Thermodyanamics XPP

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THERMODYNAMICS XPP

SINGLE CORRECT
1. One mole of a perfect gas expands isothermally to ten times of its original volume. The
change in entropy is
(A) 0.1 R (B) 10 R
(C) 2 R (D) 2.303 R
2. 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)

(A) 1165 (B) 837 (C) 865 (D) 815


3. From the given graph

Which of the following statement is correct?


(A) The point B represents the state of equilibrium
(B) The equilibrium composition strongly favours the reactant
(C) From the point B formation of product is equally spontaneous as of reactant
(D) From the point B formation of reactant is more spontaneous than that of product
4. 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)
(A) 5.763 (B) 1.013
(C) –1.013 (D) –5.763

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THERMODYNAMICS XPP
5. The standard state Gibbs free energies of formation of C(graphite) and C(diamond) at T
= 298 K are
f G°[C(graphite)] = 0 kJ mol–1
f G°[C(diamond)] = 2.9 kJ mol–1
The standard state means that the pressure should be 1 bar, and substance should be
pure at a given temperature. The conversion of graphite [C(graphite)] to diamond
[C(diamond)] reduces its volume by 2 × 10–6 m3 mol–1. If C(graphite) is converted to
C(diamond) isothermally at T = 298 K, the pressure at which C(graphite) is in
equilibrium with C(diamond), is
[Useful information : 1 J = 1 kg m2s–2; 1 Pa = 1 kg m–1 s–2; 1 bar = 105 Pa]
(A) 14501 bar
(B) 29001 bar
(C) 1450 bar
(D) 58001 bar
MORE THAN ONE CORRECT
6. Which of the following is/are extensive properties?
(A) Entropy
(B) Density
(C) Enthalpy
(D) Boiling point
7. For the given graph, which parameters will be zero?

(A) Q (B) H
(C) U (D) S

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THERMODYNAMICS XPP
8. 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?

(A) Unknown acid is strong acid

(B) Unknown acid is weak acid

(C) 3.0 kcal heat utilised to dissociate the unknown acid

(D) 10.7 kcal heat utilised to dissociate unknown acid

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)

(A) Entropy change during the condensation of steam is –26.06 cal/°C

(B) Entropy change during cooling of water from 100°C to 0°C is – 5.62 cal/°C

(C) Entropy change during freezing of water at 0°C is – 5.27 cal/°C

(D) Total entropy change is –36.95 cal/°C

10.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

(A) –335.24 kcal

(B) –669.28 kcal

(C) –470 kcal/mol

(D) –196.5 × 104 J

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THERMODYNAMICS XPP
11.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]

(A)    (B)
(C) (D)  

12.A reversible cyclic process for an ideal gas is shown below. Here, P, V, and T are
pressure, volume and temperature, respectively. The thermodynamic parameters q, w, H
and U are heat, work, enthalpy and internal energy, respectively

The correct option(s) is (are)


(A) qAC = UBC and wAB = P2(V2 – V1)
(B) wBC = P2(V2 – V1) and qBC = HAC
(C) HCA < UCA and qAC = UBC
(D) qBC = HAC and HCA > UCA

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THERMODYNAMICS XPP
COMPREHENSION
PARAGRAPH QUESTION 13 TO 15
Entropy is a measure of randomness of system. When a liquid is converted to the
vapour state entropy of the system increases. Entropy in the phase transformation is

calculated using ΔS  but in reversible adiabatic process S will be zero. The rise in

temperature in isobaric or isochoric process increases the randomness of system, which


is given by

S = 2.303nC log ( )

C = CP or CV.
13.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.)
(A) 77.30°C (B) 60.33°C
(C) 50°C (D) 100°C
14.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
(A) 20.5 JK–1mol–1 (B) 38.29 JK–1mol–1
(C) 42.50 JK–1mol–1 (D) 50.65 JK–1mol–1
15.Entropy change in a reversible adiabatic process is
(A) Zero
(B) Always positive
(C) Always negative
(D) Sometimes positive and sometimes negative

PARAGRAPH QUESTION 16 TO 18
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

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THERMODYNAMICS XPP
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)
16.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
(A) 100 kJ (B) 90 kJ
(C) 900 kJ (D) 48 kJ
17.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
(A) –2650 kcal/mol (B) –675 kcal/mol
(C) –1350 kcal/mol (D) –1100 kcal/mol
18.The heat of combustion of maltose at constant volume in the above question if water
vapour are not condensed
(A) –1350 kcal/mol (B) –1343 kcal/mol
(C) –1370 kcal/mol (D) –1400 kcal/mol

PARAGRAPH QUESTION 19 TO 21
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.
19.The standard free energy change of the reaction will be
(A) –597.8 kJ mol–1
(B) –298.9 kJ mol–1
(C) –465.2 kJ mol–1
(D) –702.3 kJ mol–1

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THERMODYNAMICS XPP
20.The efficiency of the fuel cell will be
(A) 96.7% (B) 66.2%
(C) 41.3% (D) 85.1%
21.The standard internal energy change of the cell reaction will be
(A) –727.24 kJ mol–1
(B) –724.76 kJ mol–1
(C) –728.48 kJ mol–1
(D) –723.42 kJ mol–1

PARAGRAPH QUESTION 22 TO 23
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

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


(A) Heating, cooling, heating, cooling
(B) Cooling, heating, cooling, heating
(C) Heating, cooling, cooling, heating
(D) Cooling, heating, heating, cooling
23.The pair of isochoric processes among the transformation of states is
(A) K to L and L to M
(B) L to M and N to K
(C) L to M and M to N
(D) M to N and N to K

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THERMODYNAMICS XPP
MATRIX MATCH
24.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
25.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)

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ANSWER

1. D 2. D 3. A 4. C 5. A
6. A, C 7. B, C, D 8. B, C 9. A, B, C, D 10. C, D
11. A, C 12. B, C 13. B 14. B 15. A
16. B 17. C 18. B 19. D 20. A
21. B 22. C 23. B 24. A (q, r), 25. A (r, t),
B (p, r), B (p),
C (p, q), C (q, s),
D (s) D (s)

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SOLUTIONS
1. Answer (D)

S 

2. Answer (D)

H = Bond energy in reactant – Bond energy in product

 225 = (1410 + 330) – (700 + HC  C)

 HCC = 1740 – 925 = 815 kJ/mol

3. Answer (A)

At equilibrium G = 0

4. Answer (C)

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

5. Answer (A)

Gº = V·P

 2900 = 2  10–6 P

 P = Pa

PF–1 = 14500 bar

 PF = 14501bar

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THERMODYNAMICS XPP
6. Answer (A, C)

Entropy and Enthalpy depend on amount of substance.

7. Answer (B, C, D)

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


As these are state functions.
8. Answer (B, C)
Since heat of neutralisation is less than 13.7 hence acid used is weak.
Heat of dissociation = 13.7 – 10.7 = 3.0 kcal
9. Answer (A, B, C, D)

10.Answer (C, D)
Moles of methanol = 1

Bomb calorimeter determines u,


hence, u = 1 × – 470 = – 470 kcal

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THERMODYNAMICS XPP
u = – 470 × 10 × 4.18 J
3

= –1.965 × 106 J
= –196.5 × 104 J
11.Answer (A, C)
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
12.Answer (B, C)
A – C (Isochoric process)  wAC = 0 and UAC = qAC
B – C (Isobaric process)  UBC = qBC + wBC
wBC = –P2(V1 – V2) = P2(V2 – V1)
qBC = HBC
∵ (T)A–C = (T)B–C
 UBC = UAC = qAC
HBC = HAC = qBC
∵ T2 > T1
HCA and UCA are negative

 HCA < UCA


A – B (Isothermal process)
UAB = HAB = 0

wAB = –nRT1 In

13.Answer (B)

T=

T = 333.33 K
t (°C) = 60.33° C

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14.Answer (B)

S  nRIn =

= 2.303 × 1 × 8.314 log10


= 2.303 × 1 × 8.314 × 2
= 38.29 JK–1 mol–1
15.Answer (A)
For an adiabatic and reversible process,
arev = 0
S =

16.Answer (B)
Moles of methane =

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
17.Answer (C)

ng = 12 – 12 = 0
H = E + ng RT
H = E [∵ ng = 0]
 H = – 1350 kcal/mol
18.Answer (B)
If water vapours are not condensed then
ng = 12 + 11 – 12 = 11
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THERMODYNAMICS XPP
H = E + ng RT = – 1350 + 11 × 2.0 × 10–3 × 298 = – 1343 kcal/mole
19.Answer (D)

G  394.4 + 2 (-237.1) + 166.3


20.Answer (A)

21.Answer (B)
H = 4U + ng RT
22.Answer (C)
23.Answer (B)

As PV product increases temperature increases as PV product decreases


temperature decreases. PV product increases (K  L, N  K)
24.Answer (A(q, r), B(p, r), C(p, q), D(s))
(A) In isothermal reversible process both pressure and volume changes
W = – 2.303 nRT log

(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

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 Initial and final states are same.
25.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
NH4 OH.
(s) For 2 moles of NaOH
Hneu = 2 × 13.7 = 27.4 kcal
(t) Hneu < 13.7 kcal
CH3COOH is weak acid.

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