Thermodynamics

Chapter 6
Thermodynamics
Solutions
SECTION - A
Objective Type Questions (One option is correct)
1. Bond energies of H – H bond is 80 kJ/mol, I – I bond is 100 kJ/mol and for H – I bond is
200 kJ/mol, the enthalpy of the reaction :
H2(g) + I2(g)  2HI(g) is
(1) –120 kJ (2) –220 kJ (3) +100 kJ (4) +120 kJ
Sol. Answer (2)
H2 (g) + I2 (g)  2HI (g)
H = B.Er – B.Ep = 80 + 100 – 2 × 200 = – 220 kJ
2. The enthalpy of formation of H2O(l) is –280.70 kJ/mol and enthalpy of neutralisation of a strong acid and strong
base is –56.70 kJ/mol. What is the enthalpy of formation of OH– ions?
(1) –22.9 kJ/mol (2) –224 kJ/mol (3) –58.7 kJ/mol (4) –214 kJ/mol
Sol. Answer (2)
Hf(OH¯) = – 280 – (56.70) = – 224 kJ/mole
3. The heat of neutralisation of a strong dibasic acid in dilute solution by NaOH is nearly
(1) –27.4 kcal/eq (2) 13.7 kcal/mol (3) –13.7 kcal/eq (4) –13.7 kcal/mol
Sol. Answer (3)
H+ + OH–  H2O H = – 13.7 kcal/eq
4. The heat released in neutralisation of HCl and NaOH is 13.7 kcal/mol, the heat released on neutralisation of NaOH
with CH3COOH is 3.7 kcal/mol. The H° of ionisation of CH3COOH is
(1) 10.2 kcal (2) 10 kcal (3) 3.7 kcal (4) 9.5 kcal
Sol. Answer (2)
H = 13.7 – 3.7 = 10 kcal
5. Which of the following reactions represents the enthalpy of formation of water?

(1) H+(aq) + OH–(aq)  H2O(l ) (2) H2(g) + ½O2(g)  H2O(l )
(3) 2H2(g) + O2(g)  2H2O(l ) (4) 2H+(aq) + 2OH–(aq)  2H2O(l )
Sol. Answer (2)
Enthalpy associated with formation of one mole of water from its constituent elements in their natural states.
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124 Thermodynamics Solution of Assignment (Set-2)
6. The energy required to break 76 gm gaseous fluorine into free gaseous atom is 180 kcal at 25°C. The bond
energy of F – F bond will be
(1) 180 kcal (2) 90 kcal (3) 45 kcal (4) 104 kcal
Sol. Answer (2)
F2  2F
38g
∵ 76 g F2 needs 180 kcal energy

180
 38 g F2 needs energy =  38 = 90 kcal
76
7. For the reaction 2HgO(s)  2Hg(l ) + O2(g)

(1) H > 0 and S < 0 (2) H > 0 and S > 0
(3) H < 0 and S < 0 (4) H < 0 and S > 0
Sol. Answer (2)
2HgO(s)  2Hg(l) + O2(g)
It is endothermic and spontaneous process [∵  ng > 0]
 H > 0 and S > 0
8. The heat of combustion of yellow phosphorus and red phosphorus are –9.91 kJ/mol and – 8.78 kJ/mol
respectively. Then the heat of transition of yellow phosphorus to red phosphorus is
(1) –18.69 kJ (2) +1.13 kJ (3) +18.69 kJ (4) –1.13 kJ
Sol. Answer (4)
P  P
(yellow ) (red)
HTransition = – 9.91 – (–8.78) = – 1.13 kJ
9. If the entropy of vaporisation of a liquid is 110 JK–1 mol–1 and its enthalpy of vaporisation is 50 kJmol–1. The
boiling point of the liquid is
(1) 354.5 K (2) 454.5 K (3) 554.5 K (4) 445.5 K
Sol. Answer (2)
Svap = 110 J/K/mol
Hvap = 50 × 103 J/mol
H
S = T
B.P.
50  103
TB.P.  = 454.54 K
110
10. Which of the following represents heat of formation (Hf)?

(1) C(diamond) + O2(g)  CO2(g) (2) 2CO(g) + O2(g)  2CO2(g)
(3) ½H2(g) + ½F2(g)  HF(g) (4) N2(g) + 3H2(g)  2NH3(g)
Sol. Answer (3)
There is formation of one mole of gas from its constituent elements in their standard states.
1 1
H2 (g)  F2 (g)  HF(g)
2 2
Solution of Assignment (Set-2) Thermodynamics 125
11. 1 mole of an ideal gas is expanded from an initial pressure of 1 bar to final pressure of 0.1 bar at constant
temperature of 273 K. Predict which of the following is not true?
(1) E = 0 (2) H = 0 (3) PV is constant (4) S < 0
Sol. Answer (4)
For an isothermal process, E = 0, PV = constant, H = 0 and S > 0.
12. Which of the following conditions should be satisfied for the given reaction to be spontaneous at 0°C and 1 atm?
H2O(s) H2O(l )
(1) H = G (2) H < TS (3) H > TS (4) H = TS
Sol. Answer (2)
If H < TS
The G < 0 (–ve) and reaction will be spontaneous
13. The heat of formation of CO2 is –407 kJ/mol. The energy required for the process
3CO2(g)  3C(g) + 2O3(g) is
(1) Less than 1221 kJ (2) More than 1221 kJ
(3) Is equal to 1221 kJ (4) Cannot be predicted
Sol. Answer (2)
Hf(CO2 ) for 3 moles will be = 3 × 407 = 1221 kJ
 With O3 it should be greater than 1221 kJ
14. The free energy change due to a reaction is zero when

(1) The reactants are initially mixed (2) A catalyst is added
(3) The system is at equilibrium (4) The reactants are completely consumed
Sol. Answer (3)
At equilibrium G = 0
15. From the given graph

A
Free energy
B
Reactant Product
Which of the following statement is correct?

(1) The point B represents the state of equilibrium
(2) The equilibrium composition strongly favours the reactant
(3) From the point B formation of product is equally spontaneous as of reactant
(4) From the point B formation of reactant is more spontaneous than that of product
Sol. Answer (1)
16. The heat of combustion of sucrose C12H22O11 (s) at constant volume is –1348.9 kcal mol–1 at 25°C, then the heat
of reaction at constant pressure, is
(1) – 1348.9 kcal (2) – 1342.344 kcal (3) 1250 kcal (4) – 1250 kcal
Sol. Answer (1)
C12H22O11  12O2  12CO2  11H2O

(s) (g) (g) (l)
17. For the reaction,
C7H8 (l)  9O2 (g)  7CO2 (g)  4H2 O(l),

the calculated heat of reaction is 232 kJ mol–1 and observed heat of reaction is 50.4 kJ mol–1, then the resonance
energy is
(1) – 181.6 kJ mol–1 (2) + 181.6 kJ mol–1 (3) 172 kJ mol–1 (4) – 172 kJ mol–1
Sol. Answer (1)
Resonance Energy = –232 – (–50.4) = –182.2 kJ mol–1
18. Given that
A(s)  A(l) H = x
A(l)  A(g) H = y

The heat of sublimation of A will be
(1) x – y (2) x+y (3) x or y (4) –x+y
Sol. Answer (2)
According to Hess’s law Hsub 
x y
19. AB, A2 and B2 are diatomic molecules. If the bond enthalpies of A2, AB and B2 are in the ratio 1 : 1 : 0.5 and
enthalpy of formation of AB from A2 and B2 is –100 kJ mol–1. What is the bond enthalpy of A2?
(1) 400 kJ mol–1 (2) 200 kJ mol–1 (3) 300 kJ mol–1 (4) 100 kJ mol–1
Sol. Answer (1)
1 1 1
A 2  B2  AB
2 2 2
1 1
H B.E. of H2  B.E. of B2  B.E. of A–B
2 2
20. One mole of a perfect gas expands isothermally to ten times of its original volume. The change in entropy is
(1) 0.1 R (2) 10 R (3) 2R (4) 2.303 R
Sol. Answer (4)
V2
S nRln
V1
21. The value of log10 K for a reaction A B is

(Given : rH°298K = –54.07 kJ mol , rS°298K = 10 JK –1 mol–1 and R = 8.314 JK–1mol–1; 2.303 × 8.314 × 298 = 5705)
–1
[IIT-JEE 2007]
(1) 5 (2) 10 (3) 95 (4) 100
Sol. Answer (2)
G° = H° – TS° = –2.303 RT log10K
= – 54.07 × 103 – 298 × 10 = – 57050 JK–1mol–1
G° = – 2.303 RT log10K
– 57050 = –2.303 × 8.314 × 298 log10K
 10 = log10K
22. For the process H2O(l) (1 bar, 373 K)  H2O(g) (1 bar, 373 K), the correct set of thermodynamics parameters
is [IIT-JEE 2007]
(1) G = 0, S = +ve (2) G = 0, S = –ve
(3) G = +ve, S = 0 (4) G = –ve, S = +ve
Sol. Answer (1)
At 373 K H2O(l) is in equilibrium with H2O(g).
23. The species which by definition has ZERO standard molar enthalpy of formation at 298 K is
[IIT-JEE 2010]
(1) Br2(g) (2) Cl2(g) (3) H2O(g) (4) CH4(g)
Sol. Answer (2)
Cl2 is considered as standard state of chlorine and enthalpy of formation in standard state is zero (assumed).
24. The bond energy (in kcal mol–1) of a C—C single bond is approximately [IIT-JEE 2010]
(1) 1 (2) 10 (3) 100 (4) 1000
Sol. Answer (3)
Bond energy of C—C is considered to be 100 kcal mol–1 approximately.
25. Using the data provided, calculate the multiple bond energy (kJ mol–1) of a C  C bond in C2H2. That energy is
(take the bond energy of a C – H bond as 350 kJ mol–1) [IIT-JEE 2012]
2C(s)  H2 (g) 
 C2H2 (g) H = 225 kJ mol–1
2C(s) 
 2C(g) H = 1410 kJ mol–1
H2 (g) 
 2H(g) H = 330 kJ mol–1
(1) 1165 (2) 837 (3) 865 (4) 815
Sol. Answer (4)
H = Bond energy in reactant – Bond energy in product
 225 = (1410 + 330) – (700 + HC  C)
 HCC = 1740 – 925 = 815 kJ/mol
26. The standard enthalpies of formation of CO 2 (g), H 2 O(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 [JEE(Advanced)-2013]
(1) +2900 kJ (2) –2900 kJ (3) –16.11 kJ (4) +16.11 kJ
Sol. Answer (3)
C6H12O6(s) + 6O2(g)  6CO2(g) + 6H2O(l)
H° = 6 (–400) + 6(–300) – (–1300)
H° = –2900 kJ/mol
2900
H    16.11kJ / gm
180
27. For the process [JEE(Advanced)-2014]

H2O(I)  H2O(g)
at T = 100 ºC and 1 atmosphere pressure, the correct choice is
(1) Ssystem > 0 and Ssurroundings > 0 (2) Ssystem > 0 and Ssurroundings < 0
(3) Ssystem < 0 and Ssurroundings > 0 (4) Ssystem < 0 and Ssurroundings < 0
Sol. Answer (2)

Given conditions are boiling conditions for water due to which
Stotal = 0
Ssystem + Ssurroundings = 0
Ssystem = –Ssurroundings
For process, Ssystem > 0
Ssurroundings < 0
28. One mole of an ideal gas at 300 K in thermal contact with surroundings expands isothermally from 1.0 L to
2.0 L against a constant pressure of 3.0 atm. In this process, the change in entropy of surroundings (Ssurr)
in JK–1 is (1 L atm = 101.3 J) [JEE(Advanced)-2016]
(1) 5.763 (2) 1.013 (3) –1.013 (4) –5.763
Sol. Answer (3)
For isothermal change U = 0
 q= – w
= Pex U  3  (2  1)
= 3 L atm = 3  101.3 J
Heat released from surrounding = –3 × 101.3 J
–3  101.3
So, Ssurrounding   –1.013 JK –1
300
SECTION - B
Objective Type Questions (More than one options are correct)
1. Which of the following is/are extensive properties?
(1) Entropy (2) Density (3) Enthalpy (4) Boiling point
Sol. Answer (1, 3)
Entropy and Enthalpy depend on amount of substance.
2. At 25° and 1 atm, which one(s) of the following has nonzero H°f?
(1) Fe (2) O (3) C(diamond) (4) Ne
Sol. Answer (2, 3)
Standard form of carbon is graphite not diamond.
Out of O, O2 and O3 only O2 is in standard state.
C(diamond) and O will have nonzero Hf° while Fe, Ne will have zero Hf°
3. The factors which influence the heat of reaction are

(1) Physical state of reactants and products
(2) The temperature of the reaction
(3) The method by which the final products are obtained
(4) Whether the reaction is carried out at constant pressure or constant temperature
Sol. Answer (1, 2, 4)
Heat of reaction does not depend on path followed.
4. For the given graph, which parameters will be zero?
P
1 atm 1 2
0.5 atm 3
20 L 40 L V
(1) Q (2) H (3) U (4) S
Above is a cyclic process hence U, H and S will be zero

As these are state functions.
5. Which of the following is/are state function?

(1) Enthalpy (2) Heat
(3) Entropy (4) Gibb's free energy (G)
Enthalpy, Entropy and Gibb’s free energy are state functions and Heat, work are path functions.
6. Enthalpy of neutralization of strong acid with strong base is 13.7 kcal. When an unknown acid (1 eq) is neutralized
with (1 eq.) strong base, the enthalpy change is 10.7 kcal which of the following statements is/are correct
regarding unknown acid?
(1) Unknown acid is strong acid
(2) Unknown acid is weak acid
(3) 3.0 kcal heat utilised to dissociate the unknown acid
(4) 10.7 kcal heat utilised to dissociate unknown acid
Sol. Answer (2, 3)
Since heat of neutralisation is less than 13.7 hence acid used is weak.
Heat of dissociation = 13.7 – 10.7 = 3.0 kcal
7. Which of the following statements is/are correct?

(1) For spontaneous process, G must be negative
(2) At equilibrium, G = 0
(3) At equilibrium, G° = 0
(4) At equilibrium, G° = –2.303 RT log KP
For spontaneous process,
G = –ve
G = G° + RT lnK
0 = G° + RT lnK
G° = – RT lnK
G° = – 2.303 RT loge K
8. In which case of mixing of strong acid and strong base each of 1 N concentration temperature increase of
solution will be same (assume heat evolved in neutralisation is only used up to increase the temperature of
solution)?
(1) 20 ml acid and 30 ml alkali (2) 10 ml acid and 10 ml alkali
(3) 35 ml acid and 15 ml alkali (4) 50 ml acid and 50 ml alkali
Sol. Answer (2, 4)
For strong acid and strong base enthalpy of neutralisation is – 13.7 kcal when meq of acid = meq of base
In option (2) and (4)
meq of acid = meq of base
9. One mole of steam is condensed at 100° C, the water is cooled to 0°C and frozen to ice. Which of the following
statements are correct, given heat of vapourization and fusion are 540 cal/gm and 80 cal/gm? (average heat
capacity of liquid water = 1 cal gm–1 degree–1)
(1) Entropy change during the condensation of steam is –26.06 cal/°C
(2) Entropy change during cooling of water from 100°C to 0°C is – 5.62 cal/°C
(3) Entropy change during freezing of water at 0°C is – 5.27 cal/°C
(4) Total entropy change is –36.95 cal/°C
Sol. Answer (1, 2, 3, 4)
T
nCp ln 2
S2 
Q1
mL T1 Q2 
mL
Steam 
 Water 
 Water 
 ice
100C 100C 0C 0C
Q 18  540
S1 1  26.05 cal / C
T1 373
273
S2 2.303  1 18log 5.61cal / C
373
18  80
S3  
5.27 cal / C
273
S = S1 + S2 + S3
= – 36.95 cal /°C
10. For a diatomic gas, which options is/are correct?

7R 5R
(1)  = 1.40 (2) Cp = (3) Cv = (4)  = 1.67
2 2
For Diatomic gas,
7 7 5
  1.4 , CP  R , C V  R
5 2 2
11. When the gas is ideal and process is isothermal, then
(1) P1V1 = P2V2 (2) U = 0 (3) W = 0 (4) H1 = H2
Isothermal process
T = constant
PV = nRT
T = constant hence,
PV = constant
P1V1 = P2V2
U is a function of temperature, hence if temperature does not change U will not change
 U = 0
and H1 = H2
12. Which of the following relation is/are correct?
⎡ ( G) ⎤
(1) G = H – TS (2) G = H + T ⎢ ⎥
⎣ T ⎦ P
(3) G = H + TS (4) G = H + nRT

Sol. Answer (1, 2)
G = H – TS
H = E + ngRT
⎡ ( G) ⎤
G H  T ⎢ ⎥
⎣ T ⎦P
13. Heat evolved during the combustion of 32 gm methanol in a bomb calorimeter was determined to be 470 kcal/mol
at 25°C. The value of u of the reaction at the same temperature is
(1) –335.24 kcal (2) –669.28 kcal (3) –470 kcal/mol (4) –196.5 × 104 J
Sol. Answer (3, 4)
32
Moles of methanol = 1
32
Bomb calorimeter determines u,
hence, u = 1 × – 470 = – 470 kcal
u = – 470 × 103 × 4.18 J
= –1.965 × 106 J
= –196.5 × 104 J
14. Among the following, the state function(s) is(are) [IIT-JEE 2009]
(1) Internal energy (2) Irreversible expansion work
(3) Reversible expansion work (4) Molar enthalpy
Sol. Answer (1, 4)
In a reversible expansion work, process is very slow, isothermal and work done in a state function.
15. Among the following, the intensive property is (properties are) [IIT-JEE 2010]
(1) Molar conductivity (2) Electromotive force
(3) Resistance (4) Heat capacity
Sol. Answer (1, 2)
Molar conductivity and electromotive force are intensive properties.
16. For an ideal gas, consider only P-V work in going from an initial state X to the final state Z. The final state Z can
be reached by either of the two paths shown in the figure. Which of the following choice(s) is (are) correct? [take
S as change in entropy and w as work done] [IIT-JEE 2012]
P(atmosphere)
X Y
V(liter)
(1) S x  z  S x  y  S y  z (2) 
w x z w x y  w y z
(3) w x  y  z  w x  y (4) S x  y  z 
S x  y
Sol. Answer (1, 3)
Entropy is a state function. In this diagram initial state is X and final state is Z.
Therefore, SX  Z = SX  Y + SY  Z
Work is a path function. Therefore WX  Y  Z = WX  Y
17. The reversible expansion of an ideal gas under adiabatic and isothermal conditions is shown in the figure. Which
of the following statement(s) is (are) correct? [IIT-JEE 2012]
(P1, V1, T1)
P isothermal
(P2, V2, T2)
adiabatic
(P3, V2, T3)
V
(1) T1 = T2 (2) T3 > T1
(3) wisothermal > wadiabatic (4) Uisothermal > Uadiabatic
T1 = T2 since involved process is isothermal and T3 is less than T1 since involved process is adiabatic expansion.
U = 0 for isothermal process but U < 0 for adiabatic expansion. Magnitude of work done in isothermal
process is higher than adiabatic process. wisothermal > wadiabatic.
18. An ideal gas in a thermally insulated vessel at internal pressure = P1, volume = V1 and absolute temperature
= T1 expands irreversibly against zero external pressure, as shown in the diagram. The final internal pressure,
volume and absolute temperature of the gas are P2, V2 and T2, respectively. For this expansion,
[JEE(Advanced)-2014]
Pext = 0
Pext = 0 Irreversible
P2, V2, T2
P1, V1, T1
Thermal insulation
(1) q = 0 (2) T2 = T1 (3) P2V2 = P1V1 (4) P2 V2  P1V1

Work against zero external pressure is zero q = 0 due to insulated boundary
So, q = 0
U = 0
T = 0
 T2 = T1
and P2V2 = P1V1
SECTION - C
Linked Comprehension Type Questions
Comprehension-I
Entropy is a measure of randomness of system. When a liquid is converted to the vapour state entropy of the
∆H
system increases. Entropy in the phase transformation is calculated using ∆S  but in reversible adiabatic
T
process S will be zero. The rise in temperature in isobaric or isochoric process increases the randomness of
system, which is given by
⎛T ⎞
S = 2.303nC log⎜⎜ 2 ⎟⎟
⎝ T1 ⎠
C = CP or CV.
1. The temperature at which liquid H2O will be in equilibrium with its vapour is H and S for vapourisation are
50 kJmol–1 and 0.15 kJmol–1K–1.)
(1) 77.30°C (2) 60.33°C (3) 50°C (4) 100°C
Sol. Answer (2)
H 50  103 J

T 
S 0.15  103 J
T = 333.33 K
t (°C) = 60.33° C
2. The change in entropy when 1 mole O2 gas expands isothermally and reversibly from an initial volume 1 litre
to a final volume 100 litre at 27°C
(1) 20.5 JK–1mol–1 (2) 38.29 JK–1mol–1
(3) 42.50 JK–1mol–1 (4) 50.65 JK–1mol–1

Sol. Answer (2)
V2
S nRln
V1
100
= 2.303 × 1 × 8.314 log10
1
= 2.303 × 1 × 8.314 × 2
= 38.29 JK–1 mol–1
3. Entropy change in a reversible adiabatic process is
(1) Zero
(2) Always positive
(3) Always negative
(4) Sometimes positive and sometimes negative

Sol. Answer (1)
For an adiabatic and reversible process,
arev = 0
arev 0
S    0
T T
Comprehension-II
Heat of reaction is defined as the amount of heat absorbed or evolved at a given temperature when the reactants have
combined to form the products is represented by a balanced chemical equation. If the heat is denoted by q then the
numerical value of q depends on the manner in which the reaction is performed for the two methods of conducting
chemical reactions in calorimeters.
Constant volume W = 0 and qV = E Bomb calorimeter
Constant pressure W = –V.P, therefore
qP = E + PV  (V.P)
1. The heat capacity of a bomb calorimeter is 300 J/K. When 0.16 gm of methane was burnt in this calorimeter the
temperature rose by 3°C. The value of U per mole will be
(1) 100 kJ (2) 90 kJ (3) 900 kJ (4) 48 kJ

Sol. Answer (2)
0.16
Moles of methane =  1 102
16
Heat capacity = 300 J/K
∵ For 1 K temperature change heat exchanged = 300 J
 For 3 K temperature change heat exchanged = 3 × 300 = 900 J
∵ For 1 × 10–2 mole, heat exchanged = 900 J
 For 1 mole heat exchanged = 900  102 J = 90  103 J = 90 kJ
2. When maltose C12H22O11(s) burns in a calorimetric bomb at 298 K yielding carbon dioxide and water, the
heat of combustion is –1350 kcal/mol, the heat of combustion of maltose at constant pressure will be
(1) –2650 kcal/mol (2) –675 kcal/mol (3) –1350 kcal/mol (4) –1100 kcal/mol
Sol. Answer (3)
⎛ 22 11 ⎞
C12H22O11 ⎜ 12   ⎟ O2  12CO2  11H2O
(s) ⎝ 4 2⎠ g g (l)
C12H22O11  12O2  12CO2  11H2O

(S) g g (l)
ng = 12 – 12 = 0
H = E + ng RT
H = E [∵ ng = 0]
 H = – 1350 kcal/mol
3. The heat of combustion of maltose at constant volume in the above question if water vapour are not condensed
(1) –1350 kcal/mol (2) –1343 kcal/mol
(3) –1370 kcal/mol (4) –1400 kcal/mol

Sol. Answer (2)
If water vapours are not condensed then
ng = 12 + 11 – 12 = 11
H = E + ng RT = – 1350 + 11 × 2.0 × 10–3 × 298 = – 1343 kcal/mole
Comprehension-III
In a fuel cell, methanol is used as a fuel and O2 is used as oxidizer. The standard enthalpy of combustion of methanol
is –726 kJ mol–1. The standard free energies of formation of CH3OH(l), CO2(g) and H2O(l) are –166.3, –394.4 and
–237.1 kJ mol–1 respectively.
1. The standard free energy change of the reaction will be

(1) –597.8 kJ mol–1 (2) –298.9 kJ mol–1
(3) –465.2 kJ mol–1 (4) –702.3 kJ mol–1
Sol. Answer (4)
3
CH3 OH  O2  CO2  2H2O
2
G 394.4  2( 237.1)  166.3
2. The efficiency of the fuel cell will be

(1) 96.7% (2) 66.2% (3) 41.3% (4) 85.1%
Sol. Answer (1)
G

n  100
H
3. The standard internal energy change of the cell reaction will be

(1) –727.24 kJ mol–1 (2) –724.76 kJ mol–1
(3) –728.48 kJ mol–1 (4) –723.42 kJ mol–1
Sol. Answer (2)
H = 4U + ng RT
Comprehension-IV
A fixed mass 'm' of a gas is subjected to transformation of states from K to L to M to N and back to K as shown in
the figure [JEE(Advanced)-2013]
K L
Pressure
N M
Volume
1. The succeeding operations that enable this transformation of states are

(1) Heating, cooling, heating, cooling (2) Cooling, heating, cooling, heating
(3) Heating, cooling, cooling, heating (4) Cooling, heating, heating, cooling
Sol. Answer (3)
2. The pair of isochoric processes among the transformation of states is

(1) K to L and L to M (2) L to M and N to K
(3) L to M and M to N (4) M to N and N to K
Sol. Answer (2)
Pressure
As PV product increases temperature increases as PV product decreases temperature decreases.

PV product increases (K  L, N  K)
SECTION - D
Assertion-Reason Type Questions
1. STATEMENT-1 : Chemical equation H+(aq) + OH–(aq)  H2O(l); H = – X kJ represents the enthalpy of
formation of water.
and
STATEMENT-2 : Hneutralisation of strong acid and strong base is constant.
Sol. Answer (4)

1
H2  O2  H2O
(g) 2 (l)
(g)
Above reaction represents enthalpy of formation of water.

Heat of neutralisation of strong acid and strong base is 57.3 kJ
2. STATEMENT-1 : In a cyclic process, both H and U are zero.
and
STATEMENT-2 : H and U are path dependent functions.
Sol. Answer (3)

For cyclic process,
H, E, S are zero.

Heat of reaction is path independent (Hess law).
3. STATEMENT-1 : Enthalpy (H) and entropy (S) both are extensive properties.
and
STATEMENT-2 : Both are independent of mass.
Sol. Answer (3)
Enthalpy and Entropy are mass dependent.
4. STATEMENT-1 : Work done in isothermal reversible process is more than irreversible process.
and
STATEMENT-2 : Irreversible process is an infinitesimally slow process.
Sol. Answer (3)
WRev > WIrrev
Irreversible processes are fast while reversible processes are slow.
5. STATEMENT-1 : Hf° is zero for oxygen (O2).
and
STATEMENT-2 : Hf° for all the elements at S.T.P. is zero.
Sol. Answer (3)

O2 is standard state of Oxygen.
Hence, Hf° = 0
Hf° is zero, only for elements taken in standard state not in other states eg. C (diamond) has Hf° not zero
while C (graphite) has Hf° equal to zero.
6. STATEMENT-1 : H and U are the same for the reaction H2(g) + I2(g) 2HI(g).
and
STATEMENT-2 : All reactants and products are in gaseous form.
Sol. Answer (2)

H2  I2
2Hl
g g g
ng = 0 hence H = E
7. STATEMENT-1 : All the exothermic reactions are spontaneous.

and
STATEMENT-2 : For a spontaneous reaction, G must be negative.

Sol. Answer (4)
All exothermic reactions need not be spontaneous.
For spontaneous processes G = – ve
8. STATEMENT-1 : Thermochemistry involves the calculation of heat change through balanced reactions.
and
STATEMENT-2 : Enthalpy is a state function.

Sol. Answer (2)
Both are true but statement-2 is not the correct explanation.
9. STATEMENT-1 : Entropy of egg increases after boiling.

and
STATEMENT-2 : As boiling causes the denaturation of proteins.

Sol. Answer (1)
Due to boiling denaturation of protein take place.
10. STATEMENT-1 : If same amounts are considered, CO2 requires more heat than O2, for the same rise in
temperature.
and
STATEMENT-2 : CO2, being triatomic has higher heat capacity than O2.
Sol. Answer (1)
Where f is degree of freedom
In triatomic molecule due more degrees of freedom more heat is required.
11. STATEMENT-1 : There is a natural asymmetry between converting work to heat and converting heat to work.
and
STATEMENT-2 : No process is possible in which the sole result is the absorption of heat from a reservoir and
its complete conversion into work. [IIT-JEE 2008]
Sol. Answer (2)
According to second law of thermodynamics, It is impossible to convert energy into 100% work.
SECTION - E
Matrix-Match Type Questions
1. Match the following
Column-I Column-II
(A) Isothermal process (p) Temperature changes
(B) Isobaric process (q) Pressure changes
(C) Isochoric process (r) Volume changes
(D) Cyclic process (s) Initial and final states are same
Sol. Answer A(q, r), B(p, r), C(p, q), D(s)
(A) In isothermal reversible process both pressure and volume changes
V2 P
W = – 2.303 nRT log or 1
V1 P2
(B) In Isobaric process
P = 0
T and V are variables
(C) In isochoric process
V = 0 while temperature and pressure change
(D) In cyclic process
 Initial and final states are same.
2. Match the following (Assume heat of neutralisation of strong acid with strong base is 13.7 kcal).
Column-I Column-II
(Enthalpy change in kcal) (Neutralisation)
(A) < 13.7 kcal (p) HCl  NaOH

(1 mol) (1mol)
(B) = 13.7 kcal (q) HF  NaOH

(1 mol) (1 mol)
(C) > 13.7 kcal (r) NH4 OH  HCl

(1mol) (1mol)
(D) = 27.4 kcal (s) NaOH  H2SO 4

(2 mol) (1mol)
(t) NaOH  CH3 COOH

(1mol) (1mol)
Sol. Answer A(r, t), B(p), C(q, s), D(s)
(p) NaOH + HCl  NaCl + H2O
For strong acid and strong base
The heat of neutralisation is 13.7 kcal
(q)  Hneu > 13.7 kcal, For HF, heat is evolved due to hydration of F–
(r) Answer (p)
NH4OH is weak base
 Hneu < 13.7 kcal
Because some amount of heat will be used up in bond dissociation energy of NH4OH.
(s) For 2 moles of NaOH
Hneu = 2 × 13.7 = 27.4 kcal
(t) Hneu < 13.7 kcal
CH3COOH is weak acid.
3. Match the following
Column-I Column-II
(A) Enthalpy (p) Extensive property
(B) Entropy (q) H – TS
(C) Free energy (r) E + PV
(D) Pressure (s) Intensive property
Sol. Answer A(p, r), B(p), C(p, q), D(s)
(A) Enthalpy depends upon mass.
 It is extensive property and H = E + PV or, H = E + PV
(B) Entropy depends upon mass.
 It is extensive property.
(C) Free energy depends upon mass.
 It is extensive property.
and G = H – TS
G° = H° – TS°
(D) Pressure does not depends upon mass.
 It is intensive property.
4. Match the transformations in Column-I with appropriate options in Column-II. [IIT-JEE 2011]
Column I Column II
(A) CO2 (s) 

 CO2 (g) (p) Phase transition
(B) CaCO3 (s) 

 CaO(s)  CO2 (g) (q) Allotropic change
(C) 2H 
 H2 (g) (r) H is positive
(D) P(white, solid) 

 P(red, solid) (s) S is positive
(t) S is negative
Sol. Answer A(p, r, s), B(r, s), C(t), D(p, q, t)
Phase is the part which is physically and chemically uniform throughout. During phase transition from solid
to liquid or gas, S = +ve.
 H2, S is –ve because no. of entities decreases.

In 2H 
5. Match the thermodynamic processes given under Column I with the expressions given under Column II.
[JEE(Advanced)-2015]
Column I Column II
(A) Freezing of water at 273 K and 1 atm (p) q=0
(B) Expansion of 1 mol of an ideal gas into a (q) w=0
vacuum under isolated conditions
(C) Mixing of equal volumes of two ideal gases (r) Ssys < 0
at constant temperature and pressure in an
isolated container
(D) Reversible heating of H2(g) at 1 atm from (s) U = 0
300 K to 600 K, followed by reversible
cooling to 300 K at 1 atm
(t) G = 0
Sol. Answer A(r, t), B(p, q, s), C(p, q, s), D(p, q, s, t)

(A)  R, T

H2O( )
H2O(S)
It is at equilibrium at 273 K and 1 atm

So Ssys is negative
As it is equilibrium process so G = 0
(B)  P, Q, S
Expansion of 1 mole of an ideal gas in vacuum under isolated condition
Hence, w = 0
and qp = CpdT (∵ dT = 0)
 q=0
U = CvdT (∵ dT = 0)
U = 0
(C)  P, Q, S
Mixing of two ideal gases at constant temperature
Hence, T = 0
 q=0
U = 0
also w = 0 (U = q + w)
(D)  P, Q, S, T
Reversible heating and cooling of gas follows same path also initial and final position is same.
q0 ⎫
Hence, ⎬ Path same
w  0⎭
U 0⎫
⎬ State function
G 0⎭
SECTION - F
Integer Answer Type Questions
1. The maximum work done when pressure of n moles of H2 was reduced from 20 atm to 1 atm at constant
temperature of 273 K is found to be 8180 calories. What is the value of n?
Sol. Answer (5)
p1
W = –2.303 nRT log
p2
or –8180 = –2.303 n × 2 × 273 log 20/1
or n = 5
2. One mole of an ideal monoatomic gas expands reversibly and adiabatically from a volume of x litre to 14 litre
at 27°C. Then value of x will be [Given, final temperature 189 K and CV = 3/2 R].
Sol. Answer (7)
q = 0 ; T1V1–1 = T2V2–1
1
T1 ⎛ V2 ⎞ 5

or ⎜  ⎟ , ⇒ x 7
T2 ⎝ V1 ⎠ 3
3. For a reversible reaction A B . Find Keq at 2727°C temperature.
Given:
rHo = –30 kJ mol–1 (at 2727ºC)
rSo = 10 JK–1 (at 2727ºC)
R = 8.314 JK–1 mol–1
Sol. Answer (1)
G° = H° – TS°
= 30000 – 3000 × 10 = 0
G° = 0
–2.303 RT by Keq = 0
Keq = 1
4. When a system is taken from A to C through path ABC, 10 J of heat flows to the system and 4 J of work is
done by the system.
B C
A D
How much heat flows into the system in path ADC, if the work done by the system is 3 J?
Sol. Answer (9)
u will be same as u is a state function.
5. The chemical reaction : A P, H° = 2.8 kJ is spontaneous only above 400 K. Therefore S of reaction must
be at least (JK–1).
Sol. Answer (7)
T S H
2.8  103

S  7
400
6. In a constant volume calorimeter, 3.5 g of a gas with molecular weight 28 was burnt in excess oxygen at
298.0 K. The temperature of the calorimeter was found to increase from 298.0 K to 298.45 K due to the combustion
process. Given that the heat capacity of the calorimeter is 2.5 kJ K–1, the numerical value for the enthalpy of
combustion of the gas in kJ mol–1 is [IIT-JEE 2009]
Sol. Answer (9)
q = heat capacity × T
= 1.125 kJ for 3.5 g
for 1 mole = 9 kJ.
7. One mole of an ideal gas is taken from a to b along two paths denoted by the solid and the dashed lines as shown
in the graph below. If the work done along the solid line path is Ws and that along the dotted line path is Wd,
then the integer closest to the ratio Wd/Ws is [IIT-JEE 2010]
4.5
4.0 a
3.5
3.0
P
(atm.) 2.5
2.0
1.5
1.0
0.5 b
0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0
V
(lit.)
Sol. Answer (2)
Solid line path work done (Ws) is isothermal beacuse PV is constant at each point and dash line path work
done (Wd) is isobaric.
V2
Total work done on solid line path (Ws) = 2.303 nRT log
V1
V2 5.5
= 2.303 PV log = 2.303 × 2log
V1 0.5
 4.6 L atm
Total work done on dash line path (Wd) = 4 × 1.5 + 1 × 1 + 0.5 × 2.5
= 8.255 L atm.
Wd 8.25
  2(closest integer)
Ws 4.6
SECTION - G
Multiple True-False Type Questions
1. STATEMENT-1 : Neutralisation reaction is an Endothermic Process.
STATEMENT-2 : Standard Enthalpy of Neutralisation for different pairs of strong acid and strong base are
different.
STATEMENT-3 : Standard Enthalpy of Neutralisation for a pair of strong acid and strong base is higher than
that of weak acid and weak base.
(1) F F T (2) F T T (3) T F T (4) F T F

Sol. Answer (1)
Neutralisation is an exothermic process.
2. STATEMENT-1 : Entropy of all elements is zero at zero Kelvin.
STATEMENT-2 : Standard formation enthalpy of all elements is greater than zero.
STATEMENT-3 : Entropy of all elements and compounds decreases with decrease of temperature and
becomes zero at absolute zero temperature.
(1) F F F (2) T T T (3) T F F (4) FT F

Sol. Answer (2)
At absolute zero, perfect order is attained and all types of motion cease.
3. STATEMENT-1 : The third law of thermodynamics implies that absolute zero cannot be reached.
STATEMENT-2 : G° for an ideal gas reaction is a function of temperature.
STATEMENT-3 : The adiabatic expansion of a gas into a vacuum is spontaneous.
(1) F F F (2) T T T (3) T F F (4) FT F

Sol. Answer (2)
G  RTlnK p
SECTION - H
Aakash Challengers Questions
1. A heat engine carries one mole of an ideal diatomic gas around the cycle as shown in the figure, the amount
of heat added in the process AB and heat removed in the process CA are
P T2 = 600 K
B
A C
T1 = 300 K T3 = 400 K
V
(1) qAB = 750 R and qCA = –450 R (2) qAB = 650 R and qCA = –350 R
(3) qAB = 750 R and qCA = –350 R (4) qAB = 650 R and qCA = –450 R
Sol. Answer (3)

qV = nCVT
qP = nCPT
2. Calculate the average molar heat capacity at constant volume of a mixture containing 2 moles of monoatomic
and 3 moles of diatomic ideal gas.
(1) R (2) 2.1 R (3) 3.2 R (4) 4R

Sol. Answer (2)
n1CV M  n2CV M
= CV (average)
n1  n2
3. What is the change in entropy when 2.5 mole of water is heated from 27°C to 87°C?
Given CP,M(H2O) = 4.2 J/g [ln 1.2 = 0.18]
(1) 16.4 J K–1 (2) 34.02 J K–1 (3) 2.89 J K–1 (4) 18.2 J K–1
Sol. Answer (2)
T2
S nCP ∫ dln T
T1
4. Which amount the following is most soluble in water?
Compound Hhydration (kJ mol–1) Hlattice(K)

(1) A –400 +500
(2) B –300 +650
(3) C –200 +150
(4) D –100 +250
Sol. Answer (3)
5. A hungry man weighing 80 kg take quickly 20 g lunch, and then climbs up a mountain making it to a height
of 200 m. If 60% of food energy was wasted as heat and the rest was used as climbing work. The fuel intake
could have been any one of the following with given enthalpy of combustion?
(1) Glucose 16 kJ/g (2) Wheat bread 20 kJ/g

(3) Fructose syrup 13 kJ/g (4) Olive oil 35 kJ/g
Sol. Answer (2)
Work done = M × a × displacement
= 80 × 9.8 × 200 = 156.8 kJ
40% of total energy = 156.8 kJ
156.8  100
100% of total energy =  392 kJ
40
6. According to second law of thermodynamics,
(1) Heat can't flow spontaneously from a reservoir at lower temperature to a reservoir at higher temperature
(2) All spontaneous process leads to increase in entropy of universe
(3) Melting a solid increases entropy, therefore a spontaneous process
(4) All of these
Sol. Answer (4)
All statements are representing second law of thermodynamics.
1
7. Considering the reaction C(s) +  CO(g) + 200 kJ . The signs of H, S and G respectively are
O2 (g) 
2
(1) +, –, – (2) –, +, + (3) –, –, – (4) –, +, –

Sol. Answer (4)
8. Calculate enthalpy change of the following reaction : CH2 = CH2(g) + H2(g)  CH3 – CH3(g). The bond energy
of C – H, C – C, C = C, H – H are 414, 347, 615 and 435 kJmol–1 respectively.
Sol. The given reaction is

CH2 CH2  H2  CH3  CH3
∵ Hf = B.E. of reactants – B.E. of products

H H H H
| | | |
H
— C C — H  H — H  H — C — C — H
| |
H H
 Hf = [4×(C–H) + 1× (C=C) + 1 × (H–H)] – [6 (C–H) + 1 × (C–C)]
= (4 × 414 + 615 + 435) – (6 × 414 + 347) = (1656 + 615 + 435) – (2484 + 347) = 2706 – 2831
Hf = –125 kJ/mole
9. At 300 K, 4 gm calcium is dissolved in hydrochloric acid in an open vessel at the atmosphere pressure
0.821 atm. Calculate work done by the system.
Sol. ∵ Work done by the system = – PV
 W = –nRT
Ca  2HCl  CaCl2  H2
m 4
W  RT =  0.0821 300 = – 30 × 0.0821 = –2.463 L-atm
M 40
 Work done by the system = –2.463 L-atm
10. Heat of neutralisation of oxalic acid is –53.35 kJ/g.eq. using NaOH. Calculate the value of H for the given reaction
H2C2O4 C2 O 24– + 2H+
Sol. The given reaction is

2 
C 2O4  2H
H2C2O4
∵ Heat of neutralisation of oxalic acid = –53.35 kJ/mol
 Weak acid
 For the given reaction
H = –57.3 – (–53.35) = – 57.3 + 53.35 = –3.95 kJ/mol
For 1 mole, H = – 3.95 kJ/mol
 For 2 mole, H = 2 × –3.95 = –7.90 kJ/mol
 Required value of H = 7.90 kJ/mol
11. If x gm of steam at 100°C is mixed with 5x gm of ice at 0°C, calculate the final temperature of resulting mixture.
The heat of vapourisation and fusion are 540 cal gm–1 and 80 cal gm–1 respectively.
Sol. x × 540 + x × (100 – T) = 5x × 80 + 5x (T – 0)
 540 + 100 – T = 400 + 5T
 240 = 6T
 T = 40°C
12. Calculate H°f for chloride ion from the following data:
½H2(g) + ½Cl2(g)  HCl(g) H°f = –92.4 kJ
HCl(g) + nH2O  H+ (aq) + Cl–(aq); H° = –74.8 kJ
H°fH+(aq) = 0.0 kJ.

Sol. The given reactions are,
1 1
H2 (g)  Cl2 (g)  HCl (g) ; Hf° = –92.4 kJ
2 2
HCl(g)  nH2 O  H (aq)  Cl– (aq) ; H° = –74.8 kJ
Also,
Hf° H+(aq) = 0.0 kJ
 From both the reactions,
1 1
H2 (g)  Cl2 (g)  nH2O  H (aq)  Cl (aq)
2 2
 Hf° Cl–(aq) = –92.4 + (–74.8) = –92.4 –74.8
Hf° Cl– = –167.2 kJ
13. The standard molar enthalpies of formation of cyclohexane (l) and benzene (l) at 25°C are –156 and
+ 49 kJ mol–1 respectively. The standard enthalpy of hydrogenation of cyclohexene (l) at 25°C is –119 kJ mol–1.
Use these data to estimate the magnitude of resonance energy of benzene.
Sol. The reactions are
∵ After hydrogenation,
3 double bonds are breaking
and for 1 bond, H = –119 kJ/mol
 for 3 bonds, H = –119 × 3 = –357 kJ/mol
∵ Total energy = – 156 – 49 = –205 kJ/mol.
 Resonance energy = –357 – (–205)
= –152 kJ/mol
14. The specific heat at constant volume for a gas is 0.075 cal/g and at constant pressure is 0.125 cal/g. Calculate
(i) Molecular weight of gas
(ii) Atomicity of gas
(iii) Number of atoms of gas in its 1 mole

Sol. Given for 1 mole,
Cv = 0.075 cal
Cp = 0.125 cal
Cp 0.125 5
 
  =  1.66
Cv 0.075 3
  = 1.66
 The given gas is monoatomic gas.
(ii)  Atomicity = 1
(i) Now, for monoatomic gas,
Cp – Cv = R
 R = 0.125 –0.075
R = 0.050 cal/g
For 1 mole, R = 2 cal
1
 R = 0.05, for n  0.05
2
n = 0.025 moles
m
 Molecular mass =
n
1
 MmB  = 40 g
0.025
 Mol. Mass = 40 g
(iii) No. of atoms in 1 mole = 6.023 × 1023 atoms
15. The enthalpy change involved in the oxidation of glucose is – 2880 kJmol–1. 25% of this energy is available
for muscular work. If 100 kJ muscular work is needed to walk one kilometre, what is the maximum distance
that a person will be able to walk after eating 120 g of glucose?
Sol. Given,
For oxidation of glucose,
∵ 25% of this energy is available.
H = –2880 kJ/mol
25
∵ H  2880
100
H = –720 kJ/mol
∵ Mass of glucose = 120 g
120 2
n 
180 3
 n = 0.66 mole
 For 1 mole, H = –720 kJ
 For 0.66 mole, H = –720 × 0.66 = –475.20 kJ
Now,
for 1 km energy required = 100 kJ
 100 kJ = 1 km
1
 In 475.20 kJ, distance covered
  475.20
100
d = 4.75 km
 Distance covered = 4.75 4.8 km
16. Calculate standard enthalpy of formation of CS2 given that standard enthalpies of combustion of C, S and CS2
are –393.3, –293.72 and –1108.76 kJmol–1.
Sol. The reaction for the formation of CS2 is
C  2S  CS2
 Required standard heat of formation
 =
HR ( Hc )R  ( Hc )P
= –393.3 – 2 × 293.72 + 1108.76

= 128.02 kJ


Thermodynamics

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Thermodynamics

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Chapter 6

5. Which of the following reactions represents the enthalpy of formation of water?

∵ 76 g F2 needs 180 kcal energy

7. For the reaction 2HgO(s)  2Hg(l ) + O2(g)

HTransition = – 9.91 – (–8.78) = – 1.13 kJ

10. Which of the following represents heat of formation (Hf)?

Hf(CO2 ) for 3 moles will be = 3 × 407 = 1221 kJ

 With O3 it should be greater than 1221 kJ

14. The free energy change due to a reaction is zero when

15. From the given graph

Which of the following statement is correct?

Sol. Answer (1)

C12H22O11  12O2  12CO2  11H2O

17. For the reaction,

C7H8 (l)  9O2 (g)  7CO2 (g)  4H2 O(l),

18. Given that

A(s)  A(l) H = x

A(l)  A(g) H = y

21. The value of log10 K for a reaction A B is

27. For the process [JEE(Advanced)-2014]

Sol. Answer (2)

3. The factors which influence the heat of reaction are

Above is a cyclic process hence U, H and S will be zero

5. Which of the following is/are state function?

7. Which of the following statements is/are correct?

10. For a diatomic gas, which options is/are correct?

12. Which of the following relation is/are correct?

(3) G = H + TS (4) G = H + nRT

Sol. Answer (1, 3)

Therefore, SX  Z = SX  Y + SY  Z

Work is a path function. Therefore WX  Y  Z = WX  Y

(P1, V1, T1)

(3) wisothermal > wadiabatic (4) Uisothermal > Uadiabatic

Sol. Answer (1, 3, 4)

(1) q = 0 (2) T2 = T1 (3) P2V2 = P1V1 (4) P2 V2  P1V1

(1) 20.5 JK–1mol–1 (2) 38.29 JK–1mol–1

(3) 42.50 JK–1mol–1 (4) 50.65 JK–1mol–1

3. Entropy change in a reversible adiabatic process is

(2) Always positive

(3) Always negative

(4) Sometimes positive and sometimes negative

Constant volume W = 0 and qV = E Bomb calorimeter

Constant pressure W = –V.P, therefore

(1) 100 kJ (2) 90 kJ (3) 900 kJ (4) 48 kJ

Heat capacity = 300 J/K

C12H22O11  12O2  12CO2  11H2O

(1) –1350 kcal/mol (2) –1343 kcal/mol

(3) –1370 kcal/mol (4) –1400 kcal/mol

1. The standard free energy change of the reaction will be

G 394.4  2( 237.1)  166.3

2. The efficiency of the fuel cell will be

3. The standard internal energy change of the cell reaction will be

1. The succeeding operations that enable this transformation of states are

2. The pair of isochoric processes among the transformation of states is

As PV product increases temperature increases as PV product decreases temperature decreases.

STATEMENT-2 : Hneutralisation of strong acid and strong base is constant.

Sol. Answer (4)

Above reaction represents enthalpy of formation of water.

2. STATEMENT-1 : In a cyclic process, both H and U are zero.

STATEMENT-2 : H and U are path dependent functions.

Sol. Answer (3)

H, E, S are zero.

STATEMENT-2 : Both are independent of mass.

Sol. Answer (3)