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Comprehension-13

Different cases for calculation of entropy:


CASE-I:

For an ideal gas not undergoing any chemical reaction or phase change

dS

dqrev.
T

dS

For measurable change,

nC dT PdV
dU dw

T
T
m
V

nCVm dT

nRT
dV
V

Tf
Vf
S nCVm ln nR ln
Ti
Vi

Tf
S nC pm ln
Ti

Or

Pi

nR ln

Pf

These expressions are valid for both reversible & irreversible processes
CASE-II:

For reversible phase transformation


Phase change carried out at melting point or boiling point are reversible in
nature.

S fusion

H fusion
Tm. p.

&

Svap.

H vap.
Tb. p.

According to Trountons in absence of additional forces like hydrogen


1
1
bonding etc. Svap 85JK mole

CASE-III:

Entropy change in a chemical reaction

r S 0 p Sm0 (Pr oducts) R Sm0 (Re ac tan ts)


Entropy of pure element/substance in perfect crystalline form is zero at zero
Kelvin temperature (statement of III rd law of T.D.)
*Equation that gives variation of r S with temperature/pressure is(i)

( r S 2 r S1 ) r CP ln

T2
T1

(ii)

( r S 2 r S1 ) ng R ln

P1
P2

Q.1

Column-I may have more than one matching options in column-II


Column-I

Column-II

(A)

Reversible condensation of vapour

(P)

Ssystem > 0

(B)

Irreversible adiabatic compression of an ideal gas

(Q)

Ssystem < 0

(C)

Isothermal free expansion of an ideal gas in vacuum

(R)

Ssurounding < 0

(D)

Reversible adiabatic expansion of an ideal gas

(S)

Ssurounding = 0

Ans.

(A) Q (B) P,S (C) P,S (D) S

Q.2

When two equal sized pieces of the same metal at different temperatures Th (hot
piece) and Tc(cold piece) are brought into contact into thermal contact and isolated
from it's surrounding. The total change in entropy of system is given by
(T T ) 2
(T T ) 2
T T
T
(A) C ln C h
(B) C ln 2
(C) C ln C h
(D*) C ln C h
2TC
T1
2TCTh
4TCTh

Q.3

The normal boiling point of a liquid 'A' is 350 K. Hvap at normal boiling point is 35
kJ/mole. Pick out the correct statement(s). (Assume Hvap to be independent of
pressure).
(A*) Svaporisation > 100 J/Kmole at 350 K and 0.5 atm
(B) Svaporisation < 100 J/K mole at 350 K and 0.5 atm
(C*) Svaporisation < 100 J/K mole at 350 K and 2 atm
(D) Svaporisation = 100 J/K mole at 350 K and 2 atm

Q.4

Estimate enthalpy of vaporisation of ethane from its boiling point which is 88.6o C ?
Ans. 16KJmole-1

Q.5

Calculate entropy of vaporisation of water at 1000 C ? H vap 40.7 KJmole1


Ans. 109JK 1mole 1

Q.6

For the reaction at 1atm, 300K


N 2 2O2 2 NO2
0
240 JK 1mole1
Given: S N0 2 180 JK 1mole1 , SO02 220 JK 1mole1 , S NO
2

And

p
CNp2 30 JK 1mole1 , COp2 30 JK 1mole1 , CNO
40 JK 1mole1
2

Calculate S 400 K ,1atm & S 400 K ,5 atm ?

Q.7

For the given cyclic process-

1000 K

200 K

400

500
S

Calculate:
(a)
(efficiency)
(b)
Work done
(c)
Heat given to
(d)
Heat taken from the source
Ans. (a) 0.8, (b) -8 104 J, (c) 20 KJ, (d) 100 KJ