Vidya Thermo

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THERMOCHEMISTRY & THERMODYNAMICS QUESTIONS BASED ON CBSE PATTERN
1. Express the change in internal energy of a system when :

(i) No heat is absorbed by the system from the surroundings, but work (w) is done on the system. What type
of wall does the system have?
(ii) No work is done on the system, but q amount of heat is taken out from the system and given to the
surroundings. What type of wall does the system have?
(iii) W amount of work is done by the system and Q amount of heat is supplied to the system. What type of
system would it be?
2. Calculate the internal energy change in each of the following cases :
(i) A system absorbed 15 kJ of heat and does 5 kJ of work.
(ii) 5 kJ of work is done on the system and 15 kJ of heat is given out by the system.
3. Calculate the amount of work done in each of following cases :
(i) One mole of an ideal gas contained in a bulb of 10 litre capacity at 1 atm is allowed to enter into an
evacuated bulb of 100 litre capacity.
(ii) One mole of a gas is allowed to expand from a volume of 1 litre to a volume of 5 litre against the constant
external pressure of 1 atm (1 litre atm = 101.3 J)
Calculate the internal energy change (U) in each case if the process were carried out adiabatically.
4. The heat of combustion of benzene in a bomb calorimeter (i.e., constant volume) was found to be 3263.9 kJ mol–1 at
25°C. Calculate the heat of combustion of benzene at constant pressure.
5. A swimmer coming out from a pool is covered with a film of water weighing about 18 g. How much heat must be
supplied to evaporate this water at 298 K? Calculate the internal energy of vaporization at 100°C. Δ vap H for water
at 373 K = 40.66 kJ mol–1.
6. The heat of combustion of CH4(g) at constant volume is measured in a bomb calorimeter at 298.2 K and found to be
– 885389 J/mol. Find the value of enthalpy change.
7. The enthalpy change (ΔH) for the reaction N 2 ( g )  3H 2 ( g ) 
 2NH 3 ( g ) is –92.38 kJ at 298 K. What is ΔU at
298 K?
8. The internal energy change (ΔU) for the reaction CH 4 ( g )  2O2 ( g ) 

 CO2 ( g )  2H 2O(l ) is –885 kJ mol–1 at
298 K. What is ΔH at 398 K?
9. When NH4NO2(s) decomposes at 373 K, it forms N2(g) and H2O(g). The ΔH for the reaction at one atmospheric
pressure and 373 K is –223.6 kJ mol–1 of NH4NO2(s) decomposed. What is the value of ΔU for the reaction under
the same conditions? (Given R = 8.31 J K–1 mol–1)
10. When 0.532 g of benzene (C6H6), boiling point 353 K, is burnt with excess of oxygen in a constant volume system.
22.3 kJ of heat is given out. Calculate ΔH for the combustion process (R = 8.31 J K–1 mol–1).
11. The heat of combustion of naphthalene (C10H8 (s)) at constant volume was found to be –5133 kJ mol–1. Calculate
the value of enthalpy change.
12. The molar heat of formation of NH4NO3 (s) is –367.54 kJ and those of N2O (g) and H2O (l) are +81.46 kJ and
–285.78kJ respectively at 25°C and 1.0 atmospheric pressure. Calculate ΔH and ΔU for the reaction.
13. 1 g of graphite is burnt in a bomb calorimeter in excess of oxygen at 298 K and 1 atmospheric pressure according to
the equation C (graphite) + O2 (g) 
 CO2 (g)
During the reaction, temperature rises from 298 K to 299 K. If the heat capacity of the bomb calorimeter is
20.7 kJ/K, what is the enthalpy change for the above reaction at 298 K and 1 atm?
VMC | Supplementary Booklet-2 35 Chapter-6 & 7 | Chemistry

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14. Calculate the amount of heat evolved when

(i) 500 cm3 of 0.1 M hydrochloric acid is mixed with 200 cm3 of 0.2 M sodium hydroxide solution
(ii) 200 cm3 of 0.2 M sulphuric acid is mixed with 400 cm3 of 0.5 M potassium hydroxide solution.
Assuming that the specific heat of water is 4.18 J K–1 g–1 and ignoring the heat absorbed by the container,
thermometer, stirrer etc., what would be the rise in temperature in each of the above cases?
15. A 1.250 g sample of Octane (C8H18) is burned in excess of oxygen in a bomb calorimeter. The temperature of the
calorimeter rises from 294.05 K to 300.78 K. If heat capacity of the calorimeter is 8.93 kJ/K, find the heat
transferred to the calorimeter. Also calculate the enthalpy combustion of the sample of octane.
16. When 20.0 g of ammonium nitrate (NH4NO3) is dissolved in 125 g of water in a coffee-cup calorimeter, the
temperature falls from 296.5 K to 286.4 K. Find the value of q for the calorimeter. (Treat heat capacity of water as
the heat capacity of the calorimeter and its contents).
17. 0.16 g of methane was subjected to combustion at 27°C in a bomb calorimeter system. The temperature of the
calorimeter system (including water) was found to rise by 0.5°C. Calculate the heat of combustion of methane at
(i) constant volume, and (ii) constant pressure. The thermal capacity of the calorimeter system is 17.7 kJ K–1
(R = 8.314 kJ K–1 mol–1)
18. Calculate enthalpy of formation of methane (CH4) from the following data:
(i)  CO2 ( g ),Δ r H  393.5 kJ mol1
C( s)  O 2 (g) 
1
(ii)  H 2O(l ), Δ r H  285.8kJ mol1
H 2 ( g )  O2 ( g ) 
2
(iii)  CO 2 ( g )  2H 2O(l ),Δ r H  890.3kJ mol1
CH 4 ( g )  2O 2 ( g ) 
19. Calculate the enthalpy of formation of carbon monoxide (CO) from the following data:
(i)  CO2 ( g );Δ r H  393.5 kJ mol1
C( s)  O 2 (g) 
1
(ii)  CO 2 ( g ); Δ r H  283.0 kJ mol1
CO( g )  O 2 ( g ) 
2
20. Calculate the enthalpy change accompanying the transformation of C(graphite) to C(diamond). Given that the
enthalpies of combustion of graphite and diamond are 393.5 and 395.4 kJ mol–1 respectively.
21. Calculate the enthalpy of hydration of anhydrous copper sulphate (CuSO4) into hydrated copper sulphate
(CuSO4.5H2O). Given that the enthalpies of solution of anhydrous copper sulphate and hydrated copper sulphate are
–66.5 and +11.7 kJ mol–1 respectively.
22. Ethylene on combustion gives carbon dioxide and water. Its enthalpy of combustion is 1410.0 kJ/mol. If the
enthalpy of formation of CO2 and H2O are 393.3 kJ and 286.2 kJ respectively, calculate the enthalpy of formation of
ethylene.
23. Calculate the enthalpy of formation of sucrose (C12H22O11) from the following data:
(i) C12 H 22 O11  12O 2  12CO2  11H 2 O, H  5200.7kJmol 1
1
(ii) C  O 2  CO2 , H  394.5 kJmol1 (iii) H 2  O 2  H 2 O, H  285.8kJmol 1
2
24. Calculate the standard enthalpy of formation of SO3 at 298 K using the following reactions and enthalpies.
S8  s   8O 2  g   8SO 2  g  , H  2775kJmol 1 ;
2SO2  g   O 2  g   2SO3  g  , H  198 kJmol 1

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25. Calculate the enthalpy of formation of anhydrous Al2Cl6 from the following data:
(i) 2Al  s   6HCl  aq   Al 2 Cl6  aq   3H 2  g   1004.2kJ.kJmol1
(ii) H 2  g   Cl 2  aq   2HCl  g   184.1kJ.kJmol1
(iii) HCl  g   aq  HCl  g   73.2 kJmol 1
(iv) Al 2 Cl6  s   aq  Al2 Cl6  aq   643.1kJmol 1
26. From the following thermo chemical equations, calculate the standard enthalpy of formation of HCl(g).
(i) H 2  g   2H  g  , H  436.0kJmol 1 (ii) Cl 2  g   2Cl  g  , H  242.7 kJmol 1
(iii) HCl  g   H  g   Cl  g  , H  431.8 kJmol1
27. Calculate the enthalpy of combustion of benzene from the following data:
(i) 6C  s   3H 2  s   C6 H6  l  , H  49.0 kJ mol 1
1
(ii) H 2  g   O2  g   H 2 O  l  , H  285.8 kJ mol 1
2
(iii) C  s   O2  g   CO2  g  , H  389.3 kJ mol 1
28. The enthalpies of formation of methane, carbon dioxide and water (liquid) are -74.8, –393.5 and –286.2 kJ
respectively. Calculate the enthalpy of combustion of methane at ordinary temperature.
1
29. Calculate the enthalpy of reaction for CO  g   O2  g   CO 2  g 
2
Given C  s   O2  g   CO2  g  , H  393.5 kJmol 1
1
C  s   O 2  g   CO  g  , H  110.5 kJmol1
2
30. Compare quantity of heat produced by the combustion of 1.0 g glucose (C6 H12O6) with that produced by 1.0g
sucrose (C12H22O11). Given that the standard heats of formation of CO2, H2O, glucose and sucrose are –393.5,
–285.9, –1260 and –2221 kJ mol–1 respectively.
31. Calculate the enthalpy change for the reaction between CO2 and H2O to produced one mole of glucose (C6 H12O6).
What would be enthalpy change for the production of 18 g of glucose? The enthalpy of combustion of glucose is
2840 kJ mol–1.
32. (a) A cylinder of gas is assumed to contain 11.2 kg of butane. If a normal family needs 20,000 kJ of energy
per day for cooking, how long will the cylinder last? Given that the heat of combustion of butane is 2658
kJ mol–1.
(b) If the air supply of the burner is insufficient (i.e., you have a yellow instead of a blue flame), a portion of
the gas escapes without combustion. Assuming that 33% of the gas is wasted due to this inefficiency, how
long would the cylinder last?
33. An average person needs about 10,000 kJ per day. How much carbohydrates (in mass) will he have to consume,
assuming that all his energy needs are met only by carbohydrates in the form of glucose? Given that the heat of
combustion of glucose is 2900 kJ mol–1.
34. Reaction between red phosphorus and liquid bromine is an exothermic reaction represented as follows:
2P  s   3Br2  l   2PBr3  g  , H  243 kJmol –1
What will be the enthalpy change when 2.63 g of phosphorus reacts according to the above reaction? Take atomic
mass of phosphorus as 31.0.

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35. Calculate the bond enthalpy of HCl. Given that the bond enthalpies of H2 and Cl2 are 430 kJ mol–1 and
242 kJ mol–1 respectively and  f H for HCl is –91 kJ mol–1.
36. Calculate the bond energy of C–H bond, given that the heat of formation of CH4, heat of sublimation of carbon and
heat of dissociation of H2 are –74.8, + 719.6 and 435.4 kJ mol–1 respectively.
37. The net enthalpy change of a reaction is the amount of energy required to break all the bonds in reactant molecules
minus amount of energy required to form all the bonds in the product molecules.
Calculate the enthalpy change for the reaction H 2 (g)  Br2 (g) 
 2HBr(g)
Given that the bond enthalpies of H–H, Br–Br and H–Br are 435, 192 and 364 kJ mol–1 respectively.
38. Calculate the enthalpy change of the reaction H 2 (g)  I2 (g) 

 2HI(g)
Given that the bond energies of H – H, I – I and H – I are 433, 151 and 299 kJ mol–1 respectively.
39. Calculate the enthalpy of formation of water, given that the bond energies of H – H, O = O and O – H bond are
433 kJ mol–1, 492 kJ mol–1 and 464 kJ mol–1 respectively.
40. From the following data at 25°C, calculate the bond energy of O – H bond:
(i) H 2 ( g ) 
 2H( g ), ΔH1  104.2 kcal
(ii) O 2 ( g ) 
 2O( g ), ΔH 2  118.4kcal
1
(iii) H 2 ( g )  O 2 ( g ) 
 H 2O( g ), ΔH3  57.8kcal
2
41. Calculate the enthalpy of hydrogenation of C2H2 (g) to C2H4 (g). (Given bond energies: C–H = 414.0 kJ mol–1.
(C  C)  827.6 kJ mol–1, (C=C) = 606.0 kJ mol–1, H–H = 430.5 kJ mol–1)
H H
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42. ΔH for the reaction H  C  N  g   2H 2  g   H  C  N  H  g  is –150 kJ. Calculate the bond energy of
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H H
C  N bond. [Given bond energies of C–H = 414 kJ mol–1; H–H = 435 kJ mol–1; C–N = 293 kJ mol–1,
N–H = 396 kJ mol–1]
43. Is the bond energy of all the four C–H bonds in CH4 molecule equal? If not then why? How is the C–H bond
energy then reported?
44. Same mass of diamond and graphite (both being carbon) are burnt in oxygen. Will the heat produced be same or
different? Why?
45. The enthalpy of formation of gaseous iodine is 62.5 kJ mol–1 at 25°C. What will be the enthalpy of sublimation of
iodine at 25°C?
46. Calculate the enthalpy change for the process : CCl 4  g   C  g   4Cl  g 
And calculate bond enthalpy of C–Cl in CCl4(g)
Given:  vap H  CCl4   30.5 kJmol 1 ;  f H  CCl4   135.5 kJmol 1
 a H  C   715.0 kJmol1 where  a H is enthalpy of atomization;  a H  Cl 2   242 kJmol 1 .
47. An athlete is given 100 g of glucose (C6H12O6) of energy equivalent to 1560 kJ. He utilizes 50 percent of this gained
energy in the event. In order to avoid storage of energy in the body, calculate the weight of water he would need to
perspire. The enthalpy of evaporation of water is 44 kJ/mol.

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48. Using the data (all values are in kilocalories per mole at 25°C) given below, calculate the bond energy of C–C and
C–H bonds. (In kJ/mol)
H combustion (ethane) = –372.0; H combustion (propane) = –530.0
H for C(graphite)  C(g) = 172.0; Bond energy of H–H = 104.0
 f H of H2O (l) = –68.0
 f H for CO2(g) = –94.0

49. Choose the correct answer. A thermodynamic state function is a quantity :
(i) used to determine heat changes (ii) whose value is independent of path
(iii) used to determine pressure-volume work (iv) whose value depends on temperature only
50. For the process to occur under adiabatic conditions, the correct condition is :
(i) T  0 (ii) p  0 (iii) q0 (iv) w=0
51. The enthalpies of all the elements in their standard states are :
(i) unity (ii) zero (iii) 0 (iv) different for each element
52. U of combustion of methane is X kJ mol1 . The value of H is :

(i)   U (ii)   U (iii)   U (iv) =0
53. In a process, 701 J of heat is absorbed by a system and 394 J work is done by the system. What is the change in
internal energy for the process ?
54. The reaction of cyanamide, NH 2 CN(s) , with dioxygen was carried out in a bomb calorimeter, and U was found
to be 742.7 kJ mol 1 at 298 K. Calculate the enthalpy change for the reaction at

298 K R  8.314 103 kJ K 1mol1 
3
NH 2 CN(s)  O 2 (g)   N 2 (g)  CO2 (g)  H 2O(l )
2
55. Calculate the amount of kJ of heat necessary to raise the temperature of 60.0 g of aluminium from 35C to 55C .
Molar heat capacity of Al is 24 J mol1 K 1 . Molar mass of Al  27 g mol 1
56. Calculate the enthalpy change on freezing of 1.0 mole. of water at 10.0°C to ice at –10°C.  fus H  6.03kJ mol 1
at 0°C.
C p  H 2 O  l    75.3 J mol1 K 1 ; C p  H 2 O  s    36.8 J mol1 K 1
57. For an isolated system, U  0 , what will be S ?
58. For the reaction at 298 K, 2A  B 
C
H = 400 kJ mol 1 and S = 0.2 kJ K 1 mol 1
At what temperature will the reaction becomes spontaneous considering H and S to be constant over the
temperature range ?
59.  Cl 2 (g) , what are the signs of H and S ?
For the reaction, 2Cl(g) 
60. Calculate the entropy change in surroundings when 1.00 mole H 2O(l ) is formed under standard conditions.
 f H   286 kJ mol1
61. 18.0 gm of water completely vaporizes at 100C and 1 bar pressure and then enthalpy change in the process is
40.79 kJ mol–1. What will be the enthalpy change for vaporizing two moles of water under the same conditions?
What is the standard enthalpy of vaporization for water?
Standard enthalpy of vaporization at 100C and 1 bar pressure  vap HΘ   40.79kJ mol 1

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62. One mole of acetone requires less heat to vaporize than 1 mole of water. Which of the two liquids has higher
enthalpy of vaporization?
63. Standard molar enthalpy of formation  f HΘ is just a special case of enthalpy of reaction,  f HΘ . Is the  r HΘ for
the following reaction same as  f HΘ ? Give reason for your answer.
 CaCO3 (s) ; f H Θ   178.3 kJ mol1

CaO(s)  CO 2 (g) 
64. The value of  f HΘ for NH3 is –91.8 kJ mol–1.
Calculate enthalpy change for the following reaction 2NH3 (g) 

 N 2 (g)  3H 2 (g)
65. Enthalpy is an extensive property. In general, if enthalpy of an overall reaction A   B along one route is
 r H and  r H1  r H 2 ,  r H3....... represent enthalpies of intermediate reactions leading to product B. What will be
the relation between  r H overall reaction and  r H1,  r H 2 …. Etc for intermediate reactions.
66.  C(g)  4H(g) is 1665 kJ mol–1. What is the bond
The enthalpy of atomization for the reaction CH 4 (g) 
energy of C – H bond?
67. Use the following data to calculate  lattice HΘ for NaBr. sub HΘ for sodium metal = 108.4 kJ mol–1, ionization
enthalpy of sodium = 496 kJ mol–1, electron gain enthalpy of bromine = –325 kJ mol–1, bond dissociation enthalpy
of bromine = 192 kJ mol–1,  f HΘ for NaBr(s) –360.1 kJ mol–1.
68. Given that H  0 for mixing of two gases. Explain whether the diffusion of these gases into each other in a closed
container is a spontaneous process or not?
69. Heat has randomizing influence on a system and temperature is the measure of average chaotic motion of particles
in the system. Write the mathematical relation which relates these three parameters.
70. Increase in enthalpy of the surroundings is equal to decrease in enthalpy of the system. Will the temperature of
system and surroundings be the same when they are in thermal equilibrium?
71.  2NO2 (g) is 0.98. Predict whether the reaction is spontaneous or not.
At 298 K, Kp for reaction N 2 O4 (g) 
72. A sample of 1.0 mol of a monoatomic ideal gas is taken through a cyclic process of expansion and compression as
shown in figure. What will be the value of H for the cycle as a whole?
73. The standard molar entropy of H2O(l) is 70 JK–1 mol–1. Will the standard molar entropy of H2O(s) be more, or less
than 70 JK–1 mol–1?
74. Identify the state functions and path functions out of the following : enthalpy, entropy, heat, temperature, work, free
energy.
75. The molar enthalpy of vaporization of acetone is less than that of water. Why?
76. Which quantity out of  r G and  r G Θ will be zero at equilibrium?
77. Predict the change in internal energy for an isolated system at constant volume.

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78. Although heat is a path function but heat absorbed by the system under certain specific conditions is independent of
path. What are those conditions? Explain.
79. Expansion of a gas in vacuum is called free expansion. Calculate the work done and the change in internal energy
when 1L of ideal gas expands isothermally into vacuum until its total volume is 5L?
80. Heat capacity (Cp) is an extensive property but specific heat (c) is intensive property. What will be the relation
between Cp and c for 1 mole of water?
81. The difference between Cp and Cv can be derived using the empirical relation H = U + pV. Calculate the difference
between Cp and Cv for 10 moles of an ideal gas.
82. If the combustion of 1g of graphite produces 20.7 kJ of heat, what will be molar enthalpy change? Give the
significance of sign also.
83. An ideal gas is allowed to expand against a constant pressure of 2 bar from 10 L to 50 L in one step. Calculate the
amount of work done by the gas. If the same expansion were carried out reversibly, will the work done be higher or
lower than the earlier case? (Given that, 1 L bar = 100 J)
84. The enthalpy of vaporization of CCl4 is 30.5 kJ mol–1. Calculate the heat required for the vaporization of 284 g of
CCl4 at constant pressure. (Molar mass of CCl4 = 154 g mol–1)
85.  2H 2 O(l) is  r H Θ   572 kJ mol1
The enthalpy of reaction for the reaction : 2H 2 (g)  O 2 (g) 
What will be standard enthalpy of formation of H2O(l)?
86. What will be the work done on an ideal gas

enclosed in a cylinder, when it is
compressed by a constant external pressure ,
pext in a single step as shown in figure?
Explain graphically.
87. How will you calculate work done on an ideal gas in a compression, when change in pressure is carried out in
infinite steps?
88. Represent the potential energy/enthalpy change in the following process graphically.
(a) Throwing a stone from the ground to roof.
1 1
(b)  HCl(g)  r HΘ   92.32 kJ mol 1
H 2 (g)  Cl2 (g) 
2 2
In which of the processes potential energy/enthalpy change is contributing factor to the spontaneity?
89. Enthalpy diagram for a particular reaction is

given in figure. Is it possible to decide
spontaneity of a reaction from given
diagram. Explain.

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90. 1.0 mol of a monoatomic ideal gas is

expanded from state (1) to state (2) as shown
in figure. Calculate the work done for the
expansion of gas from state (1) to state (2)
as 298 K.
SOLUTIONS - QUESTIONS BASED ON CBSE PATTERN
1. (i) Here, q  0  U  q  w  0  w ad  w ad As no heat is absorbed by the system, the wall is adiabatic.
(ii) Here, w  0, q  q  U  q  w  q  0  q
As heat is taken out, the system must be having thermally conducting walls.
(iii) w   w, q   q  U  q  w  q  w. As work is done by the system on absorbing heat, it must be a closed
system.
2. (i) Here, q  15 kJ
w  5 kJ
 According to first low of thermodynamics, ΔU  q  w  15  (5)  10 kJ
Thus, internal energy of the system increases by 10 kJ.
(ii) Here, w  5 kJ
q  15 kJ
 According to first law of thermodynamics, U  q  w  15  (5)  10 kJ
Thus, the internal energy of the system decreases by 10 kJ.
3. (i) w  Pext  V
As expansion takes place into the evacuated bulb, i.e., against vacuum, Pext  0. Hence, w  0.
For adiabatic process, q  0  U  q  w  0  0  0.
(ii) V  V2  V1  5  1  4 litres
P  1 atm  w  PΔV  1 4 litre atm = –4 litre atm  4101.3 J = –405.2 J
Alternatively, using the SI units directly,
P  1 atm = 101325 Pa ; ΔV  4L  4103 m3
 w  P Δ V  1013254103 J = –405.3 J
The negative sign implies that the work is done by the system.
For adiabatic process, q  0. Hence, ΔU  q  w  0  405.2 J = –405.2J.
1
4. The reaction is: C6 H 6 (l )  7 O2 ( g ) 
 6CO2 (g)  3H 2O(l )
2
In this reaction, O2 is the only gaseous reactant and CO2 is the only gaseous product.
1 1 3
 Δn g  n p  n r  6  7  1  
2 2 2
Also, we are given ΔU (or qv )  3263.9 kJ mol–1
T = 25°C = 298 K
8.314
R = 8.314 J K–1 mol–1  kJ K1 mol1
1000
Vidyamandir Classes
 3  8.314 
ΔH (or q p )  ΔU  Δn g RT  3263.9 kJ mol1   mol kJ K 1mol1  (298 K)
 2 
 1000 
 3263.9  3.7 kJ mol1 = –3267.6 kJ mol–1.
5. The process of evaporation is: 18g H 2O(l ) 

18g H 2O(g)
18g
Number of moles in 18g H 2 O   1mol ; Δng  1 0  1mol
18g mol1
 Δ vap U  Δ vap H  Δng RT  40.66 kJ mol1  (1mol) (8.314 103 kJ K 1 mol1) (298 K)
= 40.66 kJ mol–1 –3.10 kJ mol–1 = 37.56 kJ mol–1
6. –890347 J mol–1 7. –87.42 kJ 8. –889.96 kJ mol–1 9. –232.9 kJ mol–1
10. –3274.2 kJ mol–1 11. –5138 kJ mol–1 12. ΔH = –122.56 kJ mol–1, ΔU = – 125.04 kJ mol–1
13. Rise in temperature of the calorimeter = 299 – 298 K = 1 K

Heat capacity of the calorimeter = 20.7 kJ K–1
 Heat absorbed by the calorimeter  C v  ΔT  (20.7 kJ K 1 ) (1 K)  20.7 kJ
This is the heat evolved in the combustion of 1 g of graphite.
 Heat evolved in the combustion of 1 mole of graphite, i.e., 12 g f graphite = 20.7 × 12 kJ = 248.4 kJ
As this is the heat evolved and the vessel is closed, therefore, enthalpy change of the reaction (ΔU)
= – 248.4 kJ mol–1
0.1
14. (i) 500 cm3 of 0.1 M HCl  500 mole of HCl = 0.05 mole of H+ ions 200 cm3 of 0.2 M
1000
0.2
NaOH  200 mole of NaOH = 0.04 mole of NaOH = 0.04 mole of OH– ions
1000
Thus, 0.04 mole of H+ ions will combine with 0.04 mole of OH– ions to form 0.04 mole of H2O and 0.01
mole of H+ ions will remain unreached.
Heat evolved when 1 mole of H+ ions combine with 1 mole of OH– ions = 57.1 kJ.
 Heat evolved when 0.04 mole of H+ ions combine with 0.04 mole of OH– ions
= 57.1 × 0.04 = 2.284 kJ
0.2
(ii) 200 cm3 of 0.2 M H2SO4 =  200 mole of H2SO4 = 0.04 mole of H2 SO4 = 0.08 mole of H+ ions
1000
0.5
400 cm3 of 0.5 M KOH  400 mole of KOH = 0.2 mole of KOH = 0.2 mole of OH– ions
1000
Thus, 0.08 mole of H+ ions will neutralize 0.08 mole of OH– ions. (out of 0.2 mole of OH– ions) to form
0.08 mole of H2O.
Hence, heat evolved = 57.1 × 0.08 = 4.568 kJ
In case (i), heat product = 2.284 kJ = 2284 J Total mass of the solution = 500 + 200 = 700 g
–1 –1
Specific heat = 4.18 J K g
Q 2284
Q = m × C × Δt  Δt    0.78°
mC 700 4.18
In case (ii), heat produced = 4.568 kJ = 4568 J
Q 4568
Total mass of the solution = 200 + 400 = 600 g  Δt    1.82°
mC 600 4.18
15. Heat transferred = 60.1 kJ , ΔC H  5481.1kJmol 1

Vidyamandir Classes
16. –5.28 Kj 17. q v  885 kJmol1 , q p  890 kJmol 1
18. We aim at : C(s )  2H 2 ( g ) 

 CH 4 ( g ); Δ f H  ?
Multiplying equation (ii) with 2, adding to equation (i) and then subtracting equation (iii) from the sum, i.e.,
operating equation (i) + 2 × equation (ii) – equation (iii), we get
 CH 4 ( g ); Δ r H  393.5  2(285.8)  (890.3)  74.8kJ mol1
C (s )  2H 2 ( g ) 
or  CH 4 ( g ); Δ f H  74.8kJ mol1
C( s)  2H 2 ( g ) 
Hence, enthalpy of formation of methane is : Δ f H   74.8 kJ mol–1
1
19. We aim at : C  s   O2  g   CO  g ; Δ f H   ?
2
Subtracting equation (ii) from equation (i), we get
1
C  s   O2  g   CO  g ; Δ r H   393.5  283.0  110.5kJmol 1
2
1
C  s   O2  g   CO  g ; Δ r H   110.5 kJ
2
20. We are given
(i) C(graphite) + O2(g)  CO2(g); ΔC H   393.5kJmol 1
(ii) C(diamond) + O2(g)  CO2(g) ; ΔC H   395.4kJmol 1
We aim at C(graphite)  C(diamond), Δtrans H   ?
Subtracting equation (ii) from equation (i) we get
C(graphite)  C(diamond) ; Δ r H   393.5  395.4  1.9kJ
C(graphite)  C(diamond) ; Δtrans H  1.9kJ
21. We are given :

(i) CuSO 4  s   aq  CuSO 4  aq  ; sol H  66.5kJmol1
(ii) CuSO 4 .5H 2 O  s   aq  CuSO4  aq  ;  sol H  11.7kJmol 1

We aim at CuSO 4  s   5H 2 O  l   CuSO4 .5H 2 O  s  ;  hyd H  ?
Equation (i) can be written in two steps as:
(iii) CuSO 4  s   5H 2 O  l   CuSO 4 .5H 2 O  s  ; H  H1kJmol1
(iv) CuSO 4 .5H 2 O  s   aq  CuSO4  aq  ; H  H 2 kJmol 1
According to Hess’s law, H1  H 2  66.5kJmol 1
Further, equation (ii) and (iv) are same;  H 2  11.7 kJmol1
Putting this value above, we get H1  11.7  66.5or H1  66.5  11.7kJ  78.2kJmol1
Thus, equation (iii) may be written as CuSO 4  s   5H 2 O  l   CuSO 4 .5H 2 O  s  ;  hyd H  78.2 kJmol1
This is what we aimed at. Hence, the required value of the enthalpy of hydration is  hyd H  78.2kJmol1
22. +51.0 kJ mol–1 23. –2677.1 kJ mol–1 24. -445.9 kJ mol–1 25. –1352.6 kJ mol–1
26. –92.45 kJ mol–1 27. –3242.2 kJ mol–1 28. –891.1 kJ mol–1 29. –283 kJ mol–1
30. ΔH for glucose = –15.6 kJ g–1, ΔH for the sucrose = –16.5 kJ g–1.

Vidyamandir Classes
31. (i) ΔH  2840kJ ii  ΔH  284 kJ 32. 26 days approx; 17 days approx.
33. –10.30 kJ/mol 34. 620.7 g
35. By applying the relation  f H   Bond enthalpies of Reactants –  Bond enthalpies of products
For the formation of HCl,
1 1
H 2 (g)  Cl2 (g) 
 HCl(g),  r H   f H
2 2
1 1
  r H   B.E. (Reactants)   B.E. (Products)  2 H H H  2 Cl ClH  H Cl H
1 1
91   430   242  H  Cl H
2 2
  H  Cl H°  215  121  91  427 kJ mol–1
36. Here, we are given

C(s)  2H 2 (g) 
 CH 4 (g),  r H   74.8 kJ … (i)
C(s) 
 C(g),  r H  719.6 kJ … (ii)
H 2 ( g ) 
 2H( g ), Δ r H  435.4 kJ … (iii)
We aim at: CH 4 (g) 

 C(g)  4H(g);  r H   f H … (iv)
Equation (ii) + 2 × equation (iii) – Equation (i) gives
C( s)  2H 2 ( g ) 
 C( g )  4H( g )
C( s)  2H 2 ( g )   CH 4 ( g )
0  C( g )  4H( g )  CH 4 ( g ),Δ r H  719.6  2(435.4)  (74.8)
or CH 4 ( g ) 
 C( g )  4H( g ) ΔH  1665.2 kJ
This gives the enthalpy of dissociation of four moles of C–H bonds (called enthalpy of atomization).
Hence, bond energy for C–H bond (average value) i.e.,
1665.2
Δ CH H°   416.3 kJ mol–1
4
37. Energy absorbed for dissociation of 1 mole of H–H bon = 435 kJ
Energy absorbed of dissociation of 1 mole of Br–Br bond = 192 kJ
Total energy absorbed = 435 + 192 = 627 kJ
Energy released in the formation of 1 mole of H–Br bonds = 364 kJ
 Energy released in the formation of 2 moles of H–Br bonds = 2 × 364 kJ = 728 kJ.
Energy released > Energy absorbed
Hence, net result is the release of energy.
Energy released = 728 kJ –627 kJ = 101 kJ ; i.e., for the given reaction, Δ r H = – 101 kJ
38. –14 kJ 39. –249 kJ mol–1 40. 110.6 kcal 41. –175.9 kJ mol–1 42. 893 kJ mol–1
43. No because after breaking of C–H bonds one by one, the electronic environments change. The reported value is the
average value of the bond dissociation energies of the four C–H bonds.
44. Heat evolved will be different. This is because they have different crystal structure.

Vidyamandir Classes
45. By definition of enthalpy of formation, I2  s   I 2  g  ,  f H  62.5kJmol 1

This is also the enthalpy of sublimation by definition. Hence, Δ f H  I 2 , g   Δ sub H  I 2 , s 
46. The given data imply as under:

(i) CCl 4  l   CCl 4  g  , H  30.5 kJmol 1 (ii) C  s   2Cl 2  g   CCl 4  l  , H  135.5 kJmol1
(iii) C  s   C  g  , H  715.0 kJmol 1 (iv) Cl 2  s   2Cl  g  , H  242 kJmol 1

Aim: CCl 4  g   C  g   4Cl  g  , H  ?
Eqn. (iii) + 2×eqn. (iv) – eqn. (i) - eqn. (ii) gives the required equation with
ΔH = 715.0+2(242)- 30.5 – (-135.5) kJ mol–1 = 1304 kJmol–1
1304
Bond enthalpy of C-Cl in CCl4 (average value) =  326kJmol 1
4
1560
47. Energy left unutilized = kJ  780kJ
2
For losing 44 kJ of energy, water to be evaporated = 1 mole = 18 g
18
 For losing 780 kJ of energy, water to be evaporated =  780 g  319 g
44
48. We are given
7
(i) C2 H 6  g   O2  g   2CO 2  g   H 2O  l  , H  372.0 kcal
2
(ii) C3 H8  g   5O 2  g   3CO 2  g   4H 2 O  l  , H  530.0 kcal
(iii) C(s)  C(g) ; H  172.0 kcal (iv) H2(g)  2H(g) , H  104.0kcal
1
(v) H 2  g   O2  g   H 2O  l  , H  68.0kcal
2
(vi) C(g) + O2(g)  CO 2  g  , H  94.0 kcal
Suppose the bond energy of C–C bond = x kcal mole–1 and that of C–H bond = y kcal mol–1. Then for C2H6 (g), i.e.,
H H
| |
H  C  C  H  2C  g   6 H  g  , ΔH  x  6 y ....(vii)
| |
H H
H H H
| | |
H  C  C  C  H  3C  g   8H  g  , ΔH  2 x  8 y ….(viii)
| | |
H H H
To get equation (vii), operate equation (i) + 2×equaton, (iii) + 3× equation (iv) – 3×Eqn. (v) – 2×equation (vi)
This gives H  676 kcal
To get equation (viii), operate equation (ii) + equation (iii) + 4×eqn. (v) –3×equn. (vi).
Thus, x  6 y  676
2 x  8 y  956
On solving these equations, we get x = 82, y = 99
Hence, C–C bond energy = 82 kcal mol–1 and C-H bond energy = 99 kcal mol–1

Vidyamandir Classes
49. (ii) A thermodynamic state function is a quantity whose value is independent of path. Its value depends only
upon the state of the system.
50. (iii) For the process to occur under adiabatic conditions, q = 0, i.e., heat cannot flow from system to
surroundings or vice-versa.
51. (ii) The enthalpies of all elements in their standard states are taken as zero. The standard state of an
elementary substance means the most stable form of that substance at 298 K temperature and 1 bar
pressure.
52. (iii) CH 4 (g)  2O2 (g) 

 CO2 (g)  2H 2 O(l )
 
n g  n p  n r  1  3   2
H  U  n g RT
H   X  2RT
H  U , hence option (iii) is correct
53. Given, q   701J (heat is absorbed, hence q is positive)

W   394 J (work is done by the system, hence W is negative)
By first law of thermodynamics;
Internal energy change, U  q  W   701J   394 J    307 J
Hence, internal energy of the system increases by 307 J.
3
54. NH 2 CN(s)  O 2 (g)   N 2 (g)  CO2 (g)  H 2O(l )
2
Difference of moles of gaseous products and reactants,
3 1
n g  n p  n r  2    0.5mol
2 2
H  U   n g RT

H   742.7 kJ mol 1  0.5 mol  8.314 103 kJ mol 1  298K 
 
H  742.7 kJ  1238.786 10 3 kJ mol1   741.46 kJ mol1
55. Given, mass of Al = 60.0g

Molar mass of Al  27 g mol 1
Molar heat capacity, C  24 J mol 1 K 1
T  55C  35C  20C or 20 K
Heat, q  n .C. T
60  60 
q  24 J mol1 K 1  20K n  mol 
27  27 
 1066.66 J  1.067 kJ
56. Enthalpy change for the conversion of 1 mole liquid water at 10°C into 1 mole liquid water at 0°C,
H1  C p H 2 O(l )  T   75.3 J mol1 K 1 10K   753 J mol 1
Enthalpy of fusion,
H 2  Hfreezing   H fusion   6.03 kJ mol1
Enthalpy change for the conversion of 1 mole of ice at 0°C to 1 mole of ice at 10°C,
H3  Cp H 2 O(s)  T   36.8 J mol1 K 1 10 K   368 J mol 1
H total    0.753  6.03  0.368  kJ mol1   7.151kJ mol1

Vidyamandir Classes
57. For an isolated system, U  0 and for a spontaneous process, total entropy change must be positive. For example,
consider the diffusion of two gases A and B into each other in a closed container which is isolated from the
surroundings. The two gases A and B are separated by a movable partition. When partition is removed, the gases
begin to diffuse into each other and the system becomes more disordered. It shows that S  0 and U  0 for this
process.
q rev H U  pV pT
Moreover, S     ( U  0 )
T T T T
i.e., TΔS or ΔS > 0
58. Given, H  400 kJ mol1 , S  0.2 kJ K 1 mol1 ,

Gibbs free energy, G  H  TS (for spontaneous reaction G  0 )
0  400 kJ mol1  T  0.2 kJ K 1 mol1
400 kJ mol1
Temperature, T   2000 K
0.2 kJ K 1 mol1
Therefore, above 2000 K, the reaction will become spontaneous.
59. In the given reaction, a molecule of Cl 2 is formed from its two gaseous atoms and the energy is released with the
formation of bond. Hence, H is ve . In this reaction, randomness (entropy) also decreases because 2 mol atoms
of Cl have more randomness than one mole molecules of chlorine. Hence, S is ve .
60. Enthalpy change for the formation of 1 mole of H 2O(l ) ,
1
H 2 (g) O2 (g)   H 2 O(l );  f H   286 kJ mol 1
2
Energy released in the above reaction, is absorbed by the surroundings.
It means qsurr   286 kJ mol 1
qsurr 286 kJ mol 1
S    0.9597 kJ K 1 mol1  959.7 JK 1 mol1
T 298 K
61. Given that, quantity of water = 18.0 g, pressure = 1 bar
As we know that, 18.0 g H2O = 1 mole H2O
Enthalpy change for vaporizing 1 mole of H2O = 40.79 kJ mol–1.
 Enthalpy change for vaporizing 2 moles of H 2O  2  40.79 kJ  81.358kJ
Standard enthalpy of vaporization at 100C and 1 bar pressure  vap HΘ   40.79kJ mol 1
62. One mole a acetone requires less heat to vaporize than 1 mole of water. Hence, acetone has less enthalpy of
vaporization and water has higher enthalpy of vaporization. It can be represented as
(H v ) water  (H v ) acetone .
63. No, the  r HΘ for the given reaction is not same as  r HΘ . The standard enthalpy change for the formation of one
mole of a compound from its elements in their most stable states (reference states) is called standard molar enthalpy
of formation,  f HΘ .
3
Ca(s)  C(s)  O2 (g)   CaCO3 (s)   t HΘ
2
This reaction is different from the given reaction.
Hence,  r H   f H

Vidyamandir Classes
1 3
64. Given N 2 (g)  H 2 (g)   NH3 (g) ;  f HΘ   91.8kJ mol 1
2 2
 Enthalpy change for the formation of 2 moles of NH3 is 2   91.8    183.6 kJ / mol
And for the reverse reaction.
 N 2 (g)  3H 2 (g);  f H Θ   183.6 kJ mol 1
2NH3 (g) 
Hence, the value of  f HΘ for NH3 is + 183.6 kJ mol–1
65. In general, If enthalpy of an overall reaction A 

B
along one route is  r H and  r H1 ,  r H 2 , r H3 .......
representing enthalpies of reaction leading to same
product B along another route, then we have
 r H   r H1   r H 2   r H3  .......
66. In CH4, there are four C – H bonds. The enthalpy of atomization of 1 mole of CH4 means dissociation of four moles
of C – H bond.
1665 kJ
 C – H bond energy per mol  = 416.25 kJ mol–1
4 mol
67. Given that, sub HΘ for Na metal = 108.4 kJ mol–1
IE of Na = 496 kJ mol–1,  eg HΘ of Br = –325 kJ mol–1,  diss HΘ of Br = 192 kJ mol–1,  f HΘ

For NaBr = 360. 1 kJ mol–1
Born – Haber cycle for the formation of NaBr is as
By applying Hess’s law :  f HΘ  sub HΘ  IE   diss HΘ   eg HΘ  U
–360.1 = 108.4 + 496 + 96 + (–325) –U

U = + 735.5kJ mol–1
68. The mixing of two gases have H equal to zero. Therefore, it is spontaneous process because energy factor has no
role to play but randomness increases i.e., randomness factor favours the process.
69. Heat has randomizing influence on a system and temperature is the measure of average chaotic motion of particles
q
in the system. The mathematical relation which relates these three parameters is S  rev
T
Here, S = Change in entropy
qrev = heat of reversible reaction
T = temperature

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70. Yes, the temperature of system and surroundings be the same when they are in thermal equilibrium.
71.  2NO2 (g) K p  0.98

For the reaction, N 2 O4 (g) 
As we know that  r G   2.303 RT log K p
Here, Kp = 0.98 i.e., Kp < 1 therefore,  r G  is positive, hence the reaction is non-spontaneous.
72. The net enthalpy change, H for a cyclic process is zero as enthalpy change is a state function, i.e., H (cycle) = 0
73. The standard molar entropy of H2O(l) is 70 JK–1 mol–1. The solid from of H2O is ice. In ice, molecules of H2O are
less random than in liquid water. Thus, molar entropy of H2O(s) < molar entropy of H2O(l). The standard molar
entropy of H2O(s) is less than 70 JK–1 mol–1.
74. State functions are those value which depend only on the state of the system and not on how it is reached
e.g., enthalpy, entropy, temperature and free energy. Path functions are those values which depend on the path of
the system, e.g., heat and work.
75. Amount of heat required to vaporize one mole of a liquid at constant temperature and under standard pressure
(1 bar) is called is molar enthalpy of vaporization  vap HΘ . Molar enthalpy of vaporization of water is more than
that of acetone because there is strong hydrogen bonding in H2O molecule.
76. Gibbs energy for a reaction in which all reactants and products are in standard state  r GΘ is related to the
equilibrium constant of the reaction as follows
 r G   r GΘ  RT ln Q
At equilibrium, 0   r G  RT ln K (  r G  0) & Q  k eq
or  r G Θ   RT ln K
 r GΘ  0 when K  1
For all other values of K,  r GΘ will be non-zero.
77. For isolated system there is no transfer of energy as heat, i.e., q = 0 and three is no transfer of energy as work
i.e., W = 0. According to the first law of thermodynamics.
U  q  W
U  0  0  0
78. The two condition under heat becomes independent of path are
(i) when volume remains constant (ii) when pressure remains constant
79. Work done of a gas in vacuum, W   ext (V2  V1 ) . As ext  0 so W   0 (5  1)  0 . As internal energy of
an ideal gas depends only on temperature, therefore, for isothermal expansion of an ideal gas, internal energy
remains constant.
i.e., U  0
It is to be remember that as H = U + PV, H  H   (U  pV)  U  pV  U  nR(T) . For isothermal
process, T  0 and also U  0 , as stated above, therefore, H  0
80. For water, molar heat capacity, Cp  18  Specific heat, c

Cp  18  c Specific heat
C  4.18 Jg 1K 1 (for water)

Heat capacity, C p  18  4.18 JK 1mol1  75.3JK 1mol1

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81. Given that Cv = heat capacity at constant volume.

Cp = heat capacity at constant pressure
Difference between Cp and Cv is equal to gas constant (R).
Cp  Cv  nR (where, n = no. of moles)
 10  4.184 J = 41.84 J
82. Given that, enthalpy of combustion of 1g graphite = 20.7 kJ
Molar enthalpy change for the combustion of graphite, H = enthalpy of combustion of 1 g graphite × molar mass
H   20.7kJg 1  12g mol1 ; H   2.48  102 kJ mol 1
Negative sign in the value of H indicates that the reaction is exothermic.
83. In the first case, as the expansion is against constant external pressure
W   ext  V2  V1    2bar  50  10  L
  80L bar (1L bar = 100 J)
  80  100 J
  8kJ
If the given expansion was carried out reversibly, the internal pressure of the gas should be greater than the external
pressure at every stage. Hence, the work done will be more.
84. Given that, 1 mol of CCl4 = 154 g

30.5  284
 vap H for 154 g CCl4 = 30.5 kJ   vap H for 284 g CCl4 = kJ  56.25 kJ
154
85. Given that,  2H 2O(l) is  r H    572 kJ mol 1
2H 2 (g)  O 2 (g) 
Enthalpy of formation is the enthalpy change of the reaction when 1 mole of the compound is formed from its
elements then
1
H 2 (g)  O 2 (g)   H 2 O(l),  r H  ?
2
This can be obtained by dividing the given equation by 2.
572kJ mol1
Therefore.  f H(H 2 O)     286 kJ mol1
2
86. Suppose total volume of the gas is Vi and pressure of the gas inside cylinder is p. After compression by constant
external pressure, (pext) in a single step, final volume of the gas becomes Vf.
Then volume change, v   Vf  Vi 
If W is the work done on the system by movement of the piston, then
W = pext ( V )
W =  pext (Vf – Vi)
This can be calculated from p – V graph as shown in the figure. Work done is equal to the shaded area ABVfVi
The negative sign in this expression is required to obtain conventional sign for W which will be positive. Because
incase of compression work is done on the system, so V will be negative.

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87. When compression is carried out in infinite steps

with change in pressure, it is a reversible process.
The work done can be calculated from p – V plot as
shown in the given figure. Shaded area under the
curve represents the work done on the gas.
88. Representation of potential energy/enthalpy change in the following processes

(a) Throwing a stone from the ground to roof.
1 1
(b)  HCl(g) ;  r HΘ   92.32 kJ mol 1
H 2 (g)  Cl 2 (g) 
2 2
Energy increases in (a) and it decreases in (b) process. Hence, in process (b), enthalpy change is the contributing
factor to the spontaneity
89. No, enthalpy is one of the contributing factors in deciding spontaneity but it is not the only factor. Another
contributory factor, entropy factor has also to be taken into consideration.
90. The given diagram represent that the process is carried out in infinite steps, hence it is isothermal reversible
expansion of the ideal gas from pressure 2.0 atm to 1.0 atm to 1.0 atm 298 K.
1
W   2303nRT log
2
 1 2 
W   2.303  1mol  8.314 JK 1 mol 1  298 K log 2   
 2 1 
W   2.303  1 8.314  298  0.3010J
W   1717.46 J

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THERMOCHEMISTRY QUESTIONS BASED ON JEE MAINS PATTERN

CHOOSE THE CORRECT ALTERNATIVE. ONLY ONE CHOICE IS CORRECT.
1. Which one of the following is an exothermic reaction?
(A) N 2 (g)  O 2 (g)  180.8 kJ 
 2NO(g) (B) N 2 (g)  3H 2 (g)  90 kJ 
 2NH3 (g)
(C) C(g)  H 2 O(g) 
 CO(g)  H 2 (g) 131.1 kJ
(D) C(graphite)  2S(s) 
 CS2 (l )  91.9 kJ
2. Which of the following taking place in the blast furnace is endothermic?

(A) CaCO3 
 CaO  CO 2 (B) 2C  O2 
 2CO
(C) C  O 2 
 CO 2 (D) Fe 2 O3  3CO 
 2Fe  3CO 2
3. Which one of the following is not a state function?

(A) Enthalpy (B) Entropy (C) Work (D) Free energy
4. Which is an extensive property?

(A) Temperature (B) Molar heat capacity (C) Gibb’s free energy (D) Molar volume
5. Which of the following is a path function?

(A) Internal energy (B) Enthalpy (C) Work (D) Entropy
6. For the following two reactions,

I. CH 4 (g)  2O 2 (g) 
 CO 2 (g)  2H 2 O ; H   890.4 kJ
II. 2HgO(s) 
 2Hg(l )  O2 (g) ; H   181.6 kJ
Which one of the following statements is correct?
(A) Both of them are exothermic (B) Both of them are endothermic
(C) I is exothermic and II is endothermic (D) I is endothermic and II is exothermic
7. Which is correct for an endothermic reaction?

(A)  H is positive (B)  H is negative (C)  E is negative (D) H  0
8. C(s)  O 2 (g) 
 CO 2 (g); H   94 kcal
2CO(g)  O2 
 2CO2 (g); H  135.2 kcal
The heat of formation of CO (g) is :
(A) 26.4 kcal (B) 41.2 kcal (C) 26.4 kcal (D) 229.2 kcal
9. Internal energy is sum of :
(A) Kinetic energy or potential energy (B) All type of energy of the system
(C) Energy of internal system (D) None of the above
1
10. If C(s)  O 2 (g)  CO 2 (g); H  r and CO(g)  O 2 
 CO 2 (g); H  s then the heat of formation of CO is:
2
(A) r+s (B) rs (C) sr (D) rs
11. Hess’s law is based on :

(A) Law of conservation of mass (B) Law of conservation of energy
(C) First law of thermodynamics (D) None of the above

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12. A hypothetical reaction A  2B , proceeds through following sequence of steps

1
I. A  C ; H  q II. C  D; H  v III. D  B; H  x
2
Then the heat of reaction is :
(A) q  v  2x (B) q  v  2x (C) q + v + 2x (D) q  2v  2x
13. The first law of thermodynamics is expressed as :

(A) q  W  E (B) E  q  W (C) q  E  W (D) W  q  E
14. The sublimation energy of I2 (s) is 57.3 kJ/mol and the enthalpy of fusion is 15.5 kJ/mol. The enthalpy of
vaporization of I2 is :
(A) 41.8 kJ/mol (B) 41.8 kJ / mol (C) 72.8 kJ/mol (D) 72.8 kJ / mol
15. The value of E for combustion of 16 g of CH4 is 885389 J at 298 K. The H combustion for CH4 in J mol 1 at
this temperature will be : (Given that, R  8.314 JK 1 mol 1 )
(A) 55337 (B) 880430 (C) 885389 (D) 890348
16. Hess’s law states that :
(A) The standard enthalpy of an overall reaction is the sum of the enthalpy changes in individual reactions.
(B) Enthalpy of formation of a compound is same as enthalpy of decomposition of the compound into
constituent elements, but with opposite sign.
(C) At constant temperature the pressure of a gas is inversely proportional to its volume.
(D) The mass of a gas dissolved per litre of a solvent is proportional to the pressure of the gas in equilibrium
with the solution.
17. The value of enthalpy change (H) for the reaction C2 H5 OH(l )  3O 2 (g) 
 2CO2 (g)  3H 2 O(l ),
at 27 C is  1366.5kJ mol1 . The value of internal energy change for the above reaction at this temperature will be:
(A) 1371.5 kJ (B) 1369.0 kJ (C) 1364.0 kJ (D) 1361.5 kJ
18. Consider the reaction, 4NO 2 (g)  O2 (g)   2N 2 O5 (g),  r H  111kJ .

If N2O5(s) is formed instead of N2O5 (g) in the above reaction, the  r H value will be :
(Given, H of sublimation for N 2 O5 is 54 kJ mol 1 )
(A) 165 kJ (B) + 54 kJ (C) + 219 kJ (D) 219 kJ
19. The amount of the heat released when 20 mL 0.5 M NaOH is mixed with 100 mL 0.1 M HCl is x kJ. ? The heat of
neutralization is:
(A) 100 x kJ / mol (B) 50 x kJ / mol (C) + 100x kJ/mol (D) + 50x kJ/mol
20. The species which by definition has zero standard molar enthalpy of formation at 298 K is :
(A) Br2 (g) (B) Cl2 (g) (C) H2O (g) (D) CH4 (g)
21. The standard enthalpy of formation of NH3 is 46.0kJ mol 1 . If the enthalpy of formation of H2 from its atoms is
436 kJ mol1 and that of N2 is 712kJ mol1 , the average bond enthalpy of N  H bond in NH3 is :
(A) 964 kJ mol1 (B)  352 kJ mol1 (C) 1056 kJ mol 1 (D) 1102 kJ mol1
5
22. C2 H 2  O 2 
 2CO 2  H 2 O ; H  310 kcal
2
C  O2 
 CO 2 ; H  94 kcal
1
H 2  O2   H 2O ; H  68 kcal
2

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On the basis of the above equations, H f (enthalpy of formation) of C2H2 will be :

(A) 148 kcal (B) + 54 kcal (C) 54 kcal (D) + 80 kcal
23. The enthalpy of formation of NH3 is  46 kJ mol1 . The enthalpy change for the reaction
2NH 3 (g)  N 2 (g)  3H 2 (g) is :
(A) + 184 kJ (B) + 23 kJ (C) + 92 kJ (D) + 46 kJ
24. Calculate H in kJ for the following reaction : C (g)  O2 (g) 

 CO 2 (g)
Given that, H 2 O(g)  C(g) 
 CO(g)  H 2 (g); H   131kJ
1
CO(g)  O 2 (g)   CO2 (g); H   282 kJ
2
1
H 2 (g)  O 2 (g)   H 2 O(g); H   242 kJ
2
(A)  393 (B) + 393 (C) + 655 (D)  655
25. The heat of formations for CO2 (g), H2O (l) and CH4 (g) are  400 kJ mol 1 ,  280 kJ mol 1 and  70 kJ mol 1
respectively. The heat of combustion of CH4 in kJ mol 1 is :
(A) 800 (B) 160 (C) 890 (D) 90
26. Using the following thermochemical equations :
3
I. S(rhombic)  O 2 (g)   SO3 (g) ; H   2x kJ mol 1
2
1
II. SO 2 (g)  O2 (g)   SO3 (g) ; H   y kJ mol 1
2
Find out the heat of formation of SO2 (g) in kJ mol 1 .
(A) (2x + y) (B) (x + y) (C) 2x  y (D)  y  2x 
27. Which of the following reaction defines Hf ?
1 1
(A) C(diamond)  O2 (g) 
 CO 2 (g) (B) H 2 (g)  F2 (g) 
 HF(g)
2 2
1
(C) N 2 (g)  3H 2 (g) 
 2NH3 (g) (D) CO (g)  O2 (g)   CO 2 (g)
2
28. Consider the reaction, N 2  3H 2   2NH3 carried out at constant temperature and pressure. If H and U are
the enthalpy and internal energy changes for the reaction, which of the following expressions is true?
(A) H  U (B) H  U (C) H  U (D) H  0
29. The relation between H and U is :

(A) H  U  RT (B) H  U  nRT
(C) H  U  nRT (D) U  H  nRT
30. The bond energy is the energy required to :
(A) Dissociate one mole of the substance (B) Dissociate bond in 1 kg of the substance
(C) Break one mole of similar bonds (D) Break bonds in one mole of substance
31. For an ideal gas, the heat of reaction at constant pressure and constant volume are related as :
(A) H  E  pV (B) E  H  pV (C) q p  q v  nRT (D) None of these
32.  2C (g)  3D (g) the change of enthalpy at 27 C is 19 kcal. The value of
For the reaction, A (g)  2B (g) 
E is:
(A) 21.2 kcal (B) 17.8 kcal (C) 18.4 kcal (D) 20.6 kcal

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33. The enthalpy of reaction,

1 1
H 2 (g)  O 2 (g)  H 2O (g) is H1 and that of H 2 (g)  O2 (g)   H 2 O (l ) is H 2 . Then :
2 2
(A) H1  H 2 (B) H1  H 2  0 (C) H1  H 2 (D) H1  H 2
34. Identify the reaction for which H  E
(A) S(rhombic)  O2 (g) 

 SO2 (g) (B) N 2 (g)  O2 (g) 
 2NO (g)
1
(C) H 2 (g)  Cl2 (g) 
 2HCl (g) (D) CO (g)  O2 (g) 
 CO 2 (g)
2
35. Which of the following indicates the heat of reaction equal to heat of formation?
(A) C (graphite)  O2 (1 atm) 
 CO 2 (1 atm) (B) C (diamond)  O 2 (1 atm) 
 CO 2 (2 atm)
(C) C (graphite)  O 2 (1 atm) 

 CO 2 (2 atm) (D) C (diamond)  O 2 (1 atm) 
 CO2 (1 atm)
36. The H – H bond energy is 430 kJ mol1 and Cl  Cl bond energy is 240 kJ mol 1 , H for HCl is  90 kJ .
The H – Cl bond energy is about :
(A) 180 kJ mol 1 (B) 360 kJ mol 1 (C) 213 kJ mol 1 (D) 425 kJ mol1
37. The amount of energy released when 20 mL of 0.5 M NaOH are mixed with 100 mL of 0.1 M HCl is x kJ. The heat
of neutralization is (in kJ mol1 ) .
(A) 100 x (B) 50 x (C) + 100 x (D) + 50 x
38. If the bond dissociation energies of XY, X2 and Y2 (all diatomic molecules) are in the ratio of 1 : 1 : 0.5 and H f
for the formation of XY is 200 kJ mol1 . The bond dissociation energy of X2 will be :
(A) 400 kJ mol1 (B) 300 kJ mol 1 (C) 20 kJ mol1 (D) None of these
39. For the gaseous reaction involving the complete combustion of iso-butane :
(A) H  E (B) H  E (C) H  E (D) None of these
40. If S  O 2 
 SO 2 ; H   298.2 kJ
1
SO 2  O 2 
 SO3 ; H   98.7 kJ
2
SO3  H 2 O 
 H 2SO4 ; H   130.2 kJ
1
H2  O 2   H 2 O ; H   287.3 kJ
2
Then the enthalpy of formation of H2SO4 at 298 K will be :
(A)  814.4 kJ (B) + 320.5 kJ (C)  650.3 kJ (D)  933.7 kJ
41. The heat of neutralization of any strong acid and a strong base is nearly equal to :
(A) 75.3kJ (B) + 57.3 kJ (C)  57.3 kJ (D) + 75.3 kJ
42. Enthalpy of formation of HF and HCl are 161 kJ and  92 kJ respectively. Which of the following statements is
incorrect?
(A) HCl is more stable than HF
(B) HF and HCl are exothermic compounds
(C) The affinity of fluorine to hydrogen is greater than the affinity of chlorine to hydrogen
(D) HF is more stable than HCl

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43. The enthalpies of formation of Al2O3 and Cr2O3 are 1596 kJ and  1134 kJ respectively. H for the reaction,
2Al  Cr2 O3  2Cr  Al 2 O3 is :
(A) 2730 kJ (B) 462 kJ (C) 1365 kJ (D) + 2730 kJ

44. Which of the following equations correctly represents the standard heat of formation (H f ) of methane?
(A) C (diamond)  4H (g) 
 CH 4 (g) (B) C (diamond)  2H 2 (g) 
 CH 4 (g)
(C) C (graphite)  2H 2 (g) 
 CH 4 (g) (D) C (graphite)  4H (g) 
 CH 4 (g)
45. Average C – H bond energy is 416 kJ mol1 . Which of the following is correct?
(A) CH 4 (g)  416 kJ 
 C(g)  4H (g) (B) CH 4 (g) 
 C(g)  4H (g)  416 kJ
(C) CH 4 (g)  1664 kJ 
 C(g)  4H (g) (D) CH 4 (g) 
 C(g)  4H (g)  1664 kJ
46. For the reaction, A (s)  3B(g) 

 4C (g)  D (l ) H and U are related as :
(A) H  U (B) H  U  3RT (C) H  U  RT (D) H  U  3RT
47. For the gaseous reaction, N 2 O4 
 2NO2
(A) H  E (B) H  E (C) H  0 (D) H  E
48. For the reaction, PCl5 (g)  PCl3 (g)  Cl 2 (g)
(A) H  E (B) H  E (C) H  E (D) None of these
49.  2N(g)  4H (g) is 1724 kJ mol1 . If the bond energy

The enthalpy change (H) for the process N 2 H 4 (g) 
of N – H bond in ammonia is 391 kJ mol 1 , what is the bond energy for N – N bond in N2H4?
(A) 391 kJ mol1 (B) 160 kJ mol1 (C) 1173 kJ mol 1 (D) 320 kJ mol 1
50. Factors that influence the heat of reaction is(are) :

I. The physical state of reactants and products II. The temperature
III. The pressure or volume IV. The method by which the final products are obtained
The correct option is :
(A) I, II (B) II, III (C) I, II, III (D) IV
51. For the reaction, 2H 2 (g)  O 2 (g)  2H 2 O (g); H   573.2 kJ

The heat of decomposition of water per mole is :
(A) 286.6 kJ (B) 573.2 kJ (C) 28.66 kJ (D) zero
52. The bond energy of O – H bond is 109 kcal/mol. When a mole of water is formed, then :
(A) 109 kcal is released (B) 218 kcal is absorbed
(C) 109 kcal is absorbed (D) 218 kcal is released
53. The standard enthalpies of formation of CO2(g), H2O(l) and glucose(s) at


25 C are  400 kJ / mol,  300 kJ / mol and  1300 kJ / mol , respectively. The standard enthalpy of combustion per
gram of glucose at 25 C is:
(A) + 2900 kJ (B) 2900 kJ (C) 16.11 kJ (D) + 16.11 kJ
54. Consider the following reactions.

I.  CO 2 (g); H    x1 cal
C  graphite   O2 (g) 
1
II. CO(g)   CO2 (g); H   x 2 cal
O 2 (g) 
2

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Based on the above data, Hf  CO2  is :

(A) x1 cal (B)  x 2 cal (C)  x 2  x1  cal (D)  x1  x 2  cal
55. From Q.(54) above, Hf  CO  is:
(A) x1 (B) x 2 (C) x 2  x1 (D) x1  x 2
56. Consider the following reactions,
I. N 2  O2 
 2NO, H  x1 II. 2CO  O2 
 2CO 2 , H  x 2
III. 2H 2 O  O 2 
 2H 2 O 2 , H  x 3 IV. PCl3  Cl 2 
 PCl5 , H  x 4
H
In which case(s), H f  ?
2
(A) I, II, III (B) IV (C) II, III (D) I
57. Heat of reaction A(s)  B(g) 
 2C(g) is 40 kJ at 300 K and constant volume. Hence, heat of reaction at
constant pressure and at 300 K is,
(A) 42.5 kJ (B) 37.5 kJ (C) 40.0 kJ (D) 30.0 kJ
58. Heat of combustion of CH4, C2H6 and C2H6 are respectively 210,  368.4 and  526.3 kcal mol1 . Hence, heat of
combustion of C6H16 is approximately.
(A) 1310 kcal mol1 (B) 684 kcal mol1 (C) 840 kcal mol1 (D) 1000 kcal mol1
59. Calorific value of H2 is 143 kJ g 1 . Hence, Hf of H2O is:
(A) 143 kJ mol 1 (B) 286 kJ mol1 (C) 143 kJ mol 1 (D) 286 kJ mol1
60. Consider the following reactions,

1
I. C(s)  O 2 (g)   CO(g), H1  x1
2
1
II. CO(g)  O2 (g)   CO2 (g), H 2  x 2
2
III. C(s)  CO2 (g) 
 2CO(g), H 3  x 3
Select the correct statements:
(A) Heat of formation of CO2 is (x1 + x2) (B) Heat of combustion of C is (x1 + x2)
(C) H3  H1  H 2 (D) All of the above are correct statement(s)
61. The dissolution of CaCl2 · 6H2O in large volume of water is endothermic to the extent of 3.5 kcal mol 1 .
For the reaction CaCl 2 (s)  6H 2O(l) 
 CaCl2 ·6H 2 O(s) H   23.2 kcal
Hence, heat of solution of CaCl2 (anhydrous) in a large volume of water is:
(A) 26.7 kcal (B) 26.7 kcal (C) 19.7 kcal (D) 19.7 kcal
62. Lattice energy of NaCl(s) is 788 kJ mol 1 and enthalpy of hydration is 784 kJ mol 1 . Hence, heat of solution of
NaCl(s) is:
(A) 4 kJ mol1 (B) 4 kJ mol1 (C) 1572 kJ mol1 (D) 1572 kJ mol 1
63. Bond energies of N  N bond, H  H bond and N  H bond are respectively x1 , x 2 and x3 kJ mol 1 .
Hence, Hf (NH3 ) is:
(A) x1  3x 2  x 3 (B) x1  x 2  x3
x1 3
(C)  x 2  3x3 (D) x1  3x 2  6x3
2 2

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64. Born-Haber cycle has some of the following facts :

I. It is used to determine lattice energy.
II. It is used to determine electron affinity.
III. It is based on Hess’s law of constant heat summation.
IV. It is based to determine heat of formation of hydrocarbons.
Correct facts are:
(A) I, II, III (B) II, III, IV (C) I, II (D) I, II, III, IV
65. The heat of atomisation of PH3(g) and P2H4(g) are 953kJ mol 1 and 1485 kJ mol1 respectively. The P – P bond
energy in kJ mol 1 is:

(A) 213 (B) 426 (C) 318 (D) 1272
66. (H  E) for the formation of NH3 from N2 and H2 is:
(A) RT (B) 2RT (C) RT (D) 2RT
1
67. H 2 (g)  O 2 (g)   H 2 O(l) ; BE(H  H)  x1 ; BE(O  O)  x 2 ; BE(O  H)  x 3
2
Latent heat of vaporization of water liquid into water vapour = x4 then H f (heat of formation of liquid water) is:
x2 x2 x2 x2
(A) x1   x 3  x 4 (B) 2x3  x1   x 4 (C) x1   2x 3  x 4 (D) x1   2x 3  x 4
2 2 2 2
68. Which combination of the following equations have enthalpy changes equal to H comb (C) ?
1 1
I. C  O 
 CO 2 II. C O 2  CO III. CO  O2 
 CO2
2 2
(A) I, II (B) I, II, III (C) I, III (D) I
69. The bond energy (in kcal mol 1 ) of C  C single bond is approximately
(A) 1 (B) 10 (C) 100 (D) 1000
70. An imaginary lattice Cl  Cl is formed as given
Cl 2 
 2Cl x1
 Cl   e
Cl  x2
Cl  e  
 Cl  x2
   
Cl  Cl 
 Cl Cl x4
Thus, enthalpy change when Cl  Cl  is formed is:
 x1   x1 
(A)    x 2  x3  x 4  (B)    x 2  x3  x 4 
 2   2 
(C) (x1 + x2 + x3 + x4) (D)   x1  x 2  x3  x 4 

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SOLUTIONS - QUESTIONS BASED ON JEE MAINS PATTERN
1.(B) The reactions in which products have lesser energy than reactants, then energy is released in the reaction and such
reactions are known as exothermic reactions e.g.
N 2  3H2 
 2NH3  90 k J
In this equation energy is released, so, it is an example of exothermic reaction.
2.(A) Bond breaking process or decomposition process are endothermic process.
3.(C) Macroscopic properties which determine the state of a system are referred as state functions. The change in the state
properties depends only upon the initial and final state of the system. All thermodynamics functions are state
functions except work and heat.
4.(C) The properties of the system whose value is depends upon the amount of substance present in the system is called
extensive property. Gibb’s free energy is an extensive property.
5.(C) Internal energy, enthalpy and entropy are state functions but work and heat are path functions.
6.(A) For exothermic reaction, H     for endothermic reaction, H     .
7.(A) For an endothermic reactions H is positive because in endothermic reaction heat is always absorbed.
8.(A) The heat of formation of CO is calculated by using Hess’s law. According to it, the total heat changes occurring
during a chemical reaction are independent of path.
2CO (g)  O2 (g) 
 2CO 2 (g) ; H  135.2 kcal
1 135.2
I. CO (g) 
 CO(g)  O2 (g) ; H  kcal
2 2
II. C (s)  O2 (g) 

 CO2 (g) ; H   94 kcal
1
Required equation : C (s)  O2 (g) 
 CO(g) ; H  ?
2
1
Add Eqs. (I) and (II) C (s)  O2 (g) 
 CO(g) ; H   26.4 kcal
2
9.(B) Every system having some quantity of matter, is associated with a definite amount of energy. This energy is known
as internal energy. It is sum of many type of energies, such as translation energy, rotational energy, vibrational
energy, electronic energy and bonding energy of the molecule.
E  E trans  E rot  E vib  Ebonding  Eelectronic
10.(B) C(s)  O 2 (g) 

 CO 2 (g) ; H  r
1
CO(g)  O2 (g) 
 CO 2 (g); H  s
2
1
C(s)  O2 (g) 
 CO(g); H  ?
2
Subtract Eq. (ii) from Eq. (i)
C(s)  O 2 (g) 
 CO 2 (g); H  r
1
CO(s)  O2 (g) 
 CO 2 (g); H  s
2
   
1
C(s)  O2 (g) 
 CO(g); H  r  s
2
11.(B) Hess’s law is based upon law of conservation of energy i.e., first law of thermodynamics.

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12.(C) According to Hess’s law, the total heat changes

occurring during a chemical reaction are
independent of path.
13.(C) The first law of thermodynamics can be expressed as: E  q  W

q  E  W
14.(A) According to Hess’s law total heat changes during a chemical reaction are independent of path of reaction.
Given, I2 (s)  I2 (g), H1  57.3 kJ / mol …(i)
I2 (s)  I2 (g), H 2   15.5 kJ / mol …(ii)
Required equation I2 (l )  I 2 (g), H  ? subtract
Eq. (ii) from Eq. (i)
 I2 (l ) 
 I2 (g), H  57.3  ( 15.5)   41.8 kJ / mol
15.(B) CH 4 (g)  2O 2 (g) 

 CO 2 (g)  2H 2O(l ) n g  1  3   2
We know that, E  H  n g RT
 H   885389    2   8.314  298 =  885389  4955.1440 =  880433.86 J mol1
16.(A) According to second law of thermo chemistry the law states that the total heat change ( H ) accompanying a
chemical reaction is the same whether the reaction takes place in one or more steps. It means that heat of a reaction
depends only on the initial reactants and final products and not on intermediate products that may be formed.
Now, H  H1  H 2  H 3
Enthalpy change in a reaction is always constant and independent of the path followed.
17.(C) Relation between H (enthalpy change) and E (internal energy change) is : H  E   n g RT
Where,  n g = moles of gaseous products-moles of gaseous reactants

= 2  1
 1366.5  E 1  8.314  103  300
E   1364.0 kJ mol1
18.(D) 4NO 2 (g)  O 2 (g)  2N 2O 5 (g); 111 kJ

2N 2O5 (g)  2N 2O5 (s); s H   54  2  kJ
4NO2 (g)  O2 (g)  2N2O5 (s);  r H   219 kJ
Note: H of sublimation of N 2O5 (s) is  54 kJ mol1 .
Thus, for reverse process, it is  54 kJ mol1
19.(A) NaOH  HCl 

 NaCl  H 2O
20  0.5 100  0.1 10 millimole produced
20.(B) Hf of elements in their standard state is taken to be zero. Cl2 is gas, Br2 is liquid and I2 is solid at room
temperature.
1 3
21.(B) Given, N2 (g)  H 2 (g)  NH3 (g)
2 2
Hf  46.0 kJ mol 1

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2H(g)  H 2 (g) H f   436 kJ mol1
2N(g)  N 2 (g) H f   712 kJ mol 1

Assuming X is the bond energy of N – H bond in kJ mol 1 
1 3
  712     436   3X   46.0
2 2
3X  1056 kJ mol1
So, X  352 kJ mol1 .
5
22.(B) I. C2 H5  O2  2CO2  H 2O; H  310 kcal II. C  O2  CO 2 ; H   94 kcal
2
1
III. H2  O2  H 2O; H   68 kcal
2
(Equation (II) × ) + Equation (I) gives 2C  H 2 

 C2H2 ; H   94  2    68    310  = + 54 kcal
23.(C) 2NH3 (g)  N 2 (g)  3H 2 (g)

Hr    2  enthalpy of formation of NH3  =   2   46   92 kJ
24.(A) Given, H 2O(g)  C(g) 

 CO(g)  H 2 (g); H   131kJ …(i)
1
CO(g)  O2 (g) 
 CO 2 (g); H   282 kJ …(ii)
2
1
H 2 (g)  O2 (g)   H 2O(g); H   242 kJ …(iii)
2
C (g)  O2 (g) 
 CO2 (g); H  ? …(iv)
On adding Equations (i), (ii) and (iii), we get Equation (iv)
H 2O(g)  C(g) 
 VO(g)  H 2 (g); H  131 kJ
1
CO(g)  O2 (g)  CO 2 (g); H   282 kJ
2
1
H 2 (g)  O2 (g)  H2O(g); H  242 kJ
2
C(g)  O2 (g)   CO2 (g) H  131  282  242  KJ
=  393 kJ
25.(C) Hreaction   Hf product   Hf reactant
Hf of a single element O2, H2 Cl2 is considered equal to zero.
CH 4  2O2 
 CO2  2H 2O
Hreaction  Hf (CO2 )  2 H f · (H 2O)  H f (CH 4 )  2H f (O 2 )
= 400  2(280)   70)  0  =  890 kJ mol1

3
26.(D) Given, S(rh)  O 2 (g) 
 SO3 (g); H   2x kJ mol1 …(i)
4
1
SO2 (g) O2 (g) 
 SO3 (g); H   y kJ mol1 …(ii)
2
S(s)  O2 (g) 
 SO2 (g); H  ?
Subtract Equation (ii) from Equation (i)
3
S(rh(  O2 (g) 
 SO3 (g); H  2x kJ mol1 …(i)
2

Vidyamandir Classes
1
 SO3 (g); H   y kJ mol1
SO2 (g)  O2 (g)  …(ii)
2
   
3 1
 SO2 (g); H   2x  y  kJ mol1
S(rh)     O2 (g) 
 2 2
 SO 2 (g); H   y  2x  kJ mol1
S(rh)  O2 (g) 
27.(B) Hf is the enthalpy change when 1 mol of the substance is formed from its elements in the standard state.
Reaction (a) does not represent Hf because standard state of carbon is graphite and not diamond.
28.(B) H  U  n g RT
H = enthalpy change (at constant pressure)
U = internal energy change (at constant volume) given reaction is exothermic)
ng = mole of (gaseous products – gaseous reactants)
= ve
Thus, H  U
29.(C) The relationship between H and U is H  U  nRT
30.(C) The bond energy is the energy required to break one mole of similar bonds.
31.(C) The heat of reaction for an ideal gas, at constant pressure and constant volume are related as
 H  E  nRT  q p  q v  nRT
32.(B) A(g)  2B(g) 

 2C(g)  3D(g)
n  5  3  2
 H  E  nRT
19000  E  2  2  300
E  17800 cal = 17.8 kcal
33.(A) The enthalpy of H2O(l) is less than that of H2O (g), hence more energy will be released when H2O(l) is formed,
therefore H1  H 2 .
1
34.(D) H  E for CO(g)  O2 (g) 
 CO 2 (g)
2
35.(A) The amount of heat evolved or absorbed in the formation of one mole of product from its elements. So, the correct
answer is C  O2 1 atm  
 CO2 1 atm  .
1 1
36.(D) The formation of one mole of HCl can be represented as,  H  H    Cl  Cl   H  Cl; H   90kJ
2 2
Hence, for the reaction,
Heat evolved = heat evolved in bond formation – heat required for bond breaking
1 1 
 90 KJ   H  Cl bond energy     430   240 
2 2 
  H  Cl bond energy   90   215  120  = 425 kJ mol1
37.(A) Given, 20 mL, of 0.5 M NaOH
100 mL of 0.1 M HCl
Milliequivalents (or millimoles) of NaOH = 20 × 0.5 = 10

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Milliequivalents (or millimoles) of HCl = 100 × 0.1 = 10

 10 milliequivalents on neutralisation give =  x kJ heat
 lg-eq (i.e., 1000 milliequivalents) will give =  x  100 =  100 x kJ heat
38.(D) Formation of XY is known as : X 2  Y2 

 2XY
H   BE X  X   BE Y  Y  2  BE X  Y
If (BE) of X  Y  a
Then (BE) of (X  X)  a
a
And (BE) of  Y  Y  
2
 Hf (X  Y)   200 kJ
a
 400(for 2 mol XY)  a   2a
2
a
400  
2
a = + 800 kJ
The bond dissociation energy of X 2  800 kJ mol 1 .
CH3
39.(C) | 13
CH3  C H  CH3 (g)  O 2 (g) 
 4CO 2 (g)  5H 2 O(g)
2
H  E  nRT
n = mole of (gaseous products–gaseous reactants)
= –ve
Thus, H  E
40.(A) Enthalpy of formation of H2SO4 can be represented by the following equation:

H 2  S  2O 2 
 H 2SO4
Given, S  O 2 
 SO2 , H  298.2 kJ
1
SO2  O 2 
 SO3 , H   98.7 kJ
2
SO3  H 2O 
 H 2SO4 , H  130.2 kJ
1
H 2  O2 
 H 2O, H   287.3 kJ
2
On adding all the four equations, we get the equation (i),
Hence, Hf   298.2    98.7     130.2    287.3 = 814.4 kJ
41.(C) The heat of neutralisation of strong acid and strong base is constant because it is infact heat of formation of water
by H  and OH  . Its value is almost equal to 57.3 kJ .
42.(A) HF is more stable than HCl. The reason is that in the formation of HF, more energy is produced. It means, HF has
less energy than HCl and hence is more stable.
In other words, we need more energy to break H–F bond, hence HF is more stable.
43.(B) According to question,
3
2Al  O2 
 Al2O3 ; H  1596 kJ …(i)
2
3
2Cr  O2 
 Cr2O3 ; H  1134 kJ …(ii)
2

Vidyamandir Classes
Reversing Equation (ii) and adding both reactions, we get :

2Al  Cr2O3 
 2Cr2  Al 2O3 ; H  462 kJ
44.(C) Standard heat of formation of substance is the amount of heat evolved or absorbed when one mole of substance is
formed from its elements in their standard states.
 Graphite is the standard state of carbon and hydrogen is found in form of H2.
 Standard heat of formation of methane is C  graphite   2H2 (g) 
 CH 4 (g)
45.(C) CH4 has four C – H bonds. So, 4 × 416 kJ is required to break CH4 into C and 4H.
46.(C) We know, H  U  nRT

n = [total number of moles of gaseous products] – [Total number of moles of gaseous reactants]
 4C(g)  D (l ) n   4  3 = 1
For this reaction A(s)  3B(g) 
H  U  RT
47.(D) We know that, H  E  ng RT
For reaction, N 2O4 

 2NO2
ng  2  1  1
 H  E  RT or H  E
48.(B) H  E  pV  E  n g RT
PCl5 (g) 
 PCl3 (g)  Cl2 (g)
n g  n (p)g  n (r)g  2 1  1
 H  E  1  RT  H  E
49.(B) The structure of N2H4 is as follows
Hence, in the reaction,

N 2H 4 (g) 
 2N(g)  4H (g);
H   N  N bond energy    N  H bond energy  4 
 1724  N  N bond energy = 1724  1564 = 160 kJ/mol
50.(B) The amount of heat either evolved or absorbed when one gram mole of a substance is formed form its constituent
elements, is known as the standard heat of formation ( Hf ) .
For standard state temperature is 25 C or 298 K and pressure of gaseous substance is one atmosphere.
Thus, in given thermochemical equation 'b' represents the standard heat of formation of HF.
1 1
H 2 (g)  F2 (g) 
 HF(g); Hf  ? [standard heat of formation of HF (g)].
2 2
1  573.2
51.(A) Heat of decomposition of water is H 2O(g) 
 H 2 (g)  O2 (g) H   286.6 kJ / mol
2 2
52.(D) Bond energy O – H bond = 109 kcal/mol
 Energy absorbed in the dissociation of 1 mol of water (H2O) = 2 × 109 = 218 kcal
 Energy released in the formation of 1 mole of water = 218 kcal.

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53.(C) C6 H12O2(s)  6O 2(g) 

 6CO 2(g)  6H 2 O()
H  6(400)  6(300)  1300
  4200  1300
H   2900 kJ / mole
2900
 Enthalpy of combustion program =  16.11kJ / gm (Molar weight of glucose = 180)
180
C(graphite)  O2(g)  CO2(g)
 
54.(A) Standard Standard
elemental form elemental form
1
55.(C) C(graphite)  O2 (g) 
 CO2(g)  x1 . . . . (i)
2
1
CO(g)  O2 (g)   CO(g)  x 2 . . . . .(ii)
2
Rewriting equation as (i) and (ii)
1
C(graphite)  O2 (g) 
 CO (x 2  x1 )
2
56.(D) Formation of a compound (H f ) is represented by the reaction of its constituents atoms in their basic elemental
form. Hence only 1 is correct.
N 2  O 2 
 2NO H  x1
1 1 x
 NO H  1
N 2  O2 
2 2 2
57.(A) Q V  U
Q P  H  ?
Also H  U  n (g) RT
H  40kJ  (2  1)  8.314  300  103 = 40 + (8.314 × 0.3)= 40 + 2.4942
H  42.5kJ
58.(A) CH 4  C2 H6  C3 H 6   C 6 H16
Product molecules has same number of C and H as the total number of C and H in reactant, but has higher bond
energy corresponding to extra C  C bonds.
1
59.(B) H 2(g)  O 2(g) 
 H 2 O(  )
2
H f  ?
In the above reaction for 1 mole formation of H2O we need to burn 2g H2 molecule
 H f (H 2 O)   2  143 kJ / mol   286 kj / mol
60.(D) C(s) graphite  O2(g) 

 CO2(g) The above reaction both formation of CO2 and combustion of Carbon
61.(D) Apply Hess’s law 62.(A) H disolution  H lattice  H Hyd.

1 2
63.(C) N 2(g)  H 2 (g)  NH3 (g)
2 3
Hj  (B.E)R  (BE)p
1 2
(1 )  (2 )  33
2 3

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64.(A) Refer to theory
65.(A) 4  (3(P  H)  953)
3(2(P  P)  4(P  H)  1485)

12(P  H)  4  953 . . . .(i)
6(P  P)  12(P  H)  3  1485 . . . . (ii)
Rewriting equation as (i) and (ii)
6(P  P)  (3  1485  4  953)
(P  P)  213
N2 3
66.(C)  H2 
 NH3(g)
2 (g) 2 (g)
1 3
n g  1       1
2 2
 H  E  ngRT   RT
1
67.(C) H 2(g)  O2 (g) 
 H 2O(g)
2
x
H1  x1  2  2x 3
2
H 2 O( )  H 2O(g) H 2  x 4
Now H1  H 2
1 x 2 2x3
Gives H 2(g)  O2 
 H 2 O( )  H net  x1    x4
2 (g) 2 2
68.(D) C  O2 
 CO2
Depends for complete combustion
69.(C) 70.(C) Apply Hess’s law

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CHEMICAL THERMODYNAMICS QUESTIONS BASED ON JEE MAINS PATTERN

1. An ideal gas expands in volume from 1  103 m3 to 1  102 m3 at 300 K against a constant pressure
of 1  105 Nm2 . The work done is:
(A) 900 J (B) 800 kJ (C) 270 kJ (D) 900 kJ
2. The work done during the expansion of a gas from a volume of 4 dm3 to 6 dm3 against a constant external pressure
of 3 atm is :
(A) 6 J (B)  608 J (C)  304 J (D)  304 J
3. In an adiabatic process :
(A) p . V  0 (B) q=+W (C) E  q (D) q=0
4. A process is taking place at constant temperature and pressure. Then :

(A) H  E (B) H  TS (C) H  0 (D) S  0
5. In an isothermal process :
(A) q  0 and E  0 (B) q  0 and E  0 (C) q  0 and E  0 (D) q  0 and E  0
6. Which of the following is an endothermic reaction?

(A) N 2 (g)  3H 2 (g)  92 kJ 
 2NH 3 (g) (B) N 2 (g)  O2 (g)  180.8kJ 
 2NO(g)
(C) H 2 (g)  Cl2 (g) 

 2HCl(g)  184.6 kJ (D) C (graphite)  2H 2 (g) 
 CH 4 (g)  74.8 kJ
7. To calculate the amount of work done in joules during reversible isothermal expansion of an ideal gas, the volume
must be expressed in :
(A) m3 only (B) dm3 only (C) cm3 only (D) Any of these
8. A gas can expand from 100 mL to 250 mL under a constant pressure of 2 atm. The work done by gas is :
(A) 30.38 J (B) 25 J (C) 5 kJ (D) 16 J
9. What is E for system that does 500 cal of work on surrounding and 300 cal of heat is absorbed by the system?
(A) 200 cal (B) 300 cal (C)  200 cal (D)  300 cal
10. For the reaction A  B; H   24 kJ / mol and B  C; H  18 kJ / mol , the decreasing order of enthalpy of A, B, C
follows the order:
(A) A, B, C (B) B, C, A (C) C, B, A (D) C, A, B
11. In an isochoric process, H for a system is equal to :
(A) p . V (B) pV (C) E  p . V (D) E
12. The heat of neutralization of HCl by NaOH is 55.9 kJ / mol , the energy of dissociation of HCN is if heat of
neutralization of HCN by NaOH is 12.1 kJ / mol .
(A) 43.8 kJ (B)  43.8 kJ (C)  68 kJ (D) 68 kJ
13. The cooling in refrigerator is due to :
(A) Reaction of the refrigerator gas (B) Expansion of ice
(C) The expansion of the gas in the refrigerator (D) The work of the compressor
14. What would be the heat released when an aqueous solution containing 0.5 mole of HNO3 is mixed with 0.3 mole of
OH  (enthalpy of neutralization is 57.1 kJ ) ?
(A) 28.5 kJ (B) 17.1 kJ (C) 45.7 kJ (D) 1.7 kJ

Vidyamandir Classes
15. Heat required to raise the temperature of 1 mole of a substance by 1 is called :

(A) Specific heat (B) Molar heat capacity
(C) Water equivalent (D) Specific gravity
16. In view of the signs of  r G for the following reactions :
PbO2  Pb 
 2PbO,  r G  0 ; SnO2  Sn   2SnO,  r G  0
Which oxidation states are more characteristic for lead and tin?
(A) For lead + 4, for tin + 2 (B) For lead + 2, for tin + 2
(C) For lead + 4, for tin + 4 (D) For lead + 2, for tin + 4
17. A plot of ln k against 1/T (abscissa) is expected to be a straight line with intercept on coordinate axis equal to :
S S S
(A) (B) (C)  (D) R  S
2.303 R R R
18. For a chemical reaction, G will always be negative if :

(A) H and TS both are positive (B) H and TS both are negative
(C) H negative and TS positive (D) H positive and TS negative
19. For which reaction change of entropy will be positive?

(A) 

H 2 (g)  I 2 (g) 
 2HI(g) (B) 

HCl(g)  NH 3 (g) 
 NH 4Cl(s)
(C) 

NH 4 NO3 (s) 
 N 2 O(g)  2H 2 O(g) (D) 

MgO(s)  H 2 (g) 
 Mg(s)  H 2 O ( l )
20. The correct relationship between free energy change in a reaction and the corresponding equilibrium constant Kc is :
(A) G  RT ln K c (B) G  RT ln K c (C) G  RT ln Kc (D) G   RT ln K c
21. For a chemical reaction, the free energy change ( G) is negative. The reaction is :
(A) A spontaneous reaction (B) An equilibrium reaction
(C) A non-spontaneous reaction
(D) Characterized by rf = rb (where, rf and rb are rates of forward ad backward reaction respectively)
22. For the reaction at 298 K


A(g)  B(g) 
 C (g)  D(g)
H   29.8 kcal, S   0.100 kcal K 1

What is the value of G ?
(A) 1 (B) 0 (C) 2 (D) 4
23. Unit of entropy is :
(A) JK 1 mol 1 (B) J mol 1 (C) J 1K 1 mol 1 (D) JK mol 1
24. For a system in equilibrium, G  0 under conditions of constant :
(A) Temperature and pressure (B) Temperature and volume
(C) Pressure and volume (D) Energy and volume
25.  2HCl (g) will be : [Given that, S (HCl)  187 JK 1 mol 1
The entropy change for the reaction H 2 (g)  Cl2 (g) 
S (H 2 )  131JK 1 mol 1 and S (Cl 2 )  223 JK 1 mol 1 ]
(A) 20 JK 1 mol 1 (B) 20 JK 1 mol 1 (C) 167 JK 1 mol 1 (D) 167 JK 1 mol1
26. The free energy for a reaction having H  31400 cal, S  32 cal K 1 mol 1 at 1000 C is :
(A) 9336 cal (B) 7386 cal (C) 1936 cal (D) 9336 cal

Vidyamandir Classes
27. Spontaneous adsorption of a gas on solid surface is an exothermic process because :

(A) H increases for system (B) S increases for gas
(C) S decreases for gas (D) G increases for gas
28. The enthalpy change for the transition of liquid water to steam is 40.8 kJ mol 1 at 373 K . What is the entropy of
vaporization of water?
(A) 209.4 (B) 109.4 (C) 250.0 (D) 209.4
29. Which of the following statements is true?

(A) G is always less than H (B) G is always more than H
(C) G is always proportional to H (D) G may be lesser, greater or equal to H
30. In a reversible process, Ssystem  Ssurrouding is :

(A) >0 (B) <0 (C) 0 (D) =0
31. Which one is true from the following for isobaric process ?
(A) P  0 (B) q  0 (C) H  0 (D) U  0
32. Under which of the following conditions is the relation, H  U  P V valid for a closed system ?
(A) Constant pressure (B) Constant temperature
(C) Constant temperature and pressure (D) Constant temperature, pressure and composition
33. Heat of neutralisation for the reaction, NaOH  HCl 
 NaCl  H 2O
is 57.1kJ mol1 . The heat released when 0.25 mole of NaOH is titrated against 0.25 mole of HCl will be :
(A) 22.5kJ (B) 57.1kJ (C) 28.6kJ (D) 14.3kJ
34. In thermodynamics, a process is called reversible when :

(A) Surrounding and system change into each other
(B) There is no boundary between system and surrounding
(C) The surrounding are always in equilibrium with the system
(D) The system changes into the surrounding spontaneously
35. An ideal gas expands in volume from 1  103 m3 to 1  102 m3 at 300 K against a constant pressure of
1  105 Nm 2 . The work done is :
(A)  900 J (B)  900 kJ (C) 270kJ (D)  900 kJ
36. The enthalpy of vaporization of a liquid is 30 kJ mol1 and entropy of vaporization is 75J mol1 K 1 .
The boiling point of the liquid at 1 atm is :
(A) 250 K (B) 400 K (C) 450 K (D) 600 K
37. 

For the gas phase reaction, PCl5 (g) 
 PCl3 (g)  Cl2 (g)
Which of the following conditions are correct :
(A) H  0 and S  0 (B) H  0 and S  0 (C) H  0 and S  0 (D) H  0 and S  0
38. The Haber’s process for production of ammonia involves the equilibrium : 

N 2 (g)  3H2 (g) 
 2NH 3 (g)
Assuming H and S for the reaction do not change with temperature, which of the statements is true ?
( H   95kJ and S   190 JK 1)
(A) Ammonia dissociates spontaneously below 500 K
(B) Ammonia dissociates spontaneously above 500 K
(C) Ammonia dissociates at all temperatures
(D) Ammonia does not dissociates at any temperature

Vidyamandir Classes
39. In which reaction, there will be increase in entropy ?

1
(A) Na(s)  H 2O(l ) 
 NaOH(aq)  H2 (g)  (B) Ag  (aq)  Cl (aq) 
 AgCl(s)
2
1
(C) H 2 (g)  O2 (g) 
 H 2O(l ) (D) Cu 2 (aq)  4NH3 (g)  2
 [Cu(NH3 ) 4 ](aq)
2
SOLUTIONS - QUESTIONS BASED ON JEE MAINS PATTERN
1.(D) Work done against constant external pressure  Pext (V2  V1 )

In adiabatic condition q = 0 therefore w  u
3
 Pext (V2  V1 )  R(T2  T1 ) [Expansion work is negative]
2
2
On solving T2  T1 
3  0.0821
2.(B) Word done  W    pext  V2  V1 
= 3   6  4   6 Latm
= 6  101.32 J  1 L atm  101.32 J 
= 607.92   608 J
3.(D) In the adiabatic process no heat enters or leaves the system i.e., q = 0.
4.(A) For an isothermal process, E  0

As the process is taking place at constant T and p hence, from
Equation, H  E  p.V
We have, H  0  0  V  0
Hence, for the process, H  E  0
5.(B) For an isothermal process T  0 and E  0 and q  0 .
6.(A) Endothermic reaction are those in which heat energy is absorbed.
7.(D) As we know that,

V2
Work done (W)  2.303 nRT log .
V1
Hence, V1 and V2 are in ratio in the relation. So, unit may be expressed in any one of m3, dm3 or cm3.
8.(A) V1 = 100 mL ; V2 = 250 mL

Pressure p  2 atm or 2 1.01 105 Nm 2
Work done by the gas W  pV or p  V2  V1 
 
Put the value in given formula W  2 1.01  105 0.250  103  0.100  103 = 2  1.01  105  0.15  10 3 = 30.30 J
9.(A) From first law of thermodynamic.

E  q  W Given, q   300 cal (  Heat is absorbed)
W   500 cal (  Work done on surroundings)
 E  q  W  300    500  =  200cal
10.(B) A  B, H   24 kJ / mol
 H B  H A   24 …(i)

Vidyamandir Classes
B  C, H  18 kJ / mol
 HC  H B   18 …(ii)
 H B  H C   18
From Equations (i) and (ii), we have HC  H A  6
H B  HC  H A
11.(D) H  E  p V For isochoric process V  0  H  E
 
12.(A) Given, H  OH 
 H 2O; H   55.9 kJ …(i)
HCN  OH  
 H 2O  CN  H  12.1 kJ …(ii)
 H   OH  ; H   55.9 kJ
On reversing (i) we get : H 2O  …(iii)
 H   CN ;
On adding (iii) to (ii) we get : HCN  H   43.8 kJ
13.(C) This is based on Joule-Thomson effect.

14.(B) 0.5 mol HNO3  0.5 mol H  and 0.3 mol OH 
0.5 H  (aq)  0.3 OH  (aq) 
 0.3 H 2O(l )
(0.3 mole of OH  is neutralised by 0.3 mole of H+)

= 17.13 kJ
H  0.3  57.1 = 17.1 kJ
15.(B) Molar heat capacity Heat required to raise the temperature of 1 mole of a substance by 1 C is called molar heat
capacity.
16.(D) PbO2  Pb 
 2PbO
4 0 2
Since,  r G 0 , hence + 2 state of lead is favourable.
SnO2  Sn 
 2SnO
4 0 2
Since,  r G   0 , it means forward reaction is not spontaneous.
2SnO 
 SnO 2  Sn
2 4 0
For this  r G  0 , thus + 4 state of tin is favourable.
17.(B) G   RT ln K
H S
or, H  TS   RT ln K or, ln K  
RT R
S
Comparing with y = m.x + c  y intercept is
R
18.(C) Gibbs-Helmholtz equation is a follows: G  H  TS
From Gibbs-Helmholtz equation, it is clear that G will always be negative, if H is negative and TS is positive.
19.(C) Entropy is a measure of randomness of the system, so entropy of a substance in different physical states is in the
order Gas > liquid > solid
S  Sproduct  Sreactant
In option (c) solid is converted into gaseous state, so S will be positive.
20.(D) The standard free energy change ( G  ) is related to equilibrium constant K as
G   RT ln K ; G   2.303 RT log K
21.(A) For spontaneous reaction, the energy change ( G) should be negative.
22.(B)  G  H  T · S = 29.8  298   0.1 = 29.8  29.8 = 0 23.(A) The unit of entropy is J mol1 K 1 .

Vidyamandir Classes
24.(A) For a system in equilibrium, G  0 , when all the reactants and products are in the standard state [at constant
temperature and pressure] and Kc = 1.
25.(A)  2HCl(g) S   Sp   SR = 2 187  131  223 = 374  354 = 20 JK 1 mol1
H 2 (g)  Cl2 (g) 
26.(A) Given, H  31400 cal
S  32 calK 1 mol 1
T  1000  273  1273K
G  ?
From Gibb’s-Helmholtz equation G  H  T · S = 31400 1273  32 = 31400  40736   9336 cal
27.(C) For spontaneous adsorption process, standard Gibb’s free energy ( G) must be negative as well as the degree of
randomness of gas molecule on the surface of solid decreases. For exothermic process, H must be negative.
Hence, with the help of following equation.
H  G  T · S
T · S is negative. Thus, during adsorption S decreases.
 vap H 40.8 103

28.(B)  vapS   vapS   109.4 JK 1 mol1
T 373
29.(D) As we know that, G  H  TS Hence, G may be greater, lesser or equal to H .
30.(D) For a reversible process Ssystem  Ssurroundings  0 31.(A) For isobaric process, pressure is kept constant.
32.(D) For cyclic process, change in state function is zero. Since U and H are state variables, U  0 and H  0 .
33.(D)  H 2 O  NaCl . One mole of H+ and OH ions neutralisation produces 57.1 kJ.
NaOH  HCl 
Thus 0.25 mol H   0.25 OH will produce  57.1  0.25  14.3 kJ
34.(C) In reversible process, system is in equilibrium with surrounding always. (Thermal equilibrium)
35.(A) Work done (W)  Pext (V2  V1 )  1 105 Nm 2  (1 102  1 103 )m3  105  9 103 J  900J
30  103 J / mol
36.(B) At boiling point, liquid and gaseous phase are at equilibrium, so G  0  H  Tb S  Tb 
75 J / mol
Tb  400K
37.(D)  PCl3 (g)  Cl 2 (g)  G  0

PCl5 (g) 
0  H  T S
Since gaseous moles are increasing S  0
Thus H  TS  H  0
38.(B) G  H  TS   95  1000  500   190    95000  95000  0
Upto T  500 K the synthesis of ammonia is spontaneous. After 500 K synthesis becomes non-spontaneous,
so ammonia will dissociate spontaneously.
39.(A) Formation of gaseous product from solid or liquid state reactants implies increase in randomizes, so, the entropy.

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CHEMICAL THERMODYNAMICS BASED ON JEE ADVANCED PATTERN

1. A gas expands isothermally against a constant external pressure of 1 atm from a volume of 10 dm3 to a volume of
20 dm3. It absorbs 800 J of thermal energy from its surroundings. The U is :
(A) –312 J (B) + 123 J (C) –213 J (D) + 231 J
2. If gas, at constant temperature and pressure expands then it.

(A) Entropy increases and then decreases (B) Internal energy increases
(C) Internal energy remains the same (D) Internal energy decreases
3. In which of the following reactions, the enthalpy is the least?

(A)  CH 3COONa  H 2 O (B)
CH 3COOH  NaOH  HCl  NH 4 OH 
 NH 4 Cl  H 2 O
(C) HCl  NaOH 

 NaCl  H 2 O (D) HCN  NH 4OH 
 NH 4CN  H 2O
4. For a particular reversible reaction at temperature T, H and S were found to be both +ve. If Te is the temperature
at equilibrium, the reaction would be spontaneous when :
(A) Te > T (B) T > Te (C) Te is 5 times T (D) T = Te
5. Which of the following reaction define Gf ?

1 1
(A) C (diamond)  O2 (g) 
 CO2 (g) (B) H 2 (g)  F2 (g) 
 HF (g)
2 2
1
(C) H 4 P2 O7  H 2 O 
 2H 3PO4 (D) SO2 (g)  O2 (g)   SO3 (g)
2
6. Considering the reaction, C (s)  O2 (g)   CO2 (g)  393.5 kJ the signs of H, S and G respectively are :
(A) +, –, – (B) –, +, + (C) –, –, – (D) –, +, –
7. The direct conversion of A of B is difficult, hence it is carried out by the following shown path C 
D
 
A B
Given; S(A  C)  50 eu ; S(C  D)  30 eu ; S(B  D)  20 eu
Where eu is entropy unit, then S(A  B) is :
(A) + 100 eu (B) + 60 eu (C) 100 eu (D) 60 eu
8. A schematic plot of ln Keq versus inverse of temperature

for a reaction is shown below :
The reaction must be :

(A) Highly spontaneous at ordinary temperature
(B) One with negligible enthalpy change
(C) Endothermic
(D) Exothermic
9. If an endothermic reaction is non-spontaneous at freezing point of water becomes feasible at its boiling point then :
(A) H is  ve, S is  ve (B) H and S both are  ve
(C) H and S both are  ve (D) H is  ve, S is  ve

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10. Molar heat change is 16J mol 1 K 1 , the boiling points of the liquid is if molar heat of vaporization is 6 kJ/mol :
(A) 375 C (B) 375 K (C) 273 K (D) 102 C
11. H vap  30 kJ / mol and S vap  75 J mol 1 K 1 . Find temperature of vapour, at 1 atm.
(A) 400 K (B) 350 K (C) 298 K (D) 250 K
12. For a process to be spontaneous, the most favourable condition is :

(A) H  0, S  0 (B) H  0, S  0 (C) H  0, S  0 (D) H  0, S  0
13. For the reaction of one mole zinc dust with one mole sulphuric acid in a bomb calorimeter, U and w correspond
to :
(A) U  0, w  0 (B) U  0, w  0 (C) U  0, w  0 (D) U  0, w  0
14. A particular reaction at 27°C for which H  0 and S  0 is found to be non-spontaneous. The reaction may
proceed spontaneously if :
(A) The temperature is decreased (B) The temperature is kept constant
(C) The temperature is increased (D) It is carried in open vessel at 27°C
15. Considering entropy(s) as a thermodynamic parameter, the criterion for the spontaneity of any process is :
(A) Ssystem  Ssurroundings  0 (B) Ssystem  Ssurroundings  0
(C) Ssystem  0 only (D) Ssurroundings  0 only
16. Assuming H and S do not change with temperature. Calculate, the boiling point of liquid A using the
thermodynamic data given below :
Thermodynamic data A l  A(g)
H  kJ / mol   130  100
1 1 100 200
S(J K mol )
(A) 300 K (B) 130 K (C) 150 K (D) 50 K
17.  H 2 O  g 
For a phase change : H 2O  l  
0°C, 1 bar
(A) G  0 (B) S  0 (C) H  0 (D) U  0
18.  CaO(s)  CO2 (g) the values of H and S are
In the conversion of limestone to lime, CaCO3 (s) 
 179.1kJ mol1 and 160.2 JK 1 mol 1 respectively at 298 K and 1 bar. Assuming that, H and S do not
change with temperature above which conversation of limestone to lime will be spontaneous is :
(A) 1118 K (B) 1008 K (C) 1200 K (D) 845 K
19. Assuming that, water vapour is an ideal gas, the internal energy change (U) when 1 mol of water is vaporized at
1 bar pressure and 100°C, (given : molar enthalpy of vaporized of water at 1 bar and 373K  41kJ mol1 and
R  8.314 J K 1 mol1 ) will be :
(A) 41.00 kJ mol 1 (B) 4.100 kJ mol 1 (C) 3.7904 kJ mol 1 (D) 37.904 kJ mol 1
20. For the process, H 2O  l 1 bar, 373K  

 H 2O  g 1 bar, 373K 
The correct set of thermodynamic parameters is :
(A) G  0, S   ve (B) G  0, S   ve (C) G   ve, S  0 (D) G   ve, S   ve

Vidyamandir Classes
21. Standard entropy of X 2 , Y2 and XY3 are 60, 40 and 50 JK 1 mol 1 respectively. For the reaction :
1 3
X 2  Y2 
 XY3 , H   30 kJ
2 2
to be at equilibrium, the temperature will be :
(A) 1000 K (B) 1250 K (C) 500 K (D) 750 K
22. The incorrect expression among the following is :
GSystem V 
(A)  T (B) In isothermal process, w  reversible   nRT ln  f 
STotal  Vi 
H  TS
(C) ln K  (D) K  e G  / RT
RT
SOLUTIONS - QUESTIONS BASED ON JEE ADVANCED PATTERN
1/ 2 8.314 JK 1 mol1
1.(C) W 1/1 pdV   p  V2  V1  W  1 20  10   10 dm 3 atm = 10dm3   1013 J
0.0821 dm3 K 1 mol1
From, 1st law of thermodynamics U  q  W = 800 J   1013 J    213 J
2.(C) Internal energy of a gas depends upon its pressure and temperature. Thus, if a gas expands at constant temperature
and pressure, then its internal energy remains same.
3.(D) In neutralization reaction, when acid and base both are weak, a large amount of heat is utilized to ionise them. Thus,
for such reactions, enthalpy of the reaction is least.
Hence, enthalpy is least for HCN  NH 4OH 
 NH 4CN  H2O
4.(B) G  H  T S At equilibrium, G  0
For a reaction to be spontaneous G should be negative, so T should be greater than Te.
5.(B) Standard Gibb’s energy of formation ( Gf ) of a substance is defined as the Gibb’s energy change when mole of
the substance is formed from its elements in their standard states. The following reaction define Gf ,
1 1
H2 (g)  F2 (g) 
 HF(g)
2 2
6.(D) H   ve (combustion reaction) S   ve (spontaneous at all temperature)
G   ve (because reaction is spontaneous)
7.(B) C 
D
 
A B
Given, S(A C)  50eu
S(CD)  30eu ; S(BD)  20 eu
Where, eu is entropy unit
Therefore, S(A  B)  S(A  C)  S(C  D)  S(D  B) = S(A C)  S(C  D)  S(B  D) = 50  30  20  60 eu
H S
8.(D) Variation of Keq with temperature t is given by van’t Hoff equation log K eq   
2.303RT R
A B
Slope of the given line is positive indicating that term A is positive thus H is negative. Thus, reaction is
exothermic.

Vidyamandir Classes
9.(B) For a reaction to be spontaneous G must be negative. According to relationship of G , G  H  T · S

If H and S both are positive, then term T. S will be greater than H at high temperature and consequently G
will be negative at high temperature. (Boiling point of water) and reaction becomes feasible.
H vapour 6  1000
10.(B) S  16 J mol1 K 1 H v  6 kJ mol1 Tbp    375K
Svapour 16
11.(A) Given that, 3

H vaps  30 kJ / mol  30  10 J / mol ; Svaps  75 JK 1 mol 1
We know that, G  H  T S
At equilibrium, G  0
 H  T S or 30  103  T  75
30  103
T  400 K
75
12.(A) For spontaneous process, G   ve
G  H  TS
 For G to be negative H  0 (i.e., negative) and S  0 (i.e., positive)
13.(A) In bomb calorimeter, volume is constant, so, w = 0 and U  q .
Since q is calculated by the change in temperature of calorimeter, we have to notice the sign of U .
For exothermic U is negative and for endothermic U is +ve.
Since Zn  H 2 SO4 
 H 2  ZnSO 4 is exothermic U  0 .
14.(C) G  H  T S
If G  ve  reaction is spontaneous H  0 and S  0
It implies that entropy term can make G negative which is possible at higher temperature.
15.(A) For spontaneous process, system and surrounding entropy should be positive  Ssys.  Ssurr.  0
16.(A)  A(g) at boiling point

A() 
H  100  (130)  30 kJ / mol ; S  200  100  100 kJ / mol
H
For equilibrium G  0  Tb   300K 17.(A) For equilibrium G  0
S
 298  160.2 
18.(A) G  H  T S  179.1   kJ / mol  179.1  47.74  131.36 kJ   ve  non-spontaneous at 298K.
 1000 
Let at T, reaction is spontaneous.
G  0  H  T S  0
H 179.1 1000
T  K
S 160.2
T  1118K
19.(D)
 1 8.314  373 
U  q  W  41000  1105    0   (41000  3101.122)J  37.9 kJ
5
 110 
20.(A) H 2 O(1 bar, 373 K) 
 H 2 O(g) (1bar, 373 K)  equilibrium  G  0
Since liquid 
 gaseous phase S  0

Vidyamandir Classes
1 3
21.(D) X2   XY3
Y2 
2 2
1 3 
S  50    60   40   50  90  40kJ / mol
2 2 
G  0  30  103  T  (40)
40T  30  103  T  750 K
22.(C) G  G   RT nQ
At equilibrium G  0 and G  H  T S and Q  K
H  T S
nK  
RT
THERMOCHEMISTRY BASED ON JEE MAINS PATTERN
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
B A C C C A A A B B B C C A B
16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
A C D A B B B C A C D B B C C
31 32 33 34 35 36 37 38 39 40 41 42 43 44 45
C B A D A D A D C A C A B C C
46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
C D B B C A D C A C D A A B D
61 62 63 64 65 66 67 68 69 70
D A C A A C C D C C
CHEMICAL THERMODYNAMICS BASED ON JEE MAINS PATTERN
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
A B D A B A D A A B D A C B B
16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
C B C C A A B A A A A C B D D
31 32 33 34 35 36 37 38 39 40
A C D C A B D B A D
CHEMICAL THERMODYNAMICS BASED ON JEE ADVANCED PATTERN
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
C C D B B D B D B B A A A C A
16 17 18 19 20 21 22
A A A D A D C

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THERMOCHEMISTRY & THERMODYNAMICS QUESTIONS BASED ON CBSE PATTERN

1. Express the change in internal energy of a system when :

8. The internal energy change (ΔU) for the reaction CH 4 ( g )  2O2 ( g ) 

VMC | Supplementary Booklet-2 35 Chapter-6 & 7 | Chemistry

14. Calculate the amount of heat evolved when

2SO2  g   O 2  g   2SO3  g  , H  198 kJmol 1

VMC | Supplementary Booklet-2 36 Chapter-6 & 7 | Chemistry

(ii) H 2  g   Cl 2  aq   2HCl  g   184.1kJ.kJmol1

(iii) HCl  g   aq  HCl  g   73.2 kJmol 1

(iv) Al 2 Cl6  s   aq  Al2 Cl6  aq   643.1kJmol 1

(iii) HCl  g   H  g   Cl  g  , H  431.8 kJmol1

VMC | Supplementary Booklet-2 37 Chapter-6 & 7 | Chemistry

38. Calculate the enthalpy change of the reaction H 2 (g)  I2 (g) 

 a H  C   715.0 kJmol1 where  a H is enthalpy of atomization;  a H  Cl 2   242 kJmol 1 .

VMC | Supplementary Booklet-2 38 Chapter-6 & 7 | Chemistry

 f H for CO2(g) = –94.0

52. U of combustion of methane is X kJ mol1 . The value of H is :

Molar heat capacity of Al is 24 J mol1 K 1 . Molar mass of Al  27 g mol 1

VMC | Supplementary Booklet-2 39 Chapter-6 & 7 | Chemistry

the following reaction same as  f HΘ ? Give reason for your answer.

 CaCO3 (s) ; f H Θ   178.3 kJ mol1

64. The value of  f HΘ for NH3 is –91.8 kJ mol–1.

Calculate enthalpy change for the following reaction 2NH3 (g) 

VMC | Supplementary Booklet-2 40 Chapter-6 & 7 | Chemistry

86. What will be the work done on an ideal gas

89. Enthalpy diagram for a particular reaction is

VMC | Supplementary Booklet-2 41 Chapter-6 & 7 | Chemistry

90. 1.0 mol of a monoatomic ideal gas is

SOLUTIONS - QUESTIONS BASED ON CBSE PATTERN

1. (i) Here, q  0  U  q  w  0  w ad  w ad As no heat is absorbed by the system, the wall is adiabatic.

5. The process of evaporation is: 18g H 2O(l ) 

13. Rise in temperature of the calorimeter = 299 – 298 K = 1 K

VMC | Supplementary Booklet-2 43 Chapter-6 & 7 | Chemistry

16. –5.28 Kj 17. q v  885 kJmol1 , q p  890 kJmol 1

18. We aim at : C(s )  2H 2 ( g ) 

21. We are given :

(ii) CuSO 4 .5H 2 O  s   aq  CuSO4  aq  ;  sol H  11.7kJmol 1

(iv) CuSO 4 .5H 2 O  s   aq  CuSO4  aq  ; H  H 2 kJmol 1

According to Hess’s law, H1  H 2  66.5kJmol 1

Further, equation (ii) and (iv) are same;  H 2  11.7 kJmol1

VMC | Supplementary Booklet-2 44 Chapter-6 & 7 | Chemistry

33. –10.30 kJ/mol 34. 620.7 g

36. Here, we are given

We aim at: CH 4 (g) 

VMC | Supplementary Booklet-2 45 Chapter-6 & 7 | Chemistry

45. By definition of enthalpy of formation, I2  s   I 2  g  ,  f H  62.5kJmol 1

46. The given data imply as under:

(iii) C  s   C  g  , H  715.0 kJmol 1 (iv) Cl 2  s   2Cl  g  , H  242 kJmol 1

VMC | Supplementary Booklet-2 46 Chapter-6 & 7 | Chemistry

52. (iii) CH 4 (g)  2O2 (g) 

53. Given, q   701J (heat is absorbed, hence q is positive)

55. Given, mass of Al = 60.0g

VMC | Supplementary Booklet-2 47 Chapter-6 & 7 | Chemistry

58. Given, H  400 kJ mol1 , S  0.2 kJ K 1 mol1 ,

0  400 kJ mol1  T  0.2 kJ K 1 mol1

VMC | Supplementary Booklet-2 48 Chapter-6 & 7 | Chemistry

65. In general, If enthalpy of an overall reaction A 

67. Given that, sub HΘ for Na metal = 108.4 kJ mol–1

IE of Na = 496 kJ mol–1,  eg HΘ of Br = –325 kJ mol–1,  diss HΘ of Br = 192 kJ mol–1,  f HΘ

By applying Hess’s law :  f HΘ  sub HΘ  IE   diss HΘ   eg HΘ  U

–360.1 = 108.4 + 496 + 96 + (–325) –U