C) 14 (D) cannot be predicted.

7.38 If the angles  Q'QP be changed to 150°, then what will be the
contribution of atom at this position per unit cell ?
1 1 1 5
(A) (B) (C) (D)
24 12 6 24

7.39 If only the angles of position P, P', K and K' is changed from 120° to 60°,
and the angle of positions Q, Q', R,R', M, M', L and L' is changed from
120° to 150° shown in figure, then what will be effect in density of the
crystal ?
(A) will decrease (B) will increase
(C) no effect (D) cannot be predicted.

Comprehension # 3

Only those atoms which form four covalent bonds produce a repetitive three
dimesional structure using only covalent bonds, e.g., diamond structure. The
latter is based on a FCC lattice where-Iattice points are occupied by carbon
atoms.Every atom in this structure is surrounded tetrahedrally by four others.
Germanium, silicon and grey tin also crystallize in the same way as
diamond. (Given : NA= 6 x1023, sin 54°44' = 0.8164).
7.40 If edge length of the cube is 3.60A, then radius of carbon atom is
(A) 0.78 A (B) 0.92 A (C) 0.64 A (D)0.35 A.

7.41 If the edge length is 3.60A, density of diamond crystal is

(A) 3.92 gm/cc (B) 2.40 gm/cc
(C) 3.37 gm/cc (D)2.58 gm/cc.

7.42 Total number of diamond unit cells in 1.2 gm of diamond sample is

(A) 6.0 x 1021 (B) 6.0 x 1022
21
(C) 7.5 x 10 (D) 5.0 x 1022.

Comprehension #4

CuSO4 crystallise in rock salt structure. Its cell parameter can be

determined by various experimental methods like electrical conductivity
measurement, colligative properties measurement, pH measurment etc.
A cubic crystal of CuSO4 of edge length 17.1 mm is dissolved in water to
make 500 ml solution of pH 5.(31.5 = 1.14)
Given : Cu(H2O)62+ +H20[Cu(H2O)5(OH)]+ + H30+ ; K 10-5

7.43 Moles of CuSO4 dissolved in water to make above solution is

(A) 10-5 (B) 2 x 10-5 (C) 2 x 10-4 (D) 10 –4

7.44 Edge length of FCC unit cell of copper sulphate is

(A) 120A (B) 170A (C) 150A (D) 200 A

7.45 If the given solution is made 1 M with respect to [Cub+] becomes 10-15 M
therefore Kf for the formation of Cu(NH3)42+ is
(A) 101° (B) 108 (C) 2 x 108 (D)2x 1010

SECTION - VI : MATRIX - MATCH TYPE

7.46 Match the column :

Column-I Column-II
(A) Cubic (p) Have 2-fold axis of symmetry.
(B) Orthorhombic (q) Have all axial angles identical.
(C) Tetragonal (r) Have all edge lengths identical.
(D) Rhombohedral (s) More than one types of Bravias lattices are
found.

7.47 Column-I Column-II

(Arrangenment in unit cell, (Coordination number of cation :
radius ratio in higher limit) Anion)
(A) Cations in CCP and anions (p) ratio of number of cation to anion
in alternate tetrahedral voids in one unit cell is 1 : 1
 (B) Cations in simple cubic and (q) ratio of coordination number of cation
anions in the body centre. to anion is 1 : 1.
.(C) Anions in CCP and cations (r) ratio of number of cation to anion
in all tetrahedral voids. just ' touching each other is not 1.
(C) Cations in CCP and anions in (s) number of next neighbours of ion
all octahedral voids is greater than 10.

7.48 Match the followings

Column 1 (Arrangement of the atoms/ions) Column II (Planes in fcc lattice)

7.49 Match the column

Column-1 Column-II
(A) AB (Zinc blended) (p) d(gm/cm3) =
4×molar mass
Avogardo'snumber × Volume of unit cell
(B) AB (Rock salt) (q) All the voids along one of the body
diagonal are not occupied
.(C) AB 2 (Fluorite) (r) Voids along one face plane are not
occupied.
(D) AB2(Anti-Fluorite) (s) Anion & cation have similar
surroundings.

7.50 Match the column :

Column-l Coloumn–II
(A) Arrantment of vilurtzite structure (p) non stoichimetric effect
(B) Packing fractions in diamond (q) HCP
 Ea
–
(C) ZnO become yellow on heating (r) Ne 2KT

(D) Schottky defects (s) 0.34

SECTION - VII : SUBJECTIVE ANSWER TYPE

SHORT SUBJECTIVE
7.51 Show the atomic arrangements, given below in three crystallographic
planes in cubic lattice (FCC or BCC or SC). Draw the unit cells of the
corresponding structure and identify these planes in your diagram.

7.52 Consider the arrangement of circles of equal radii with their centres-arranged as
per the 2-dimensional lattice defined by a = b,  = 60° such that each circle is
touching alt its nearest neighbours. If all the void areas present are additionally
occupied by smaller circles of relevant size so that the void circles are just
contacting their neighbours find the packing efficiency of the configuration in
percent.

7.53 Assume an FCC unit cell cube (edge length a) with one of its corners at the
origin of cartesian coordinates.

Find :
(i) .the coordinates of tetrahedral and octahedral voids nearest and farthest to
the origin.
.(ii) find the distance between two succesive tetrahedral voids.
(iii) .the distance between two successive octahedral voids.

7.54 What will be the maximum radius of an atom which can occupy empty spaces
(voids) in a body centred structure, of an element having atomic radius R,
without causing any distortion.
7.55 Ionic solid BMA- crystallizes in rock salt type of structure. 1.296 gm ionic solid
salt B+A- is dissolved in water to make one litre solution. The pH of the solution is
measured to be 6.0. If the value of face diagonal in the unit cell of B+A– be 600.
2 pm. Calculate the density of ionic solid in gm/cc. [T = 298 K, Kb for BOH is
10-5, (Avogadro Number = 6.0 x 1023)]

LONG SUBJECTIVE :

7.56 An ionic solid AB2 isomorphous to the rutile structure (a tetragonal system
with effective number of formula units = 2) has edge lengths of the unit
cell of 4Å, 4Å and 5Å. Calculate the density of the substance if its formula weight
is 81. Take NA = 6 x 1023 and express your answer in mg/cc using four ignificant
digits.

7.57 The face diagonal length of FCC cubic cell is 660pm. If the radius of the cation
is 110 pm, What should be the radius of the anion following radius ratio rules

7.58 How many units cells are there in a

(a) 1.0 g cubic crystal of NaCI ?
(b) Along each edge of the crystal ?
The unit cell content of NCI is 4 and molar mass of NCI is 58.5

7.59 A group 3A metal has a density of 2.7 g/cm3 and a cubic unit cell with an edge
length of 405.5 pm. Reaction of a 1 cm3 chunk of the metal with an excess of
hydrochloric acid gives a colourless gas that occupies 4 L at 27°C and a
pressure of 701.1 mm Hg. ( R = 0.082 It-atm / mol-K, NA = 6 x 1023, 3 66.67 =
405.5 pm),
(a) Identify the metal ?
(b) Is the unit cell primitive, body-centered, or face-centered ?
What is the atomic radius of the metal atom in picometers ?

7.60 A cube-shaped crystal of an alkali metal, 1.62 mm on an edge, was vaporized in

a 500.0 ml. evacuated flask.
The pressure of the resulting vapour was 12.5 mm of Hg at 802°C. The structure
of the solid metal is known to be body-centered cubic. (R = 0.082 It-atm/mol-K).
(a) What is the atomic radius of the metal atom in picometers ?
(b) Use following data to identify the metal
(the radii of metals atoms are Li-152 pm, Na-186, K = 227 pm, Rb = 248 pm)
(c) What are the densities of the solid metal and the vapour of metal (in
gm/cm3) 2

7.61 A solid cube of edge length = 25.32 mm of an ionic compound which has
NaCItype lattice is added to 1kg of water. The boiling point of this solution is found
to be 100.52°C (assume 100% ionisation of ionic compound). If radius of anion of
ionic solid is 200 pm then calculate radius of cation of solid in pm '(picometer).
 (Kb of water = 0.52 K kg mole1, Avogadro's number, NA = 6 x 1023, ( 3 75 ) = 4.22)

7.62 5.35 g of a salt ACI (of weak base AOH) is dissolved in 250 ml of solution. The
pH of the resultant solution was found to be 4.85. Find the ionic radius of A+
& Cl– if ACI forms CsCI type crystals having density 2 2g/cc .Given Kb(AOH)
r
= 2 x 10-5 – .= 0.731 for this unit cell.
r
 7. SOLID STATE
7.1 (A)

7.2 (D) When all particle along are body diagonal one removed, these 2 X
atoms from corner are removed, one Y particle removed & 2 Z particle
removed.
1 1 15
Hence new arrangement, X particle =  6   6  ; Y particle = 6 ;
8 2 4
Z particle = 3
Hence formula = X15/4Y3Z6 = X5/4YZ6 = X5Y4Z8

7.3 (C) From the sizes of octahedral and tetrahedral voids, it is clear that the
atoms occupying these voids will not touch each other as we have along
body diagonal of FCC.

7.4 (B) HCP = AB AB AB ………… pattern repeat

For calculating voids between two layers A and B.
Total tetrahedral voids = 12 (represented by dots) out of which 8 are
completely inside but rest are shared by other unit cells. Total
octahedral voids = 6 (represented by cross).
All are completely inside.

1 1 1 3
7.5 (A) dc-c =    and a F C C = 1
16 16 16 16

7.6 (A)

7.7 (B)

7.8 (A) Formula Zn Al2O4

Total volume of particles present in one unit cell
Packing fraction =
volume of one unit cell
  4 3   2 4 3   4 4 3 
 πrZn 2    πrA/3 +    πrO2 
 3   3   3 
= 3
a
 4 a (0.225)   4 a 3 (0.414)3   4
3 3
a3 
 π 
  2  π 
  4  π 
 3 (2 2) 3   3 (2 2) 3   3 (2 2) 3 
= = 0.77
a3

.(1).___ .................................
(2)________
(3)________
(4)________ 13
2
R
2 3
7.9 (C) Parallel layer are at a distance of 2 R (5)________
3 (6)________
(7)________
………………………………..
________

7.10 (D) In 1 mole of MxO, mole of M2+ ion = y  mole of M3+ ion = x – y.
Applying charge balance, 2y + 3(x – y) – 2 = 0  y = 3x – 2
3+
M x  y x  (3x  2) 2(x  1)
 2+   
M y 3x  2 3x  2

7.11 (D) d8  Ni2+, d7  Ni3+.

Total charge of nickel.
(0.96 × 2) + (0.04 × 3) = 2.04.
2.04
No. of O2- ion =  1.02. = 1.02.
2
Formula of solid = NiO1.02 = Ni0.98O.

7. 12 (C) Based on theory.

7.13 (D) At room temperature, thermal energy causes some electrons of the Si-Si
bonds to leave. The electron deficient bond becomes a positive hole. Both
the positive holes and electrons released account for the conduction of
electricity.

7.14 (B, C) In ftourite structure, cations form the lattice & anions occupy each of
tetrahedral voids.

7.15 (B, C) From FCC unit cell.

7.16 (C) Atoms along one edge or at corners do not touch each other in FCC cell.

7.17 (A, B, C, D)
7.18 (A, B, C, D)

Based on FCC crystal

 4 3   4 3 
 4  πrA+    4  πrB- 
3   3
Packing frection =  3

a
3
 4 a   4 a (0.414) 3 
3

 4  π  4 π
3   
 3 (2 2)   3 (2 2) 3 
=  0.79
a3

7.19 (A)

7.20 (A, C)

7.21 (C) Based on Fluorite structure of CaF2

7.22 (A) 7.23 (A) 7.24 (A) 7.25 (B)

7.26 False

7.27 True

C.N. of cation charge of cation 3

7.28 True   3
C.N. of anion charge of anion 1
No w Co-ordination no. of A is as shown so of B is 2.

7.29 False 7.30 False 7.31 False 7.32 True

7.33 False Using vector algebra, calculate box product of vectors along three
a3
sides of given unit cell and volume is
2
7.34 (A)
7.35 (C)

7.36 (A) 3x + (0.93 – x) × 2 = 2

x = 0.14
0.14
% of Fe as Fe (III) = 100 15%
0.93

7.37 (A)

7.38 (D)

7.39 (A) Any arrangement formed are less packed then closest packed
arrangement.

dc  c
7.40 (A) 4dc – c sin (54°44’) = 2  r =  0.78
2

8 12
7.41 (C) d= = 3.37 gm/cc.
NA  a 3

1.2  N A
7.42 (C) Total number of unit cells =  7.5 1021 .
12  8
Sol. (7.43 lb 7.45)
Cu(H2O)42+ + H2O [Cu(H2O)5(OH)]+ + H3O+
C
C- x x x
x2 (105 )2
10-5 = 
C  x C  105
C = 2 × 10-5 mol/lt
 moles of CuSO4 dissolved 2 × 10-5 × 0.5 = 10-5
105  N A 6
 Number of unit cells =  1018  1.5 1018
4 4
3
Number of unit cells along one edge of the cube = 1.5 1018  1.14 106
If edge length of FCC unit cell is a
 a × 1.14 × 106 = 17.1 mm  a = 150 Å
Now, Cu2+ + 4NH3 Cu(NH3)42+
2 × 10-5
10-15 1 2 × 10-5
[Cu(NH 3 )42  ] 2 105
Kf = 2+ 4
 15  2 1010
[Cu ][NH 3 ] 10 1
 7.43 (A) 7.44 (C) 7.45 (D)

7.46 (A – p, q, r s), (B – p, q, s), (C – p, q, s), (D – p, q, r)

7.47 (A – p, q, s), (B – p, q, r), (C – s), (D – p, q, s)

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

7.49 (A – p, q, r, s), (B – p, q, r, s), (C – p, q, r), (D – p, q, r).

7.50 (A – q), (B – s), (C – p), (D – r)

7.51

1 2
πR  π(0.155R) 2
7.52 Packing fraction = 2 100  95%
1 2 3
(1R)
2 2

7.53 (i) Tetrahedral: nearest-(a/4, a/4, a/4), farthest-(3a/4, 3a/4, 3a/4);

Octahedral: nearest- (a/2, 0, 0), (0, a/2, 0), (0, 0, a/2), farthest- (a, a,
a/2), (a, a/2,a), (a/2, a, a)
(ii) a/2 (iii) a/ 2

 5 
7.54  1 R
 3 
Ina body centred lattice this position where the atom of maximum size can be
fitted should not be lying on the edge centre as the distance between surfaces
of two atoms which are at comers of a cube is very small so will be off the
 a
 
edge so will be at distance of 4  4  from edge centre on I bisector of edge of
cube. Hence
a2 a2 5a 2 5 5 16R 2  5 
We get R + r =      so r =  1 R
4 16 16 16 16 3  3 
1 5 1
7.55 pH = {pKw – pKb – log C}   6 = 7.0 -  log C  C = 0.01M
2 2 2
1.296 1
 C=   molar mass of salt = 129.6
Molar mass 100
For rock salt 600 2 = 2 a
 a = 600 pm = 600 × 10-10 cm.
Z M 4  129.6 
Now density =  3  = 6.0 1023  3 30 
= 4 gm/cc.
NA  a   (600) 10 
Ans. 4 g/cc

81 21000
7.56 d= mg/cc = 33 mg/cc.
6 10 [4  4  5]1024
23

7.57 2 a = 660 2 pm
so a = 660 pm
now if tetrahedral void is occupied by cations than
3
a = (r+ + r-)
4
 3  660  3 
r- =  100  = 110  3 1 = 1.598 × 110.
 4  2 
r 1 1 10
so,    0.625
r 1.598 1.6 16
r
but > 0.414 so it must not be occupying tetrahedral void then
r
a = 2 (r+ + r-)  330 = r+ + r-
r
r- = 220 pm {  = 0.5 it can occupy octahedral void}
r

58.5
7.58 Mass of 1 units cell = 4 × mass of 1 NaCl unit = 4 × g = 3.885 ×
6.022 1023
10-22 g.
1.0
 Number of unit cells per 1.0 g of NaCl =  2.57 1021.
3.885 1022
3
No. of unit cells per edge = 2.57 10 21 = 1.37 × 107.
 701.1 4
7.59 (a) Moles of H2 gas =  0.15.
760  0.082  300
3
M + 3H+   M3+ + H 2
2
2.7 1
 moles of M used = 0.1 =  atomic weight of metal
atomic weight
= 27 gm/mol.
 metal is Al.
Z M Z  27 
(b) Density =  3  2.7 = 23  10 3 
NA  a  6 10  405.5 10 ) 
 Z = 4.
(c) For FCC unit cell, 4r = 2 a  r = 143.4 pm.

7.60 (a) 231 pm (b) K (c) density of solid = 0.875 g/cc, density of
vapour = 7.29 × 10-6 g/cc
PV 12.5 1 1
(a) n = no. of moles =     9.318 10 5
RT 760 2 0.082 1075
Number of atoms = nNA = 5.612 × 1019
nN A
So number of unit cells = = 2.806 × 1019
2
So, if there are x unit cells along one edge of given cube.
nN A
Then total number of unit cells in the cubic crystal = x3 = = 2.806 × 1019
2
 x = 3.04 × 106
Now if edge length of unit cell = a  ax = 1.62 mm.  a = 5.33 × 10-9 mm  a
= 533 pm
3a
 r=  230.8 pm
4
(b) So metal must be potassium
2  39
(c) ρ solid = 23 3
 0.86 gm/cm3
6.022 10  a
PM 12.5  39
ρ gas = =  7.27 × 10-3 gm/cm3
RT 760  0.08211075

7.61 Effective molality of solution = 1

Hence, number of moles of ionic solid in given cube = 0.5
So, number of formula units in given cube = 0.5 × 6 × 1023
1
Number of unit cells =  0.5 1023  7.5 1022
4
3
Number of unit cells along one edge of cube = 75 x 107 = 4.22 x 107
25.32 x103
edge length of unit cell = a = 7
m = 600 x 10-12 m = 600 pm
4.22 x10
for NaCl type unit cell, a = 2 (r+ + r-)  r+ = 100 pm.
7.62 r+ = 126 pm, r- = 171 pm.
1 1
pH = × [pKw – pKb – log C]  4.85 = × [14 – 4.7 – log C] 
2 2
a = 3.43 × 10-8 cm.
5.35
 C = 0.4 =  4  molar mass of the salt = 53.5 gm/mole
molar mass
1 53.5
Now, density =  2.2  a = 3.43 × 10-8 cm.
6.022 1023  a 3
and for CsCl type of crystals, 3 a  2(r+  r- )
-8
 r+ = 1.26 × 10 cm and r- = 1.71 × 10-8 cm.
 DPP-8
Chemical Equilibrium
SECTION - I : STRAIGHT OBJECTIVE TYPE

8.1 Two flasks A and B of equal volume containing 1 mole and 2 mole of 03
respectively, are heated to the same temperature. When the reaction 203
302 practically stops, then both the flasks shall have
(A) the same ratio [02] /[03] (B) the same ratio : [02]3/2/[03]
(C) only 02 (D)the same time to reach equilibrium

8.2 A 10L container at 300K contains C02 gas at pressure of 0.2 atm and an
excess solid CaO (neglect the volume of solid Ca0). The volume of container is
now decreased by moving the movable piston fitted in the container. What will be
the maximum volume of container when pressure of C02 attains its maximum
value given that
CaC03 (s) CaO(s) + C02(g) Kph = 0.800 atm
(A) 5 L (B) 2.5 L
(C) 1 L (D) The information is insufficient.

8.3 An equilibrium mixture at 700 K of 0.50 M N2, 3.00 M H2 and 2.00 M NH3 is
present in a container. Now if this equilibrium is disturbed by adding N2 so that its
concentration becomes 1.50 M just after addition then which of the following
graphs represents the above situation more appropriately –

8.4 At 1400 K, Kc= 2.5x10 +3 for the reaction CH4(g) + 2H2S(g) CS2(g) + 4H2(g) .
A 10.0L reaction vessel at 1400 K contains 2.00 mole of CH4, 3.0 mol of CS2, 3.0
mole of H2 and 4.0 mole of H2S. Then
(A) This reaction, is at equilibrium with above concentrations.
(B) The reaction will proceed in forward direction to reach equilibrium.
(C) The reaction will proceed in backward direction to reach equilibrium.
 (D) The information is insufficient to decide the direction of progress of reaction.

8.5 The graph which will be representing all the equilibrium concentrations for
the reaction
N2 O 4 (g) 2NOz (g) will be :
(the concentrations of N2O4 (g) and of NO (g) for which the following eaction
will be at equilibrium will lie

8.6 In a basic aqueous solution chloromethane undergoes a substitution

reaction in which Cl is replaced by OH– as.
CH3 CI (aq) + OH– CH3 OH(aq) + Cl (aq)
The equilibrium constant of above reaction C, =1 x 10'6. If a solution is
prepared by mixing equal volumes of 0.1 M CH3CI and 0.2 M NaOH (100%
dissociated) then [OH-] concentration at equilibrium in mixture will be:
(A) 0.1 M (B) 0.5 M (c) 0.2 M (D) 0.05 M
8.7 For the chemical equilibrium, CaCO3 (s) Ca0(s) + CO2 (g)
 Hf ° can be determined from which one of the following plots ?

8.8 At a certain temperature the following equilibrium is established, CO(g) +

N02 (g) CO( g) + NO(g) One mole of each of the four gas is mixed in
one litre container and the reaction is allowed to reach equilibrium state. When
excess of baryta water (Ba(OH)2) is added to the equilibrium mixture, the
weight of white ppt (BaCO3) obtained is 236.4 gm. The equilibrium constant
Cc of the reaction is (Ba = 137)
(A) 1.2 (B) 2.25 (C) 2.1 (D) 3.6
8.9 At temperature T, the compound AB2 (g) dissociates according to the
reaction, 2AB2 (g) 2 AB(g) + B2(g).With a degree of dissociation x,
which is small compared with unity. Deduce the expression for x in terms of the
equilibrium constant, Kp and the total pressure, P.

–1/3 1/3
 2K  K 
(A) x =  p  (B) x =  p 
 P  P
1/3 1/3
K   6K 
.(c) x =  p  (D) x =  p 
 2P   3P 

8.10 Equilibrium constant for the given reaction is C = 1020 at temperature 300 K
A(s)+2B (aq.). 2C(s) + D(aq.) K = 1020
The equilibrium conc. of B starting with mixture of 1 mole of A and 1/3
mote/titre of B at 300 K is
(A) 4  10 –11 (B) 2  10 –10 (C) 2  10 –11 (D) 10 –10

8.11 10  t box contain O3 and O2 at equilibrium at 2000 K. The  G° = –534.52

kJ at 8 atm equilibrium pressure.The following equilibrium is present in the
container
.2O3(g) 3O2(g).The partial pressure of O3 will be ( In 10 = 2.3, R = 8.3
Jmole-1K-1):
(A) 8×104 (B) 22.62 x 10-7 (C) 9.71 x 10-6 (D) 9.71 x 10-2

8.12 Solid ammonium carbamate dissociates to give ammonia and carbon dioxide
as follows:
NH2COONH4(s) 2 NH5(g) + CO2(g)
At equilibrium, ammonia is added such that partial pressures of NH5 now equals the
original total pressure. Calculate the ratio of the total pressures now to the original
total pressure.

31 60 31 62
(A) (B) (C) (D)
27 40 9 27

8.13 The reactions, PCI5 (g) PCI5(g) + CI2(g) and CI2(g) CO2(g) + Cl2(g) are
simultaneously in equilibrium in an equilibrium box at constant volume. Afew moles of
CO(g) are later introduced into the vessel. After some time, the new equilibrium
concentration of
(A) PCI5 will remain unchanged (B) CI2 will be greater
(C) PCI5 will become less (D) PCI5 will become greater

8.14 In the Haber process for the industrial manufacture of ammonia involving the
reaction,N2 + 3H2 2NH5 at 200 atm pressure in the presence of a catalyst,
 a temperature of about 500°C is used. This is considered as optimum temperature
for the process because
(A) yield is maximum at this temperature
(B) catalyst is active only at this temperature
(C) energy needed for the reaction is easily obtained at this temperature
(D) rate of the catalytic reaction is fast enough while the yield is also appreciable
for this exothermic reaction at this temperature.

1
8.15 For the equilibrium of the reaction, HgO(s) Hg(g) + O2(g), kP for the reaction
2
at total pressure of P is:
2 2 1 3/2 1
(A) K P = 3/2 p3/2 (B) K P = 1/2 p1/2 (c) K P = p (D) K P = p
3 3 32/3 32/3

8.16 What is the minimum mass of CaC05 (s), below which it decomposes completely,
required to establish equilibrium in a 6.50 litre container for the reaction : [ KC =
mole/litre]
CaCO3 (s) Ca0(s) + C02(g)
(A) 32.5g (B) 24.6 g (C) 40.9g (D) 8.0 gm
8.17 The value of kp for the reaction at 27°C
Br2(  ) + Cl2(g) 2BrCl(g)
is '1 atom'. At equilibrium in a closed container partial pressure of BrCI gas is 0.1 atm
and at this temperature the vapour pressure of Br2(  ) is also 0.1 atm. Then what will
be minimum moles of Br2(  ) to be added to 1 mole of C12 , initially, to get above
equilibrium situation :
10 5 15
.(A) moles (B) moles (C) moles (D) 2 moles
6 6 6

8.18 5 mol PCI3(g) and one mole N2 gas is placed in a closed vessel. At equilibrium
PCI5(g) decomposes 20% and total pressure in to the container is found to be 1 atm.
The kP for equilibrium PCI3(g) PCI3(g) + Cl2(g)
1 1 1 1
(A) atm (B) atm (C) atm (D) atm
24 4 16 28

8.19 Degree of association can be defined as the number of moles of a

particular substance associated per mole of the substance taken.
For example : If out of 10 mole of N2 , 3 mol of N2 combine with H2 to form
NHL. then degree of association of N2 = 0.3.
Consider the equilibrium situation : N2(g) + 3H2(g) 2NH3(g)
Initially N2 & H2 were mixed in 1 : 3 molar ratio and after long time the mean
34
molar mass of the mixture was found to be g. The degree of association
3
of N2 is
 (A) 0.5 (B) 0.4 (C) 0.9 (D) 025
8.20

Attainment of the equilibrium A(g) 2C(g) + B(g) gave the gave the
followeing graph. Find the correct option.
(% dissociation = fraction dissociated x 100)
(A) At t = 5 sec equilibrium has been reached and KC, = 128 (mol/litre)2
(B) At t = 5 sec equilibrium has been reached and % dissociation otA is 60%
(C) At t = 5 sec equilibrium has been reached and % dissociation ofA is 30%
(D) None of these

SECTION - II : MULTIPLE CORRECT ANSWER TYPE

8.21 Solid ammonium carbamate, NH4 CO2NH2 (s) dissociates into ammonia and
carbon dioxide when it evaporates as shown by
NH4CO2NH2(s) 2NH3(g) + CO2(g)
At 25°C, 'the total pressure of the gases in equilibrium with the solid is
0.116 atm. If 0.1 atm of CO2 is introduced after equilibrium is reached
then :
(A) final pressure of CO2 will be less than 0.1 atm
(B) final pressure of CO2 will be more than 0.1 atm
(C) pressure of NFI3 will decrease due to addition of C02
(D) pressure of NH3 will increase due to addition of C02

8.22 For the equilibrium, PCI3 PCI3 (g) + CI2 (g)

Which of the following sketch may represent above equilibrium. Assume
equilibrium can be achieved from either side and by taking any one or more
components initially. (Given Kc for the reaction < 2)
8.23 138 gm of N2O4 (g) is placed in 8.2L container at 300 K. The equilibrium vapour
density of mixture was found to be 30.67. Then (R = 0.082 L atm mol-1K–1)
(A)  = degree of dissociation of N204= 0.25
(B) KP, of N2 O4 2NO2(g) will be 9 atm.
(C) Total pressure at equilibrium = 6.75 atm
(D) The density of equilibrium mixture will be 16.83 gm/litre.

8.24 Solid ammonium carbamate dissociate to give ammonia and carbon dioxide as
follows
NH2COONH4(s) 2NH3(g) + CO2(g)
which of the following graph incorrectly represents the equilibrium.
8.25 2CaSO4 (s) 2Ca0(s) + 2SO2(g) + O2(g),  H > 0
Above equilibrium is established by taking sufficient amount of CaSO4(s) in a closed
container at 1600 K. Then which of the following may be correct option(Assume
thatsolid CaSO4 is present in the container in each case)
.(A) moles of CaO(s) will increase with the increase in temperature
(B) If tile volume of the container is doubled at equilibrium then partial pressure of SO2(g)
will change at new equilibrium.
(C) If the volume of the container is halved partial pressure of 02(g) at new
equilibrium will remain same
(D) If two moles of the He gas is added at constant pressure then the moles of
CaO(s) will increase.

8.26 CuSO4 5H2 O(s) CuSO4(s) + 5H2O(g) Kp = 10-10 (atm). 10–2 moles of
CuSO4 5H2O(s) is taken in a 2.5L container at 27°C then at equilibrium [Take : R =
1
litre atm mol–1 K–1]
12
(A) Moles of CuSO4 . 5H20 left in the container is 9 x 10–3
(B) Moles of CuSO4 . 5H20 left in the container is 9.8 x 10–3
(C) Moles of CuSO4 left in the container is 10–3
(D) Moles of CuSO4 left in the container is 2 x 10–4

8.27 A closed jar having waters vapours in equilibrium with liquid suddenly all the vapours
of the jar is transferred to another,identical jar and is subjected to compression.
Assume initial temperature to be the same and negligible volume occupied by the
liquid water. Select the observation in the record jar
(A) liquid water will Start forming in the jar
(B) vapour will undergo gradual compression without any condensation.
(C) temperature of the vapour will increases.
(D) final pressure will be the same as initial pressure.

828 For a reversible reaction ad + bB cC + dD) ; the variation of K with

temperature is given by

K2 -ΔH°  1 1 
log =  –  then,
K1 2.303R  T2 T1 

(A)K2 > K1 if T2 > T1 for an endothermic change.

(B) K 2 < K1 if T2 > Ti for an endothermic change.
(C) K2 > K1 if T2 > T.1 for an exothermic change.
(D) K 2 < K1 if T2 > T1 for an exothermic change.
8.29 If two gases ABA and 62C are mixed the following equilibria are readily
Established
AB2 (9) + B2C(g)  AB3 (g) + BC (g)
BC(g) + B2C(g)  B3 C 2 (g)
It the reaction is started only with AB2 with B2C, then which of the following is
necessarily true at equilibrium:
(A) [AB3leg = LBC]eq (B) [A62],1 =[B2C]eg
(C) (AB3]eq> [ B3C2].eq (D) [AB]aq > [BC]eq

8.30 The following reaction attains equilibrium at high temperature.

N2 (g) + 2H2OP(g) + heat 2NO(g) + 2H2 (g)
The yield of NO is affected by
(A) increasing the nitrogen concentration
(B) decreasing the hydrogen concentration
(C) compressing the reaction mixture
(D) none of these

SECTION - Ill : ASSERTION AND REASON TYPE

8.31 Statement-1 : At equilibrium moleculetry to attain minimum energy and
maximum entropy
Statement-2 : Free energy at equilibrium state would be zero.
(A) Statement-2 is True, Statement-1 is True; Statement-1 is a correct
explanation for Statement-2.
(B) Statement-1 is True, Statement-2 is True; Statement-1 is NOT a correct
explanation for Statement-1.
(C) Statement-2 is True, Statement-2 is False.
(D) Statement-2 is False, Statement-1 is True.

8.32 Statement-1 : A(s) B(g) + C(g) ; Kp;

X(s) B(g) + Y(g) ; Kp2 = 3Kp1
Total pressure of 6 over the mixture of solid Aand Xis greater than pressure of
B either over excess solid A or over excess solid X But less then their directly
sump value when excess of solid Aand excess of solid 6 kept in different
container
Statement-2 : In presence of each other, degree of dissociation of both
solids decreases.
(A) Statement-2 is True, Statement-1 is True; Statement-1 is a correct
explanation for Statement-1.
(B) Statement-2 is True, Statement-1 is True; Statement-1 is NOT a correct
explanation for Statement-1.
(C) Statement-2 is True, Statement-1 is False.
(D) Statement-2 is False, Statement-1 is True.
8.33 Statement-1 : For the equilibrium N2O4(g) 2NO2(g) then mean molar mass of
the equilibrium mixture is always more than 46 and less than 92.
Statement-2 : Addition of Xenon(9), at constant volume to the equilibrium mixture will
result in decrease in the mean molar mass of the mixture.
(A) Statement-2 is True, Statement-1 is True; Statement-1 is a correct explanation
for Statement-1.
(B) Statement-1 is True, Statement-1 is True; Statement-1 is NOT a correct
explanation for Statement-2
(C) Statement-2 is True, Statement-1 is False
(D) Statement-1 is False, Statement-1 is True

8.34 Statement-1 : Ice melts at 0°C under normal conditions, it would melt at lower
temperature under higher pressure.
Statement – 2 : Formation of ice is an exothermic process.
(A) Statement-1 is True, Statement-1 is True; Statement-1 is a correct
explanation for Statement.
(B) Statement-2 is True, Statement-1 is True; Statement-2 is NOT a correct
explanation for Statement-1
(C) Statement-2 is True, Statement-1 is False
(D) Statement-1 is False, Statement-1 is True

SECTION - V : COMPREHENSION TYPE

Comprehension # 1
Le chateliees principle
If a system at equilibrium is subjected to a change of any one of the factors such as
concentration, pressure temperature, the system adjusts itself in such a way as to
(Nulify) the effect of that change.
Change of pressure : If a system in equilibrium consists of gases, then the
concentrations of all the components can be altered by changing the pressure.
When the pressure on the system is increased, the volume decreases
proportionately. The total number of moles per unit volume will now be more and the
equilibirum will shift in the direction in which there is decrease in number of moles
ice., towards the direction in which there is decrease in volume.
Effect of pressure on melting point : There are two types of solids :
(a) Solids whose volume decreases on melting, egg., ice, diamond, carborundum,
magnesium nitride and quartz
Solid (higher volume) Liquid (lower volume)
Them process of melting is facilitated at high pressure, thus melting point is
lowered.

.(b) Solids whose volume increase on melting, e.g., Fe, Cu, Ag, Au, etc.
Solid (lower volume) Liquid (higher volume)
 In this case the process of melting become difficult at high pressure; thus
melting point becomes high.

(c) Solubility of substances : When solid substance are dissolved in water,

either heat is evolved (exothermic) or heat is absorbed (endothermic).

KCI + aq KCl(aq) – heat

In such cases, solubility increase with increase in temperature.
Consider the case of KOH; when this is dissolved, heat is evolved.
KOH + aq KOH(aq) + heat
In such cases, solubility decrease with increase in temperature.

(d) Solubility of gases in liquids : When a gas dissolves in liquid, there is

decrease in volume. Thus, increase of pressure will favour the dissolution of
gas in liquid.
Effect of temperature : Le-Chatelier's principle predicts a system at
equilibrium will tend to shift in the endothermic direction when temperature is
raised, for then energy is absorbed as heat and the rise in temperature is
opposed. Conversely, an equilibrium will shift in the exothermic direction if the
temperature is lowered, for then that energy is released and the reduction in
temperature is opposed. Van't Hoff equation shows the dependence of
equilibrium constant K on temperature as:
d ΔH° ΔH° 1
nK= 2
or nK=constant – .
dT RT R T

8.35 A gas 'X when dissolved in water heat is evolved. Then solubluty of 'X' will
Increase
(A) Low pressure, high temperature (B) Low pressure, low temperature
(C) High pressure; high temperature (D) High pressure, low temperature

8.36 Au(s) Au(  )

Above equilibrium is favoured at :
(A) High pressure low temperature (B) High pressure high temperature
(C) Low pressure, high temperature (D) Low pressure, low temperature

1 1
8.37 For the reaction, N2 (g )  O2 (g ) NO(g )
2 2
pressure is increased by reducing the volume of the container then
(A) total pressure at equilibrium will change.
(B) concentration of all the component at equilibrium will change.
(C) concentration of all the component at equilibrium will remain same.
(D) .equilibrium will shift in the forward direction.

8.38 The plot of log K against 1 -- is a straight line with positive slope (K being
 the equilibrium constant of a reaction), which of the following is then
correct ?
(A) The reaction is endothermic in nature
(B) The reaction will be exothermic in nature
(C) The reaction goes to farther extent on raising the temperature
(D) None of these
Comprehension #2
In gaseous dissociation reactions, the total mass remains unchanged and the
number of moles increases as a result of the reaction. Thus the average
molecular weight and hence the vapour density decreases. In other words, the
volume increases at constant temperature and pressure and hence the
vapour density decreases.The relationship between vapour density in the
beginning and vapour density at equilibrium can be found as follows:
At constant temperature and constant pressure for a fixed mass of
gaseous mixtures,
1
Vapour density  density 
volume
 PV = nRT
 Volume  number of moles

1
 Vapour density 
Number of moles
D n0
 =
D0 n

Where Do and D are the vapour densities in the beginning and at equilibrium
and no and n are the number of moles in the beginning and at
equilibrium.The vapour density of PCI5 at 200°C and 252°C are 70.2 and
57.2 respectively at one atmosphere

8.39 The observation shows that the dissociation constants (KP) for the reaction are
(A) 1 and 2 respectively. (B) 1.19 and 0.37 respectively
(C) 0.307 and 1.19 respectively (D) 2 and 1 respectively

8.40 This observation shows that

(A) The reaction is endothermic
(B)The reaction is exothermic
(c) The reaction is not affected by change in pressure
(D) The reaction is not affected by adding inert gas at constant
pressure.

8.41 From the given data, it can be interpreted that

.(A) If degree of dissociation is more, then vapour density is more for PCI5
(B) More the degree of dissociation, less is the vapour density of PCI5
. (C) Degree of dissociation and vapour density cannot be correlated.
 (D)  is independent of temperature.

Comprehension #3

The rate of chemical reaction at a particular temperature is proportional to the product of

the molar concentration of reactants with each concentration term raised to the
power equal to the number of molecules of the respective reactant taking part in
the reaction. aA + bB   products, rate of reaction a [Aka [Bib = k [Aka [Bib,
where k is the rate constant of the reaction.
EQUILIBRIUM CONSTANT (k)
For a general reaction aA + bB <=> cC + dD, forward rate rf = kf [A]a [B]b,
backward rate rb = kb [Cicpyi ,
concentrations of reactants & products at equilibrium are related by
Kf [C ]c [D ]d
=K C  where all the concentrations are expressed in mole/liter.
Kb [ A]a [B ]b
.e.g. PCl 5 PCI 3 (g) + Cl 2 (g)
[PCl3 ][Cl2 ]
KC=
[PCl5 ]
In the expression of equilibrium constant those components are kept
whose concentration changes with time.
If equilibrium is estabilished by taking all the components in the reaction
then to predict the direction of reactions we calculate the reaction quotient
(Q).

[C]C [D]d
The values of expression Q=
[A]a [B]b
at any time during reaction is called reaction quotient
if Q > Kc reaction proceed in backward direction until equilibrium in
reached
if Q < Kc reaction will proceed in forward direction until equilibrium is
established
if Q = KC Reaction is at equilibrium

8.42 A(g) + B(g) 2C(g)

Initial concentration of 'A’ is twice the initial concentration of `B'. At equilibrium
concentration of 'A and 'a are same then equilibrium constant for the reaction
is
4 4 16
(A) (B) (C) (D) 4
3 9 9
8.43 A(g) + B(g) C(g) + D(g)
Above homogeneous reaction is carried out in a 2 litre container at a
particular temperature by taking 1 mole each of A, B, C and D respectively.
If Kc for the reaction is then equilibrium concentration of C is
 1 2 4 1
(A) M (B) M (C) M (D) M
3 3 3 2

8.44 When C2H5OH and CH3COOH are mixed in equivalent proportion

equilibrium is reached when 2/3 of acid and alcohol are used. How much
ester will be present when 2 moles of acid were to react with 2 moles of
alcohol?
.(A) 1.33 (B) 1 (c) 2.33 (D) 2

Comprehension # 4
X,Y and Z react in the 1 : 1 : 1 stoichiometric ratio. The concentration of X, Y
and Z where found to vary with time as shown in the figure below.

8.45 Which of the following equilibrium reaction represents the correct variation
of concentration with time.
(A) x(g) + y(g) z(g) (B) x(g) + y(s) z(g)
(C) z(g) + y(s) x(g) (D) z(g) + x(g) y(g)

8.46 Value of the equilibrium constant (Kc) for the equilibrium represented in above
sketch will be.
9 21 2 12
(A) (B) (C) (D)
2 4 3 7

8.47 If above equilibrium is established in a 2L container by taking reactants in sufficient

amount then how many moles of component Y must have reacted to establish the
equilibrium.
(A) 0 (B) 6 (C) 12 (0) 8

Comprehension # 5
For certain substances such as ammonium chloride, nitrogen peroxide, phosphorus
pentachloride, etc. the measured densities are found to be less than those calculated
from their molecular formula. The observed densities decrease towards a limit as the
temperature is raised. This is due to the splitting of the molecules into simpler ones.
 The process is reversible and is called thermal dissociation.
.
Examples : NH4CI NH3 + HCI J2 2I

N2 04 2NO2 PCI 5 PCI 3 + Cl 2

With increase in the number of molecules, the volume increases (pressure
remaining constant) and, in consequence, the density decreases. As the
temperature rises, more and more dissociation takes place, and when practically
complete dissociation occurs the density reaches its lowest limit.The extent of
issociation, ice., the fraction of the total number of molecules which suffers
dissociation is called the degree of dissociation. Gas density measurements can be
used to determine the degree of dissociation. Let us take by general case where
one molecule of a substance A splits up into n molecule of B on heating; i.e.,

An (g) n A (g)
t=0 a 0
x
t = teq a—x nx =  x =a .
a
a—a  na

Total no. of moles = a – a  + na 

= [1 + (n — 1)  ] a

Observed molecular weight or molar mass of the mixture

MA n
Mmixture = ,MA n =Molar massof gas A n
[1+(n-1)α]

8.48 A sample of mixture of A(g), B(g) and C(g) under equilibrium has a mean molecular
weight (observed) is 80.
The equilibrium is A(g) B(g) + C(g)
(mol. wt. = 100) (mol. wt. = 60) (mo. wt. = 40)

Find the degree of dissociation  for A(g).

(A) 0.25 (B) 0.5 (C) 0.75 (D) 0.8

8.49 If the total mass of the mixture in the above case is 300 gm, the moles at C(g)
present are.
1 4 3
(A) mole (B) mole (C) mole (D) None
4 3 4

8.50 The K for the reaction N2 O 4 2NO2 is 640 mm at 775 K. The

percentage dissociation of N2 O4 at equilibrium pressure of 160 mm is :
(A) 80 % (B) 30 % (C) 50 % (D) 70%
 D
8.51 x (degree of dissociation) varies with in the above reaction according to :
d

Dd
8.52 The equation  = is correctly matched for :
 n  1 d
(A) A nB/2 + nC/3 (B) A nB/3 + (2n/3)C
(C) A (2n/2)B + (n/4)C (D) A (n/2)B + C

Comprehension # 6

2
. 2A2 A4 (i) KP1 = atm1
81
A2 + 2C A2C2 (ii)
A2C2 2AC (iii)

A2 and C are taken in 3 : 1 mole ratio in a closed container of a certain

volume at a fixed temperature and aobve three equilibriums are established
simultaneously. Kopf for the first reaction is 2/81 atm-1. At equilibirum partial
pressure of A4(g) and AC(g) are found to be 1/2 atm each and the total
27
pressure at equilibirum is found to be atm. Then
4

8.53 The partical pressure of A2C2 at equilibrium is

(A) 1/2 (B) 1/4 (C) 2/4 (D) 1

8.54 The mole ratio of gases A 2 and AC at equiliburm is

(A) 9/2 (B) 7I2 (C) 8 (D) 9

8.55 Equilibrium constant Kp for the reaction, 2AC A2C2 is

(A) 2/4 (B) 2 (C) 4 (D) ½
SECTION - VI : MATRIX - MATCH TYPE

8.56 Match the following

Column-I Column-II
(A) C2H4(g) + H2(g) C2 H6 + Heat (p) Doubling the volume causes
forward shift
(B) 2HH3 + Heat H2 + 2H2 (q) Kp is less than Kc
(C) 2SO2 + O2 2SO3 + Heat (r) Yield of reactant can be
increased by increasing

(D) 2SO 2 + O 2 2S03 + Heat (s) Forward reaction is forward on

decreasing temperature
8.57 Match the following (multiple)
Left column : Represents an equilibrium situratton through a chemical
equation and below each equation a stimulus is given which may or may not
disturb the equilibrium situration.
Right coloumn : Represents the responses immediately after the
disturbance is created.
With R1 : Rate of forward reaction.
R b Rate of backward reaction.
Q : Reaction quotient
K : Equilibrium constant

Column-I Column-II
(A) H2(g)+I 2HI(g) (p) Rf increases
Pressure is increased

1 3
(B) N2(g)  H2(g) NH3(g) (q) Rb increases
2 4
Volume is halved

(C) PCl3(g) + Cl (r) R1 = Rb

PCI5 is added

(D) 2S03(g) 2S02(g) +O2(g) (s) Q  K

Inert gas added at court volume.
8.58 Column-I Column-II
(A) N2 04 (g) 2NO+2 (g) (p) Density of reacting mixture remain
.On increase in volume at constant constant
Temperature
.(B) H2(g) + I2(g) 2HI(g) (q) Density of reacting mixture
On addition of inert gas at constant Decreases
P&T

(C) 2N0(g) + Br2 (g) 2N0Br(g) (r) Average molar mass of reacting
On decrease in pressure at constant mixture increases.
Temperature.

. (D) .2ICI3(g) I3(g) + 3Cl2(g),  0 (s) Average molar mass of reacting

On increase in pressure at constant mixture decreases
Temperature

8.59 Column – I Column — II

(A), NH 2 C00N,4 (s) 2NH3(g) + C02 (g) ; (p) High pressure and low
ΔH < 0 temperature will favour
formation of products.
(B) CaCO3 (S) CaO(s) + CO2(g) ; (q) Increase in the
H>0 amount of any of the
product will
definitely favour
backward reaction.
(C) N2 (g) + 02 (g) 2O(g) ; ΔH > 0 (r)Increaseintemperature
and doubling the volume
of reaction vessel will
cause the equilibrium to
shift in similar direction.
(D) 2SO 2 (g) + O 2 (g) 2SO 3 (g) ; ΔH < 0 (s) A decrease in
temperature will cause
decrease in the
value of equilibrium
constant.
 8.60 Match the following.
Reaction Degree of dissociation in terms
(Homogeneous gaseous phase) of equilibrium constant

(A) A(g) + AB 2 C(g) (p)  k  / 1  k 

(B) 2 A (g) B(g) + C(g) (q)  k  /  2+ K 
(c) A(g) + B(g) C(g) + D(g) (r) 2k/(1+2k)

A B 2 k
(D) A B ( g ) (g)+ (g) (s)
2 2 1 2 k

8.61 Match the following:

Column I Column II
(A) For the equilibrium NH4I(s) NH3(g)+ HI(g), (p) Forward shift
if pressure is increased at equilibrium

(B) For the equilibrium N2 + 3H 2 2NH3 (q) No change

at equilibrium volume is increased at equilibrium

.(C) For the equilibrium H 2O(g) + C0(g) H2(g) + C02 (g) (r) Backward
inert gas is added at constant pressure at equilibrium shift

(D) For the equilibrium PCI5 PCl3 + Cl2 (s) Final

CI2 is removed at equilibrium Pressure is
More than

initial pressure
SECTION - VII : SUBJECTIVE ANSWER TYPE
SHORT SUBJECTIVE

8.62 The equilibrium constant for the following reaction is 1.6 x 105 at 1024 K,
H2(g) + Br2(g) 2HBr(g)
Find the equilibrium pressure of all gases if 10.0 bar of HBr is introduced
into a sealed container at 1024 C.

8.63 For the reaction;CO (g) + 2H2 (g) CH3 OH (g), hydrogen gas is introduced
into a five litre flask at 327°C,containing 0.2 mole of CO (g) and a catalyst, until
the pressure is 4.92 atmosphere. At this point 0.1 mole of CH3OH(g) is
formed. Calculate the equilibrium constants Kp &Kc .

8.64 NH3 is heated initially at 15 atm from 27°C to 127°C at constant volume. At
127°C equilibrium is established.The new pressue at equilibrium at 127°C
 becomes 30 atm for the reaction 2NH3(g) N2(g) + 3H2(g).
Then find the % of moles of NH3 actually decomposed.

8.65 For the equilibrium

LiCI.3NH3(S) LiCI . NH3(s) + 2NH3(g) [Kp = 9 atm2]
at 40°C. A5 litre vessel contains 0.1 mole of LiCI.NH3. How many mole of
NH3 should be added to the flask at this temperature to derive the backward
reaction for completion?

8.66 Following two equilibria are established on mixing two gases A 2 and C.
.(i) 3A2 (g) A6 (g) Kp = 1.6 atm2
.(ii) A2(g) + C(g) A2C (g)
If A2 and C are mixed in 2:1 molar ratio, calculate the equilibrium partial
pressure of A2, C, A2C and Cps for the reaction (ii). Given that the total
pressure to be 1.4 atm and partial pressure of A6 to be 0.2 atm at
equilibrium.

LONG SUBJECTIVE
8.67 At certain temperature, the equilibrium constant for the gaseous reaction of
CO with O2 to produce CO2 is 5.0 x 103 lit/mole. Calculate [CO] at
equilibrium, If 1.0 mol each of CO and 02 are placed in a 2.0 L vessel and
allowed to come to equilibrium.

8.68 When equal volumes of 0.2 M AgNO3 and 1 M CCN solutions were mixed
then at equilibrium, concentration of Ag was found to be 10-6M. While when
equal volumes of 0.2 M Zn(NO3)2 solution and of 1 M CCN solution were mixed
then at equilibrium, concentration of Zn2 ion was found to be 10-12M. Then find
the equilibrium constant of following.
2[Ag(CN)2]– (aq.) + Zn2 (aq.) [Zn(CN)4]2– (aq.) + 2Ag+ (aq.).
8.69 At 827°C, Cps for the reaction between CO (g) and excess hot graphite(s) is 10
atm. Calculate the equilibrium concentration of gases at 827°C and total
equilibrium pressure equal to 5.6 atm
[R = 0.082 L-atm mol-1 C-1]
{ Fill the answers in the order : first concentration of CO2 (g) and then
concentration of CO (g) in the multiple of 10-4 and use three significant
figures to represent your answers. For example if [CO2] = 0.0235 M & [CO]
= 0.0356 M, then your answers should be=235356.}

8.70 A container of volume V litre contains an equilibrium mixture which consists

Of 2 mol each of PC  5, PC  3 and C  2 (all gases). The equilibrium pressure
is 3 tm. and temperature is TK. Acertain amount of C  2(g) is now introduced
into he container keeping the pressure and temperature constant, until the
equilibrium volume becomes 2V litre. Calculate the number of moles of C  2
that were added.
 [Fill your answer in the multiple of 10-2, for example if your answer is 2.53
then fill 253 as your answer.]

8.71 In a container of constant volume at a particular temparature N2 and H2 are

mixed in the molar ratio of 9:13.The following two equilibria are found to be
coexisting in the container
N2 (g) + 3H2 (g) 2NH3(g)
N2 (g) + 2H2 (g) N2H4(g)
The total equilibrium pressure is found to be 3.5 atm while partial pressure of
NH3(g) and H2(g) are 0.5 atm and 1 atm respectively. Calculate of
equilibrium constants of the two reactions given above.
 8. CHEMICAL EQUILIBRIUM
8.1 (B) For reaction
[O 2 ]3 [O 2 ]3/2
 constant so KC = = constant
[O3 ]2 [O3 ]
= will be same for both the containers

8.2 (B) 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
PCO2 = 0.8 should get converted into CaCO3(s).
so V(0.800 atm) = (10 L) (0.2 atm)
so v = 2.5 L

8.3 (A) Let reaction be

N2 + 3H2 2NH3
3
[NH3 ] (2) 2 2 8
Kc = 3
=   
[N 2 ][H 2 ]  1  3  3  27
  (3)
2
Now after distrubing equilibrium then N2 concentration will be > 0.5 M
and there will be some time taken for attainment of equilibrium hence
graphs (B) and (C) can be discarded from calculations itcan be proved
that the amount by which N2 should reaction should be less than 0.2
Hence the result.

4
 3  3
    243
10 10
8.4 (C) QC     2  10 2  7.59 102  K C
 2  4  32
 10  10 
  
so, reaction will proceed in backward direction.

8.5 (B) All the equilibrium concentrations will satisfy the equation
[NO 2 ]2
K=  y 2 = kx the required parabolic graph
[N 2 O 4 ]

8.6 (D) CH3Cl (aq) + OH- CH3OH (aq) + Cl- (aq)

As equilibrium constant is very large so reaction will be almost 100%
complete.

8.7 (A) CaCO3(s) CaO(s) + CO2(g)

Kp = PCO2
H 0r
log Kp = log A -
2.303RT
 H 0r l
log PCO2 = log A = …… (i)
2.303R T
Graph (a) represents (i) and its slope will be used to determine the heat of the reaction.

8.8 (B) CO(g) + NO2(g) CO2(g) + NO(g)

t= 0 1 mole 1 mole 1 mole 1 mole
Al eq. 1 - x 1-x 1+x 1+x
CO2 + Ba(OH)2   BaCO3
236.4
mole of BaCO3 = = 1.2
197
So mole of CO2 at eq. = 1.2
or 1 + x = 1.2
x = 0.2
2 2
 1  x   1.2 
KC =      2.25
 1  x   0.8 
8.9 (D) 2AB2 (g)   2AB (g) + B2 (g)
Mole before dissociation 1 0 0
x
Mole after dissociation (1 - x) x
2
x x
Total mole at equilibrium (  n) = 1 - x + x + 1 +
2 2
2 n
n B  (n AB )  P 
Now, Kp = 2 
(n ) 2 AB2   n 
1
x  
.(x)2  
p
Kp = 2 2
 
(1  x) 1  x 
 2
x3 p  x 
Kp =  x is small,1- x and1+ 1
2 2 
3
2K p
x=
p
1/3
2 k 
Ans. X =  p 
 p 

8.10 (A) A(s) + 2B(aq) 

 2C(s) + D(aq)
1
Initial 1 0 0
3
1
At eq. 1 – x x 2x x
3
a
 x  1/3
1
1020 = 3 2
[B]
1
1020 = 32
a
1 10 20
a2 = =
3 1020 3
10 10
a=  4 × 10-11 M
3

8.11 (B)  G° = - RT In K = - 2.3 × 2000 × 8.3 log K

534.52 x103
 log K
2.3x 8.3 x 2000
K = 1014
2O3(g) 3O2(g) K = 1014
So PO2 <<< PO2
So PO2 + PO3 = 8
PO2 = 8 atm
(PO2 )3 (8)3
K = 1014 = 
(PO3 )2 PO3
PO3 = 22.62 × 10-7 atm.
8.12 (A) NH2COONH4(s) 2NH3(g) + CO2(g)
Initial 3P P’
2

Kp = PNH3  P 
CO2

2
Kp = (2P) (P) …… (i)
PT(initial) = 3P
NH2COONH4(s) 2NH3(g) + CO2(g)
Final 3P P’
2
Kp = (3p) (p’) …… (ii)
From eq. (i) and (ii)
(2P)2 = (3P)2 (P')
4P
P’ =
9
4P
3P 
p T (New) 3P  P' 9  31
= =
p T (Old) 3P 3P 27
8.13 (C) If CO is added 2nd equilibrium will proceede in the backward direction and
concentration of Cl2 will decrease. This Cl2 will be further formed by the
decomposition of PCI5.

8.14 (A) Formation of ammonia is an exothermix process therefore it is favorable at lower

temperature. But at lower temperature rate of the reaction becomes slow.

1
8.15 (A) HgO(s) Hg (g) + O2 (g)
2
1
Kp = PHg(g) x (PO2)
2
3x
Total moles at equilibrium =
2
x 2
PHg = P P
3x / 2 3
x/2 1
PO2 = P P
3x/2 3
1/ 2
2 1  2 3/2
Kp = P  P  = P
3 3  33/2

8.16 (a) Kc = [Cl2] = 0.05 mole/litre

so moles of CO2= 6.50 × 0.05 moles = 0.3250 moles
CaCl3 CaO + Cl2
1 mole of CO2 = 1 mole of CaCO3
0.3250 moles of CO2 = 0.3250 moles of CaCO3= 0.3250 × 100 gm of CaCO3 =
32.5 gm of CaCO3

8.17 (C) Br2(  ) + CI2(g) 2Br Cl(g)

t=0 1 0
(1 – x) 2x
2
(P )
Kp = BrCl = 1 so, PCl2 = (PBrCl ) 2 = 0.01 atm
PCl2
n BrCl 0.1 2x
them at equilibrium,   10 
n Cl2 0.01 1 x
10 5
so, 10 – 10x = 2x or x= moles
12 6
Moles of Br(  ) required for maintaining vapour pressure of 0.1 atm
5 10
= 2 × moles = moles = moles of BrCl(g).
6 6
5
Moles required for taking part in reaction = moles of Cl2 used up =
6
moles.
8.18 (D) PCI3(g) PCI 3 (g) + Cl 2(g)
t = 0 50 0 0
t=teq 5-5 × 0.2 5 × 0.2 5 × 0.2
4 mole 1 mole 1 mole
Total moles at equilibrium = 4 + 1 + 1 + 1 (N2) = 7 moles
1  1 
 1atm  1atm  1
7  7
Kp =   = atm
4  28
 1atm 
7 

8.19 (A)

8.20 (C)

8.21 (B, C) the pressure of NHL will decrease due to addition of CO2 (backward,
shifting Le-chatelies's principle.
The pressure of C02 will be more than 0.1 atm.

2 4 4
8.22 (B, D)Given K c < 2 therefore in case of B and C K c = 
6 3
and concentration of PCI3 and Cl2 together will decrease or increase as
reaction can go in the forward or backward direction.

8.23 (B, C, D)
N2O4 2NO2
t= 0 a 0
t a (1 - α ) 2a α
46
vapour density =  30.67
1 α
so 1 + α = 1.5 = 0.5 = 50%
1.5 1.5  0.082  300
Total pressure =  6.75atm
8.2
4α 2
So Kp = P = 9 atm
1 α2
138
And for density of mixture = gm/L = 16.83 gm/L.
8.2

8.24 (A, B, D)

8.25 (A, C, D)
(A) As reaction is endothermic therefore it will go in the forward direction hence
moles of Ca0 will increase.
 (C) With the increase or decrease of volume particle pressure of the gases will
remain same.
(D) Due to the addition of inest gas at constant pressure reaction will proceede in
the direct in which move number of gaseous moles are formed.

5 PV 10 2
8.26 -10
(B, D) 10 atm = P5
H 2O  P H 2O = 10-2 atm. n =   103
RT 1  300
12

8.27 (A, D)

8.28 (A, D)

8.29 (C, D) Let reactions is started with a mole of AB2 and b mole of B2C
 AB2(g) + B2C(g)   AB3(g) + BC(g)
a b 0 0
a–x b–x–y x x–y
BC(g) + B2C(g)   B3C2(g)
x–y b–x–y y As y > x (why ??)
Clearly [AB3]eq > [B2C2]eq and [AB3]eq > [BC]eq

8.30 (A, B,C)

As concentration of reaction (gaseous) are increased at equilibrium reaction will
go in the forward direction. Also above reaction is endothermic therefore increase
in temperature will favoaur it.

8.31 (C) 8.32 (A) 8.33 (C) 8.34 (B)

8.35 (D) Solubility of gas is favourable at high pressure and this process is exothermic
hence solubility will be more at low temperature.

8.36 (C) Since density of gold decreases after melting therefore it is favourable at low
pressure and high temperature.

8.37 (A, B)

1
8.38 (B) Since the slope of the straight line graph between log and is positive, ΔHreaction
2
would be negative, i.e., the forward reaction would be exothermic.

8.39 (C) PCI 5 PCI 3 + CI 2

1- α α α
Dd α12 α 22
Since α = & Kc 1 = & Kc 2 =
d 1  α1 1 α2
 Hence Kp for different conditions can be calculated and kp = 0.307 and 1.19
respectively at 200°C and 250°C.

8.40 (A) As Kp value increases with increase in temperature, this implies the reaction is
endothermic.

8.41 (B) More the degree of dissociation, less is the vapour density of PCI5.

8.42 (D) A + B 2C
at t = 0 2a a 0
t = teq 2a – x a–x 2x
2
 2a – x = 2x  x= a
3
2
2
2 4 
(2x) 3 4 4
 Kc =   4
(29  x) (a  x)  2  2  4 1
 2   1  
 3  3 
8.43 (A) A(g) + B(g) C(g) + D(g)
at t = 0 1 1 1 1
t = teq 1+x 1+x 1–x 1–x
(1/ 2) (1/ 2)
QC = 1  K C
(1/ 2) (1/ 2)
(1  x) (1  x) 1 (1  x) 1
   
(1  x) (1  x) 4 (1 x) 2
2 – 2x = 1 + x
1
 x=
3
1 x 1
 [C] =  M
2 3

8.44 (A) Case – I

C2H5OH + CH3COOH CH3COOC2H5 + H2O
Mole before reaction 1 1 0 0
Mole at equilibrium 1–x 1–x x x
2
 x=
3
 2  2 2 2
 Mole at equilibrium  1   1 
 3  3 3 3
2 2

 Kc = 3 3 4
1 1

3 3
 Note: Volume terms are eliminated
Case – II
C2H5OH + CH3COOH CH3COOC2H5 + H2O
Mole before reaction 1 1 0 0
Mole at equilibrium (2 – x) (2 – x) x x
2
x x
Kc = 4 = or  2
(2  x)2 (2  x)
Or x = 1.33

8.45 (B) Clearly concentration of Y is not changing with the time hence it will be
pure solid or liquid. Concentration of X decreasing hence it will be in
reactant and Z will be in product.

[Z(g)]eq 4 2
846 (C) Kc =  
[X(g)]eq 6 3

8.47 (D) From the graph we can see that 4 mole/litre of Z is formed therefore
4 × 2 moles of solid will be required.

8.48 (A) A(g) B(g) + C(g)

M th
Mob =
M  (n 1) α
100
80 =
1 α
1
α = = 0.25
4

8.49 (C) Mols of C = a α

300
Where a = moles of ‘A’ =
100
3
 moles of C = 3 × 0.25 = .
4

8.50 (D) N2O4 2NO2

Mole before equilibrium 1
Mole at equilibrium (1 – x)
n
4x 2  P 
Kp = 
(1  x)   n 
4x 2 160
640 =
(1  x) (1  x)
 4x 2
4= or 1 – x2 = x2 or 2x2 = 1
(1  x)
 x2 = 1/2 or x = 0.707 = 70.7%

D
8.51 (B) =1+x [n = 2]
d
D
 =1+x [n = 2]
d
Which is a line with positive slope and X intercept = 1.

Dd D
8.52 (B) α =  (n – 1) α = 1
(n 1) d
D
 = 1 + (n – 1) α
d
Hence one mole of reactant should produce total n moles of product.

Sol. (8.53 to 8.55)

2A2 (g) A4 (g)
3p – x – y x/2
A2 + 2C A2C2
3p – y – x p – 2y y–z
A2 C2 2AC
y–z 2z
1
PA 4 2 PA4 81
 K P1  P  A2   2 
PA2 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
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
8.53 3p – x – y =
2
1 9
6- -y=
2 2
y = 1 atm.

9
n A2 PA2 3P  x  y 2
8.54 =   9
n AC PAC 2z 1/ 2

n A 2 C2 3/ 4
8.55 Kp = 2
= 2
3
P AC 1
2
 

8.53 (C) 8.54 (D) 8.55 (B)

8.56 (A – q, s), (B – p, r), (C –q, s), (D – p,r)

8.57 (A – p, q, r), (B – p, q, s), (C – q, s), (D – p, q, r)

8.58 (A – q, s), (B – p), (C – q, s), (D – r)

8.59 (A – q), (B – r, s), (C – q, s), (D – p, q, r)

8.60 (A – q), (B – s), (C – p), (D – r)

8.61 (A – r, s), (B – r), (C – q), (D – p, s)

(A) As Δ n > 0 therefore if P  , reaction will go in the backward direction.
(B) As Δ < 0 therefore if V  p  , reaction will go in the direction in which more
number of gaseous moles are formed ice. backward direction.
(C) As Δ n = 0 hence no effect.
(D) If concentration of product is decreased reaction will go in the forward
direction.

8.62 H2(g) + Br2(g) 2HBr(g)

Initial pressures 0 0 10.0 bar
p/2 p/2 (10.0-p)
p2 HBr
Kp =
PH2  PBr2
(10  p)2
1.6 × 105 =
(p/2)(p/2)
200 p = 10 – p
 10
P= bar
201
1  10 
PH 2  p / 2    bar = 2.5 × 10-2 bar
2  201 
p Br2 = p/2 = 2.5 × 10-2 bar
pHBr = 10 – p  10 bar.

8.63 CO(g) + 2H2(g) CH3OH(g)

Initial mole 0.2 a 0
Mole at equilibrium (0.2 – 0.1) (a – 0.2) 0.1
Now total at equilibrium are = 0.1 + a - 0.2 + 0.1 = a
PV 4.92  5
Also Mole (n) = = = 0.499
RT 0.0821 600
a = 0.499
0.1 0.2  0.1 0.1 0.499  0.20 0.299
 [CH3OH] = ; [CO] =  ; [H2] =
5 5 5 5 5
[CO][OH] 0.1/ 5
 Kc = 2
= = 279.64 litre2 mol-2
[CO]OH 2 ] 0.1/ 5  (0.299 / 5) 2
Kp = Kc (RT) Δ n
Kp = 279.64 × (0.0821 × 600)-2 = 0.115 atm-2
Ans. Kc = 279.64 litre2 mol-2, kp = 0.115 atm-2

864 2NH3 N2 + 3H2

a 0 0
a – 2x x 3x
P1 P2 15 P
   2  P2 = 20 atm.
T1 T2 300 400
a  2x 30
Now =
a 20
2a + 4x = 3a
1
 x = a.
4
2x
 % of NH3 decomposed = 100  50% Ans. 50
a

8.65  LiCl. 3NH3 (s) LiCl. NH3 (s) + 2NH3(g) [Kp = 9 atm2]
 1 
 LiCl. NH3 (s) + 2NH3 (g) LiCl. 3NH3 (s)  K P1  (atm)-2 
 9 
Initial mole 0.1 a 0
Final mole at eq. 0 (a – 0.2) 0.1
Let initial mole of NH3 should be a to bring in completion of reaction.
1
At eq. K P1 = ' 2
(PNH3 )
 1 1
Or  ' 2
9 (PNH3 )
'
 PNH 3
= 3 atm
 PV = nRT
3 × 5 = n × 0.0821 × 313
n = 0.5837
i.e., (a – 0.2) = 0.5837
 Initial mole of NH3 = a = 0.5837 + 0.2 = 0.7837 mole

8.66 3A2 (g) A6 (g) Kp = 1.6 atm-2

PA' 2
Kp = 1.6 =
(PA 2 )3
0.2
3
PA 2 =  0.5 atm
1.6
Also pressure of A2 used for the formation o 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
1
At eq. 2P – P – 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 PA2C = 0.3 3 atm
Also Kp for A2 (g) + C(g) A2C (g)
P 0.3
Kp = A2 C   1.5 atm-1
PA 2  PC 0.5  0.4

8.67 2CO(g) + O2(g) 2CO2(g)

1 1
Initial conc. = 0.5 = 0.5 0
2 2
x
Conc. At equal. 0.5 – x 0.5 - x
2
2
[CO 2 ]
 Kc = 2
= 5 × 103
[CO] [O 2 ]
 x2
 5 × 103 =
 x
(0.5  x)2  0.5  
 2
3
If Kc > 10 so one of less amount of reactant will have negligible conc.
So, 0.5 - x = y (y  0) approxly and x = 0.5
x
So, [CO] = y , [O2] = 0.5 - = 0.25 approxly
2
[CO2] = 0.5
3 (0.5)2
So, Kc = 5 × 10 = 2
y  0.25
-2
y = 1.4 × 10
[CO] = y = 1.4 × 10-2 M Ans.

8.68 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 = 4
1015
(0.1) 1012
st nd
Substracting two times I reaction from II reaction, we will get the required reaction,
so
12015 103  81
Keq = 2
  810 Ans. 810
 10  12
100
  10
9

8.69 Co2(g) + C(s) 2CO(g)

Partial pressure at equilibrium P1  P2
2
P
Kp = 2 = 1-0 or P1 = 0.1 P22 … (1)
P1
But p1 + p2 = 5.6 atm
Solving p1 = 1.6 atm and p2 = 4 atm
Using p = CRT
1.6
C1 (for CO2) =  0.0195 M
0.082 1000
4.0
C2 (for CO) = = 0.0488 M
0.082 1000
Ans. 195488

8.70 PC  5 PC  3 + C  2
Let y moles of C  2 are introduced then at new equilibrium
PC  5 PC  3 + C  2
 6 + x y – x = 12 …….. (1)
Total moles of PC  5 + PC  3 = 4 and moles of C  2 = 8
(2  x)3 2  x
 PPCl5 = 
12 4
(2  x)3 2  x
PPCl3 = 
12 4
8  3)
PPCl2 = 2
12
(2  x)  2 
 
4 1
 Kp = 1 =
2 x
4
2 20
 x = and hence from equation (1) y =  6.67 moles
3 3
 Ans. Is 667 – 666

8.71 Let the initial partial pressures of N2 and H2 be 9P and 13 P respectively

N2 (g) + 3H2 2NH3 (g)
9P – y – x 13P – 3x – 2y 2x
N2 ( g) + 2H2 (g) N2H4 (g)
9P – y – x 13P – 3x – 2y y
Total pressure = PN2 + PH 2 + PNH3 + PN2H4 = 3.5 atm
= (9P – x – y) + (13 P – 3x – 2y) + 2x + y = 3.5 atm … (1)
PNH3  2x  0.5 atm … (2)
PH 2 = (13P – 3x – 2y) = 1 atm … (3)
From (1)  (9P – x – y) + 1 atm + 0.5 + y = 3.5
 (9P – x) = 2 atm
So 9P = 2.25
P = 0.25 atm
From (3) equation 2y = 1.5 atm
y = 0.75 atm
so PN2 = 9P – x – y = 1.25 atm
PH 2 = 1 atm
PNH3 = 0.5 atm
PN2H4 = 0.75 atm
2
PNH 0.5  0.5
So, K P1  3
3
  0.2 atm -2
P .PN 2
H2 1111.25
PN2 H4 0.75
K P2  2
  0.6 atm-2
PN 2 .P H2 111.25
1 3
K A 2 C2 = y – z = 1 -  atm.
4 4
 DPP-9
Gaseous State
SECTION - I: STRAIGHT OBJECTIVE TYPE

9.1 If density of vapours of a substance of molar mass 18 gm / mole at 1 atm pressure

and 500 K is 0.36 kg m-3 , then value of Z for the vapours is : (Take R = 0.082 L atm
mole K-1)
41 50
(A) (B ) (C) 1.1 (D) 0.9
50 41

9.2 Equal amount (mass) of methane and ethane have their total translational kinetic
energy in the ratio
3: 1 then their temperatures are in the ratio.
(A) 5 : 8 (B) 45 : 8 (C) 15 : 8 (D) 8 : 5

 nR 
9.3 Which of the following sketches is an isobar   1
 p 

9.4 For a certain gas which deviates a little from ideal behaviour, the values of density, p
were measured at different values of pressure, P. The plot of Pip on the Y-axis
versus P on the X-axis was nonlinear and had an intercept on the Y-axis, which
was equal to
RT M RT
(A) (B) (C) RT (D)
M RT V
Where M = molar mass.

9.5 A sample of water gas has a composition by volume of 50% H2, 45% CO and 5% CO2.
Calculate the volume in litre at S.T.P. of water gas which on treatment with excess of
stream will produce 5 litre H2. The equation for the reaction is : CO + H2O   CO2
+ H2
(A) 4.263 Litre (B) 5.263 Litre (C) 6.263 Litre (D) 7.263 Litre

9.6 Flask A of volume 10 liter containing 20 gram of H2

and flask B of volume 10 litre containing 88 gram CO2
are connected by a connector having negligible volume.
When valve of the connector is opened what is the
composition of H2 gas in flask B after openening the
valve.

(A) 10% (B) 13% (C) 15% (D) 20%

9.7 Consider the reaction, 2X(g) + 3Y(g)   Z(g)
Where gases X and Y are insoluble and inert to water and Z form a basic solution. In an
experiment 3 mole each of X and Y are allowed to react in 15 lit flask at 500 K. When the
reaction is complete, 5L of water is added to the flask and temperature is reduced to 300
K. The pressure in the flask is (neglect aqueous tension)
(A) 1.64 atm\ (B) 2.46 atm (C) 4.92 atm (0) 3.28 atm

9.8 Three gases A, B and C are at same temperature if their r.m.s speed are in the ratio
1 1
1: : then their molar masses will be in the ratio
2 3
(A) 1 : 2 : 3 (B) 3 : 2 : 1 (C) 1 : 2 : 3 (D) 3 : 2 :1

9.9 There are n containers having volumes V, 2V, ……, nV. A fixed mass of a gas is
filled in all containers connected with stopcock. All containers are at the same
temperature if pressure of first container is P then final pressure when all stopcocks are
opened is:
np 2np 3np np
(A) (B) (C) (D)
n(n  1) n(n  1) n(n  1) 2n(n  1)

9.10 SO2 and CH4 are introduced in a vessel in the molar ratio 1 : 2. The ratio of molecules
of two gases present in the container when their rate becomes equal is
(A) 1 : 2 (B) 2 : 1 (C) 4 : 1 (D)1:4

9.11 A mixture of two gases A and B in the mole ratio 2 : 3 is kept in a 2 litre vessel. A
second 3 litre vessel has the same two gases in the mole ratio 3 : 5. Both gas
mixtures have the same temperature and same total pressure. They are allowed to
intermix_the final temperature and total pressure are the same as the initial values, the
final volume being 5 litres. Given that the molar masses are MB and MB, what is the
mean molar mass of the final mixture?
77M A  123M B 123M A  77M B 77M A  123M B 123M A  77M B
(A) (B) (C) (D)
200 200 250 250

9.12 A 2 m long tube closed at one end is lowered

vertically into' water until the closed end is flush with
the water surface. See figure below. Calculate the water
level height in the tube. (Barometric pressure -1 atm =10
m of hydrostatic water head, Temperature = 25°C,
Density of, water = 1.00 g/ml. Neglect water vapour
pressure).

(A) 1.01 m (B) 0.29 m

(C) 1.71-m (D) 0.92 m
9.13 At a certain temperature for which RT = 25 lit. atm. mot -1 , the density of a gas, in gm
lit-1, is d = 2.00 P + 0.020 P2, where P is the pressure in atmosphere. The
molecular weight of the gas in gm mot -1 is
(A) 25 (B) 50 (C) 75 (D) 100

9.14 A mixture of carbon monoxide and carbon dioxide is found to have a density of 1.7
g/lit at S.T.P. The mole fraction of carbon monoxide is
(A) 0.37 (B) 0.40 (C) 0.30 (D) 0.50

9.15 If equal weights of oxygen and nitrogen are placed in separate containers of equal
volume at the same temperature, which one of the following statements is true?
(mol wt: N2 = 28, O2 = 32)
(A) Both flasks contain the same number of molecules.
(B) The pressure in the nitrogen flask is greater than the one in the oxygen flask.
(C) More molecules are present in the oxygen flask.
(D) Molecules in the oxygen flask are moving faster on the average than the ones in the
nitrogen flask.

9.16 The molecular radius for a certain gas = 1.25 A. What is a reasonable estimate
of the magnitude of the van der Wails constant, b, for the gas?
(A) 0.98 x 10-2 litre/mole (B) 1.43 x 10-2 litre/mole
(C) 1.97-x 10-2 litre/mole (D) 3.33 x 10-2 litre/mole

9.17 Given the value of their van der Wails' constant 'a' arrange the following gases
in the order of their expected liquification pressure at a temperature T. T is
below the critical point of all the gases.
Gas CH4 Kr N2 Cl2
-1
‘a’ (atmL2. Mol ) 2.283 2.439 1.408 6.579
(A) CH4 < Kr < N2 < Cl2 (B) N2 < CH4 < Kr < Cl2
(C) Cl2 < Kr < CH4 < N2 (D) Cl2 < N2 < Kr < CH4

9.18 The critical volume of a gas is 0.072 lit. mo1-1. The radius of the molecule will
be, in cm
1 1 1 1
 3 3  4π 3  3π 3  3 3
(A)  1023  (B)  1023  (C)  10 23  (D)  108 
 4π   3   4   4π 

9.19 The van der Waal's constant 'b' for N 2 and H 2 has the values 0.039 lit
moil -1 and 0.0266 lit mo1-1. The density of solid N2 is 1 g cm-3. Assuming the
molecules in the solids to be close packed with the same percentage void, the
density of solid H2 would be (in g cm-3)
(A) 0.114 (B) 0.682 (C) 1.466 (D) 0.071

9.20 Which of the following statements is not true?

(A) The ratio of the mean speed to the rms speed is independent of the
temperature.
 (B) The square of the mean speed of the molecules is equal to the mean squared
speed at a certain temperature.
(C) Mean kinetic energy of the gas molecules at any given temperature is
independent of the mean speed.
(D) The difference between rms speed and mean speed at any temperature for
different gases diminishes as larger if larger molar masses are considered.

9.21 If the number of molecules of SO2 (molecular weight = 64) effusing through an
orifice of unit area of cross-section in unit time at 0°C and 1 atm pressure is n.
The number of He molecules (atomic weight = 4) effusing under similar
conditions at 273°C and 0.25 atm is
n n
(A) (B) n 2 (C) 2n (D)
2 2

9.22 A capillary tube of uniform diameter contains gas samples A and B, separated
by a short column of Hg,  mm in length. The ends are sealed. In horizontal
position, the confined gases occupy 'a' mm and 'b' mm in length with a common
unknown pressure (P). In vertical position, the lengths become respectively a' mm
and b' mm. Then P is equal to
  a b b a
(A) (B) (C)     (D)    
b a a b  a' b'   b' a' 
     
 b' a'   a' b' 

9.23 Two glass bulb A and B are connected by a very small tube (of negligible
volume) having stop cock. Bulb A has a volume of 100 cm3 and contains certain
gas while bulb B is empty. On opening the stop cock, the pressure in 'A' fell
down by 60%. The volume of bulb B must be
(A) 200 mL (B) 150 mL (C) 250 mL (D) 100 mL

9.24 A certain gas effuses out of two different vessels A and B. A has a circular
orifice while B has a square orifice of length equal to the radius of the orifice of
vessel A. The ratio of rate of diffusion of the gas from vessel A to that from vessel
B is
(A) π : 1 (B) 1 : π (C) 1 : 1 (D) 3 : 2

9.25 If 1023 gas molecules each having a mass of 1a-25 kg, placed in a 1 L container,
moving with rms speed of 105 cm/sec. then the total KE of gasseous molecules and
pressure exerted by molecules, respectively are :
(A) 10 kJ, 3.33 × 106 Pa (B) 5 kJ, 3.33 × 108 Pa
7
(C) 10 kJ, 3.37 × 10 Pa (D) 5 kJ, 3.33 × 107 Pa
 SECTION - II: MULTIPLE CORRECT ANSWER TYPE

9.26 Following graph is constructed for the fixed amount of the gas.
(A) From 1 - 2 pressure will increase
(B) From 2 - 3 pressure remains constant
(C) Gas pressure at (3) is greater at state (1)\
(D) From 1 - 2 pressure will decrease

9.27 Which of following statements are correct

(A) Average velocity of molecules of a gas in a container is zero.
(B) All molecules in a gas are moving with the same speed.
(C) If an open container is heated from 300 K to 400 K the fraction of air which goes out
1
with respect to originally present is .
4
(D) If compressibility factor of a gas at STP is less than unity then its molar volume is less
thin 22.4 L at STP.

9.28 If the pressure of the gas contained in a closed vessel is increased by 20% when heated
by 273°C then it's initial temperature must have been.
(A) 1092°C (B) 1029 K (C) 1365°C (D) 1365 K

9.29 Two flask A and B have equal volumes. Flask A contains hydrogen at 600 K while flask
B has same mass of CH4 at 300 K. Then choose the correct options.
(A) In flask A the molecules move faster than B
(B) In flask B the molecules move faster than A
(C) Flask A contains greater number of molecules than B
(D) Flask B contains more molecules than A

9.30 There are three closed containers in which equal amount of the gas are filled.

If the containers are placed at the same temperatures then find the correct options:
(A) Pressure of the gas is minimum in (III) container
(B) Pressure of the gas is equal in (I) &, (II) container
(C) Pressure of the gas is maximum in (I)
(D) The ratio of pressure in II and III container is 3: 4
9.31 If the rms velocity of nitrogen and oxygen molecule are same at two different
temperature and same pressure then.
(A) Average speed of molecules is also same
(B) density (gm/It.) of nitrogen and oxygen is also equal.
(C) Number of moles of each gas is also equal.
(D) most probable velocity of molecules is also equal.

9.32 The pressure of 11 gm of a gas which is placed in a 4 litres container at 127°C is 2

atm, then the gas would be? (Take R = 0.08 Itr. atm/mol K).
(A) N2O (B) O3 (C) NO2 (D) CO2

9.33

With reference to the above graph, choose the correct alternatives

(A) PB > PA (B) PA > PB
(C) Pressure first increases then decreases (D) Pressure first decreases then
increases

SECTION -11I: ASSERTION AND REASON TYPE

9.34 Statement-1: The value of vender wail's constant (a) is larger for ammonia than for
nitrogen.
Statement-2: Hydrogen bonding is present in ammonia.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for
Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation
for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-2 is False, Statement-2 is True.

9.35 Statement-1: At constant temperature of pressure on the gas is doubled, Density is

also doubled.
Statement-2: At constant temperature molecular mass of a gas is directly proportional to
the density and inversely proportional to the pressure.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for
Statement-1.
 (B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation
for Statement-1.
(C) Statement-2 is True, Statement-2 is False.
(D) Statement-2 is False, Statement-2 is True.

9.36 Statement-1: At Boyle's temperature a real gas behaves as ideal gas for wide range of
temperature and pressure.
Statement-2: At Boyle's temperature vanderwaal constant 'a' and b compensate each
other.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for
Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation
for Statement-1.
(C) Statement-2 is True, Statement-2 is False.
(D) Statment-1 is False, Statement-2 is True.

9.37 Statement-1: The area under the maxwells distribution molecular speed curve remains
same irrespective of temperature of gas.
Statement-2: The fraction of molecules with most probable speed increases with
increase of temperature.
(A) Statement-2 is True, Statement-2 is True; Statement-2 is a correct explanation for
Statement-1.
(B) Statement-2 is True, Statement-2 is True; Statement-2 is NOT a correct explanation
for Statement-1.
(C) Statement-2 is True, Statement-2 is False.
(D) Statement-2 is False, Statement-2 is True.

9.38 Statement-1: Greater is critical temperature more easily a gas can be liquefied.
Statement-2: Critical temperature depends on the magnitude of intermolecular forces of
attraction between the gas.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for
Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation
for Statement-1.
(C) Statement-2 is True, Statement-2 is False.
(D) Statement-2 is False, Statement-2 is True.

SECTION - IV: TRUE AND FALSE TYPE

9.39 The correct order of True/False of the following statements is:

S1: Rate of diffusion and effusion of a gas increases by increasing the pressure and
decreasing the temperature.
S2: An ideal gas has Vander wail's constant a and b equal to zero.
 S3: If an ideal gas is expanded adiabatically against a constant pressure then
TV γ-1 = constant
(A)TTF (B) F F T (C) T TT (D) F F F

9.40 S1: Speed proceeds by maximum number of molecules of gas is called most
probable speed.
S2: Molecular speeds are function of temperature for a particular gas.
S3: If amount of gas increased than most probable speed also increased.
1
S4: The root mean square speed of an ideal gas is proportional to
d
(A)TTTF (B) F FT F (C) TTFT (D)TFTF

SECTION - V: COMPREHENSION TYPE

Comprehension #1
The system shown in the figure is in equilibrium, where A and B are isomeric
liquids and form an ideal solution at T.K. standard vapour pressure of A and B
are PA° and PB° respectively at TK. We collect the vapour of A and B in two
container of volume V, first container is maintained at 2TK and second container
3T
is maintained at K. At the temperature greater than TK, both A and B exist
2
in only gaseous form. Total vapour pressure of the system at TK is given as
PT = PA° XA + PB° XB
Where XA and XB are the mole fraction of A and B in liquid a mixture.
In container (1)
We assume that collected gases behave ideally at 2TK and there can take place
isomerisation reaction in which A converted into B by first order kinetics
Reaction is given as
K
A  B
In Container (II)
3T
At the given temperature , A and B are ideal in
2
nature and non mixing in nature. A small pin hole is
made into container. We can determine the initial
rate of effusion of both gases in vacuum by the
expression
kp
r=
m
Where P = pressure difference between system and
surrounding
K = positive constant
M = Molecular weight of the gas.
9.41 If partial vapour pressure of A is twice that of partial vapour pressure of B and
total V.P. is equal to 2T at T = 50 K and V = B.21 lit, then number of mole of A
and B in vapour phase is :
8 4
(A) , (B) 3, 1 (C) 2, 2 (D) 1, 3
3 3

9.42 Vapour is collected and passed into a container of volume 8.21 lit, maintainer at
8
50 K and after 5 min number of mole of B = . Then calculate pressure develop
3
into the container after two half lives.
(A) 2 atm (B) 4 atm (C) 1 atm (D) 0.5 atm

9.43 If vapour is collected in container of volume 8.21 lit maintained at 75 K then

ratio of initial rate of effusion of Gas A and B is given as:
(A) 2 : 1 (B) 1 : 2 (C) 4:1 (D) 1 : 4

Comprehension # 2
Gas 'A' (Molar Mass of A= 128 g mol-1) is taken in a closed container at the initial
total pressure of 1000 mm of Hg. Pressure of the gas decreases to 900 torr in 5
seconds due to the diffusion though square cross section. Another similar size
container is taken in which gaseous mixture of A and B are taken. (Molar mass of
472
the mix is ) at the total pressure of 5000 torr (molar mass of B = 72 g moll.
5
A rectangular cross-section is made in this container and gases are allowed to
duffuse. Width of this rectangular cross-section is same as the side of the
square cross section and length of the rectangular cross-section is 50% more
than the width. Assume that the gases A and B are non reacting and rate of
diffusion of the gases are only dependent upon the initial total pressure and it is
independent of the change in the pressure due to diffusion. Assume all other
conditions to be identical.

9.44 Gas diffused out initially from 2nd container has composition:
1 3 3 1 1
(A)  (B) XB = (C) XA = (D) XB =
A 7 5 3 4

9.45 Ratio of the number of moles of A and B left in the container after 10 seconds
from the diffusion starts is:
7 2 8 9
(A) (B) (C) (D)
9 3 11 13

9.46 What is the time after which container will have same number of moles of A and
B:
50
(A) 15 sec. (B) 50 sec. (C) 25 sec. (D) sec.
3
Comprehension # 3

When a sample of ideal gas is changed from an initial state to a final state,
various curves can be plotted for the process like P  V curve, V  T curve, P  T
curve etc.

For example, P  V curve for a fixed amount of an ideal gas at constant temperature
is a rectangular hyperbola, V  T curve for a fixed amount of an ideal gas at
constant pressure is a straight line and P  T curve for a fixed amount of an ideal
gas at constant volume is again a straight line. However, the shapes may vary if
the constant parameters are also changed.
Now, answer the following questions:

9.47 Which of the following statements is correct regarding

a fixed amount of ideal gas undergoing the following
process:

(A) Root mean square (RMS) speed of gas molecules

increases during the process A  B.
(B) Density of the gas increases during the process A
B.
(C) Such a graph is not possible.
(D) If PBS = PA, then VA = 4VB (where PA, VA, PBS & VB
represent pressure and volume values at states A and
B).

9.48 Two moles of an ideal gas is changed from its initial state (16 atm, 6L) to final
state (4 atm, 15L) in such a way that this change can be represented by a
straight line in P  V curve. The maximum temperature attained by the gas during
1
the above change is: (Take R = L atm K-1 mo1-1)
12
(A) 324 K (B) 648 K (C) 1296 K (D) 972 K

9.49 Which of the following graphs is not possible for a fixed amount of ideal gas
upon moving from initial state A to final state B:

(D) None of these

Comprehension # 4

In the Figure, isotherms of CO2 at several

temperatures near the critical point are shown. At
the critical point (critical state), the distinction
between the liquid and gaseous states disappear
and the density of the gaseous substance is equal
to that in the liquid state. For every gas this
occurs at specific values of temperature and
pressure, called critical temperature and critical
pressure respectively. At temperatures and
pressures above the critical point value, a gas is
said be in a supercritical state. Critical constants
are evaluated by solving the Vander Waals
equation which is a cubic in volume. The values
8a
are Tc = ,
27Rb
8a
Pc = , V c = 3b. (where a and b are Van Der Waals constants).
27b2
PV 3
At critical point Z = C C 
RTC 8
In the supercritical region the behaviour is studied by
plotting Z vs P plots. The variation in this region is
a
studied with respect to boyles temperature a (TB  ).
Rb
At temperature higher than CB the variation is linear
(Plot I) and at temperature lower than CB the variation
is non linear (Plot II)
With reference to the passage answers the following
questions:

9.50 For a real gas at a given temperature, which of the following facts is not
correct?
(A) PV may increase with the increase in pressure.
(B) PV may decrease with the increase in pressure
(C) PV will not change with the change in pressure
(D) PV will increase with the increase in pressure

9.51 In the figure representing variation of the compressibility factor z of a real gas
with pressure:
 (A) ab shows that the gas is more compressible than ideal gas
(B) bc shows that the gas is less compressible than ideal gas.
a
(C) bc may be explained by P V = RT -
V
(d) be may be explained by p V = RT + Pb

9.52 A gas at C2° is condensed to liquid following the path XYAB. The liquid
appears at the point:

(A) Y at C2° (B) A at C2° (C) B at C1° (D) A at C1°

9.53 Which statement(s) about the behaviour of a real gas is/are wrong?
(A) A gas exerts more pressure compaired to an ideal gas.
(B) A gas can be compressed more compaired to an ideal gas.
(C) A gas with high value of Vander wails constant, a is highly liquefiable.
(D) H2 and He are less compressible compaired to an ideal gas at ordinary

9.54 The figure shows the effect of pressure on the compressibility factor, Z of a gas :

The wrong conclusion(s) is/are:

(A) The curve AE can be explained by PV = RT
(B) The curve AF and CD can be explained by PV = KT + Pb
a
(C) The curve AB can be explained by PV = RT -
V
(D) All the three curves AF, AE and AD shows the real behaviour

9.55 Two vandaer waals gases have same value of 'a' but different value of b which
of the following statement is correct.
(A) The smaller the value of b larger will be compressibility
(B) The larger the value of b, larger will be compressibility
(C) Both have same compressibility
(D) All the with smaller value of b will occupy larger volume

9.56 Two Vander waals gases have same value 'b' but different 'a' value then which of
the following statement is correct under similar condition.
(A) Both gases will occupy same volume
 (B) Gas having a larger value of 'a' will occupy lesser volume
(C) Gas having a larger value of 'a' will occupy larger volume
(D) Can not be predicted

9.37 From the given plot between z and P for a real gas the correct is:

2a a a 2a
(A) T1 = (B) T2 = (C) T3 = (D) T4 =
Rb Rb Rb Rb

9.58 A gas can be condensed to liquid through the paths I, II, and Ill, as shown in figure.
The path(s) through which the gas changes to liquid abruptly is (are)

(A) I and II (B) II and III (C) I and III (D) II

Comprehension # 5
Sketch shows the plot of Z v/s P for of a hypothetical gas for one mole at three distinct
temperature.

Boyle’s temperature is the temperature at which a gas shows ideal behaviour over a pressure
a
range in the low pressure region. Boyle's temperature (Tb) = . If a plot is obtained at
Rb
temperatures well below Boyle's temperature then the curve will show negative deviation, in
low pressure region and positive deviation in the high pressure region. Near critical
temperature the curve is more likely as CO2 and the temperature well above critical
temperature curve is more like H2 at 0°C as shown above. At high pressure suppose all the
constant temperature curve varies linearly with pressure according to the following equation:
 pb
Z=1+ (R = 2 cal mol-1 K-1).
RT
9.59 Which of the following is correct:
a a
(A) < 0.4 k cal mol-1 (B) 0.4 k cal mol-1 < < 2 k cal mol-1
b b
a a
(C) < 0.4 k cal mol-1 (D) = 1 K Cal mol-1
b b

9.60 For 500 K plot value of Z changes from 2 to 2.2 if pressure is varied from 1000 atm to
b
1200 atm (high pressure) then the value of will be
RT
(A) 10-3 atm-1 (B) 2 × 10-3 atm-1 (C) 5 × 10-4 atm-1 (D) 10-4 atm1

9.61 As shown in the figure at 200 K and 500 atm value of compressibility factor is 2 (approx).
Then volume of the gas at this point will be
(A) 0.01 L (B) 0.09 L (C) 0.065 L (D) 0.657 L

9.62 Plot at Boyle's temperature for the gas will be

9.63 In very high pressure region if Z v/s P is plotted at 1200 K for the above gas then it will
have greatest slope.
(A) True (B) False
(C) Can't say (D) not related to the paragraph

SECTION - VI: MATRIX - MATCH TYPE

9.64 Match the following:

Column-I Column-II
2 -2
(A) H2 (a = 0.244 litre - atm mole ; (p) Maximum boiling point
b = 0.02 litre mole-1)
(B) He (a = 0.03412 litre2-atm mole-2; (q) Minimum boiling point
-1
b = 0.02370 litre mole )
(C) CO2 (a = 3.592 litre2 - atm mol-2; (r) Critical temperature < Boyle temp.
-1
b = 0.0426 litre mole )
(D) H2O (a = 5.464 litre2-atm mol-2; b = 0.03049 litre mole-1) (s) Minimum critical
temperature
9.65 For a fixed amount of the gas match the two column:

aolumn-I Column II

(P) T1 > T2 > T3

(q) p1 > p2 > p3

(r) V1 > V2 > V3

(s) d1 > d2 > d3

9.66 Match the following

Column I Column II

(p) Temperature is increasing

(q) Temperature is constant

(r) Volume is constant

(s) Pressure is increasing

9.67 Column I Column II
(A) An unknown gas at STP having (p) Behaves as an ideal gas Boyle's
temperature 0°C
(B) He gas at NTP having density less (q) Attractive tendencies are dominant
1
between molecules than g/L.
5.6
(C) H2 gas at NTP (r) Gas is less compressible with
respect to an ideal gas
0
(D) O2 gas at NTP having density g/L. (s) For gas, Critical temperature <
7
Boyle's temperature
(t) Molar volume of gas is greater
than 22.4 L

9.68 Match the column:

Assume the gas to be ideal and match the following :

Column-I Column-II
5
(A) K.E. of 4gram of Helium molecule (p) R
2
(B) Increase in the energy of 32 gram of oxygen (q) 3 R
Molecule on raising temperature
(C) Increase in energy of 1 mole of NO2 on raising (r) 4 R
Temperature by 1°C at constant volume
(D) Increases in energy of 1 mole of NO2 on raising (s) 1.5 RT
Temperature

SECTION - VII : SUBJECTIVE ANSWER TYPE SHORT SUBJECTIVE :

9.69 Calculate the change in pressure (in atm) when 2 mole of NO and 16 g O2 in a
6.25 litre originally at 27°C react to produce the maximum quantity of NO2
possible according to the equation.
1
(Take R = ltr. Atm/mol K)
12
2NO(g) + O2(g)  2NO(g)

9.70 2 moles of Ne gas and 5 moles of He gas, both samples having average velocity
7 × 102 mIs, are mixed. Find the average translational kinetic energy per mole of
the given gas mixture (in joules). Report your answer as 'X' where X = (Average
translational KE in joules) X 0.002. The reported answer should be upto nearest
integer.

9.71 A 1L gas mixture of CO, CO2 and N2 was mixed with 1L O2 and allowed to burn
completely. The product gas mixture, when passed subsequently through KOH
solution and alkalline pyragallol solution, suffered a total contraction of 1.6 L. On
 the other hand, if the product gas mixture was mixed with excess of CO gas
and again allowed to burn, the new product mixture suffered a contraction of 2.3
L on passing through KOH solution. Find the volume % of CO in the initial
mixture. Report your answer as 'Y' where Y = (Volume % of CO)/10.

9.72 A flask of 8.96 L capacity contains a mixture of N2 and H2 at 273 K and 1 atm
pressure. If the mixture is made to react to form NH3 gas at the same
temperature, the pressure in the flask reduces to 0.85 atm. Find the partial
pressure of NH3 gas in the final mixture in atm. Report your answer as 'y' where
y = (Partial pressure of NH3) × 20.

9.73 According to Maxwell's distribution of molecular speeds, the following graph has
been drawn for two different samples of gases A and B at temperature T1 and T2
respectively. Then, give the correct set of INCORRECT statements: Report your
answer as sum of the numbers of incorrect statements.
For example, if statements (1) & (2) are incorrect, then report answer as (1 + 2)
= 3.

(1) If T1 = T2, then gas B can be SO2 and gas A can be CO2.
(2) If gases A and B are CO2 & N2O, then T1 > T2.
(3) If T1 < T2, then gases A and B cannot be CO2 and SO2 respectively
(4) None of these

9.74 A vessel contains two gases A and B in the mass ratio 2: 1 respectively. If the
above gas mixture is allowed to diffuse through a hole, the molar composition of
the mixture coming initially out of the hole is 1 : 4. Find the simplest whole number
ratio of the mole fractions of gases A and B present in the vessel in the beginning
respectively. If the simplest whole number ratio is a : b, then report your answer
a
as 'X' where X =   × 6
b
 LONG SUBJECTIVE:

9.75 A bulb of constant volume is attached to a

manometer tube open at other end as shown in
figure. The manometer is filled with a liquid of density
(1/3)rd that of mercury. Initially h was 228 cm. Through
a small hole in the bulb gas leaked causing pressure
dp
decrease as = - kP. If value of h is 114 cm after 7
dt
minutes. Calculate value of k in units of hour-1.
(Report answer in multiple of 10-1)
[Use : in (4/3) = 0.28 & density of Hg = 13.6 g/ml]

9.76

If above tube is placed vertically with the open end upward then find the
length of the air column.

9.77 The pressure exerted by 12 g of an ideal gas at temperature t° C in a vessel

of volume V litre is one atm .When the temperature is increased by 10 degree at
the same volume, the pressure increases by 10%. Calculate the temperature t
and volume V. (Molecular weight of the gas = 120)

9.78 The density of the vapours of a substance at 1 atm pressure and 500 K is 0.36
Kg m-3.The vapour effuses through a small hole at a rate of 1.33 times faster
than oxygen under the same conditions.
Determine (i) molecular weight (ii) molar volume (iii) compression factor(z) of the
vapours and (iv) which forces among gas molecules are dominating, the
attractive or repulsive.
If the vapours behave ideally at 1000 K determine the average translational
kinetic energy of a molecule
9.79 In a tyre of "Ferrari" car of Mr. Obama, a tube having a volume of 12.3 litres is
filled with air at a pressure of 4 atm at 300 K. Due to travelling, the temperature
of the tube and air inside it raised to 360 K and pressure reduced to 3.6 atm in 20
minutes. If the porosity (number of pores per unit area) of the tube material is 5 × 105
pores/cm2 and each pore can transfer air from inside to outside of the tube with
the rate of 6.023 × 108 molecules per minute. Calculate the total surface area
(m2) of the tube. (R = 0.082 Lt - atm / mole – K)
 9. GASEOUS STATE
Molar mass 18
9.1 (B) Vreal =  .
density 0.36
nRT 1 0.082  500
Videal =  .
P 1
V 50 50
So, Z = real   .
Videal 0.082  500 41

3 M
9.2 (D) E1 =  RT1
2 30
3 M E1 30 T1 3 30 T1
E2 =  RT2    
2 30 E 2 16 T2 1 16 T2
T1 8
 
T2 5

9.3 (B) At constant pressure

PV = nRT.
 nR   nR 
V=   T So, log V = log   + log T.
 P   P 

9.4 (A) For constant pressure V α T, hence linear dependence with the slope

9.5 (B) Let suppose we use x-litre water gas at S.T.P.

So it contain 0.5x litre H2.
Now according to given equation
CO + H2O   CO2+ H2
0.45x Excess 0.05x 0.5x
0  (0.05x + 0.45x) (0.5x + 0.45x)
So total volume of H2 = 0.95x
But according to question
It is 5 litre
So 0.95x = 5
x = 5.263 litre

9.6 (B)

Thermo state at 500 K Thermo state at 200 K

20
No. of mole of H2 in flask A = = 10 mole
2
 88
No. of mole of CO2 in flask B = = 2 mole
2
Now pressure of Gas in flask A
PV = nRT
PA x 10 = 10 x R x 500
PA = 500 R
Now pressure of Gas in flask B
PB x 10 = 2 x R x 200
PB x 40R
Because flask A is on higher pressure that why H2 is flow from flask A to
flask B.
Let suppose x mole of H2 move from flask A to B.
So mole of H2 remain in A = (10 – x) and total mole in B = (2 + x)
Now after opening stop cock pressure of both flak become equal.
nA TA = nB TB
(10 – x) x 500 = (2 + x) x 200
x= 6.57
6.57 x 2
Composition of H2 in B = x 100 = 13%.
101.14

9.7 (B) 9.8 (A) 9.9 (B) 9.10 (B)

9.11 (A)

nA 2 n A' 3
 
nB 3 n B' 5
nA = 2/3 nB nA’ = 3/5 nB’
Put the value of nA’ nB” nA’ and bB’ and get.

Mean molar mass = A

 n  n A'  m A   n B  n B'  m B
 n A  n B  nA'  n B' 

9.12 (8) Applying boil's law.

P1V1 = P2V2
10Pw.2 = (10 + h) pw h = 1.7 m
High of water level in the tube = 2 – h = 2 - 1.71 = 0.29 m

9.13 (B) PV = nRT

nR
V= .T  V = KT
P
 log P = log T + log K
 Linear dependence with positive slope
At the Y-intercept P/ T 0 and p  0 inplying p  0, under such
conditions all gases show ideal behavour.

PM mix 1.7  0.0821 273

9.14 (A) Pmix =  Mmix = 1.7  22.4gms
RT 1
Mmix = XCO × MCO + (1 – XCO). M CO2
= XCO × 18 + (1 – XCO) × 44
 XCO = 0.37

9.15 (B)

16 3
9.16 (C) b= πr  N a
3

9.17 (C)

16 3
9.18 (A) b= πr  N a
3
16
0.72 × 1000 = × 6.023 × 1023 × πr 3
3
Calculate r.

9.19 (A) For equal weights, N2 will have more number of moles and hence
more molecules.

9.20 (B) 9..21 (A) 9.22 (A) 9.23 (B)

9.24 (A) Under different conditions of pressure and temperature.

PA r1 P1 A1 T2 M 2
rate α  
T.M. r2 P2 A 2 T1M1

9.25 (B) According to KTG

1 1 1
PV = mN (Vms)2 so p= × 106 Pa and KET = m (Vms)2 × N = 5 KJ
3 3 2

9.26 (A, B, C)
V-T curve for a given mass of gas is given
9.27 (A, C, D)

P 1.2 P
9.28 (A, D) 
t  273 t  273  2

9.29 (A, C, D)
P 1.2 P

t  273 t  273  2
 Vrms N 2
=  Vrms O
2

1.2t + 273 × 1.2 = t + 273 × 2

 0.2 t = 273 × 0.8
t = 273 × 4

9.30 (A, C, D)

9.31 (A, B, D)  Vrms  N =  Vrms O

2 2

3RTN2 3RTO2 TN2 TO2

 
M N2 M O2 M N 2 M O2
Then Vav and Vmps is also same
PN M N2 PO M N 2
d N2  2 d O2  2 if PN 2  PO2 then d N 2  d O2
RTN2 RTO2

9.32 (A, D)
W
PV = RT
M
WRT 11x 0.08 x 400
M= = = 44
PV 2x4
Gases are N2O & CO2

9.33 (B, C) At const temperature V α 1/p

9.34 (A) 9.35 (D) 9.36 (A) 9.37 (D) 9.38 (A)

P  Pressure 
P A  Area of hole 
9.39 (A) 1. Rate of diffusion  A   True
TM T  Temperature 
M  Molecular wt.
2. For ideal gas PV = nRT [a = 0, b = 0]  True
3. The process is irreversible adiabatic  PV γ 1  constant
9.40 (C) 1. See maximum wells distribution of speed curve.
2. C = f(T)
3. Depends only on temperature
3p
4. Crms =
d

9.41 (A) PT = PA + PB = 3PB

2 2 4
So, Pa = and PA = 2 - =
3 3 3
P n
Now A  1  2
PA n 2
So, n1 = 2n2 … (1)
PTV = nT RT
2 x 8.21 = nT x 0.082 x 50
nT = 4 = n1 + n2
4 8
So, n2 = n1 =
3 3

9.42 (A) A   B
8 4
t=0
3 3
4 8
t = 5 min
3 3
Now a after two half life
2 10
nA = and nB =
3 3
PTV = (nA + nB)RT
12
PT x 8.21 = x 0.082 x 50
3
PT = 2 atm

rA PA MB
9.43 (A) 
rB PB MA
rA n A M B (8 / 3) 1
 
rB n B M A (4 / 3) 1
rA
= 2.
rB

n A / t PA MB n1M1  n 2 M 2
9.44 (C)   M mix
n B / t PB MA x1  x 2
X1M1 + (1 – X1)M2 = Mmix
 2 3
 X1 = , x2 
5 5
X A 2 72 1
  
X B 3 128 2
1 2
 XA = , XB =
3 3

1000  900
9.45 (A) Initially rA = = 20 torr/s
5
In the mix.
Mmix = XAMA + (1 – XA)MB
472
 = XA x 128 + (1 – xA) 72
5
472
= 56XA + 72
5
472 = 280XA + 360
12 2 3
XA = = , XB =
280 5 5
The mix.
rA 1 x2 1
 x 
r'A 2 x x 3x 3
2
rA’ = 3rA = 3x 20 = 60 torr/s
rA' 0 PA' M B 2 72 1
'
 '  x 
rB0 PB M A 3 128 2
rB' = 120 torr/s
After 10 sec
PA" = 2000 – 60 x 10 = 1400 torr
PB" = 3000 – 120 x 10 = 1800 torr
n "A 7

n"B 9

9.46 (D) 2000 – 60t = 3000 – 120 t

50
60t = 1000  t= sec.
3

9.47 (B) (A) Temperature decreases A to B, so RMS speed decreases

(VRMS  T )
PM
(B) dgas = . Upon moving from A to B, K increases and temperature
RT
decreases. So, density of gas increases.
 1
(C) This graph is possible if during the process: P  .
V1/2
 PV 
 PT = Constant  P  = Constant  P2V = Constant or PV1/2
 nR 
= Constant
(D) If PB = 4PA, then VA = 16VB (according P2V = Constant for process).

9.48 (B) Equation of straight line

 y y 
(y – y1) =  2 1  (x – x1)
 x 2  x1 
 4  16 
 (P – 16) =   (V  6)
 15  6 
 3P + 4V = 72
(PV)max
Tmax =
nR
72 72
For (PVmax’ 3P = and 4 V =
2 2
 P = 12, V = 9
12  9
 Tmax =  648K.
1 (1/12)

9.49 (D) (A) This graphs is possible if temperature of gas is kept constant and
pressure is increased from A to B.
(B) This graphs is possible if temperature of gas is increased continuously
during the process A to B.
1
(C) This graphs is possible if during the process: P  2
V
 PV 
 VT = constant  V  = Constant or PV2 = constant.
 nR 
9.50 (C) 9.51 (A, B, C, D) 9.52 (D) 9.53 (A, B) 9.54 (D)

9.55 (A) 9.56 (B) 9.57 (B) 9.58 (B)

9.59 (B) 200 < TB < 1 000

a
 200 < < 1000
Rb
a
 400 cal < < 2000 cal
b
9.60 (A) In the high pressure region
Rb
z= +
RT
solve for the two points.
 PVM z.RT
9.61 (C) Use z =  Um =
RT P

9.62 (C) At boyles temp, a real gas shows ideal behaviour in the low pressure region.

1  Pb b
9.63 (B) z= , slope z and hence is inversely proportional to T.
RT RT

9.64 (A – r), (B – q, r, s), (C – r), (D – p, r).

9.65 (A – p, r), (B – q, s), (C – r), (D – p, s)

9.66 (A – p, s), (B – p, r, s), (C – q), (D – p, r, s)

9.67 (A – p, s), (B – r, s, t), (C – r, s, t), (D – p, s)

9.68 (A – s), (B – p), (C – q), (D – r)

4
(A) 4 g of the He = 1 mole
4
3 3
KE =  nRT =  R  T  1.5 RT
2 2
32
(B) 32 gram of O2 = = 1 mole
32
KE = KE (Translational) + KE rotational
3 2  RT
RT + (Two rotational degree of freedom)
2 2
(C) NO2 is triatomic and non linear molecule and thus possesses three
translational and three rotational degree of freedom vibrational degree
of freedom do not contribute at ordinary temperature
(D) At constant pressure increase in energy = Δ E + P Δ V = 3R + R = 4R

9.69 2NO(g) + O2(g) 2NO2(g)

Moles 2 0.5 0
2 – 2 × 0.5 0 2 × 0.5
1 0 1
Nf = 1 + 1 nf = 2 + 0.5
 Δ n = (2.5 – 2) = 0.5 moles
 Change in pressure
ΔnRT 1 300
Δp =  0.5    2atm.
V 12 6.25

9.70 Average Translational kinetic energy (per mole of gas)

3 3M RT 3πM 8RT
= RT =  = 
2 2 M 16 πM
 2
3πM  8RT  3πM
=      (Vav )2
16  πM  16
 For one mole of gas mixture,
Average translational kinetic energy
3πM mix
=  (Vav )2
16
3 22  (2  20  5  4) / 7 
=     (7 102 )2 [M mix is in Kg/mole]
16 7  1000 
= 2475 Joules.
Reported answer = 2475 × 0.002 = 4.95  5.

9.71 Let volume of CO, CO2 and N2 in the initial mixture be xL, yL and (1 – x – y)L
respectively.
Upon mixing 1L O2 and burning, CO will combine with O2 to form CO2O
1
CO + O2   CO 2
2
x
xL xL
2
 Product gas mixture will be composed of CO2 produced, CO2 initial, unreacted N2 and
 x
left O2 having volume xL, yL, (1 – x – y)L and 1   L .
 2
Upon passing subsequently through KOH solution and alkalline pyragallol, all CO2 and O2
will be absorbed.
x
 x + y + 1 - = 1.6  x + 2y = 1.2 ... (1)
2
On mixing the product mixture with excess CO, whole of unreacted O2 via convert into
CO2
1
CO + O2   CO2
2
 x  x
1   L 2  1   (2 – x)L
 2  2
 Total CO2 in the final gas mixture = (x + y) + (2 - x) = 2.3
 y = 0.3
Put y = 0.3 in equation (1)
 x = 0.6
0.6
 Vol % of CO in original mixture = × 100 = 60%.
1
 Reported answer = 60/10 = 6.

9.72 N2 + 3H 2   2NH3
t = 0 aatm batm 0 (At constant V & T, n  P)
t = f (a – x)atm (b – 3x)atm (2x)atm
 a + b = 1 and (a – x) + (b – 3x) + 2x = a + b – 2x = 0.85
 2x = 0.15
 y = Partial pressure of NH3 = 2x = 0.15 atm
 y = (Partial pressure of NH3) × 20 = 0.15 × 20 = 3.
9.73 At constant temperature, decreases in molecular masses causes flattening of
the graph. For same molecular mass of gas, increase in temperature causes
flattening of the graph.
From the above graph.
V  V 
mp T
1
mp T
2

T1 T T M
 2  2 B
 M A M B T1 M A
MB
But may be less than or greater than 1.
MA
 Statements (1), (2) & (3) are wrong
 Reported answer = 1 + 2 + 3 = 6.

rA n A MB
9.75  
rB n B MA
2x
 (Moles of A coming out initially) t = M A  M B
(Moles of B coming out initially / t 1x MA
MB
3/2
  MB 1
 1  2  MB   
4 1  MA  MA 4
 nA   2x 
  n M  2M
 Ratio of Mole fractions = X A   n A  n B  A  A  B

XB  n B  nB  1x  MA
 n n  M 
 A B   B 
1 1
=2× 
4 2
 Reported answer =  1   6  3
2

9.75 P = P0e-kt
228
P0 =  76  152 cm Hg.
3
At t = 7 min.
114
P= + 76 = 114 cm gh
3
 152e-kt = 114
1 152 1
 k = In  × 0.28 = 0.04 min-1 = 0.04 × 60 hr-1 = 2.4 hr-1]
t 114 7
9.76 P1 = 75 cm of Hg, V1 = 30 × A
20.4 10
P1 = 75 + 10 + = 100 cm of Hg
13.6
 75 × 24 = 100 × x
x = 18 cm

9.77 PV = nRT
1
1×V= × R × (t + 273)
10
There pressure now is 1.1 atm.
1
 1.1 × U  R (t  283)
10
Solve for ‘v’ and ‘t’
Ans. 100K, 0.82 litre

9.78 (a) 18.1, 50.25 × 10-3 m-3, 1.225 (b) 2.07 × 10-20 J
P = 1atm T = 500 K, d = 0.36 kg nr3
rvapour
 1.33
rO2
rvapour m O2
(i) molecular weight = 
rO2 m vapour
32
 1.33 =
m vapour
molecular weight
 
(ii) Molar volume V 
density of vapour
pv
(iii) Compression factor z =
RT
(iv) Here z > 1, then repulsion force is more dominating
(v) Translational kinetic energy = 3/2 KT
= 3/2 × 1.23 × 10-23 × 1000

4 12.3
9.79 Initial moles of air inside the tube = 2
0.082  300
3.6 12.3
Moles of air after 20 minutes = 1.5
0.082  360
 Moles of air leaked in 20 minutes = 2 - 1.5 = 0.5
 Molecules of air leaked in 20 minutes = 0.5 NA
Let the total surface area of tube = A cm2
Total molecules escaped in 20 minutes = (5 × 105) A × 6.023 × 108 × 20
= 0.5 NA
0.5  6.0231023
 A= 5  107 cm2 5000 m2
5 105  6.023108  20
 DPP-10
Atomic Structure
SECTION – I: STRAIGHT OBJECTIVE TYPE

10.10 Probability of finding the electron' mg of’s’ orbital doesn't depend upon –
(A) Distance from nucleus (r) (B) Energy of’s’ orbital
(C) Principal quantum number (D) Azimuthal quantum number

10.2 For a hypothetical H like atom which follows

Bohr's model, some spectral lines were
observed as shown. If it is known that line 'E'
belongs to the visible region, then the lines
possibly belonging to ultra violet region will be
(n1 is not necessarily ground state)
[Assume for this atom, no spectral series shows
overlaps with other series in the emmission
spectrum]

(A) B and D (B) D only

(C) C only (D) A only

10.3 The number of photons emitted in 10 hours by a 60W sodium lamp ( λ , of

photon = 6000 Å)
(A) 6.50 × 1024 (B) 6.40 × 1023 (C) 8.40 × 1023 (D) 3.40 × 1023

[Take he = 12400 EvÅ, h = Planck's constant, c = speed of light]

10.4 Radius of 3rd orbit of Li2+ ion is ‘ x ’ cm then de-broglie wavelength of electrons
in the 1st orbit is
2πx 2πx
(A) cm (B) 6 π x cm (C) 3 π x cm (D) cm
3 6

10.5 Ratio of frequency of revolution of electron in the 2nd excited state of He and 2nd
state of hydrogen is:
32 27
(A) (B) (C) 1/54 (D) 27/2
27 32

10.6 In any subshell, the maximum number of electrons having same value of spin
quantum number is:
(A)  (  1) (B)  + 2 (C) 2  + 1 (D) 4  + 2

10.7 A proton accelerated from rest through a potential difference of 'V' volts has a
wavelength λ associated with it. An alpha particle in order to have the same
wavelength must be accelerated from rest through a potential difference of
V
(A) V volt (B) 4V volt (C) 2V volt (D) volt
8
10.8 Consider the ground state of Cr atom (Z = 24). The numbers of electrons with
the azimuthal quantum numbers,  = 1 and 2 are, respectively:
(A) 16 and 5 (B) 12 and 5 (C) 16 and 4 (D) 12 and 4

10.9 Number of electrons having  + m value equal to zero in 26Fe may be

(A) 13 (B) 14 (C) 7 (D) 12

10.10 4000 A photon is used to break the iodine molecule, then the % of energy
converted to the K.E. of iodine atoms if bond dissociation energy of I2 molecule
is 246.5 kJ/mol.
(A) 8% (B) 12% (C) 17% (D) 25%

SECTION - II: MULTIPLE CORRECT ANSWER TYPE

10.11 If the wave number of 1st line of Balmer series of H-atom is 'x' then:
108 x
(A) wave number of 1st line of lyman series of the He+ ion will be
5
36 x
(B) wave number of 1st line of lyman series of the He ion will be
5
5
(C) the wave length of 2nd line of lyman series of H-atom is
32 x
32 x
(D) the wave length of lyman series of H-atom is
5

10.12 The wave functions of 3s and 3pz orbitals are given by

1/2 3/2
1  1   z   4zr 4 z 2r 2   zr/3a 0
ψ 3s =     6  e
9 3  4π   a 0   a 0 9 a 02 
1/2 3/2
1  3   z   2zr  2zr   zr/3a0
    4  e cos θ
9 6  4π   a 0   3a 0  3a 0 
from these we can conclude
(A) number of nodal surface for 3pz & 3s orbitals are equal
(B) the angular nodal surface of 3pz orbital has the equation θ = π /2
(C) The radial nodal surfaces of 3s orbital and 3pz orbitals are at equal distance
from the nudes
(D) 3s electron have greater penetrating power into the nucleus in comparison to
3p, electrons

10.13 In a hydrogen like sample electron is in 2nd excited state, the Binding energy of 4th
state of this sample is 13.6 eV, then
(A) A 25 eV photon can set free the electron from the second excited state of
this sample.
 (B) 3 different types of photon will be observed if electrons make transition up to
ground state from the second excited state
(C) If 23 eV photon is used then K. E. of the-ejected electron is 1 eV.
(D) 2nd line of Balmer series of this sample has same energy value as 1st
excitation energy of H-atoms.

10.14 1st excitation potential for the H-like (hypothetical) sample is 24 V. Then:
(A) Ionisation energy of the sample is 36 eV (B) Ionisation energy of the sample
is 32 eV
(C) Binding energy of 3rd excited state is 2 eV (D) 2nd excitation potential of the
32 x 8
sample is V
9

10.15 A hydrogen like atom in ground state absorbs 'n' photons having the same energy
and it emits exactly 'n' photons when electronic transition takes place. Then the
energy of the absorbed photon may be
(A) 91.8 eV (B) 40.8 eV (C) 48.4 eV (D) 54.4 eV

10.16 In a hydrogen like sample two different types of photons A and B are produced by
electronic transition. Photon B has it's wavelength in infrared region if photon A has
more energy then B, then the photon A may belong to the region.
(A) ultraviolet (B) visible (C) infrared (D) None

10.27 Hydrogen atoms in a particular excited state 'n', when all returned to ground
state, 6 different photons are emitted. This of the following is/are incorrect.
(A) Out of 6 different photons only 2 photons have speed equal to that of
visible light.
(B) If highest energy photon emitted from the above sample is incedent on the
metal plate having work function 8 eV, AKE of liberated photo-electron may
be equal to or less than 4.75 eV.
(C) Total number of radial nodes in all the orbitals of nth shell is 24.
(D) Total number of angular nodes in all the orbitals in (n-1)th shell is 23.

10.18 In a H-like sample electrons make transition from 4th excited state to 2nd state
then
(A) 10 different spectral lines are observed
(b) 6 different spectral lines are observed
(C) number of lines belonging to the balmier series is 3
(D) Number of lines belonging to paschen series is 2.

SECTION - III: ASSERTION AND REASON TYPE

10.29 Statement-1: 'He' has lowest ionisation energy among all the elements.
Statement-2: Addition of extra electrons even in fully filled orbitals releases
energy
 (A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct
explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct
explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

10.20 Statement-1: If an electron is located within the range of 0.2 Å then the
uncertainty in velocity is approximately 6 × 206 m/s.
Statement-2: Trajectory (path of motion) of above electron can be defined.
[h = 6.6 × 20-34, me = 9.2 × 20-31 kg]
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct
explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct
explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

SECTION - IV: COMPREHENSION TYPE

Comprehension # 2
If hydrogen atoms (in the ground state) are passed through an homogeneous
magnetic field, the beam is split into two parts. This interaction with the
magnetic field shows that the atoms must have magnetic moment. However,
the moment cannot be due to the orbital angular momentum since  = 0.
Hence one must assume existence of intrinsic angular momentum, which as
the experiment shows, has only two permitted orientations.

h
Spin of the electron produces angular momentum equal to S = s (s  1)
2π
1
where S = .
2
n n
Total spin of an atom = + or 
2 2
Where n is the number of unpaired electron.
The substances which contain species with unpaired electrons in their orbitals
behave as paramagnetic substances. The paramagnetism is expressed in
terms of magnetic moment.
The magnetic moment of an atom
eh n  n  eh n
μ s  s(S +1)    1 s=
2πmc 2  2  2πmc 2
 μ s  n(n + 2) B.M
n - number of unpaired electrons
 eh
1. B.M. (Bohr magneton) =
4πmc
If magnetic moment is zero the substance is di-magnetic.

10.21 Which of the following ion has highest magnetic moment.

(A) Fee+ (B) Mn2+ (C) Cr3+ (D) V3+

10.22 If an ion of 25Mn has a magnetic moment of 3.873 B. M. Then Mn is in which

state.
(A) + 2 (B) + 3 (C) + 4 (D) + 5

10.23 Which of the following is a paramagnetic substance.

(A) Mg2+ (B) Cu+ (C) Mn+7 (D) Ti+2

10.24 The number of unpaired electrons in Mn4+ (Z = 25) is –

(A) Four (B) Two (C) Five (D) Three

Comprehension # 2
The French physicist Louis de Broglie in 1924 postulated that matter, like
radiation, should exhibit a dual behaviour. He proposed the following relationship
between the wavelength λ of a material particle, its linear momentum p and
planck constant h.
h h
λ = 
p mv

The de Broglie relation implies that the wavelength of a particle should decrease
as its velocity increases. It also implies that for a given velocity heavier particles
should have shorter wavelength than lighter particles. The waves associated
with particles in motion are called matter waves or de Broglie waves. These
waves differ from the electromagnetic waves as they
(i) have lower velocities
(ii) tame RE electrical and magnetic fields and
(iii) are not emitted by the particle under consideration.
The experimental confirmation of the de Broglies relation was obtained when
Davisson and Gerber, in 1927, observed that a beam of electrons is diffracted by
a nickel crystal. As diffraction is a characteristic property of waves, hence the
beam of electron behaves as a wave, as proposed by de broglie.

10.25 If proton, electron and a-particle are moving with same kinetic energy then the
order of their de-Broglie's wavelength.
(A) λ p > λ e > λ a (B) λ a > λ p > λ e (C) λ a < λ p < λ e (D) λ e = λ p < λ a

10.26 Using Bohr's theory, the transition, so that the electrons de-Broglie
wavelength becomes 3 times of its original value in He+ ion will be
(A) 2 
 6 (B) 2   4 (C) 1   4 (D) 1   6
10.27 De-Broglie wavelength of an electron travelling with speed equal to 1% of the
speed of light
(A) 400 pm (B) 120 pm (C) 242 pm (D) 375 pm

Comprehension #3
If an electron is in any higher state n = n and makes a transition to ground
n  (n  1)
state, then total no. of different photons emitted is equal to .
2
If an electrons is in any higher state n = n2 and makes a transition to another
excited state n = n1, then total no. of different photons emitted is equal to
Δn (Δn  1)
, where Δ n = n 2 – n 1 .
2

Note: In case of single isolated atom if electron make transition from nthstate to the
ground state then max. number of spectral lines observed = ( n – 1).

10.28 Two samples are taken, in 1st sample mole ratio of H to H+ is 1: 2. In IInd
sample mole ratio of H to He+ is 2: 1. If n1 is number of spectral lines produced
by 1st sample and number of spectral lines produced by lino sample is n2 then n1:
n2 will be –
(There is sufficient number of both types of atom and both are in same excited
state in both sample)
(A) 2 : 1 (B) 1 : 2 (C) 1 : 1 (D) None of these

10.29 Which of the following statements is/are true?

(I) If H atoms are in 3rd state then number of maximum spectral line produced by 2 atoms will
be equal to number of maximum spectral lines produced by 3 H-atoms
(II) For third excited state, maximum number of spectral line produced by He+ and
maximum number of spectral line produced by 4 H  atom are not equal.
(III) Energy evolved from 3 to 2 transitions in He cannot used for any transition in Li2+.
(A) I & III (B) II & III (C) All (D) I & II.

10.30 In a sample one H atom is in 1st excited state, two He+ ions is in IInd excited state and three
Li2+ ions is in Illrd excited state are present then maximum, number of spectral line which can
be obtained when all possible transition terminated at n = 1.
(A) 11 (B) 12 (C) 13 (D) 17

SECTION - V: MATRIX - MATCH TYPE

10.31 Match the following:

Pn = potential energy, En = total energy
f = frequency, Z = atomic number
vn = velocity in nth orbit
Tn = time period in nth orbit
 Column I Column II
(A) En α r y , y =? (p) 1/2
(B) En/Pn (q) 1
1
(C)  x αz, x  ? (r) 2
fn
(D) (vn × Tn)t α rn , t =? (s)  1

10.32 Match the following:

B.E.  Binding energy
I.E.  Ionization energy:
Column I Column II
(A) of He atom in an excited state (p) Infrared region
(B) 7  3 transition in H-atom (q) 3.4 eV
(C) 5  1 transition in H-atom (r) 13.6 eV
(D) Series limit of Balmer series in H-atom (s) 10 Spectral lines observed

10.33 Match the following:

Column I Column II
(A) n = 6  n = 3 (In H-atom) (p) 10 lines in the spectrum
(B) n = 7  n = 3 (In H-atom) (q) Spectral lines in visible region
(C) n = 5  n = 2 (In H-atom) (r) 6 lines in the spectrum
(D) n = 6  n = 2 (In H-atom) (s) Spectral lines in infrared region

SECTION - VI: SUBJECTIVE ANSWER TYPE

SHORT SUBJECTIVE:

10.34 Find out the number of waves made by a Bohr electron in one complete
revolution in its 3rd orbit.

10.35 In the assembly as shown below, the potential

difference across the plates is 4 volts. A positive particle
of charge +4e is projected from the negative plate with an
initial kinetic energy of 4eV and the negative particle of
charge (-2e) is projected from'the positive plate. Both the
particles reach point 'A' with zero kinetic energy.
Find the initial kinetic energy of the negative particle in eV.

10.36 Electrons in a sample of H  atoms make transitions from state n = x. to

some lower excited state. The emmission spectrum from the sample is found to
contain only the lines belonging to a particular series. If one
 Of the photons had an energy of 0.6375 eV. Then find the value of ×. [Take
3
0.6375 eV = × 0.85eV]
4

10.37 Find the number of electrons in chromium (24Cr) which have orbital angular
h
momentum equal to .
2π

10.38 A hydrogen like atom (atomic; number Z) is in a higher excited state of quantum
number n. This excited atom can make a transition to the first excited state by
successively emitting two photons of energies 10.20 eV and 17.00 eV
respectively. Alternatively, the atom from the same excited state can make a
transition to the second excited state by successively emitting two photons of
energy 4.25 eV and 5.95 eV respectively. Determine the values of n and Z
(ionisation energy of hydrogen atom = 13.6 eV).

LONG SUBJECTIVE:

10.39 In a sample of hydrogen atom in ground state electrons make transition from
ground state to a particular excited state where path length is five times de-
broglie wavelength, electrons make back transition to the ground state producing
all possible photons. If photon having 2nd highest energy of this sample can be
used to excite the electron in a particular excited state of Li2+ atom then find the
final excited state of Li2+ atom.

10.40 A chemist has one mole of H-atom. He finds that on absorption of 410 kJ, half
of X-atoms transfer one electron to the other half. If all the resulting X- ions are
subsequently converted to X+ ions, an addition of 735 kJ is required. Find the
electron affinity of X.

3/2 r
1  1  r   a0
10.41 (a) The wave function of 2s electron is given by ψ2s     2   .e
4 2π  a 0   a0 
It has a node at r = r0, find relation between r0 and a0.
(b) Find wavelength for 100 g particle moving with velocity 100 mis.

10.42 The radial wave function for 1s orbit for a single electron specie is given by
2Zr
ψr  k e  σ/2 where σ = and K is constant [a0 = radius of first Bohr's orbital in H-
na 0
atom = 52.9 pm, n = Principal quantum number. Calculate the most probable
distance of 1s electron in Be3+ ion. Give your answer in the form most probable
distance in pm × 1000?
10.43 (a) Calculate the number of radial nodes and angular nodes in 4d orbital.
(b) Write all four quantum numbers of 12th electron of Mg atom.
(c) Calculate spin only magnetic moment (in unit of Bohr magneton) of Co3+.

10.44 The famous alien Jadu on his visit to our planet earth brought a sample containing 100
identical H-like atoms (hypothetical atoms, Z can be fractional) from his planet. He gave
these atoms to Rohit (Hritik Roshan) asking him to analyze them. He further gave Rohit
the following information:
1. Out of the given atoms, some are in ground state and some others are in a higher energy
level (n = x) and the potential energy of electron in the ground state of given atom is  192
eV.
2. When the sample is exposed to radiations of wavelength 155 nm, the electrons jump to
another higher energy level (n = x + 3). Upon back-transition upto ground state, a total of
10 different spectral lines are produced.
Then, Jadu asked Rohit two questions:
(a) “What is the final state in which the electrons move after absorbing photons of
wavelength 155 nm?"
(b) “What is the maximum number of atoms which had their electron in ground state initially?"
Surprisingly, Rohit answered the questions correctly.
Instead of Rohit, if you were asked the same questions by Jadu, what would have been
your answers for the two questions? Take he = 12400 eV Å.
 10. ATOMIC STRUCTURE
10.1 (D) Azimuthal quantum number gives the shape of orbital.

10.2 (D) In the given figure if line 'E' is in visible region then line belonging to
ultraviolet region will have more energy than 'E' i.e. line A

10.3 (A) Let n be the number of photons emitted

12400
 × 1.6 × 10-19 × n = 60 × 10 × 60 × 60
600
 n = 6.5 × 1024

32
10.4 (A) r3 = r 1
3
r x
 r1 = 3  cm
3 3
2π x
 De-brogalies wavelength = .
3

f1 z12 z 32 n1 = 3 n 2 = 3 2 2 32
10.5 (A)    , 
f 2 n13 z 22 z1 = 2 z 2 =1 33 27

10.6 (C) Maximum number of electron having same spin quantum number is
equal to the number of orbitals = 2  + 1

h h
10.7 (D) λ = λα = 2 × 4 × mp × 2eV α
2m p eV 2m α (2e) Vα
V
 Vα =
8

10.8 (B)  = 1 for p and  = 2 for d.

Now 24Cr has configuration
1s2 2s2 2p6 3s2 3p6 3d5 4s1
Hence there are 12, p-electrons and 5, d-electrons.
1s2 2s2 2p6 3s2 3p6 3d5 4s1

10.9 (A) 26Fe  1s2, 2s2 2p6, 3s2 3p6, 3d6, 4s2
 +m=0   = 0, m = 0 i.e. s-subshell
 = 1, m = - 1 i.e. one orbital of p.
 = 2, m = 2 i.e. one of d-orbitals
Hence there are 13 or 14 electron as in d-orbital it may be one or two
electron having m = -2.
 12400
10.10 (C) Energy of one photon = = 3.1 ev
4000
Energy supplied by one mole photon in KJ/mole = 3.1 × 1.6 × 10-19 × 6
× 1023 × 10-3 = 297 kJmol-1
297  246.5
% of energy converted to K. E. = 17%
297

 1 1 
10.11 (A, C) v = RZ2  2  2 
 n1 n 2 
 1 1  5R
x=R  2  2  =
 2 3  36
 1 36 108 x
v = R × 22 1  2  = 3R = x×3=
 2  5 5

10.12 (A, B, D)
3s orbital has two radial node at the values of radius given by solutions
 4Zr 4 Z 2 r 2 
of  6   . 0
 a 0 9 a 02 
 4Zr 
3pz orbital has on radial nodal surface at  4   = 0 & one angular
 3a 0 
node at θ = π /2
for 3 pz , at r = 0 ψ = 0 while for
3 s at r = 0 ψ = maximum so, 3s has greater penetrating
power than 3pz orbital

th z2 z2
10.13 (A,B) B.E. of 4 state = 13.6 2  13.6 2 = 13.6  z=4
n 4
sample is Be3+  energy of electron in 3rd state
state = 1.5 × 42 = 24 ev
therefore 25 eV photon will cause ionisation.

10.14 (B, C, D)
 1
1st excitation energy = 13.6 z2 1  2  = 24 eV
 2 
 (13.6 z2) = 32 eV
 I.E. = 32 eV
3.6z 2 32
B.E. of 3rd excited state = 2
=  2eV
4 16
 1 8
2nd excitation energy = 13.6 z2  1  2  = 32 x eV.
 3  9
10.15 (A, B) since it obsorbes 'n' photons and it also emits exactly n-photons
therefore transition must have taken place from 1 to 2.
  Energy of photon =10.2 Z2
where Z = 1, 2, 3, 4.

10.16 (A, B, C)
Since B is in infrared region and A has more energy than B hence it will
have lesser wave length i.e. ultra violet, visible or infrared region.

10.17 (A, C, D)

10.18 (B, C, D)

10.19 (D) 'He' has highest first ionisation energy therefore assertion is wrong and
also addition of extra electron to the outer most shelf of fully filled
orbitals absorbes energy. Hence reason is also wrong.

h
10.20 (C) mΔ VΔ x =
4π
6.62 1034
 Δv = 6 × 106 m/s
9.11031  4  3.14 1011
as uncertainty in velocity is very high so we cannot define the trajectory of an
electron.

10.21 (B) Fe2+  [Ar] 3d6

Mn2+  [Ar] 3d5
Cr3+  [Ar] 3d1

Clearly Mn2 has maximum number of unpaired electrons therefore it

has highest magnetic moment.

10.22 (B) Magnetic moment = n (n + 2)  3.873  number of unpaired electron

n=3
 25Mn – [Ar] 3d5 4s2 therefore Mn should be
in + 4

10.23 (D) There is two unpaired electron in Ti2+

10.24 (D) Mn4+  [Ar] 3s5 4s3

10.25 (C) 10.26 (A) 10.27 (C)

10.28 (C) 10.29 (A) 10.30 (A)

10.31 (A  s), (B – p), (C – p), (D – q)

 kze 2
(A) Tn = -  TN αr 1
2r
p Tn
(B) Tn = n  =½
2 Pn
1
(C) αz  fn × α z
f n-x
f n α z2
2π
(D) Tn × vn = r  v n  t = 1.
vn

10.32 (A – q, r), (B – p, s), (C – s), (D – q)

13.6  22
(A) B.E. of He+ atom = n = 1, 2, 3 ……
n2
Hence it cane be 13.6 ev, 3.4ev both
(B) In 7  3 transition Δ n = 7 – 3 = 4
4 (4  1)
 Maximum number of spectral line observed =  10
2
It is line of paschen series hence infrared region
(C) 5  1 – 10 lines
(D) series limit of Balmer series is the last line having 3.4 ev energy.

10.33 (A – r, s), (B – p, s), (C – q, r), (D – p, q)

(A) 6  3 Δn = 3
3(3  1)
 no. of lines = =6
2
All lines are in infrared region
(B) 7  3 Δn = 4
4 (4  1)
 no. of lines =  10
2
All lines are in infrared region
(C) 5  2 Δn = 3
All lines are in visible region
(D) 6  2 Δn = 4
AlI lines are in visible region.

hr hr
10.34 From Bohr model mvr = mv =
2π 2πr
h h 2πr
De broglie wavelength λ =  λ=  λ=
mv nh n
2πr 2πr
 number of waves made in one revolution =  = n = Orbit number
λ 2πr
n
= 3.
10.35 For the positive particle, applying energy conservation initially and at a point A.
K.E.i + P.E.i = K.E.f + P.E.f
 4eV + (+4e) (0V) = 0 + (+4e) (x volt) {x = potential at point A}
 x = 1 volt
Now applying energy conservation for the negative particle at point 'A' and initially
 K.E.i + (  2e) (4V) = 0 + (  2e) (1 volt)
K.E.i  8 eV = – 2eV
 K.E.i = 6eV.
10.36 We have
3
ΔE =  0.85eV
4
As energy = 0.6375 the photon will belong to bracket series (as for bracket
0.31 < E < 0.85)
 1  1 1 
0.85 ×  1   13.6  2  2 
 4 4 n 
2
 1  13.6   4   4 1
0.85  1    1        n=8
 4  16   n   n 2
Hence x = 8.

h h
10.37 Given  (   ) 
2π 2π
  =1
Hence we have to find out the number of p-electrons
2 2 6 2 6 5 1
24Cr – 1s 2s 2p 3s 3p 3d 4s
Hence their are 12 electrons which has this angular momentum.

10.38

 1 1  1 1 
10.2 + 17 = 13.6 Z2  2  2  and 4.25 + 5.95 = 13.6 Z2  2  2 
2 n  3 n 
Solving the avove two equation we get, Z = 3, n = 6.

10.39 Since electron goes the state where the path length is 5 times de-broglie
wavelength.
 2πr 5 λ
2πr
Also λ  n=5
n
Hence electron goes to the 5th state.
 2nd highest energy line

If this photon is used for Li+2 then

 1  1 1 
13.6 1  2  = 13.6 × Z2  2  2 
 4   n1 n 2 
 3  12
Hence final excited state = 12.

X X+ 1
10.40  e I.E. …… (i)
2 2 2
X X- 1
e    E.A. (- ve) …… (ii)
2 2 2
(i) + (ii)
1  1  1
X 
 X  X (I.E. – E. A.) = 410 KJ
2 2 2
I.E. – E.A. = 820 KJ
1  1
Now X   X   2e  …… (iii) Δ H = 735
2 2
Now equation (iii) can be achieved by (i) + reverse (ii) and we will get
1 1
I.E. + E.A. = 375
2 2
I.E. + E.A. = 1470 …… (iv)
2E. A. = 325 KJ/mol.

1/2
1 1  r  -r/2a 0
10.41 (a) ( ψ )2s =   2 e
2 2 π  a0   a0 
 r 
For radical node at r = r0 , ψ 22s = 0. this is possible only when  2    0
 a0 
r
Or 2= 0
a0
 r0 = 2a0
(b) Given: m = 100 , g = 0.1 kg ; u = 100 ms-1
h 6.626 1034
Wavelength λ=   6.626 10 35 m
mu 0.1100
2zr

2 2 na 0
10.42 Probability of finding electron at a distance r and (r + dr), f(r) = 4πr ψr 2  k'r e
For 1S orbital, n = 1
2zr

na 0
f(r) = k’ r2 e
 df (r)
For maximum of f(r), 0
dr
2zr 2zr

na 0

na 0  2z 
 e × 2r + 2r × e ×  0
 a0 
2rz
2- =0
a0
a 52.9
r= 0   13.225 pm
z 4
Reported Answer = 13225.

10.43 (a) Radial nodes = n    1 = 4  2  1 = 1.

Angular nodes =  = 2.
(b) Mg  1s2 2s2 2p6 3s2.  For last electron, n = 3,  = 0, m = 0, s = ± 1/2.
3+ 2 2 6 6 6
(c) Co  1s 2s 2p 3e 3p 3d .  Number of unpaired electrons = 4.
 Magnetic moment (spin only) = n (n  2)  24 = 4.9 B.M

10.44 (a 6 (b) 96
(PE)n = 1 = - 192 eV   27.2 Z2=  192
or 27.2 Z2= 192 13.6 Z2 = 192/2 = 96 eV
12400
λ = 1550 Å  E = = 8 eV
1550
Electrons from ground state cannot gain this energy as the I excitation energy (10.2
Z2 = 72eV) is greater than supplied energy.
 Electrons from (n = x) state jump to (n = x + 3) state absorbing 8eV energy.
1 1 
 13.6 Z2  2  2 
8
 n (n + 3) 
1 1 
 96  2  2 
8
 n (n + 3) 
 n=3
So, electron jumps from 3   6
Upon back transition, max 10 lines are produced
 To produce max 10 lines, minimum 4 atoms should be present in (n = x + 3)
state, which were initially present in (n = x) state.

So, maximum number of atoms which had their electron in ground state initially
= 100  4 = 96.
 DPP-11
Surface Chemistry
SECTION - I: STRAIGHT OBJECTIVE TYPE

11.1 When a graph is plotted between log x/m and log p, it is straight line
With an angle 45° and intercept 0.3010on y-axis. If initial pressure is
0.3 atm, what will be the amount of gas adsorbed per gm of adsorbent :
(A) 0.4 (B) 0.6 (C) 0.8 (D) 0.1
11.2 Which of the following statements about physical adsorption is not
correct ?
(A) It is usually monolayer
(B) It is reversible in nature
(c) It involves van der Weals interactions between adsorbent and
adsorbate
(D) It involves small value of adsorption

11.3 Following is the variation of physical adsorption with temperature:

11.4 Finally divided catalyst has greater surface area and has greater
catalytic activity then the compact solid. If a total surface area of
6291456 cm is required for adsorption of gaseous reaction in a
catalysed reaction, then how many splits should be made of cube
exactly 1 cm in length.
(A) 60 (B) 80 (C) 20 (D) 22

11.5 Which of the following is not characteristic of chemisorption?

(A) it is irreversible
` (B) it is specific
(C) it is multilayer phenomenon
(D) heat of adsorption of about – 400 kJ

11.6 A colloidal solution can be purified following the method of

(A) 4 dialysis (B) peptization (C) filtration (D) oxidation

11.7 Gold number of a lyophilic sol is such property that:

(A) the larger its value, the greater is the peptising power
(B) the lower its value, the greater is the peptising power
(C) the lower its value, the greater is the protecting power
(D) the larger its value, the greater is the protecting power

11.8 For the coagulation of 200 mL of As2S3 solution, 10 ml. of 1 M NCI is

required. What is the coagulating value of NCI.
(A) 200 (B)100 (C) 50 (D) 25
11.9 At CIVIC, the surfactant molecules :
(A) Decomposes
(B) Become completely soluble
(C) Associate
(D) Dissociate
11.10 Some type of gels like gelatin loose water slowly. The process is
known as :
(A) Synerisis (B) Thixotropy (C) Peptisation (D) Imbibition

11.11 Coagulation value of the electrolytes AlCl3 and NaCI for As2S3 sol are
0.093 and 52 repectively. Now many times AlCl3 has greater
coagulating power than NCI.
(A) 930 (B) 520 (C) 560 (D) None

11.12 Size of colloidal particles may range from

(A) 1 to 1000 nm (B) 10 to 100 pm
(C) 1 to 1001.1M (D) 1 to 10 mm
11.13 Select correct statement (s) :
(A) hydrophilic colloid is a colloid in which there is a strong attraction
between the dispersed phase and water
(B) hydrophobic colloid is a colloid in which there is a lack of attraction
between the dispersed phase and water
(C) hydrophobic soils are often formed when a solid crystallises
rapidly from a chemical reaction or a supersaturated solution
(D) all of the above

11.14 Gold number of haemoglobin is 0.03. Hence, 100 ml. of gold sol will
require haemoglobin so that gold is not coagulated by 10 mL of 10%
NaCI solution
(A) 0.03 mg (B) 30 mg (C) 0.30 mg (D) 3 mg

11.15 Which one of the following statements is false for hydrophilic sots ?
(A) they do not require electrolytes for stability
(B) their coagulation is reversible
(C) their viscosity is of the order of that of water
(D) their surface tension is usually lower than that of dispersion
medium.
11.16 Which one of the following statements is correct:
(A) Brownian movement is more pronounced for smaller particles
than for bigger ones
(B) Sols of metal sulphides are lyophilic
(C) Schulze-Hardy law states, the bigger the size of the ion, the
greater is its coagulating power
(D) Onewould expect charcoal to adsorb chlorine more strongly than
hydrogen sulphide.
11.17 What can adsorb larger volume of hydrogen gas :
(A) Colloidal solution of palladium (B) Finely divided nickel
(C) Finely divided platinum (D) Colloidal Fe(OH)3.

SECTION - II : MULTIPLE CORRECT ANSWER TYPE

11.18 Which of the following are correct statements

(A) Spontaneous adsorption of gases on solid surface is an
exothermic process as entropy decreases during adsorption
(B) Formation of micelles takes place when temperature is below
Kraft Temperature (Tk) and concentration is above critical micelle
concentration (CMC)
(C) A colloid of Fe(OH)3 is prepared by adding a little excess (required
to completely precipitate Fe3+ ions as Fe(OH)3)) of NaOH in FeCI3
solution the particles of this sol will more towards cathode during
electrophoresis.
(D) According to Hardy-Schulze rules the coagulation (flocculating)
value of Fe3+ ion will be more than Ba2+ or Na+

11.19 Which of the following statements are true for physisorption?

(A) Extent of adsorption increases with increase in pressure.
(B) It needs activation energy
(C) It can be reversed easily
(D) It occurs at high temperature.

11.20 Which of the following are incorrect statements ?

(A) Hardy schulz rule is related to coagulation
(B) Brownian moment and Tyndall effect are the characteristic of
colloids.
(C) In gel, the liquid is dispersed in liquid
(D) Lower the gold number, more is the protective power of lyophillic
soils.

11.21 The origin of charge on colloidal solution is

(A) Frictional rubbing
(B) Electron capture during Bredig's arc method
(C) Selective adsorption of ion on their surface
(D) It is due to addition of protective colloids

SECTION - III : ASSERTION AND REASON TYPE

11.22 Statement-1 : All colloidal dispersions give very low osmotic pressure
and show very small freezing point depression or boiling pointelevation.
Statement-2 : Tydall effect is due to scattering of light from the surface
of colloidal particles.
(A) Statement-2 is True, Statement-2 is True; Statement-2 is a correct
explanation for Statement-1.
 (B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a
correct explanation for Statement-1.
(C) Statement-2 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

22.23 Statement-1 : The Brownian movement is due to the bombardment of

collodial particles by the molecules of dispersion medium which are in
the constant motion like molecules in a gas.
Statement-2 :Brownian movement provides a visible proof of the
random kinetic motion of molecules in a liquid.
(A) Statement-2 is True, Statement-2 is True; Statement-2 is a correct
explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a
correct explanation for Statement-1.
(C) Statement-2 is True, Statement-2 is False.
(D) Statement-2 is False, Statement-2 is True.

11.24 Statement-1: In the coagulation of negatively charged arsenic sulphide

soil, the coagulating power decreases in the order, Al3+ > Ba2+ > Na+.
Statement-2 : Generally greater the valence of coagulating ion, the
greater is its power of coagulation.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct
explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a
correct explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

22.25 Statement-1 : Isoelectric point is pH at which colloidal can move

towards either of electrode
Siatement-2 : At isoelectric point, colloidal solution become electrically
neutral
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct
explanation for Statement-2.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a
correct explanation for Statement-1.
(C) Statement-2 is True, Statement-2 is False.
(D) Statement-2 is False, Statement-2 is True.

22.26 Statement-1 : Gelatin is added to ice cream as a protective agent so

as to preserve its smoothness.
Statement-2 : whipped cream is colloidal in nature.
(A) Statement-2 is True, Statement-2 is True; Statement-2 is a correct
explanation for Statement-1.
(B) Statement-2 is True, Statement-2 is True; Statement-2 is NOT a
correct explanation for Statement-2.
 (C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

22.27 Statement-1 : Medicines in the colloidal state are more effective.

Statement-2: In the colloidal state, the medicines are easily
assimilated by the body.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct
explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a
correct explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

SECTION - IV : TRUE AND FALSE TYPE

11.28 Colour of a colloidal solution depends upon the size and shape of soil
particles.

11.29 Brownian motion is due to continuous bombardment of soil particles by

molecules of disperson medium.
11.30 When negatively charged smoke comes in contact with positively
charged clouds, rain fall takes place.
11.31 For a positive sol, flocculation values are in the order NCI > K2S04 >
Na3PO4 > K4[Fe(CN)6].

SECTION - V : COMPREHENSION TYPE

Comprehension # 1
The clouds consist of charged particles of water dispersed in air. Some of
them are +vely charged, others are —vely charged. When +vely charged
clouds come closer they causer they cause lightening and thundering
whereas when +ve and —Ave charged colloids come closer they cause heavy
rain by aggregation of minute particles. It is possible to cause artificial rain by
throwing electrified sand or silver iodide from an aeroplane and thus
coagulating the mist hanging in air.
11.32 When excess of AgNO3 is treated with KI solution, Agi forms
(A) +ve charged soil (B) —rely charged sol (C) neutral sol (D) true
solution
11.33 AO helps in artificial rain because :
(A) it helps in condensation process (B) it helps in dispersion process
(C) it helps in coagulation (D) all of them
11.34 Smoke screens consist of
fine particles of Ti02 dispersed in air by aeroplanes
fine particles of Age dispersed in air by aeroplanes
fine particles of Al203 dispersed in air by aeroplanes
None of these
Comprehension # 2
Adsorption is the presence of excess concentration of any particular
component at the surface of liquid or solid phase as compared to bulk. This is
due to presence of residual forces at the surface of body. In the adsorption of
hydrogen gas over a sample, of charcoal, 1.12cm3 of H2(g) measured over
S.T.P. was found to adsorb per gram of charcoal. Consider only monolayer
adsorption. Density of H2 is 0.07gm/cc. In another experiment same 1 gm
charcoal adsorbs 100m1 of 0.5M CH3COOH to form monolayer and thereby
the polarity of CH3COOH reduces to 0.49.
(3 x 47.73 )1/3
47t =2.24.
(2.24)2 = 5
11.35 Numbers of molecules of hydrogen over 1 gram charcoal are —
(A) 3.01 x 1015 (B) 3.01 x 1013 (C) 3.01 x 1021 (D) 3.01 x 1022
11.36 What is the radius of adsorb hydrogen molecule
(A) 2.24 x 10-7 cm (B) 2.24 x 10-5 cm (C) 2.24 x 10-gcm (D) 2.24 x 10-
15cm
11.37 Specific surface area of charcoal is (cm2/gm) —
(A) 4.72 x 103 (B) 4.72 x 104 (C) 4.72 x 105 (D) 4.72 x 106
11.38 Molecule of acetic acids adsorbed —
(A) 6.023 x 1025 (B) 6.023 x 1021 (C) 6.023 x 1022 (D) 6.023 x 1023
11.39 Surface area of charcoal adsorbed by each molecule of (acetic acid) is
—
(A) 7.8 x 10-'9 cm2 (B) 7.8 x 10-15 cm2 (C) 7.8 x 10-17 cm2 (D) 7.8 x 10-16
cm2

SECTION - VI : MATRIX - MATCH TYPE

11.40 Match list I with list II and select the correct answer : List I List II
Coagulation (p) Scattering of light
Dialysis (q) Washing of precipitates
Peptization (r) Purification of colloids
Tyndall effect (s) Electrolyte
11.41 Match list I (Colloidal system) with list II (Example) and select the
correct answer : List I List II
Emulsifies (p) Colloidal solution
Xerogel (q) Soaps
Colloidal electrolyte (r) Foil of cellophane
Purple of Cassius (s) Dextrin

SECTION - VII : SUBJECTIVE ANSWER TYPE SHORT SUBJECTIVE :

11.42 5m1. of standard gold sol, needs 0.5 mg of gelatin for its protection
from coagulation, calculate the gold no. of gelatin.
11.43 100 ml of a colloidal solution is completely precipitated by addition of
0.5 ml of 1M NaCI solution, calculate the coagulation value of NCI.
11.44 On addition of the 1m1. solution of 10% NCI to 10 ml gold sol in the
presence of 0.00399 gm of starch, calculate the gold no.
11.45 Coagulation experiment, 5m1 of As2S3 is mixed with distilled water and
0.01 M solution of an electrolyte AB so that total volume is 10m1. it was found
that all solution containing more than 5 ml of AB coagulate within 5 min. What
is the Flocculation value of AB for As2S3 sol.
 11. SURFACE CHEMISTRY

x 1 1
11.1 (B) log = log K + log P  = tan 45°  n = 1  log K = 0.3010,
M n n
K=2
x
 = 2 x (0.3)1  x = 0.6
M

11.2 (A) Physical adsorption is a multilayer phenomenon

11.3 (B) Rate of physical adsorption gradually decreases with increase the
temperature.

2
1 1
11.4 (C) Total surface area of eight cubes = 8 × 6 ×   
2 2
Apply the formula
2n
n 1
Surface area on n split of a cube = 8 × 6 ×  
2
2n
n 1
6291456 = 8 × 6 ×  
2

11.5 (C) Chemical adsorption is a mono layer phenomenon.

11.6 (A)

11.7 (C) Lower is the value gold number; greater will be the protecting power.

11.8 (C) 10 ml of 1 M NCl contains NaCl = 10 × 1 = 10 milli mole

200 ml of As2S3 required NCI for the coagulation = 10 milli mole
 1000 ml of As2S3 required NaCl for the coagulation = 10 × 1000%200 =
50 milli mole

11.9 (C) 11.10 (A) 11.11 (C) 11.12 (A) 11.13 (D)

11.14 (C) 0.03 = weight of Hb in mg × 10 / 100

11.16 (A)

11.17 (A) It is because of more surface area of colloidal Pd

11.18 (A, C) (A) Δ G = Δ HD - T Δ BS < O as Δ S < 0 so Δ H has to be negative

(B) Micelles formation will take place above Tk and above CMC
 (C) This solution will be negatively charged.
(D) Fe3+ ions will have greater flocculatibility power so smaller
flocculating value.

11.19 (A, C)

11.20 (C, D) In gel, liquid is dispersed in solid,

11.21 (A, B, C) 1122 (B) 1123 (B) 11.24 (A)

11.25 (B) 1126 (B) 11.27 (A) 11.28 True

11.29 True 11.30 True 11.31 True 11.32 (A)

11.33 (C) 14.34 (A) 1135 (B) 11.36 (B)

11.37 (B) 11.38 (A) 11.39 (C)

11.40 (A – s); (B – r); (C – q); (D – p)

11.41 (A – s); (B – r); (C – q); (D – p)

11.42 5 ml of gold sols, required gelatin for protection from coagulation = 0.5 mg.
0.5 10
10 ml of gold soil. ,, ,, ,, = 1
5

11.43 M Mole of NaCl = M × V = 0.5 × 1 = 0.5

0.5 1000
Coagulation Value = 100 5
100

11.44 Gold no. = 1000 × 0.00399 = 4

11.45 A minimum of 5 ml of AB is required to coagulate the soil, the moles of AB in

sol. is
5  0.01
= = 0.005 moles
10
this means that a minimum of 0.005 moles or 0.005 × 1000 = 5 milli moles are
required for coagulation 1 litre of sol. flocculation value of AB for As2S3 sol
= 5.