CHAPTER PRACTICE PROBLEMS (CHEMISTRY)

THERMODYNAMICS & THERMOCHEMISTRY

Q.1. Calculate the work done by 1 mole of an ideal gas in piston fitted cylinder at the initial pressure of
24.83 atm pressure and 300 K to expand its volume to 10 litre if
(a) external pressure is reduced to 1 atm in single step
(b) external pressure is reduced to 5 atm in 1st operation and then 1 atm in next step
(c) gas is allowed to expand into an evacuated space of 10 litre.

Q.2. A stem boiler made up of steel mass 900 kg. The boiler contains 400 kg of water. Assuming 70% of
the heat is delivered to boiler and water, how much heat is required to raise the temperature of the
whole from 10C to 100C? Heat capacity of steel is 0.11 kcal/kg-K and heat capacity of water is
1 kcal/kg-K.

Q.3. A system is provided 50 joule of heat and work done on the system is 10 joule. What is the change
in internal energy?
Q.4. The work done by a system is 8 joule, when 40 joule heat is supplied to it. Calculate the increase in
internal energy of system.

Q.5. One mole of a monatomic ideal gas is confined into a piston fitted cylinder occupying 10 litre at
300 K. On heating the gas upto 400 K, the gas is also shows expansion and finally occupies 20
litre. Calculate:
(a) Change in internal energy in L-atom.
(b) Change in heat enthalpy in L-atom.
Q.6. A gas occupies 2 litre at STP. It is provided 300 J heat so that its volume becomes from 2.5 litre at
1 atm. Calculate change in internal energy.

Q.7. 1 mole of iron is completely allowed to react with dilute HCl at 300 K. Calculate the work done if
reaction is made in an open beaker and in a closed container separately.

Q.8. 10 g of argon gas is compressed isothermally and reversibly at a temperature of 27C form 10 litre
to 5 litre. Calculate q, w, U and H for this process. R = 2.0 cal K1, log 2 = 0.30, atomic mass of
A = 40.

Q.9. One mole of an ideal gas undergoes reversible isothermal expansion from an initial volume V1 to a
final volume 10 V1 an does 10 kJ of work. The initial pressure was 1  107 Pa.
(a) Calculate V1.
(b) If there were 2 mole of gas, what must its temperature have been?

Q.10. Calculate q, w, U and H for the isothermal reversible expansion of one mole of an ideal gas from
an initial pressure of 1.0 bar to a final pressure of 0.1 bar at a constant temperature of 273 K.

Q.11. Using the data (all values in kcal mol1 at 25C) given below, calculate bond enthalpy of C – C and
C- H bonds.
C  s   C  g  ; H  172 kcal
H2  2H ; H  104 kcal
1
H 2  O2  H2 O    ; H  68.0 kcal
2
C  s   O2  CO2 ; H  94.0 kcal
Heat of combustion of C2H6 = 372.0 kcal
Heat of combustion of C3H8 = 530.0 kcal

Q.12. Calculate work done of the process when one mole of gas is allowed expand freely into a vacuum.

Q.13. A gas expands from 3 dm3 to 5 dm3 against a constant pressure of 3 atm. The work done during
expansion is used to heat 10 mole of water of temperature 290 K. Calculate final temperature of
water. Specific heat of water = 4.184 J g1K1.
Q.14. In an insulated container 1 mole of liquid molar volume 100 mL at 1 bar. Liquid is steeply taken to
100 bar, when volume of liquid decreases by 1 mL. Find H and U for the process.
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 CHAPTER PRACTICE PROBLEMS (CHEMISTRY)
Q.15. 5 mole of ideal gas at 293 K are expanded isothermally form an initial pressure of 4.053  105 Pa
to a final pressure of 1.013  105 Pa against a constant external pressure of 1.014  105 Pa.
(a) Calculate q, w, U and H.
(b) Calculate q, w, U and H, if process is carried out reversibly.

Q.16. In an insulated container 1 mole of an ideal gas is reversibly expanded at 600 K to 300 K. Calculate
the work done by gas if:
(a) Gas is monoatomic (b) Gas is diatomic

Q.17. 0.40 mole of a monoatomic gas fills a 1 dm3 container to a pressure 1.013 106 Pa. It is expended
reversibly and adiabatically until a pressure of 1.013  105 Pa is reached. Calculate:
(a) What is final volume of gas?
(b) Initial and final temperature of gas.
(c) Work done by gas during expansion.

Q.18. 14 g oxygen at 0C and 10 atm is subjected to reversible adiabatic expansion to a pressure of
1 atm. Calculate the work done in: (a) litre- atm (b) calories.

Q.19. A sample of argon gas at 1 atm pressure and 27C expands reversibly and adibatically from
1.25 dm3 to 2.50 dm3. Calculate the enthalpy change in this process. Cv.m for argon is
12.48 JK1mol1.

Q.20. Two mole of an ideal monoatomic gas (Cv = 12.55 JK1 mol1) expands irreversibly and adibatically
from an initial pressure of 1.013 106 Pa against a constant external pressure of 1.013  105 Pa
until the temperature drops from the initial volume of 325 K to a final value of 275 K. Calculate the
work done by the gas and its final volume.

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 CHAPTER PRACTICE PROBLEMS (CHEMISTRY)
HINTS & SOLUTIONS
1. P  V1 = nRT
1 0.0821 300
V1   1 litre
24.63
(a) W = PV = 1  (10 – 1) = 9 L – atm

or Wsystem = 9 L-atm and Wsurr = +9 L – atm

(b)  P1V1  P2 V2 ; 24.63  1  5  V2 ;  V2  4.926
W = W1 + W2 = 5  (V2 – V1) + [1  (10 – V2)]
= 5  (4.926 – 1) + [-1  (10 – 4.926)]
=  24.630 – 5.074
= - 29.704 L – atm
 Wsys = 29.704 L – atm; Wsurr = +29.704 L – atm
(c) W = P  V = 0  (10 – 1) = 0 L - atm

2. H required for heating = mST + mST

(boiler) (water)
= 900  0.11  90 + 400  1  90
= 44910 kcal
Since, only 70% of heat given is used upto do so.
44910  100
Thus, actual heat required =
70
= 64157 kcal

3. q = 50 J; w = +10 J
U = q + W = 50 + 10
U = 60 J

4. w = 8 J; q = 40 J
From Ist law U = q + w = 40 – 8 = 32 joule

nRT 1 0.0821 300

5. P1  Pinitial    2.463 atm
V 10
nRT 1 0.0821 400
P2  Pfinal    1.642 atm
V 20
U = nCv.T
3R
U  1   100  300 cal
2
= 300  4184 J
300  4184
 L  atm
101.3
= 12.39 L-atm
 H = U + (PV)
12.39 + P1(V2 – V1) + V2(P2 – P1)
12.39 + 2.463  (20 – 10) + 20(1.642 – 2.463)
= 12.39 + 24.63 – 16.42 = +20.6 L – atm

6. P = 1 atm = 1.01  105 N m2

V = (2.5 – 2.0) = 0.5 litre = 0.5 103 m3
5 3
= 1.01  10  0.5  10 J = -50.5 J
U = q + w = 300 – 50.5 = 249.5 J

7. Open beaker: Fe + 2HCl  FeCl2 + H2

Thus mole of H2 = 1
The work is done against external pressure by H2 which pushes a pressure of 1 atm.
W = P  V  PV  nRT

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 CHAPTER PRACTICE PROBLEMS (CHEMISTRY)
= nRT  (at constant P, T) PV = nRT
nRT
=  1  0.0821  300 or V 
P
=  24.63 L – atm
Closed beaker: Work is not done

V2
8. w  2.303nRT log
V1
10 5
 2.303   2  300  log
40 10
w = 103.635 cal
U = 0
 q = U - w
 q = -w = 103.635 cal
Also, when temperature is constant P1V1 = P2V2 is constant.
Thus, H = U + (PV)
=0+0=0

9. (a) Where w is work done by the system under isothermal reversible conditions. Note that work
done by the system is negative.
P
10  103  2.303  1 8.314  T  log 1 ... i 
P2
Also P1V1 = P2V2 at constant temperature
1  107  V1 = P2  10V1
1 10 7
 P2   10 6
10
 By equation (i)
107
10  103  2.303  1 8.314  T  log 6
10
 T = 522.27 K
Now using PV = nRT for o ne mole of gas:
P = 107 Pa = 107 N m2
1  107  v1 = 1  8.314  5.22.27
V1 = 4.34  104 m3
522.27
(b) If two mole of gas have been used, then temperature would have been
2
= 261.13 K.

10. For isotheral reversible expansion:

P
w  2.303nRT  log 1
P2
1.0
 2.303  1 8.314  log
0.1
w = 5227.2 J
At constant temperature, for expansion T = 0
Therefore, U = 0
Also, U = 1  Cv  T = 0 (for 1 mole)
and U = q + w
P1V1 = P2V2 or PV is constant
Thus, H = U + (PV)
 H = 0
q = w

11. For C3H8; 3C + 3H2  C3H8; H1 = ?

For C2H6; 2C + 3H2  C2H6; H2 = ?
 H1 = [2  e C – C + 8  eC – H] + [3Cs g + 4  eH – H] …(i)
H1 = [eC – C + 6  e C – H] + [2Cs g + 3  e H – H] …(ii)
Let bond energy of C – H be a kcal

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 CHAPTER PRACTICE PROBLEMS (CHEMISTRY)
And bond energy of C – H be b kcal
 By equation (i) H1 = (2a + 8b) + [3  172 + 4  104 …(iii)
H2 = (a + 6b) + [2  172 + 3  104…(iv)
Given, C  O2   CO2 ; H  94.0 kcal ...  v 
1
H2  O2   H2O; H  68.0 kcal ...  vi 
2
7
C2H6  O2   2CO 2  3H2 O; H  372.0 kcal ..  vii 
2
C3H8  5O2  3CO2  4H2O; H  530.0 kcal ...  viii 
By inspection method: 2  (v) + 3  (vi) – (vii) gives
2C  3H2  C2H6 ; H2  20.0 kcal ... ix 
and 3  (v) + 4  (vi) – (viii) gives
2C  4H2   C3H8 ; H1  24.0 kcal ...  x 
 By equation (iii), (iv), (ix) and (x)
a + 6b = 676
2a = 8b = 956
 a = 82 kcal and b = 99 kcal
Bond enthalpy of C – C bond = 82 kcal
And bond enthalpy of C – H bond = 99 kcal

12. For expansion of gas in vacuum.

(ie. Pext = 0) the work done is irreversible
w  Pext  V2  V1  = 0

13. Work is done against external pressure and this process is irreversible.
w = PV
 V   5  3   2 dm2  2  103 m3
P = 3 atm = 3  1.013  105 Nm2
 w = 3  1.013  105  2  103 = -607.8 J
Since the work done is used in heating water and thus
w = q  C  T
or 607.8 = 10  4.184  18  T
 T = 0.81
 Final temperature = 290 + 0.81 = 290.81 K

14. Volume of 1 mole liquid = 100 mL at pressure 1 bar

Volume of 1 mole liquid = 99 mL at pressure 100 bar
The process is irreversible as it is steeply changed from 1 bar to 100 bar. Therefore,
W  P  V2  V1   100  99  100   100 bar  mL
Also, U = q + W
q = 0 since container is insulated
 U = 100 bar – mL
Also H = U + PV = U + P2V2 – P1V1
= 100 + (100  99 – 1  100) = 9900 bar – mL

15. (a) For an isothermal irreversible expansion against a constant pressure

 nRT nRT 
w  Pext  V2  V1   Pext   
 P2 P1 
 1 1  P  P2 
 nRTPext     nRTPext  1 
P
 2 P1   P1P2 
 4.053  10 5  1.013  105 
 5  8.314  293  1.013  105  5 5 
 4.053  10  1.013  10 
= - 9135.7 J = 9.136  103 kJ
Since, temperature is constant
 U = 0, H = 0 and q = w
(b) For isothermal reversible expansion, we have

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 CHAPTER PRACTICE PROBLEMS (CHEMISTRY)
V2 P
w  2.303nRT log  2.303nRT log 1
V1 P2
 4.053  105 
w  2.303  5  8.314  293  log  5 
 1.013  10 
= 6891 J = 16.89 kJ
U = 0, H = 0 and q = w

16. For adiabatic expansion:

nR
w  T2  T1 
 1
(a) For monoatomic gas:
1 8.314
w  300  600     1.66 
0.66
= 3779.1 J = 3.779  103 kJ
(b) For diatomic gas:
1 8.314   300  600 
w    1.40 
0.40
= 6235.5 J = 6.236  103 kJ

17. (a) We have PV = constant or P1V1 = P2V2

 5
 1.013  106  1  1.013  106  V2    
 3
 V2 = 103/5 = 3.98 dm3
(b) Also, we have PV = nRT
P = 1.013  106, V = 1 dm3 = 1  103 m3
n = 0.40, R = 8.314 J
For initial condition
1.013  106  103 = 0.40  8.314  T1
 T1 = 304.6 K
Also TV-1 = constant or T1V1-1 = T2V2-1
 304.6  (1) -1 = T2  3.98)-1
304.6  5
 or T2  2/3    3 
 3.98   
= 121.28 K
(c) Work done during expansion:
nR
(i) Either by: w   T2  T1   Since T2 and T1 are already evaluated 
 1
0.4  8.314
 121.28  304.6 
5 
 3  1
 
= 923.7 J

(ii) or by : w  2 2
P V  P1V1 
 1
1.013  10 6  1 10 3  1.013  105  3.98  10 3

5 
 3  1
 
= 923.7 J

18. WO2  14g  nO2  14 / 32  mol

P1 = 10 atm, T1 = 273 K, P2 = 1 atm
For adiabatic expansion T. P1- = constant
 1 
 T1   P2 
or    
T
 2  P1 

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 CHAPTER PRACTICE PROBLEMS (CHEMISTRY)
 1 
 273  1
   
T
 2  10 
Also,  = 1.4
By equation (i) and (ii), T2 = 141.4 K
 Work done in adiabatic expansion.
 nR /    1  T2  T1 
14 0.0821
w rev    141.4  273 
32 1.4  1
wrev = 11.82 litre-atm
wrev = (11.82  1.987) / 0.0821 cal
wrev =  286.0 cal

19.  H  n  Cp   T
and Cp = Cv + R = 12.48 + 8.314 = 20.794 JK1 (R in J)
For a given sample of argon gas, mole (n)
PV 1 1.25
n   0.05
RT 0.0821 300
Also, for reversible adiabatic change (TV)-1 = constant
Or T2 V2  1  T1V1 1
 1
V 
Or T2  T1   1     1.66 for argon
 V2 
1.66 1 0.66
 1.25   1
 300     300  
 2.50  2
 T2 = 189.86 K
 T = T2 – T1 = 189.86 – 300 = 110.14
Thus, H = 0.05  20.794  110.14)
=  114.51 J

20. We have U = nCv  T = nCv (T2 – T1)

= 2  12.55   275  325 
w = U = -1255 J
Also, w = -Pext (V2 – V1)
nRT1 2  8.314  325
and V1  
P 1.013  106
3
= 5.33 10 m3
w
 V2    V1
Pext
= 17.72  103 m3 = 17.72 dm3

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