JEE (Main + Advanced) / Chemistry / Thermodynamics & Thermochemistry

THERMODYNAMICS & THERMOCHEMISTRY ASSIGNMENT - 1_SOLUTIONS

1. Ans. (1)
Heat gain by zinc = Heat loosed by water
MZn SZn (Tf − Ti ) = mH2O SH2 O (100 − Tf )
0.4J
(65.38 gm) ( °C) (Tf − 20°C) = (180 gm)(4.20J/g°C)(Tf − 100°C)
g
(65.38)(0.4)(20)+(180)(4.20)(100)
Tf =
(65.38)(0.4)+(180)(4.20)
Tf = 97.3°C
2. Ans. (3)
First Law of thermodynamics
∆U = Q – w Q = 45J (heat absorbed)
∆U = 45 – 70 Q = 70J (work done by the system)
∆U = –25 J ∆U = change in internal Energy
3. Ans. (2)
First Law of thermodynamics
∆U = Q + w
w = –P∆V, V = 0, w = 0
∆U = q = 500 J
w=0
Heat supplied to the system = +ve
[∆U = 500] [Q = 500]
4. Ans. (2)
q = nCp∆T
5
q = 0.25  R  T ; Ar is monoatomic gas
2
5 5
q = 0.25   8.314  (36 − 20) ; CP = R
2 2
5
q = 0.25   8.314  16 ; T2 = 36°C
2
q = 83.2 joule. ; T1 = 20C
5. Ans. (2)
CV = 12.5 Joule/k mol
Cp
=
Cv
Cv + R
=  Cp − C v = R
Cv
8.314 + 12.5
=
12.5
 = 1.665
An adiabatic reversible process of ideal gas equation we have
PV = K
Cp
=
Cv
Adiabatic process, pressure and volume of a sample of gas changes from (P1V1) to (P2V2) then

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We have
P1 (V1) = P2 (V2)
Thus
K
P= 
V
Work done by gas in this process is
w = −  p.dV
Where limit integration goes from V1 to V2
K
Putting P = 
V
− ( P1V1 − P2V2 )
w=
 −1
−nR ( T1 − T2 )
w=
 −1
−2  8.314  (300 − 200 )
=
1.665 − 1
= –2500 J
= –2.5 kJ
6. Ans. (1)
∆H = ∆U + ∆ngRT
∆H = Heat given at constant pressure
∆U = Heat given at constant volume
∆H – ∆U = ∆ngRT
∆ng = the difference between the number of gaseous moles of products and number of gaseous mol/ es
in the reactant
2C6H6 (l) + 15O2Cg ⎯→ 12CO2 (g) + 6H2O(l)
∆ng = –3
∆H – ∆U = –3 × 8.314 × 298 J
= –7.432 KJ
7. Ans. (2)
Heat capacity is the amount of Heat added to a substance to raise it’s temperature by one kelvin.
dH
Hence at constant pressure, the molar Heat capacity is given by the ratio
dT
At constant pressure, water is in equilibrium with ice.
When Heat dH is supplied to the system.
The temperature change dT is zero as the heat supplied is utilized for the phase transition.
Hence, the molar Heat capacity of water in equilibrium with ice at constant pressure is infinite.
8. Ans. (3)
T = const  U = 0 U = q + w  q = –w
Pext = 2 bar Pext =1bar
(8 bar 4L) ⎯⎯⎯⎯⎯⎯ → (2bar,16L) ⎯⎯⎯⎯⎯ → (1bar, 32L)
w1 w2
w = w1 + w2 = – Pext(V2 – V1) – Pext(V3 – V2)
= – 2(16 – 4) – 1(32 – 16)
= – 24 – 16 = – 40 bar L = – 4000 J.
 q=–w= 4000 J

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9. Ans. (2)
1
T∝
V
TV1/2 = constant
For adiabatic process, TV1/2 = TVγ – 1 = constant
 3
∴ γ–1= ,=
2 2
10. Ans. (3)
From the question, U = w …(i)
But from the 1st law of thermodynamics
U = q + w …(ii)
From equation (i) and (ii)
q=0
Therefore, the process is adiabatic.
11. Ans. (4)
H° (reaction) = 4 × H°f (HCl) + H°f (TiO2) – H°f (TiCl4)
= (4 × – 92.3) + (–944.7) + 763.2 + 2 × 241.8
= –369.2 – 344.7 + 763.2 + 483.6
= –67.1 kJ
12. Ans. (3)
1 3
N2 + H2 → NH3
2 2
1 3
H = (N – N) + (H – H) – 3(N–H)
2 2
1 3
–46 = 712 + (436) – 3(N – H)
2 2
N – H = + 352 kJ
13. Ans. (2)
2 C(s) + 3 H2(g) → CH3CH3(g)
1 mole of C2H6 is formed from elements in their stable standard state.
14. Ans. (4)
C(s) + O2(g) ⎯→ CO2(g) ; H = –394 …(i)
H2(g) + 1/2O2(g) ⎯→ H2O(); H = –285.8 …(ii)

C3H8(g) + 5O2(g) ⎯→ 3 CO2(g) + 4 H2O(); H = –2221.6 …(iii)

3C(s) + 4H2(g) ⎯→ 1C3H8(g); fH = ?

Using Hess Law,
fH = 3 (i) + 4(ii) – (iii)
= –1182 + (–1143.2) + 2221.6
= –2325.2 + 2221.6
= –103.6

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15. Ans. (4)
C(s) + O2(g) ⎯→ CO2(g); fH = –394 kJ/mol …(i)
H2(g) + 1/2O2(g) ⎯→ (); fH = –285.8 kJ/mol …(ii)

2C2H2(g) + 5O2(g) ⎯→ 4CO2(g) + 2H2O(); HComb = –2601kJ/mol …(iii)

2C(s) + H2(g) ⎯→ C2H2(g); fH (C2H2, g) =?

fH (C2H2, g) = 2(i) + (ii) – (iii)/2
= 2(–394) –285.8 + 2601/2
= –1073.8 + 1300.5
= 226.7
16. Ans. (3)
2 Na(s) + 2 H2O() ⎯→ 2 NaOH(s) + H2(g); Hreaction = – 281.9 kJ/mole

Hreaction =f Hproduct − f HReactant

= 2x + 0 – [0 + 2(–285.8)]
= 2x + 2(285.8) = –281.9
= –571.6 – 281.9 = 2x
x = –853.5/2 = –426.8 kJ/mol = fH(NaOH)
17. Ans. (3)
H = [fH(CO2, g) × 1 + fH(H2O,) x 2] – [fH(CH4, g)]

–890.4 = –393.5 + (–285.9) × 2 –fH(CH4, g)

fH = –395.5 – 571.8 + 890.4 = –74.9
18. Ans. (2)
Hc
H2(g) + 12 O2(g) H2O() X4
H2O(g)
Hr

x2
HC + x4 = x1 + – 2x3
2
x2
HC = x1 + – 2x3 – x4
2
19. Ans. (4)
C3H4(g) + 4 O2(g) ⎯→ 3 CO2(g) + 2 H2O()

12g C3H4 = 12/40mole = 3/10 moles

1 mole ⎯⎯⎯→
gives out
1939.1kJ
3/10 mole ⎯⎯⎯→
gives out
3/10 x 1939.1 kJ = 581 kJ
20. Ans. (3)
1 1
X2(g)+ Y2(g) ⎯⎯
→ XY(g)
2 2
1 1
– 200 = a + (0.5a)- a
2 2
a = 800 kJ/mole

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INTEGER TYPE
21. Ans. (8)
H2O(l) H2O(g)
rG° = Gf H2O ( g ) − G f H2O ( ) 
0 0

= – RTlnK
8.314 30
= –RTln (PH2O ) = –2.303 ×  300 log
100 750
= +8 kJ (nearest integer)
22. Ans. (348)
1 1
H2 + Br2 ( l ) → HBr ( g )
2 2
Ssurr. = – q
300
q
170 = –
300
q = qp = –51 kJ
H = U + ngRT
 1
–51 = U +  1 −  × 8.3 × 10–3 × 300
 2
–51 = U + 1.245
U = –52.245
2HBr(g) + 104.5 → H2(g) + Br2(l)
S = 104.49 = 348.3 J / K
300
23. Ans. (4)
b, c, d and e are equilibrium condition.
24. Ans. (5)
Hfusion −HFreeezing
S = =
Tf Tf
H = + 20 × 273
= 5460 = 5.4 kJ/mol
25. Ans. (52)
TL
=1–
TH
1 T
= 1– L …(1)
6 TH

1 ( T –65)
= 1– L …(2)
3 TH
1 1 65
= +
3 6 TH
TH = 6 × 65 = 390 K = 117°C
5
TL = ×390 = 325K = 52°C
6

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26. Ans. (5)
(S)system = 0.1 × 100 = 10 kJ/K
(S)surrounding = – 5 kJ/K
(S)universe = 5 kJ/K
27. Ans. (7)
q = 0; w = 0; U = 0 = T → constant
P2
G = nRT ln
P1
P2
= P1V1 ln
P1
20
= 1 × 10 ln = 10ln2
10
= 10 × 0.7 = 7 bar.L
28. Ans. (436)
G° = H° – T S°
 2×115–130 
406 = H° – 300  
 1000 
H° = 436 kJ = EH–H
29. Ans. (0)
T2 3 1000
(i) ΔSsys = nCV ln = 1× ×8.314ln = 28.72 J/K
T1 2 100

ΔSsurr = –ΔSsys ( Rev. ) andΔSTotal =0 ( Rev. )

30. Ans. (10)
T2 T
qRev 2 nCpdT 600
( )
1× 10 +10–2 T dT
(a) S =  T T T =
T1
= 
300
T
= 10 ln2 + 10–2 (600 – 300) = 10 × 0.7 + 3
1

= 10 J/K

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