Thermo DPP Question

PHYSICAL CHEMISTRY Total Marks : 24
DPP No. 37 Max. Time : 24 min.
Topic : Chemical Equilibrium
Type of Questions M.M., Min.

Single choice Objective ('–1' negative marking) Q.1 to Q.8 (3 marks, 3 min.) [24, 24]
1. For the homogeneous gaseous reaction : 4NH3 + 5O2 4NO + 6H2O, the equilibrium constant
Kc has the units of :
(A) (Conc.)–10 (B) (Conc.)1 (C) (Conc.)–1 (D) It is dimensionless.
2. Select the gaseous reaction for which the equilibrium constant is written as : [MX3]2 = K[MX2]2 [X2]
1
(A) MX3 MX2 + X (B) 2MX3 2MX2+ X2
2 2
1
(C) 2MX2 + X2 2MX3 (D) MX2 + X MX3.
2 2
3. In order to increase the rate of forward reaction : 2A(g) + 3B(g) Product, 32 times, it is necessary to
:
(A) Make the conc. of A and B three times (B) Make the conc. of A and B two times
(C) Make the conc. of A and B half (D) Make the conc. of A and B four times
4. For the reaction, A + 2B 2C, the rate constants for the forward and the backward reactions are
–4 –2
1 × 10 and 2.5 × 10 respectively. The value of equilibrium constant, K for the reaction would be :
(A) 1 × 10–4 (B) 2.5 × 10–2 (C) 4 × 10–3 (D) 2.5 × 102
5. An equilibrium system for the reaction between hydrogen and iodine to give hydrogen iodide at 765 K in a
5 litre volume contains 0.4 mole of hydrogen, 0.4 mole of iodine and 2.4 moles of hydrogen iodide. The
equilibrium constant for the reaction is : H2(g) + I2(g) 2HI(g)
(A) 36 (B) 15 (C) 0.067 (D) 0.28.
6. For a gasesous reaction, 2A + B 2C, the partial pressures of A, B and C at equilibrium are 0.3 atm, 0.4
atm and 0.6 atm respectively. The value of Kp for the reaction would be :
(A) 10 atm–1 (B) 1/10 atm–1 (C) 0.2 atm–1 (D) 5 atm–1
7. The active mass of 64 g of HI in a two litre flask would be :

(A) 2 (B) 1 (C) 5 (D) 0.25
8. For the reaction , A + B 3 C , if ' a ' moles/litre of each ' A ' & ' B ' are taken initially , then the incorrect
relation about concentrations at equilibrium is :
(A) [A]  [B] = 0 (B) 3 [B] + [C] = 3 a (C) 3 [A] + [C] = 3 a (D) [A] + [B] = 3 [C]
DPPS FILE # 49

Subjective Questions ('–1' negative marking) Q.6 to Q.9 (4 marks, 5 min.) [16, 20]
1. For the equilibrium PCI5 (g) PCI3 (g) + CI2(g) in a closed vessel, Kp is found to be double of Kc. This is
attained when :
(A) T = 2 K (B) T = 12.18 K (C) T = 24.36 K (D) T = 27.3 K
1
2. Kp / Kc for the reaction CO(g) + O (g) CO 2 (g) will be :
2 2
1
(A) 1 (B) RT (C) (D) R T
RT
3. For the reaction : N2O4 (g) 2NO2 (g) at 360 K, the value of Kc = 0.4 mole lit–1. The value of Kp for the
reaction at the same temperature would be :
(A) 12 atm (B) 1.2 atm (C) 1.2 × 102 atm (D) 1.2 × 10–3 atm
4. Starting with one mole of nitrogen and 3 moles of hydrogen, at equilibrium 50% of each had reacted
according to the reaction : N2 (g) + 3H2 (g) 2NH3 (g)
If the equilibrium pressure is P, the partial pressure of hydrogen at equilibrium would be :
(A) P/2 (B) P/3 (C) P/4 (D) P/6
5. For which of the following equilibria, is Kp = Kc :

(A) 2H2(g) + O2(g) 2H2O(g) (B) CH4(g) + H2O(g) CO(g) + 3H2(g)
(C) N2(g) + O2(g) 2NO(g) (D) COCl2(g) CO(g) + Cl2(g)
6. For the following chemical equation, write expression for equilibrium constants Kc and Kp
2NO2 (g) N2O4 (g)
Also write their proper units.
7. PCI5 dissociates into PCI3 and CI2 in a 2 L flask at about 600ºC. At equilibrium, mixture is found to contain
1 mole PCI5 and 2 moles each of PCI3 and CI2. Calculate :
(i) equilibrium molar concentrations.
(ii) equilibrium mole fractions.
(iii) equilibrium constant Kc for the chemical equilibrium : PCI5(g) PCI3(g) + CI2(g)
8. For an equilibrium A (g) + 2B (g) 2C (g) + D (g), A and B are mixed in a reaction vesel at 300 K.
The initial concentration of B was 1.5 times the initial concentration of A. After the equilibrium, the
equilibrium concentrations of A and D are same. Calculate K C for the given reaction .
9. n mole of PCl 3 and n mole of Cl 2 are allowed to react at constant temperature T to have a total
equilibrium pressure P, as : PCl 3 (g) + Cl 2 (g) PCl 5 (g)
If y mole of PCl 5 are formed at equilibrium, find K P for the given reaction.
DPPS FILE # 50

1. In a reaction A (g)+ 2B (g) 2C (g), 2 moles of ‘A’, 3 moles of ‘B’ and 1 mole of ‘C’ are placed in a 2 L
flask and the equilibrium concentration of ‘C’ is 1 mol/L. The equilibrium constant (KC) for the reaction is :
(A) 0.33 lit/mol (B) 1.33 lit/mol (C) 1.66lit/mol (D) 0.66 lit/mol
2 For the reaction : H2(g) + I2(g) 2HI(g), the equilibrium constant Kp changes with :
(A) total pressure (B) addition of catalyst
(C) the amounts of H2 and I2 taken initially (D) temperature
3. In a reversible chemical reaction having two reactants in equilibrium with one product, if the initial
concentration of both the reactants is doubled, then the equilibrium constant will :
(A) also be doubled (B) be halved
(C) become one fourth (D) remain the same.
4. For the equilibrium 2H2O(g) 2H2 (g) + O2(g), equilibrium constant is K1.
For the equilibrium 2CO2(g) 2CO(g) + O2 (g), equilibrium constant is K2.
Then, the equilibrium constant for CO2(g) + H2(g) CO(g) + H2O(g) is :
K1 K1 K2
(A) K1 K2 (B) K (C) K2
(D) K1
2
5. For the reaction A(g) + B(g) C(g) at equilibrium, the partial pressure of the species are PA = 0.15 atm,
PC = PB = 0.30 atm. If the capacity of reaction vessel is reduced, the equilibrium is re-established. In the
new situation, partial pressure A and B become twice. What is the partial pressure of C :
(A) 0.3 atm (B) 0.6 atm (C) 1.2 atm (D) 1.8 atm
6. The equilibrium constant for the reaction

A2(g) + B2(g) 2AB(g) is 20 at 500 K.
The equilibrium constant for the reaction,
2AB(g) A2(g) + B2(g) at 500 K would be :
(A) 20 (B) 0.5 (C) 0.05 (D) 10
7. The value of Kp for the reaction, A(g) + 2B(g) C(g) is 25 atm–2 at a certain temperature. The value of KP
1 1
for the reaction, C(g) A(g) + B(g) at the same temperature would be :
2 2
1 1
(A) 25 atm–1 (B) atm–1 (C) atm (D) 5 atm
25 5
8. For the gaseous reaction of XO with O 2 to form XO 2, the equilibrium constant at 398 K is
1 × 10–4 lit/mole. If 1 mole of XO and 2 mole of O2 are placed in a 1 L vessel and allowed to come to
equilibrium, what will be the equilibrium concentration of each of the species ?
9. Prove that the pressure at equilibrium obtained upon 50% dissociation of PCl5 as follows at 250ºC is
numerically three times of Kp. PCl5 (g) PCl3 (g) + Cl2 (g)
DPPS FILE # 51

1. CH3–CO–CH3(g) CH3–CH3(g) + CO(g)

Initial pressure of CH3COCH3 is 100 mm. When equilibrium is set up, mole fraction of CO(g) is 1/3. Hence
value of Kp for given reaction is :
(A) 100 mm (B) 50 mm (C) 25 mm (D) 0.6 mm
2. The degree of dissociation of N2O4 () obeying the equilibrium,

N2O4 (g) 2NO2 (g), is approximately related to the presure at equilibrium by :
1 1 1
(A)  P (B)  (C) 2 (D) 
P P P4
3. Two moles of HI were heated in a sealed tube at 440°C till the given equilibrium was reached. HI was found
to be 20% decomposed. The equilibrium constant for dissociation is :
2HI (g) H2 (g) + I2 (g)
1 1 1 1
(A) (B) (C) (D)
16 32 64 128
4. In the following reaction, 3A (g) + B (g) 2C (g) + D (g),

Initial moles of B is double of A. At equilibrium, moles of A and C are equal. Hence % dissociation of B is :
(A) 10% (B) 20% (C) 40% (D) 5%
5. For the equilibrium N2O4 2NO2 in gaseous phase, NO2 is 50% of the total volume when equilibrium is
set up. Hence percent of dissociation of N2O4 is :
(A) 50% (B) 25% (C) 66.66% (D) 33.33%
6. PCl5 is 40% dissociated according to the following reaction, when equilibrium pressure is 2 atm. It will be
80% dissociated, when equilibrium pressure is approximately : PCl5 (g) PCl3 (g) + Cl2 (g)
7. The equilibrium constant for the following reaction , H2 (g) + Br2 (g) 2 HBr (g) is 1.6  105 at 1024 K.
Find the equilibrium pressure of all gases if 10 bar of HBr is introduced into a sealed container at 1024 K
initially.
8. At a certain temperature, the equilibrium constant (Kc) is 9/4 for the reaction :
CO(g) + H2O(g) CO2(g) + H2(g)
If we take 10 mole of each of the four gases in a one-litre container, what would be the equilibrium mole
percent of H2 (g) ?
DPPS FILE # 52

Single choice Objective ('–1' negative marking) Q.1, 2, Q.4 to Q.8 (3 marks, 3 min.) [21, 21]
Subjective Questions ('–1' negative marking) Q.3 (4 marks, 5 min.) [4, 5]
Multiple choice objective ('–1' negative marking) Q.9 (4 marks, 4 min.) [4, 4]
1. For A (g) 2 B (g), equilibrium constant at total equilibrium pressure p1 is Kp & for C (g) D
1
(g) + E (g), equilibrium constant at total equilibrium pressure p2 is Kp . If degree of dissociation of A &
2
C are same, then the ratio p1/p2, if Kp = 2 Kp , is :
1 2
(A) 1/2 (B) 1/3 (C) 1/4 (D) 2
2. Match the following : (Take reactants to be in stoichiometric proportions in case of two reactants)
Reaction Degree of dissociation of reactant in terms
(Homogeneous gaseous phase) of equilibrium constant
1. A+B 2C (a)  K  1 K 
2. 2A B+C (b)  K  2  K 
3. A+B C+D (c) 2 K / (1 + 2K)
1 1 2 K
4. AB A2 + B2 (d)
2 2 1 2 K
(A) 1d, 2c, 3b, 4a (B) 1a, 2c, 3b, 4d
(C) 1b, 2d, 3a, 4c (D) 1b, 2a, 3d, 4c
3. 0.96 g of H were heated to attain equilibrium 2H(g) H2 (g) + 2 (g). The equilibrium mixture, on
reaction requires 15 mL of M/10 Hypo (Na2S2O3) solution. Calculate the degree of dissociation of H.
I2 + Na2S2O3  Na2S4O6 + NaI (unbalanced)
4. In an evacuated closed isolated chamber at 227°C, 0.02 mole PCl5 and 0.01 mole Cl2 are mixed and
PCl5(g) PCl3 (g) + Cl2(g) equilibrium is attained. At equilibrium, density of mixture was 2.4 g/L and
pressure was 1 atm . The number of total moles at equilibrium will be approximately :
(A) 0.012 (B) 0.022 (C) 0.032 (D) 0.0488
5. For NH4HS(s) NH3(g) + H2S(g) reaction started only with NH4HS(s), the observed pressure for reaction
mixture in equilibrium is 1.12 atm at 106°C. What is the value of Kp for the reaction ?
6. For the reaction : CaCO3 (s) CaO(s) + CO2 (g), Kp = 1 atm at 727°C. If 20 g of CaCO3 were kept in a 10
litre vessel at 727°C, then the percentage of CaCO3 remaining at equilibrium is :
(A) 40% (B) 60% (C) 46% (D) 66%
7. 200 g of CaCO3(s) are taken in a 4 L container at a certain temperature. Kc for the dissociation of CaCO3
at this temperature is found to be 1/4 mole L–1. Then, the concentration of CaO in mole/litre is : [ Given CaO
= 1.12 g cm–3]
(A) 1/2 (B) 1/4 (C) 0.02 (D) 20
8. The exothermic formation of NH3 is represented by the equation : N2 (g) + 3H2 (g) 2NH3 (g)
Which of the following will increase the quantity of NH3 in an equilibrium mixture of N2 , H2 and NH3 :
(A) Increasing the temperature (B) Increasing the volume of container
(C) Removing N2 (D) Adding H2
9.* When AgNO3 is heated mildly in a closed vessel, oxygen is liberated and AgNO2 is left behind. At equilibrium
1
according to reaction AgNO3 (s) AgNO2 (s) + O (g) :
2 2
(A) addition of AgNO2 favours reverse reaction (B) addition of AgNO3 favours forward reaction
(C) increasing temperature favours forward reaction (D) increasing pressure favours reverse reaction
DPPS FILE # 53

Multiple choice objective ('–1' negative marking) Q.4 to Q.5 (4 marks, 4 min.) [8, 8]
Comprehension ('–1' negative marking) Q.6 to Q.8 (3 marks, 3 min.) [9, 9]
1. CaCO3(s) CaO(s) + CO2(g),

At equilibrium in the above case, ‘a’ moles of CaCO3, ‘b’ moles of CaO and ‘c’ moles of CO2 are found.
Then, identify the wrong statement :
(A) Moles of CaCO3 will decrease with the addition of inert gas at constant pressure.
(B) Moles of CaCO3 will remain constant with the increase in volume.
(C) If volume of the vessel is halved, then moles of CaCO3 will increase.
(D) Moles of CaO will decrease with the increase in pressure.
2. For the equilibrium CuSO 4.5H2O(s) CuSO 4.H2O(s) + 4H2O(g), the equilibrium constant
Kp = 2.56 × 10–10 atm4 at 27ºC. Now, if an air sample 40% saturated with water vapour is exposed to the
above reaction at equilibrium, which of the following statements is/are correct :
Given : Saturated vapour pressure of water at 27ºC is 12.5 torr.
(A) Mass of CuSO4.5H2O will increase. (B) Mass of CuSO4.5H2O will decrease.
(C) Mass of CuSO4.H2O will increase. (D) Mass of CuSO4.H2O will decrease.
3. 2Pb(NO3)2(s) 2PbO(s) + 4NO2(g) + O2(g), H > 0

Above equilibrium is established by taking some amount of Pb(NO3)2 (s) in a closed container at 1600 K.
Then which of the following is the INCORRECT option :
(A) moles of PbO(s) will increase with the increase in temperature
(B) If the volume of the container is doubled at equilibrium, then partial pressure of NO2(g) will change at
new equilibrium.
(C) If the volume of the container is halved, partial pressure of O2(g) at new equilibrium will remain same
(D) If two moles of He gas is added at constant pressure, then the moles of PbO(s) will increase.
4.* 1 mole each of N2(g) and 2(g) are introduced in a 1L evacuated vessel at 523K and equilibrium
N2(g) + 2(g) 2NO (g) is established. The concentration of NO(g) at equilibrium :
(A) Changes on changing pressure. (B) Changes on changing temperature.
(C) Changes on changing volume of the vessel.
(D) Remains same even when a platinum gauze is introduced to catalyse the reaction.
DPPS FILE # 54
1 1
5.* For the reaction, H2(g) + I2(g) HI(g)
2 2
If pressure is increased by reducing the volume of the container, then :
(A) Total pressure at equilibrium will change.
(B) Concentration of all the components at equilibrium will change.
(C) Concentration of all the components at equilibrium will remain same.
(D) Equilibrium will shift in the forward direction.
Comprehension # (Q. 6 to Q. 8)
Variation of equilibrium constant K with temperature T is given by Vant Hoff's equation as :
H

K = Ae RT (A – Pre exponential factor)
For a certain reaction, a graph between n K and 1/T was observed to be

straight line as shown in the figure below :
Given : (1) As T   , nK = 46.06
(2)  = 30°
(3) Use n K = 2.303 log10K
6. The value of H° (standard enthalpy change) for the given reaction is :
R R
(A) – (B) –R 3 (C) R 3 (D)
3 3
7. The value of pre-exponential factor A for the given reaction is :

(A) 102 (B) 1020 (C) 10–2 (D) 10–20
8. Which of the following statements is INCORRECT regarding the given reaction :

(A) The given reaction is an endothermic reaction.
(B) For the given reaction, standard entropy change (S°) is positive.
(C) The value of equilibrium constant K decreases with increase in temperature.
(D) The value of equilibrium constant K is unaffected by pressure changes.
DPPS FILE # 55

1. The equilibrium constant of the reaction, A2 (g) + B2 (g) 2 AB (g) at 100º C is 50. If a one litre flask
containing one mole of A2 is connected to a two litre flask containing two moles of B2, how many moles
of AB will be formed at 373 K ?
2. The progress of reaction : A(g) nB(g)
with time, is presented in fig. given below. Determine :
(i) the value of n (ii) the equilibrium constant, KC and

3. One mole of Cl2(g) and 3 moles of PCl5(g) are placed in a 100 litre vessel heated to 227ºC.The equilibrium
pressure is 2.05 atm. Assuming ideal behaviour, calculate the degree of dissociation of PCl5(g) and KP for
the reaction, PCl5 (g) PCl3 (g) + Cl2 (g).
4. When equal volumes of 0.2 M AgNO3 and 1 M KCN solutions were mixed then at equilibrium, concentration
of Ag+ was found to be 10–6 M. While when equal volumes of 0.2 M Zn(NO3)2 solution and of 1 M KCN
solution were mixed then at equilibrium, concentration of Zn2+ ion was found to be 10–12 M. Then find the
equilibrium constant KC of following reaction : 2[Ag(CN)2]– (aq.) + Zn2+ (aq.) [Zn(CN)4]2– (aq.) + 2Ag+ (aq.).
5.* Consider two equilibrium 2Cl2(g) + 2H2O(g) 4HCl(g) + O2(g) and N2(g) + O2(g) 2NO(g)
simultaneously established in a closed vessel. When some amount of HCl is added at equilibrium, which of
the following statements is correct :
(A) amount of N2 gas will decrease. (B) amount of N2 gas will increase.
(C) amount of O2 gas will decrease. (D) nothing can be said with certainty.
Comperhension # (Q.6 to Q.8)
Solid NH4I rapidly decompose as follows : NH4I (s) NH3 (g) + HI (g)
At equilibrium, total pressure = 0.5 atm.
Now, HI starts decomposing as follows : 2HI (g) H2(g) + I2 (g)
3
At final equilibrium, partial pressure of H2 = atm.
16
Now answer the following questions :
6. Calculate new total pressure :
(A) 0.9 atm (B) 1 atm (C) 0.6 atm (D) 0.5 atm
7. Calculate Kp for the reaction 2HI(g) H2(g) + I2(g) :
9 9 9
(A) (B) (C) (D) None of these
4 8 16
8. Partial pressure of HI at equilibrium is :
DPPS FILE # 56
Topic : Thermodynamics & Thermochemistry

1. In thermodynamics, a process is called reversible when :

(A) surrounding and system change into each other.
(B) there is no real boundary between system and surrounding.
(C) the surrounding is always in equilibrium with the system.
(D) the system changes into the surrounding spontaneously.
2. Choose the incorrect statement :
(A) System and surrounding are always separated by a real or imaginary boundary.
(B) Perfectly isolated system can never be created.
(C) In reversible process, energy change in each step can be reversed.
(D) Irreversible process is also called quasi-equilibrium process.
3. For the process on an ideal gas, which of the following statements is true :
(A) v mps at 1 > v mps at 2 > v mps at 3 > v mps at 4. (B) v mps at 1 = v mps at 4 < v mps at 2 < v mps at 3.
(C) v mps at 1 = v mps at 4 < v mps at 3 < v mps at 2 . (D) v mps at 2 > v mps at 3 > v mps at 4 = v mps at 1.
4. 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 in B, on an average.
(B) In flask B, the molecules move faster than in A, on an average.
(C) Flask A contains greater number of molecules than B.
(D) Flask B contains greater number of molecules than A.
5. Categorise the following into state and path functions :
(a) Internal energy (b) Pressure (c) Volume (d) Temperature (e) Heat
(f) Work (g) Free energy (h) Entropy (i) Molar heat Capacity (j) Height of a hill
(k) Distance travelled in climbing the hill
6. Categorise these properties into extensive and intensive property :
(a) Pressure of gas (b) Volume (c) Density (d) Temperature
(e) Heat capacity (f) Specific heat capacity (g) Molar heat capacity (h) Molarity
(i) Dielectric constant (j) Internal energy (k) Specific internal energy (l) Mass
7. Classify the following among closed, open and isolated system :
(a) Pressure cooker (b) Boiler (c) Liquid cooling system of an automobile (d) Thermos flask
(e) Universe (f) Living things (g) Human body (h) Electrochemical cells
(i) A cup of tea (j) A closely packed room in which a split air-conditioner is working.
8. 7.5 KJ heat is added to a closed system and its internal energy decreases by 12 KJ. So, how much energy
is transferred as work? For a new process, if the work is zero, then how much heat is transfered for the
same changes in state of system?
DPPS FILE # 57

1. For a reversible process, calculate magnitude of work done from the following PV diagram :
(A) 4 (B) 6 (C) 2 (D) 0
2. 2 mole of an ideal gas expands isothermally and reversibly from 1 L to 10 L at 300 K. What is the internal
energy change :
(A) 4.98 kJ (B) 11.47 kJ (C) –11.47 kJ (D) 0 kJ
3.* For isothermal expansion of an ideal gas sample, the correct relation(s) is/are : (Consider all quantities with
sign according to IUPAC convention and the reversible and irreversible processes are carried out between
same initial and final states.)
(A) W rev > W irrev (B) W irrev > W rev (C) qrev < qirrev (D) Erev = Eirrev
4.* 1 mole of argon gas is expanded isothermally and reversibly from 10L to 100L. Which of the following
options is/are incorrect for the process :
(A) E = 0 (B) W = 0
(C) heat supplied (q) = 0 (D) T = 0
DPPS FILE # 58
5. When a system is taken from state 'a' to state 'b' in fig. along path 'acb', 100 J of heat
flows into the system and the system does 40 J of work. How much heat flows into
the system along path 'aeb' if work done by the system is 20 J? The system
returns from 'b' to 'a' along path 'bda'. If the work done on the system is 30 J, does
the system absorb or liberate heat ? How much ?
6. Calculate the energy needed to raise the temperature of 20 g iron from 25ºC to 500ºC, if specific heat
capacity of iron is 0.45 JºC–1g–1.
7. The energy required to vapourise one mole of benzene at it's boiling point is 31.2 kJ mol–1. For how long a
100 W electric heater has to be operated in order to vaporize a 100 g sample of benzene at it's boiling
temperature ?
Comprehension # (Q.8 to Q.10)
When a system is taken from state A to state B along path ACB as shown in figure C B
below, 80 J of heat flows into the system and the system does 30 J of work. P
Now answer the following questions : A D

V
8. How much heat flows into the system along path ADB if the work done by the system is 10 J :
(A) 40 J (B) 60 J (C) 80 J ( D )
100 J
9. When the system is returned from state B to A along the curved path, the work done on the system is 20 J.
Does the system absorb or liberate heat and how much :
(A) 70 J ; heat is liberated. (B) 60 J ; heat is liberated.

(C) 70 J ; heat is absorbed. (D) 60 J ; heat is absorbed.
10. If ED – EA = –40J, then the heat corresponding to the processes AD and DB is respectively :
(A) qAD = 30 J and qDB = – 90 J (B) qAD = – 60 J and qDB = 30 J
(C) qAD = 30 J and qDB = 90 J (D) qAD = – 30 J and qDB = 90 J
DPPS FILE # 59

True or False (no negative marking) Q.9 (2 marks, 2 min.) [2, 2]
1. In a system, a piston caused an expansion against an external pressure of 1.2 atm giving a change in
volume of 32 L for which E = –51 kJ. What was the value of heat involved : (Take 1 L atm = 100 J)
(A) –36 kJ (B) –13 kJ (C) –47 kJ (D) 24 kJ
2. The q value and work done in isothermal reversible expansion of one mole of an ideal gas from initial
pressure of 1 bar to final pressure of 0.1 bar at constant temperature 273 K are :
(A) 5.22 kJ, –5.22 kJ (B) –5.22 kJ, 5.22 kJ (C) 5.22 kJ, 5.22 kJ (D) –5.22 kJ, –5.22 kJ
3. What is the difference between change in enthalpy and change in internal energy at constant volume :
(A) 0 (B) VdP (C) –VdP (D) +PdV
4. Calculate work done when 1 mole of an ideal gas is expanded from 10 L to 20 L against a constant 1 atm
pressure at constant temperature of 300 K :
(A) 7.78 kJ (B) –1.013 kJ (C) 11.73 kJ (D) –4.78 kJ
5. A thermodynamic system goes in cyclic reversible process as

represented in the following P–V diagram :
The net work done during the complete cycle is given by the area
: A
(A) cycle ACBDA (B) AA1B1BDA
(C) AA2B2B (D) AA1B1BCA
6. The valve on a cylinder containing initially 10 liters of an ideal gas at 25 atm and 250C is opened to the
atmosphere, where the pressure is 760 torr and the temperature is 250C. Assuming that the process is
isothermal, how much work in L atm is done on the atmosphere by the action of expanding gas ?
7. 20 g Ar gas is allowed to expand reversibly and isothermally at 300 K from 5 L to 10 L. Calculate the
approximate value of work done. (Take R = 8.3 J/K/mole, at.wt of Ar = 40)
8. A horizontal piston-cylinder arrangement is placed in a constant temperature bath. The piston slides in the
cylinder with negligible friction, and an external force holds it in place against an initial gas pressure of 14
bar. The initial gas volume is 0.03 m3.
(a) The external force on the piston is reduced gradually, allowing the gas to expand until its volume
doubles. Calculate the work done by the gas in moving the external force.
(b) How much work would be done if the same expansion is carried out by removing a part of the external
force suddenly. Also calculate efficiency of this process as compared with the reversible process.
9. Which of the following statements are correct (T/F) :
(a) Ist law of thermodynamics can be applied on the individual particle enclosed in vessel.
(b) Many thermodynamic properties cannot be measured absolutely, so change in thermodynamic property
is required for calculation.
(c) Feasibility of any chemical reaction cannot be explained by thermodynamics.
(d) When surroundings are always in equilibrium with the system, the process is called reversible.
(e) Between same initial and final states, work done by gas in isothermal irreversible expansion is less than
the work in isothermal reversible expansion.
DPPS FILE # 60

1. The graph given below shows the P-V plot for a process on an ideal gas. Select the correct statement :
(A) Enthalpy content of the gas is constantly increasing and the process is carried out slowly.
(B) Enthalpy content of the gas first increases, then decreases and the process is carried out quasistaticly.
(C) Enthalpy content of the gas is constant and the process takes infinite time for completion.
(D) Enthalpy content first decreases, then increases and the process is reversible.
2. The P-T graph, as given below, was observed for a process on an ideal gas. Which of the following
statement is true :
(A) W = +ve, H = +ve (B) W = –ve, H = – ve

(C) W = –ve, H = + ve (D) W = +ve, H = –ve
3. q, W, E and H for the following process ABCD on a monoatomic gas are :
(A) W = – 2 P0 V0 ln 2, q = 2 P0 V0 ln 2, E = 0, H = 0
(B) W = – 2 P0 V0 ln 2, q = 2 P0 V0 ln 2, E = 0, H = 2 P0 V0 ln 2
(C) W = – P0 V0 (1+ ln 2), q = P0 V0 (1+ ln 2) E = 0, H = 0
(D) W = – P0 V0 ln 2, q = P0 V0 ln 2, E = 0, H = 0
4. A system containing a real gas changes it's state form state-1 to state-2.
State-1 (3 atm, 2L, 300 K)
State-2 (5 atm, 4L, 500 K)
If change in internal energy = 30 L atm, then calculate change in enthalpy :
(A) 44 L atm (B) 35 L atm (C) 40 L atm (D) None of these
DPPS FILE # 61
5. A liquid which is confined inside an adiabatic piston is suddenly taken from state-1 to state-2 by a single
stage irreversible process. If the piston comes to rest at point 2 as shown, then the enthalpy change for the
process will be :
2  P0 V0 3  P0 V0
(A) H = (B) H = (C) H = –P0 V0 (D) None of these
 1  1
6. The correct figure representing isothermal and adiabatic expansions of an ideal gas from a particular initial
state is :
(A) (B) (C) (D)
7. P–V plots for two gases during an adiabatic process are given in the figure :
Plot A and plot B should correspond to :

(A) He and O2 (B) He and Ar (C) O2 and He (D) O2 and F2
Comprehension # (Q. Nos. 8 to 10)
One mole of Helium gas undergoes a reversible cyclic

process ABCDA as
shown in the figure. Assuming gas to be ideal, answer
the following questions:
8. What is the value of H for the overall cyclic process :

(A) – 100 Rn2 (B) +100Rn2 (C) +200Rn2 (D) Zero
9. What is the value of 'q' for the overall cyclic process :

(A) – 100 Rn2 (B) +100Rn2 (C) +200Rn2 (D) –200Rn2
10. What is the net work involved in the cyclic process :

(A) – 100 Rn2 (B) +100Rn2 (C) +200Rn2 (D) –200Rn2
DPPS FILE # 62

3
1. A monoatomic ideal gas (CV = R) is allowed to expand adiabatically and reversibly from initial volume of
2
8L at 300 K to a volume of V2 at 250 K. V2 is : (Given (4.8)1/2 = 2.2)

(A) 10.5 L (B) 23 L (C) 8.5 L (D) 50.5 L
2. A gas is expanded from volume V0 to 4V0 by following two ways : (from same initial state)
(a) st using reversible isothermal expansion from V0 to 2V0 , then using reversible adiabatic expansion from
2V0 to 4V0 .
(b) st using reversible adiabatic expansion from V0 to 2V0, then from 2V0 to 4V0 using reversible isothermal
expansion.
Then which of the following options is correct :
(A) Work done in (a) process > work done is (b) process
(B) Work done in (b) process > work done is (a) process
(C) Work done in (b) process = work done is (a) process
(D) cannot be predicted
3. Consider the cyclic process R  S  R as shown in the Fig. You told that one of the path is adiabatic
and the other one isothermal. Which one of the following is(are) true :
(A) Process R  S is isothermal (B) Process S  R is adiabatic
(C) Process R  S is adiabatic (D) Such a graph is not possible
DPPS FILE # 63
4. A sample of gas is compressed from an initial volume of 2v 0 to v 0 using three different processes.
First : Using reversible isothermal
Second : Using reversible adiabatic
Third : Using irreversible adiabatic under a constant external pressure
Then :
(A) Final temperature of gas will be highest in third process.
(B) Final temperature of gas will be highest in second process.
(C) Enthalpy change of sample will be highest in isothermal process. (magnitude wise)
(D) Final pressure of gas will be highest in second process.
5. The magnitude of enthalpy changes for irreversible adiabatic expansion of a gas from 1L to 2L is H1 and
for reversible adiabatic expansion for the same expansion, it is H2. Then :
(A) H1 > H2
(B) H1 < H2
(C) H1 = H2, enthalpy being a state function
(D) H1 = E1 & H2 = E2
6. In which process, net work done by gas is zero :

(A) Cyclic (B) Isobaric (C) Free expansion (D) Adiabatic
7. The ratio of slopes of P–V plots for reversible adiabatic process and reversible isothermal process of an
ideal gas is equal to :
(A)  (B) 1 –  (C) (– 1) (D) 1/
8. 2 moles of an ideal gas A ( = 4/3) and 4 moles of an ideal gas B ( = 5/3) are taken together in a container
and expanded reversibly and adiabatically from 2 L to 8 L starting from initial temperature of 320 K.
Calcualte the work done by the gas (in calories) in the above process. (R = 2 calories/K/mol)
9. 1 mole of an ideal gas, initially at 400 K and 10 atm is first expanded at constant pressure till the volume is
doubled. Then the gas is made to undergo an isochoric process, in which its temperature is found to
decrease. In the last final step, gas was compressed reversibly and adiabatically to initial state. Determine
the net work involved in this cyclic process (in terms of R). Given, CV for gas = 1.5 R, (4)– 1/3 = 0.63.
10. Polytropic process for ideal gas is given as PVn = constant. Show that for polytropic process for an ideal
gas, the expression for work obtained is :
 1n 
V 
P1V1  2   1
 V1  
W  
(n  1)
DPPS FILE # 64

1. The species which by definition has zero standard molar enthalpy of formation at 298 K is :
(A) CO2 (g) (B) H2O () (C) O2 (g) (D) P4 (red)
2. Consider the following processes
(i) 1/2 H2 (g) + aq.  H+ (aq.) (ii) 2O(g)  O2(g)
(iii) NH4+ (g) + Cl– (g)  NH4Cl(s) (iv) P4 (black) + 5O2(g)  P4O10(s)
Which of the above does not represent Hformation of the product :
(A) I,IV (B) II, IV (C) I, II, III (D) II , III, IV
3. The difference between heat of reaction at constant pressure and constant volume for the reaction given
below at 27ºC in kJ is : (Take R = 8.3 J/K/mole) 2 C6H6 () + 15 O2 (g)  12 CO2 (g) + 6H2O ()
(A) –7.47 (B) + 3.72 (C) – 3.72 (D) + 7.47
4. For the two reactions given below :
H2(g) + ½O2(g)  H2O () + x1 kJ mol–1
H2(g) + ½O2(g)  H2O (g) + x2 kJ mol–1
Compare the magnitude of x1 and x2 : (x1 and x2 are the heat released in above two process.)
(A) x1 > x2 (B) x1 < x2 (C) x1 = x2 (D) x2 = 2x1
5. The combustion of 0.2 mol of liquid carbon disulphide CS2 to give CO2(g) and SO2(g) releases 215 kJ of
heat. What is Ho for CS2(l) in kJ mol–1 :
 H o kJ mol–1
CO2(g) –393.5
SO2(g) –296.8
(A) 772.1 (B) 87.9 (C) –385 (D) – 475

6. Consider the following changes
Na+(g)  Na+(aq) H1 .... (1) Na(s)  Na(g) H2 .... (2)
– –
Cl (g)  Cl (aq) H3 .... (3) Cl2(g)  2Cl(g) H4 .... (4)
Na+(g) + Cl(g)  NaCl (s)+ e– H5 .... (5) NaCl(s)  Na+(aq) + Cl– (aq) H6 .... (6)
Hydration enthalpy of NaCl can be defined by sum of the following :
(A) H1 + H4 (B) H1 + H5 (C) H1 + H3 (D) H6 only
7. Given that S(s) + 3/2 O2(g)  SO3(g) + 2x Kcal ; SO2(g) + 1/2 O2(g)  SO3(g) + y Kcal
What would be the enthalpy of formation of SO2 :
(A) – 2x + y (B) 2x + y (C) x + y (D) 2x/y
8. From the follwing data :
(i) C(graphite) + O2 (g)  CO2 (g) ; H1 =  94.1 KCal
(ii) C(diamond)  C(graphite) ; H2 =  0.5 KCal
Calculate H for burning of diamond to CO2 .
9. The standard enthalpies of formation at 298 K for CCl4 (g) , H2O (g) , CO2 (g) and HCl (g) are  25.5 , 
57.8 ,  94.1 &  22.1 K Cal/mole respectively . Calculate  Hº298 for the reaction :
CCl4 (g) + 2 H2O (g)  CO2 (g) + 4 HCl (g).
DPPS FILE # 65

1. For the reaction,

1 1
A2 (g) + B2 (g)  AB (g) ; H = – 50 KCal.
2 2
x
If the bond energies of A2, B2 and 'AB' are respectively x, and x KCal, the value of x is :
2
(A) 50 (B) 100 (C) 200 (D) 400
2. The enthalpy of neutralization of 40 g of NaOH by 60 g of CH3COOH will be :
(A) 57.1 kJ equiv –1 (B) less than 57.1 kJ equiv –1
(C) more than 57.1 kJ equiv –1 (D) 13.7 kJ equiv –1
3. The heat evolved in neutralizing a solution containing 1mole of HCN with a strong alkali is 3 KCal. The
enthalpy of dissociation of HCN is :
(A) 10.2 KCal (B) 13.7 KCal (C) 10.7 KCal (D) 16.7 KCal
4. Hf° for the chloride ion (aq) from the following data will be :
1 1
H2 (g) + Cl2 (g)  HCl(g) ; Hf° = – 92.4 kJ
2 2
HCl(g) + nH2O  H+ (aq) + Cl– (aq.) ; H° = – 74.8 kJ
Hf° H+ (aq.) = 0.0 kJ

(A) 167.2 kJ (B) – 167.2 kJ (C) 334.4 kJ (D) – 334.4 kJ
5. The polymerisation of ethylene to linear polyethylene is represented by the reaction :
n CH2 = CH2  (CH2  CH2)n where n has a large integral value. Given that the average enthalpies of
bond dissociation for C = C & C  C at 298 K are  590 & + 331 KJ mol1 respectively. Then the enthalpy of
polymerisation per mole of ethylene at 298 K will be :
(A) 72 kJ/mol (B) – 72 kJ/mol (C) 36 kJ/mol (D) – 36 kJ/mol
6. Assuming that 50% of the heat is useful, how many kg of water at 15ºC can be heated to 95ºC by burning
280 litre of methane at STP ? The heat of combustion of methane is 240 KCal/mol.
7. One litre sample of a mixture of CH4 and O2 measured at 27ºC and 760 torr, was allowed to react at
constant pressure in a calorimeter. The complete combustion of CH4 to CO2 and water caused a temperature
rise in calorimeter of 0.667 K. Calculate mole % of CH4 in original mixture. (R = 1/12L atm/K/mole)
8. The specific heats of iodine vapour and solid are 0.031 Calg–1 ºC–1 and 0.055 Calg–1 ºC–1 respectively. If
heat of sublimation of iodine is 24 Cal/g at 200ºC, what is its value at 250ºC ?
9. Calculate the heat of formation of HCl (g) from :
NH3(aq) + HCl(aq.)  NH4Cl(aq.) ; H = – 12.1 KCal
1 3
N (g) + H (g)  NH3(g) ; H = – 11.0 KCal
2 2 2 2
Heat of formation of NH4Cl(s) ; H = – 75.3 KCal
Heat of solution of NH3(g) ; H = – 8.8 KCal
Heat of solution of HCl(g) ; H = – 17.5 KCal
NH4Cl(s) + Aq.  NH4Cl(aq.) ; H = + 3.8 KCal
DPPS FILE # 66

Single choice Objective ('–1' negative marking) Q.8, 10, 11 (3 marks, 3 min.) [9, 9]
Subjective Questions ('–1' negative marking) Q.1 to Q.7, 9 (4 marks, 5 min.) [32, 40]
1. The standard molar enthalpies of formation of ethane, CO2 & liquid water are  21.1,  94.1 and  68.3 kCal
respectively. Calculate the standard molar enthalpy of combustion of ethane.
2. The enthalpies of combustion of C2H4 (g), C2 H6 (g) & H2 (g) are  1409.5 kJ,  1558.3 kJ and  285.6 kJ
respectively. Calculate the enthalpy of hydrogenation of ethylene.
3. The standard enthalpy of combustion at 25ºC of hydrogen (H2), cyclohexene (C6H10) and cyclohexane
(C6H12) are  241,  3800 and  3920 kJ/mole respectively. Calculate the enthalpy of hydrogenation of
cyclohexene.
4. Calculate the enthalpy of combustion of carbon monoxide at constant volume, given the following enthalpy
of reactions at constant pressure at 17ºC :
(i) C (s) + O2 (g)  CO2 (g) ; H1 =  97000 Cal
(ii) CO2 (g) + C (s)  2 CO (g) ; H2 = 39000 Cal
5. The bond dissociation energies of gaseous H2 , Cl2 & HCl are 104 , 58 & 103 kCal/mole respectively.
Calculate the enthalpy of formation of HCl gas.
6. Determine the enthalpy of hydrogenation of ethylene from the following data .
Bond Bond energy Bond Bond energy
HH 104 kCal/mol CC 80 kCal/mol
CH 99 kCal/mol C=C 145 kCal/mol
7. Calculate the bond energy of C = C from the following data. All H units are in kCal.
2 C (s) + 2 H2 (g)  C2H4 (g) H = 12.5
C (s)  C (g) H = 170.9
H2 (g)  2 H (g) H = 104.2
Bond energy of C  H bond is 99 kCal/mol.
8. Enthalpy of atomisation of NH3 and N2H4 are x kcal mol–1 and y kcal mol–1 respectively. Calculate average
bond energy of N—N bond :
4y  3x 2y  3 x 4y  3x 3y  4 x
(A) kCal mol–1 (B) kCal mol–1 (C) kCal mol–1 (D) kCal mol–1
3 3 4 3
9. From the following bond energy and standard Hº values for the formation of elements in gaseous state,
calculate the standard enthalpy of formation of acetone(g) :
Standard Hº Bond energies
H (g) = 52 kCal/mol C  H = 99 kCal/mol
O (g) = 59 kCal/mol C  C = 80 kCal/mol
C (g) = 171kCal/mol C = O = 81 kCal/mol
10. The enthalpy of neutralization of a strong base and strong acid is 57.0 kJ eq–1 . The heat evolved when 0.5
moles of HNO3 are added to 1 L of 0.2 M NaOH solution is :
(A) 57.0 kJ (B) 28.5 kJ (C) 11.4 kJ (D) 34.9 kJ
11. For strong acid and strong base neutralization, net chemical change is :
H+ (aq) + OH– (aq) —— H2O (  ); rHº = – 57.1 kJ/mol
If enthalpy of neutralization of CH3COOH by HCl is –50 kJ/mol, then enthalpy of ionisation of CH3COOH is :
(A) 7.1 kJ/mol (B) –7.1 kJ/mol (C) 107.1 kJ/mol (D) –107.1 kJ/mol
DPPS FILE # 67

1. Given the following standard enthalpies of reaction :

(i) Enthalpy of formation of water =  68.3 kCal/mol
(ii) Enthalpy of combustion of acetylene =  310.6 kCal/mol
(iii) Enthalpy of combustion of ethylene =  337.2 kCal/mol
Calculate the heat of reaction for the hydrogenation of acetylene at constant volume and 25º C.
2. The internal energy change of the comubstion of C6H6 (g) and C2H2 (g) at 300 K are – 800 Kcal/mole and
– 300 Kcal/mole respectively. What is the enthlapy of polymerisation of C2H2 (g) to C6H6 (g) per mole of
C6H6 (g) produced ? C6H6 (g), C2H2 (g) and C2H6 (g) behave ideally. R = 2 cal K–1 mol–1.
(A) – 100 K Cal/mol (B) – 101.2 K Cal/mol (C) –98.8 K Cal/mol (D) – 103.6 K Cal/mol
3. The dissociation energy of CH4 is 360 kCal/mol and of ethane is 620 kCal/mol. Calculate C  C bond
energy.
4. Estimate rH for 2 C4H10 (g)  C8H18 (g) + H2 (g). Given bond energy of C  C and C  H are 347 and
441 kJmol 1. The enthalpy of formation of H (g) atom is 217.5 kJmol 1.
5. The average energy required to break a P – P bond in P4 (s) into gaseous atoms is 53.3 kcal mol–1. The
bond dissociation energy of H2(g) is 104.3 kcalmol–1 ; Hf0 of PH3(g) from P4(s) is 5.4 kcalmol–1. The
P-H bond energy in kcal mol–1 is : [Neglect presence of Vanderwaal forces in P4(s)]
(A) 85.2 (B) 57.6 (C) 77 (D) 63.3
6. Using the data (all values are in kilocalories per mole at 25ºC) given below, calculate the bond energy of
C  H and C  C bonds.
 Hºcombustion (ethane) g =  372 ;  Hºcombustion (propene) g =  530
 Hº for C (graphite)  C (g) = 172 ; Bond energy of H  H bond = 104
 Hfº of H2O (l) =  68 ;  Hfº of CO2 (g) =  94
7. Determine the enthalpy change of the reaction : C3H8 (g) + H2 (g)  C2H6 (g) + CH4 (g) at 25 ºC , using the
given enthalpy of combustion values under standard condition :
Compound H2 (g) CH4 (g) C2H6 (g) C (graphite)
 Hº (kJ/mole)  286  890  1560  393.5
The standard enthalpy of formation of C3H8 (g) is  104 kJ/mole.
8. The standard molar enthalpies of formation of cyclohexane () and benzene () at 25° C are –156 and +49
KJ mol–1 respectively. The standard enthalpy of hydrogenation of cyclohexene () at 25°C is –119 KJ mol–
1
. Use these data to estimate the resonance energy of benzene in KJ mol–1.
9. The enthalpy of solution of anhydrous CuSO4 is  15.9 kCal/mol and that of CuSO4 . 5 H2O is 2.8 kCal/mol.
Calculate the enthalpy of hydration of CuSO4.
10. Calculate Hfº for chloride ion (aq) from the following data :
1 1
H2 (g) + Cl (g)  HCl (g) Hºf =  92.4 kJ
2 2 2
HCl (g) + n H2O  H+ (aq) + Cl (aq) Hº298 =  74.8 kJ
Hºf (H+) aq = 0.0 kJ
DPPS FILE # 68

Single choice Objective ('–1' negative marking) Q.1 (3 marks, 3 min.) [3, 3]
1. For a gas having molar mass M, specific heat at constant pressure can be given as :
R  M  RM
(A) M (   1) (B) (C) R (   1) (D)
RM  1
2. 1 mole of ice at 0ºC and 4.6 mm Hg pressure is converted to water vapour at constant temperature and
pressure. Find H and E if the latent heat of fusion of ice is 80 Cal/g and latent heat of vaporisation of
liquid water at 0ºC is 596 Cal/g and the volume of ice in comparison to that of water vapour is neglected.
3. Calculate q, W and E when 100 g of calcite form of CaCO3 is converted into its aragonite form at 100 bar
pressure. Given density of calcite = 2 g/cc, density of aragonite = 2.5 g/cc and
CaCO3 CaCO3 H = 2 kJ/mole
Calcite Aragonite
4. A person inhales 640 g of O2 per day. If all the O2 is used for converting sugar into CO2 and H2O, how much
sucrose (C12H22O11) is consumed in the body in one day and what is the heat evolved ? H (combustion of
sucrose) = – 5472 kJ/mol.
Comprehension # (Q.5 to Q.9)
Enthalpy of sublimation may be determined experimentally, but instead of that let us explore an easier route
for its calculation. Figure-1 shows the three phases of water on an enthalpy scale. Since enthalpy is a state
function, enthalpy changes depend only on the initial and the final states and not on the path. Therefore, we
must find the same value for enthalpy change whether the system goes directly from solid to gas or through
the intermediate state of liquid. Therefore, Hsub = Hfus + Hvap ....(1)
There is a small oversight in the way we obtained Hsub . Equation (1) is true only if enthalpies are
independent of temperature or if their values are measured or deduced at the same temperature. Suppose
we have enthalpy data at different temperatures as is usually the case. How do we proceed then?
We will illustrate the procedure with an estimate of Hsub at 0°C from Hvap at 100°C and Hfus at 0°C. In
order to calculate Hsub at 0°C, figure-2 shows that the heat absorbed in the process
Solid (0°C)  Gas (0° C)
is equal to the heat absorbed in the process
Solid (0°C)  Liquid (0°C)  Liquid (100°C)  Gas (100 °C)  Gas (0°C)
Figure-1 Figure-2
DPPS FILE # 69
The enthalpy of sublimation at 0°C is therefore given by :
373 273
Hsub (0°C) = Hfus (0° C) +  Cp (liquid) dT + H (100°C) +  Cp (gas ) dT

vap
273 373
During chemical reactions also, we may not obtain the products at the temperature at which reactant were
present initially. Then too, we can calculate the enthalpy change during the reaction at temperature of
reactants. The basis of Kirchoff's equations in thermodynamics is also the same. The Kirchoff's equations
are :
T2
At constant pressure : H2º = H1º +  C

T1
P dT
Where H1º is enthalpy change of reaction at temperature T1,

and H2º is enthalpy change of reaction at temperature T2.
CP is difference in molar heat capacities at constant pressure of products and reactants.
Similarly
T2
At constant volume : E2º = E1º +  C

T1
V dT
USE THE FOLLOWING DATA :

Molar heat capacity of
H2O (solid) = 40 J K–1 mol–1
H2O (liquid) = 75 J K–1 mol–1
H2O(vapour) = 30 J K–1 mol–1
Latent heat of vaporisation = 40 kJ mol–1
Latent heat of fusion of H2O = 6 kJ mol–1
5. Molar enthalpy of vaporisation of H2O at 0°C is :

(A) 44 kJ mole–1 (B) 44.5 kJ mole–1 (C) 50.5 kJ mole–1 (D) – 44.5 kJ mole–1
6. Molar enthalpy of sublimation of H2O at 223 K is :

(A) 48 kJ mole–1 (B) 40 kJ mole–1 (C) 51 kJ mole–1 (D) 53 kJ mole–1
7. If enthalpy change of reaction :
H2O()  H2O (g) at 300 K is 43285 J mole–1, then enthalpy change at 400 K will be :
(A) 34285 J mole–1 (B) 43285 J mole–1 (C) 47785 J mole–1 (D) 38785 J mole–1
8. For a chemical reaction, CP is negative (CP < 0).

The heat required to increase temperature of reactants of this reaction by a certain amount = q1 and heat
required to increase temperature of products of the same reaction by same amount = q2. Then :
(A) q1 > q2
(B) q1 < q2
(C) q1 = q2
(D) q1 may or may not be equal to q2 and it will depend on nature of reactants and products.
9. If for reaction :
N2 (g) + 3H2 (g)  2NH3 (g),H1º = – 30 kJ/mole at temperature 300 K and if specific heat capacities
of different species are sP, N2 = 1 J/gºC, sP, H2 = 10 J/gºC and sP, NH3 = 2 J/g ºC, then H2º at 400 K for the
same reaction will be : (assume heat capacities to be constant in given temperature range)
(A) – 32 kJ/mole (B) – 28 kJ/mole (C) – 32.7 kJ/mole (D) – 27.3 kJ/mole
DPPS FILE # 70

Single choice Objective ('–1' negative marking) Q.1 to Q.4, 6, 7, 9, 10 (8 marks, 8 min.) [24, 24]
1. In which of the following cases, generally entropy decreases :

(A) Solid changing to liquid (B) Expansion of a gas
(C) Crystal dissolves (D) Polymerisation
2. Predict which of the following reaction(s) have a positive entropy change ?
I. Ba2+ (aq) + SO42– (aq)  BaSO4 (s)
II. CaCO3 (s)  CaO (s) + CO2 (g)
III. 2SO3 (g)  2SO2 (g) + O2 (g)
(A) I and II (B) III (C) II and III (D) II
3. Which of the following reactions is expected to have the most negative change in entropy ?
(A) N2 (g) + 3H2 (g)  2NH3 (g) (B) C2H2 (g) + 2H2 (g)  C2H6 (g)
(C) C (s) + O2  CO2(g) (D) 2NO2 (g)  N2O4 (s)
4. Which statement regarding entropy is correct ?

(A) A completely ordered deck of cards has more entropy than a shuffled deck in which cards are arranged
randomly.
(B) A perfect ordered crystal of solid nitrous oxide has more entropy than a disordered crystal in which the
molecules are oriented randomly.
(C) 1 mole N2 gas at STP has more entropy than 1 mole N2 gas at 273 K in a volume of 11.2 litre.
(D) 1 mole N2 gas at STP has more entropy than 1 mole N2 gas at 273 K and 0.25 atm.
5*. Select the correct option(s) :

(A) Specific volume and molar heat capacity are intensive parameters.
(B) For an irreversible adiabatic compression process, entropy change of surrounding will be equal to zero.
(C) Change in internal energy for an ideal gas for an isobaric process is expresed as U = nCV (T2 – T1),
where the terms used have their usual meaning.
(D) Free expansion is a reversible process.
6. Two moles of an ideal gas ( = 4/3) is made to expand reversibly and adiabatically to 4 times its initial
volume. The change in entropy of the system during expansion is : (Given : R = 2 cal/K/mole, log102 = 0.3,
log103 = 0.48)
(A) 5.6 cal/k (B) 11.2 cal/k (C) 2.8 cal/k (D) None of these
DPPS FILE # 71
7. Two moles of an ideal monoatomic gas expands isothermally against a constant external pressure of 2
atm from an initial volume of 22.4 L to a state where its final pressure becomes equal to external pressure.
If the initial temperature of gas is 273°C, then the entropy change of system in the above process is :
[Given : 1 mole of an ideal gas occupies 22.4 L at STP conditions]
(A) R ln 16 (B) R ln 4 (C) R ln 8 (D) Zero
8. The enthalpy of vapourisation of liquid diethyl ether is 26 kJ/mol at its boiling point (52°C). Calculate S for
conversion of : (a) liquid to vapour, and (b) vapour to liquid at 52°C.
9. When two equal sized pieces of the same metal, each of mass m at different temperatures Th (hot piece)
and TC(cold piece) are brought into contact and isolated from surrounding, the total change in entropy of
system is given by : (Specific heat capacity of metal = s)
TC  Th Th (TC  Th )2 (TC  Th )2
(A) ms ln 2T (B) ms ln T (C) ms ln (D) ms ln
C C 2Th TC 4Th TC
10. One mole of an ideal monoatomic gas at 27ºC is subjected to a reversible isoentropic compression until
final temperature reached to 327ºC. If the initial pressure was 1.0 atm, then find the value of In P2:
(Given : In 2 = 0.7).
DPPS FILE # 72

Subjective Questions ('–1' negative marking) Q.1, 2, 5, 9, 10 (4 marks, 5 min.) [20, 25]
1. A sample of certain mass of an ideal polyatomic non-linear gas is expanded against constant pressure of
1 atm adiabatically from volume 2 L, pressure 6 atm and temperature 300 K to a state, where its final
volume is 8 L. Then calculate entropy change of system (in J / K ) in the process : (Neglect vibrational
degrees of freedom) [1L atm = 100 J, log 2 = 0.3, log 3 = 0.48, log e = 2.3]
2. 2 moles of an ideal monoatomic gas undergo a reversible process for which P2V = constant. The gas
sample is made to expand from initial volume of 1L to final volume of 4L starting from initial temperature of
300K. Find the value of Ssys for the above process. Report your answer as 'X' where Ssys = XRn2.
3.* For Isothermal expansion against constant external pressure of an ideal gas :
(A) Suniv > 0 (B) Ssys > 0
(C) Ssurr < 0 (D) Ssurr = 0
4.* For an adiabatic free expansion of an ideal gas against vacuum, which of the following parameters has/
have zero value :
(A) q (B) H
(C) Ssurr. (D) Ssys.
5. How many of the given statements are correct :

I : Molar entropy of a substance follows the order (Sm)Solid < (Sm)liquid < (Sm)gas
II: Entropy change of system for the reaction H2(g) 2H(g) is +ve.
III: Molar entropy of a non-crystalline solid will be zero at absolute zero.
IV: If the path of an irreversible process is reversed, then both system and surroundings shall be restored
to their orginal states.
V : Refractive index and molarity are intensive properties.
6. The spontaneous nature of a reaction is impossible if :
(A) H is +ve and S is also +ve (B) H is – ve and S is also – ve
(C) H is – ve ; S is + ve (D) H is + ve ; S is – ve
7. If a chemical reaction is non-spontaneous at high temperatures and spontaneous at low temperatures,

then:
(A) H > 0 and S > 0 (B) H > 0 andS < 0
(C) H < 0 and S > 0 (D) H < 0 and S < 0
8. For the process H2O() (1 bar, 373 K) H2O(g) (1 bar, 373 K), the correct set of thermodynamic
parameters is:
(A) G = 0 (B)S > 0
(C) H > 0 (D) G = –ve
9. For a perfectly crystalline solid, (CP)m = aT3, where a is a constant. If (CP)m at 10K is 0.375 J/K-mol, then
find the value of molar entropy at 20K (in J/K-mol).
10. What is the free energy change (G) in KCal, when 144 g of water at 100ºC and 1 atm pressure in
converted into steam at 100ºC and 4 atm pressure ? (Take R = 2 Cal/K/mole, n 2 = 0.7).
Give your answer rounding it off to the nearest whole number.
DPPS FILE # 73
Topic : Mole Concept and Atomic Structure

Topic : Mole Concept
Topic : Atomic Structure
1. The weight of a molecule of the compound C6H12O6 is about :

(A) 180 g (B) 3 × 10–22 g (C) 22 × 10–23 g (D) 132 g
2. A person adds 1.71 gram of sugar (C12H22O11) in order to sweeten his tea. The number of carbon atoms
added are : (Mol. mass of sugar = 342)
(A) 3.6 × 1022 (B) 3 × 1021 (C) 3.6 × 1023 (D) 3 × 1022
3. If V ml of the vapours of substance at NTP weight W mg, then mol. wt. of substance in amu is :
V W
(A) (W/V) × 22400 (B) × 22.4 (C) (V/W) × 22400 (D) × 22.4
W V
4. Percentage of Se in peroxidase anhydrous enzyme is 0.5% by weight. Then min. mol. wt. of peroxidase
anhydrous enzyme is : (at. wt. of Se = 78.4 amu)
(A) 1.568 × 104 (B) 1.568 × 103 (C) 15.68 (D) 1.568 × 102
5. Caffine has a molecular weight of 194. It contains about 30% by mass of nitrogen. The number of atoms
of nitrogen in one molecule of it is :
(A) 2 (B) 3 (C) 4 (D) 5
1
6. Vapour density of a gas, if its density is g/L at NTP, is :
5.6
(A) 1 (B) 2 (C) 4 (D) 8
7. Assuming that petrol is iso-octane (C8H18) and has a density 0.8 g ml–1, 1.425 litre of petrol on complete
combustion will consume what amount of oxygen :
(A) 250 L (B) 125 L (C) 125 mole (D) 250 mole
8. The volume of gas at NTP produced by reaction of 128 g of CaC2 with excess of water is :
(A) 44.8 litre (B) 89.6 litre (C) 67.2 litre (D) 22.4 litre
9. If 0.5 mole of BaCl2 is mixed with 0.1 mole of Na3PO4, the maximum number of mole of Ba3(PO4)2 that
can be formed is :
(A) 0.166 (B) 0.05 (C) 0.6 (D) 0.1
10. A 21.6 g silver coin is dissolved in HNO3. When NaCl is added to this solution, all silver is precipitated as
AgCl. The weight of AgCl is found to be 14.35 g. Then % of silver in coin is :
(A) 50% (B) 75% (C) 100% (D) 15%
11. What is the concentration of nitrate ions if equal volumes of 0.1 M AgNO3 and 0.1 M NaCl solutions are
mixed together :
(A) 0.1 M (B) 0.2 M (C) 0.05 M (D) 0.25 M
12. 300 ml of 3.0 M NaCl is added to 200 ml of 4.0 M BaCl2 solution. The concentration of Cl– ions in the
resulting solution is :
(A) 4.5 M (B) 3.4 M (C) 6 M (D) 5 M
DPPS FILE # 74
13. One mole of potassium chlorate is thermally decomposed and excess of aluminium is burnt in the gaseous
product. How many mole of aluminium oxide are formed :
(A) 1 (B) 1.5 (C) 2 (D) 3
14. Calculate the mole of FeO produced from 1.34 g VO & 4.8 g Fe2O3 :
VO + Fe2O3  FeO +V2O5 (At. wt. of V = 51)
(A) 0.06 (B) 0.03 (C) 0.12 (D) 0.015
15. Mole fraction of A in aqueous solution is 0.2. The molality of solution is :
(A) 13.9 (B) 15.5 (C) 14.5 (D) 16.8
16. What is the quantity of water that should be added to 16 g methanol to make the mole fraction of methanol
in solution as 0.25 :
(A) 27 g. (B) 12 g. (C) 18 g. (D) 36 g.
17. If 100 ml of 1M H2SO4 solution is mixed with 100 ml of 9.8%(w/w) H2SO4 solution (d = 1 g/ml), then :
(A) concentration of solution increases (B) concentration of solution decreases
(C) mass of H2SO4 in the solution is 1.96 g (D) mass of H2SO4 in the solution is 19.6 g
18. Match List-I (Compounds) with List-II (Oxidation states of Nitrogen) and select answer using the codes
given below the lists :
List-I List-II
(a) NaN3 (1) +5
(b) N2H2 (2) +2
(c) NO (3) –1/3
(d) N2O 5 (4) –1
(Code) :
(a) (b) (c) (d) (a) (b) (c) (d)
(A) 3 4 1 2 (B) 4 3 2 1
(C) 3 4 2 1 (D) 4 3 1 2
19. The incorrect order of decreasing oxidation number of S in compounds is :

(A) H2S2O7 > Na2S4O6 > Na2S2O3 > S8
(B) H2SO5 > H2SO3 > SCl2 > H2S
(C) H2SO4 = H2S2O8 > SO2 > H2S
(D) SO3 > SO2 > H2S > S8
20. For the redox reaction MnO4– + C2O42– + H+  Mn2+ + CO2 + H2O,
the correct whole number stoichiometric coefficients of MnO4–, C2O42– and H+ are respectively :
(A) 2, 5, 16 (B) 5, 2, 8 (C) 2, 5, 8 (D) 5, 2, 16
Topic : Atomic Structure

1
1. The charge-to-mass ratio for A3+ ion is about × 108 C kg–1. Calculate the approximate mass of A atom
9
:
(A) 4.5 × 10–26 kg (B) 1.5 × 10–26 kg (C) 1.5 × 10–28 kg (D) 4.5 × 10–28 kg
2. Which of the following is isoelectronic with P3– :
(A) Cl– (B) Mg2+ (C) Both (A) & (B) (D) None of these
3. Light of wavelength  falls on metal having work function hc/0. Photoelectric effect will take place only if :
(A)   0 (B)   20 (C)   0 (D)   0/2
4. A photon of X region is more energetic than of the visible region. X may be :
(A) Infrared (B) Ultra violet (C) Microwave (D) Radio wave
5. A bulb of 40 W is producing a light of wavelength 620 nm with 80% of efficiency. Then the number of
photons emitted by the bulb in 20 seconds are :
(A) 2 × 1018 (B) 1018 (C) 1021 (D) 2 × 1021
DPPS FILE # 75
6. The ionization energy of He+ is 19.6 × 10–18 J ion–1. The energy of the first stationary state of Be3+ will be :
(A) 15.68 × 10–17 J/ion (B) 78.4 × 10–18 J/ion (C) 4.9 × 10–18 J/ion (D) 39.2 × 10–18 J/ion
7. Which of the following electron transition in a hydrogen atom will require the largest amount of energy :
(A) From n = 1 to n = 2 (B) From n = 2 to n = 3 (C) From n =  to n = 1 (D) From n = 3 to n = 5
8. S1 : Potential energy of the two opposite charge system increases with the decrease in distance.
S2 : When an electron make transition from higher orbit to lower orbit, its kinetic energy increases.
S3 : When an electron make transtition from lower energy to higher energy state, its potential energy
increases.
S4 : 11eV photon can free an electron from the 1st excited state of He+ ion.
(A) T T T F (B) F T T F (C) F T F T (D) T F F T
9. If r1 is the radius of the first orbit of hydrogen atom, then the radii of second, third and fourth orbits in terms
of r1 are :
(A) r12, r13, r14 (B) 8r1, 27r1, 64r1 (C) 4r1, 9r1 16r1 (D) 2r1, 3r1, 4r1
10. If the series limit wavelength of the Lyman series for the hydrogen atom is 912 Å, then the series limit
wavelength for the Balmer series of the Li2+ ion is :
9 4 2 4
(A) 912 × Å (B) 912 × Å (C) 912 × Å (D) 912 × Å
4 9 9 3
11. In hydrogen spectrum, which of the following has some of its lines in the wavelength range 350 –700 nm :
(A) Balmer series (B) Lyman series (C) Brackett series (D) Paschen series
12. In a sample of H-atom, electrons make transition from 5th excited state upto ground state, producing all
possible types of photons. Then, maximum number of lines in infrared region are :
(A) 4 (B) 5 (C) 6 (D) 3
13. Calculate wavelength of 3rd line of Bracket series in hydrogen spectrum :
33 33 R 784 R 784
(A) 784 R (B) (C) 33
(D) 33 R
784
14. A ball weighs 25 g and moves with a velocity of 6.6  104 cm/sec. Then find out the de Broglie wavelength
:
(A) 0.4  10–33 cm (B) 0.4  10–31 cm (C) 0.4  10–35 cm (D) 0.4  10–37 cm
15. Calculate the de-Broglie wavelength of the electron in the ground state of hydrogen atom :
(A) 3.3284 x 10–10 m (B) 1.6642 x 10–10 m (C) 6.6568 x 10–10 m (D) Cannot be determined.
16. The uncertainity in position and velocity of an object are 10–10 m and 5.27  10–24 ms–1 respectively. Calculate
the mass of the object :
(A) 0.1 g (B) 1 g (C) 10 g (D) 100 g
17. A given orbital is labelled by the magnetic quantum number m = –1. This could be :
(A) p-orbital (B) d-orbital (C) f-orbital (D) All of these
18. An electron with n = 3 is in an orbital with only one radial node. The orbital angular momentum of the
electron will be :
h h h
(A) 0 (B) 6 (C) 2 2 (D) 6
2 
19. After np orbitals are filled, the next orbital filled will be :
(A) nd (B) (n + 1) p (C) (n + 1) s (D) (n – 1) s
20. The correct set of four quantum numbers for the valence electron of Rubidium (Z = 37) is :
1 1
(A) n = 6,  = 0, m = 0, s = + (B) n = 5,  = 1, m = 0, s = +
2 2
1 1
(C) n = 6,  = 1, m = 1, s = + (D) n = 5,  = 0, m = 0, s = +
2 2
DPPS FILE # 76
Topic : Gaseous State

1. At constant temperature, if pressure of an ideal gas increases by 1 %, the percentage decrease of volume
is :
(A) 1 % (B) 100/101% (C) 1/101% (D) 1/100%
2. A sample of ideal gas occupies 100 ml at 27°C and 740 mm pressure. When its volume is changed to 80
ml at 740 mm pressure, the temperature of the gas will be :
(A) 21.6 °C (B) 33°C (C) – 33°C (D) – 21.6°C
3. The correct representation of Charles' law is given by :
(A) (B) (C) (D)
4. The ratio of fraction pressure of a gaseous component to the total pressure of the gas mixture is equal to :
(A) mass fraction of the component (B) mole fraction of the component
(C) mass % of the component (D) mole % of the component
5. Same mass of CH4 and H2 is taken in a container. The partial pressure caused by H2 (where total pressure is
P) is:
8 1 1 3P
(A) P (B) P (C) P (D)
9 9 2 4
6. The molecular weight of a gas which diffuse through a porous plug at 1/6th of the speed of hydrogen under
identical conditions is :
(A) 12 (B) 72 (C) 36 (D) 24
7. The densities of hydrogen and oxygen are 0.09 and 1.44 g L–1 under same T and P conditions. If the rate
of diffusion of hydrogen is 1, then that of oxygen in the same units will be :
(A) 4 (B) 1/4 (C) 16 (D) 1/16
8. 50 ml of hydrogen diffuses out through a small hole from a vessel in 20 minutes. The time needed for 40 ml
of oxygen to diffuse out under identical conditions is :
(A) 4 min (B) 64 min (C) 96 min (D) 48 min
9. At the same temperature and pressure, which of the following gases will have the highest average
translational kinetic energy per mole ?
(A) Hydrogen (B) Oxygen (C) Methane (D) All have the same value
10. The ratio among most probable speed, average speed and root mean square speed is given by :
(A) 2 : 8/ : 3 (B) 8/ : 2 : 3 (C) 8/ : 2 : 3 (D) 2 : 8/ : 3
DPPS FILE # 77
11. The average translational kinetic energy for 14 grams of nitrogen gas at 127°C is nearly :
(A) 25 J (B) 50 J (C) 2500 J (D) 5000 J
12. The temperature at which rms speed of SO2 molecules is half that of He molecules at 300 K is :
(A) 75 K (B) 600 K (C) 2400 K (D) 1200 K
13._ A real gas most closely approaches the behaviour of an ideal gas at :
(A) 15 atm and 200 K (B) 1 atm and 273 K (C) 0.5 atm and 500 K (D) 15 atm and 500 K
14. An ideal gas can't be liquefied because :
(A) its critical temperature is always above 0°C.
(B) its molecules are relatively smaller in size.
(C) it solidifies before becoming a liquid.
(D) forces operative between its molecules are zero.
15._ The compressibility factor for an ideal gas is :

(A) 0 (B) 1 (C) 3/8 (D) 
16._ The Vander Waal's parameters for gases W,X,Y and Z are :
Gas a (atm L2 mol –2 ) b ( L mol –1 )

W 4 .0 0.027
X 8.0 0.030
Y 6.0 0.032
Z 12.0 0.027
Which of these gases has the highest critical temperature ?

(A) W (B) X (C) Y (D) Z
17. Densities of two ideal gas samples containing same gas are in the ratio 1 : 2 and their temperatures are in
the ratio 2 : 1. Then the ratio of their respective pressure is :
(A) 1 : 1 (B) 1 : 2 (C) 2 : 1 (D) 4 : 1
18. The root mean square speed of an ideal gas at constant pressure varies with density (d) as :
(A) d2 (B) d (C) d (D) 1 d
19. A 4 : 1 molar ratio mixture of helium and methane is contained in a vessel at 10 bar pressure. Due to a hole
in the vessel, the gas mixture leaks out. The molar ratio composition of the mixture effusing out initially is
:
(A) 8 : 1 (B) 16 : 1 (C) 32 : 1 (D) 6 : 1
20. A 4.0 dm3 flask containing N2 at 4.0 bar was connected to a 6.0 dm3 flask containing helium at 6.0 bar, and
the gases were allowed to mix isothermally. Then the total pressure of the resulting mixture will be :
(A) 4.8 bar (B) 5.2 bar (C) 5.6 bar (D) 5.4 bar
21. A mixture of formic acid and oxalic acid is heated with concentrated H2SO4. The gases produced are
collected and on its treatment with KOH solution, the volume of the gas decreased by one-sixth. Calculate
the molar ratio of the two acids in the original mixture.
DPPS FILE # 78

1. The equilibrium constant of the reaction SO2(g) + ½O2(g) SO3(g) is 4 × 10–3 atm–1/2. The equilibrium
constant of the reaction 2SO3(g) 2SO2(g) + O2(g) would be :
(A) 250 atm 3
(B) 6.25 × 10 atm (C) 0.25 × 104 atm (D) 6.25 × 104 atm
Kp
2. log + log RT = 0 is the relationship for the following gaseous phase reaction :
Kc
(A) PCl5 PCl3 + Cl2 (B) 2SO2 + O2 2SO3 (C) H2 + 2 2H (D) N2 + 3H2 2NH3
3. For the reaction N2 + 3H2 2NH3, the value of KC does not depends upon :
(a) Initial concentration of the reactants (b) Pressure (c) Temperature (d) Catalyst
(A) Only c (B) Only a,b (C) Only a,b,d (D) Only b,d
4. When alcohol (C2H5OH) and acetic acid are mixed together in equimolar ratio at 27ºC, 33% is converted
into ester. Then the KC for the following equilibrium is :
C2H5OH() + CH3COOH () CH3COOC2H5 () + H2O().
(A) 4 (B) 1/4 (C) 9 (D) 1/9
5. The equilibrium constant (Kp) for the reaction PCl5(g) PCl3(g) + Cl2(g) is 16 atm. If the volume of the
container is reduced to one half its original volume, the value of Kp for the reaction at the same temperature
will be :
(A) 32 atm (B) 64 atm (C) 16 atm (D) 8 atm
6. 'a' moles of PCl5 undergo thermal dissociation as : PCl5 PCl3 + Cl2. At equilibrium, the mole fraction of
PCl3 is 0.25 and the total pressure is 2 atm. The value of Kp in atm is :
(A) 0.25 (B) 1 (C) 0.5 (D) Data insufficient
7. A reaction mixture containing H2, N2 and NH3 has their partial pressure 2 atm, 1 atm and 3 atm respectively
at 725 K. If the value of KP for the reaction : N2 + 3H2 2NH3 is 1.25 atm–2 at 725 K, in which direction
will the net reaction go :
(A) Forward (B) Backward
(C) No net reaction (D) Direction of reaction cannot be predicted
8. The extent of dissociation of PCl5 at a certain temperature is 20 % at one atm equilibrium pressure. Calculate
the equilibrium pressure in atm at which this substance is half dissociated at the same temperature :
(A) 0.125 (B) 0.1 (C) 2.5 (D) 0.25
9. Consider the following reactions :

(i) PCl5(g) PCl3(g) + Cl2(g)
(ii) 2HI(g) H2(g) + I2(g)
The addition of an inert gas at constant volume :
(A) will increase the dissociation of PCl5 as well as HI.
(B) will reduce the dissociation of PCl5 and not affect the dissociation of HI.
(C) will increase the dissociation of PCl5 and not affect the dissociation of HI.
(D) will not disturb the equilibrium of the reactions.
DPPS FILE # 79
10. The vapour density of N2O4 at a certain temperature is 30. What is the percentage dissociation of N2O4 at
this temperature ?
(A) 7.5% (B) 10% (C) 15% (D) 20%
11. aA + bB cC + dD
In above gaseous phase reaction, low pressure and high temperature shift the equilibrium in backward
direction. So correct set is :
(A) (a + b) > (c + d), H > 0 (B) (a + b) < (c + d), H > 0
(C) (a + b) < (c + d), H < 0 (D) (a + b) > (c + d), H < 0
12. On decomposition of NH4HS, the following equilibrium is established :

NH4HS(s) NH3(g) + H2S (g)
If the total pressure is P atm, then the equilibrium constant KP is equal to :
(A) P atm (B) P2 atm2 (C) P2 / 4 atm2 (D) P2 / 9 atm2
13. At room temperature, the equilibrium constant for the reaction P + Q R + S was calculated to be 4.32.
–2
At 425°C, the equilibrium constant became 1.24 × 10 . This indicates that the reaction :
(A) is exothermic (B) is endothermic
(C) could be exothermic or endothermic (D) is not possible
14. Consider the reaction :

A(s) 2B(g) + 3C(g)
If the concentration of C at equilibrium is doubled, then after the equilibrium is re-established, the
concentration of B will be :
(A) 4/3 times the original value (B) 3/4 times the original value
(C) 1 / 22 times the original value (D) 22 times the original value
15. Statement-1 : For , if more Cl2 is added, the equilibrium will shift in backward
direction and hence equilibrium constant will decrease.
Statement-2 : Addition of a product to the equilibrium mixture always cause the equilibrium to shift backward.
(A) Statement-1 is True, Statement-2 is True ; Statement -2 is a correct explanation for Statement-1
(B) Statement-1 is True, Statment-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
(E) Statement-1 and Statement-2 both are False.
16. 500 ml vessel contains 1.5 moles each of A,B, C and D at equilibrium. If 0.5 mole each of C and D are taken
out, the value of KC for A + B C + D will be :
(A) 1 (B) 1/9 (C) 4/9 (D) 8/9
17. On adding 0.01 M HCl in some amount in aqueous solution of acetic acid :
(A) Equlibrium conc. of CH3COOH decreases. (B) Equlibrium conc. of CH3COO– decreases.
(C) Equlibrium conc. of CH3COO– increases. (D) No change will occur.
18. 9.2 gram of N2O4 (g) is taken in a closed one litre vessel and heated, till the following equilibrium is reached :
N2O4(g) 2 NO2(g)
At equilibrium, 50% N2O4 (g) is dissociated. What is the equilibrium constant (in mol lit–1) :
(A) 0.1 (B) 0.2 (C) 0.4 (D) 2
19. A quantity of PCl5 was heated in a 10 dm3 vessel at 250°C : PCl5 (g) PCl3(g) + Cl2(g). At equilibrium,
the vessel contains 0.1 mole of PCl5 and 0.2 mole of Cl2. The equilibrium constant of the reaction is :
(A) 0.04 mol/L (B) 0.4 mol/L (C) 4 mol/L (D) cannot be determined
20. For the equilibrium :

H2O(l) H2O(g),
what happens if pressure is applied :
(A) More water evaporates (B) The boiling point of water is increased
(C) No effect on boiling point (D) The boiling point of water is decreased
DPPS FILE # 80

Assertion and Reason (no negative marking) Q.18 to Q.22 (3 marks, 3 min.) [15, 15]
1. An isolated system is that system in which :

(A) there is exchange of energy with the surroundings.
(B) there is exchange of mass and energy with the surroundings.
(C) There is no exchange of mass and energy with the surroundings.
(D) There is exchange of mass but not energy with surroundings.
2. As per the First Law of thermodynamics, which of the following statement would be appropriate :
(A) Energy of the system remains constant.
(B) Energy of the surroundings remains constant.
(C) Entropy of the universe is always increasing in an irreversible process.
(D) Energy of the universe remains constant.
3. One mole of an ideal monoatomic gas is caused to go through the cycle shown in figure. Then the change
in the internal energy of gas from a to b and b to c is respectively :
2P0 c
Pressure
T0
P0 b
a
V0 4V0
Volume
9Po Vo 9Po Vo 15Po Vo 15Po Vo

(A) , 6 RT
To (B) , 10 RT
To (C) , 6 RT
To (D) , 10 RT
To
2 2 2 2
4. An ideal gas is taken around the cycle ABCA as shown in P-V diagram. The net work done during the cycle
is equal to :
(A) 7 P1V1 (B) –5 P1V1 (C) 5 P1V1 (D) –7 P1V1
5. 1 mole of SO2 gas at 27° C is expanded in reversible adiabatic condition to make volume 8 times. Final
temperature and work done respectively are: (take 21.2 = 2.3)
(A) 150 K, 900 cal (B) 150 K, 750 cal (C) 130.5 K, 847.5 cal (D) 130.5 K, 508.5 cal
DPPS FILE # 81
6. The work done in an adiabatic process on an ideal gas by a constant external pressure would be :
(A) Zero (B) E (C) H (D) q
7. One mole of an ideal monoatomic gas at temperature T and volume 1L expands to 2L against a constant
external pressure of one atm under adiabatic conditions. Then final temperature of gas will be :
2 2 T T
(A) T + (B) T – (C) 5 / 3 1 (D) 5 / 3 1
3  0.0821 3  0.0821 2 2
 3 
8. One mole of an ideal gas  C v  2 R  at 300 K and 5 atm is expanded adiabatically to a final pressure of 2
 
atm against a constant pressure of 2 atm. Final temperature of the gas is :
(A) 228 K (B) 240 K (C) 248.5 K (D) 200 K
9. The enthalpy of formation of ammonia = 46.0 kJ mol–1. The enthalpy change for following reaction is :
2NH3  N2 + 3H2
(A) –92.0 kJ (B) 46.0 kJ (C) –46.0 kJ (D) 92.0 kJ
10. The standard enthalpy of formation of B2O3 is equal to :

(A) H°C (B(s)) (B) 1/2 H°C (B(s))
(C) 2H°C (B(s)) (D) 3/2 H°C (B(s))
11. Calculate the average O–H bond energy in H2O with the help of following data :
(1) H2O()  H2O(g) ; H = + 40.5 KJ mol–1
(2) 2H(g)  H2 (g) ; H = – 435.0 KJ mol–1
(3) O2(g)  2O(g) ; H = + 489.5 KJ mol–1
(4) 2H2 (g) + O2 (g)  2H2O() ; H = – 571.5 KJ mol–1

(A) 217.75 KJ mol–1 (B) 217.25 KJ mol–1 (C) 462.5 KJ mol–1 (D) 925 KJ mol–1
12. For the equations :

C(diamond) + 2H2(g)  CH4(g) ; H1 and C(g) + 4H(g)  CH4(g) ; H2
Select the correct option :
(A) H1 = H2 (B) H1 > H2
(C) H1 < H2 (D) Nothing can be said with certainty
13. Enthalpy of polymerisation of ethylene, as represented by the reaction, nCH2=CH2  CH2CH2)n is

100 kJ per mole of ethylene. Given that bond enthalpy of C=C bond is 600 kJ mol1. Enthalpy of CC bond
(in kJ mol) will be :
(A) 500 (B) 350 (C) 400 (D) indeterminate
14. 1 mole of a diatomic ideal gas at 25°C is subjected to expand reversibly and adiabatically to ten times of its
initial volume. Calculate the change in entropy of gas during expansion (in JK–1 mol–1) :
(A) R ln 10 (B) 1.5 R ln 10 (C) 2.5 R ln 10 (D) None of these
15.* If a process is both endothermic and spontaneous, then :

(A) Ssys > 0 (B) Ssys < 0 (C) Suniv > 0 (D) Suniv < 0
16.* The enthalpy change for a given reaction at 298 K is – x J mol–1 (x being positive). If the reaction occurs
spontaneously at 298 K, the entropy change at that temperature :
(A) can be negative but numerically larger than x/298.
(B) can be negative but numerically smaller than x/298.
(C) cannot be negative.
(D) can be positive.
DPPS FILE # 82
17.* The value of Htransition of C (graphite) — C (diamond) is 1.9 kJ/mol at 25ºC entropy of graphite is higher
than entropy of diamond. This implies that :
(A) C (diamond) is more thermodynamically stable than C (graphite) at 25ºC.
(B) C (graphite) is more thermodynamically stable than C (diamond) at 25ºC.
(C) Diamond will provide more heat on complete combustion at 25ºC.
(D) Gtransition of C (diamond) — C (graphite) is –ve.
Assertion / Reason
DIRECTIONS :
The following questions consist of two statements one labelled ASSERTION and the another labelled
REASON . Select the correct answers to these questions from the codes given below :
(A) Both Assertion and Reason are true and Reason is the correct explanation of Assertion.
(B) Both Assertion and Reason are true but Reason is not correct explanation of Assertion.
(C) Assertion is true but Reason is false.
(D) Assertion is false but Reason is true.
18. Assertion : The increases in internal energy (E) for the vaporisation of one mole of water at 1 atm and
373 K is zero.
Reason : For all isothermal processes on perfect gases, E = 0.
19. Assertion : The enthalpy of formation of H2O() is greater than that of H2O (g) in magnitude.
Reason : Enthalpy change is negative for the condensation reaction :
H2O (g)  H2O()
20. Assertion : Enthalpy of neutralisation of HClO4 with NaOH is same as that of HCl with NaOH.
Reason : Both HCl and HClO4 are strong acids.
21. Assertion : Decrease of free energy during a process under constant temperature and pressure provides
a criteria of its spontaneity.
Reason : A spontaneous change must have positive sign of Ssystem.
22. The standard molar enthalpies of formation of cyclohexane (l) and benzene (l) at 25º C are –156 and + 49
KJ mol–1 respectively. The standard enthalpy of hydrogenation of cyclohexene (l) at 25º is –119 kJ mol–1.
Use these data to estimate the resonance energy of benzene.
DPPS FILE # 83

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PHYSICAL CHEMISTRY Total Marks : 24

DPP No. 37 Max. Time : 24 min.

Topic : Chemical Equilibrium

Type of Questions M.M., Min.

7. The active mass of 64 g of HI in a two litre flask would be :

Topic : Chemical Equilibrium

Type of Questions M.M., Min.

5. For which of the following equilibria, is Kp = Kc :

Topic : Chemical Equilibrium

Type of Questions M.M., Min.

6. The equilibrium constant for the reaction

Topic : Chemical Equilibrium

Type of Questions M.M., Min.

1. CH3–CO–CH3(g) CH3–CH3(g) + CO(g)

2. The degree of dissociation of N2O4 () obeying the equilibrium,

4. In the following reaction, 3A (g) + B (g) 2C (g) + D (g),

Topic : Chemical Equilibrium

Topic : Chemical Equilibrium

Type of Questions M.M., Min.

1. CaCO3(s) CaO(s) + CO2(g),

3. 2Pb(NO3)2(s) 2PbO(s) + 4NO2(g) + O2(g), H > 0

For a certain reaction, a graph between n K and 1/T was observed to be

7. The value of pre-exponential factor A for the given reaction is :

8. Which of the following statements is INCORRECT regarding the given reaction :

Topic : Chemical Equilibrium

Type of Questions M.M., Min.

(i) the value of n (ii) the equilibrium constant, KC and

Topic : Thermodynamics & Thermochemistry

Type of Questions M.M., Min.

1. In thermodynamics, a process is called reversible when :

Topic : Thermodynamics & Thermochemistry

Type of Questions M.M., Min.

Comprehension ('–1' negative marking) Q.8 to Q.10 (3 marks, 3 min.) [9, 9]

(A) 4 (B) 6 (C) 2 (D) 0

(A) 4.98 kJ (B) 11.47 kJ (C) –11.47 kJ (D) 0 kJ

(C) heat supplied (q) = 0 (D) T = 0

the system absorb or liberate heat ? How much ?

Comprehension # (Q.8 to Q.10)

Now answer the following questions : A D

(A) 70 J ; heat is liberated. (B) 60 J ; heat is liberated.

Topic : Thermodynamics & Thermochemistry

Type of Questions M.M., Min.

5. A thermodynamic system goes in cyclic reversible process as

Topic : Thermodynamics & Thermochemistry

Type of Questions M.M., Min.

(A) W = +ve, H = +ve (B) W = –ve, H = – ve

3. q, W, E and H for the following process ABCD on a monoatomic gas are :

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

Plot A and plot B should correspond to :

Comprehension # (Q. Nos. 8 to 10)

One mole of Helium gas undergoes a reversible cyclic

8. What is the value of H for the overall cyclic process :

9. What is the value of 'q' for the overall cyclic process :

10. What is the net work involved in the cyclic process :

Topic : Thermodynamics & Thermochemistry

Type of Questions M.M., Min.

8L at 300 K to a volume of V2 at 250 K. V2 is : (Given (4.8)1/2 = 2.2)

Then which of the following options is correct :

(D) cannot be predicted

(A) Process R  S is isothermal (B) Process S  R is adiabatic

(C) Process R  S is adiabatic (D) Such a graph is not possible

6. In which process, net work done by gas is zero :