Problem Set #2

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Chem 205 Problem Set 2 Answers. Thermodynamics

Question 1:
n moles of an ideal gas initially at Ti and Pi atm pressure undergo an ISOTHERMAL expansion
against a constant pressure of Pext atm. The final pressure of the gas is Pf atm. Calculate the entropy
change, S, for the gas (in J/K).
Tf

dqrev
S

T
Ti

Tf

f
f
Tf
Vf
dU PdV
dT
dV
nC

Ti T
Ti v,m T Vi nR V nCv,m ln Ti nR ln Vi

For isothermal, T = const.

S nR ln

Vf

S nR ln

Pi
Pf

Vi

; and Pf V f nRT PiVi

Question 2:
n moles of an ideal gas with Cv,m = 3R/2, initially confined to a container of volume Vi liters and at
temperature Ti, expand (or are compressed) against a constant external pressure of Pext atm until the
final pressure of the gas is equal to the external pressure. During this process the system does w J of
work on the surroundings. Calculate the change in entropy, S, of the gas.
Tf
Tf
Vf
T
V
dqrev
dU PdV
dT
dV

nCv ,m
nR
nCv ,m ln f nR ln f
T
T
T Vi
V
Ti
Vi
Ti
Ti
Ti

Tf

From the equation for work w, Vf can be determined:

Vf

Vf

Vi

Vi

w Pext dV Pext dV Pext (V f Vi ); V f Vi

For Tf, it can be calculated easily from T f

w
Pext

Pf V f
nR

Question 3:

In order to answer the question, you need to calculate Stot = Ssys + Ssurr. At Tsurr = Tf, the expression
for Ssurr becomes: S surr

qsys
Tsurr

w U w nCv ,m T

Tf
Tf

If Stot > 0, process is spontaneous; if Stot = 0, process is reversible; if Stot < 0, process is impossible.

Problem Set #2

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Question 4:
Given that H0fussion,m of water is 6025 J/mol, Cp,m(ice) = 37.7 J/(Kmol) and Cp,m(water) = 75.3
J/(Kmol), calculate G for the freezing of n moles of water at 1 atm pressure and constant
temperature T.
G freez H freez TS freez ;

in order to calculate S defined as S

T2

dqrev
,
T
T1

for an irreversible process of freezing of water, a hypothetical reversible path must be considered for a
given process. In this case, irreversible process of freezing water at temperature T can be considered as
a process of isobaric cooling of water from temperature T to 0 C (path 1), then at temperature 0 C
reversible process of freezing, phase change form water to ice (path 2), and finally isobaric heating of
ice from 0 C to temperature T (path 3).

S1 nCp , m( water ) ln

S 2

273.15
T

dqrev n H fusion, m

T freez
273.15

S 3 nCp , m (ice) ln

T
273.15

S = S1 + S2 + S3

H 1 nC p ,m ( water ) T nC p , m ( water ) ( 273.15 T )

H 2 nH freez , m nH fussion , m
H 3 nC p , m (ice)T nC p , m (ice) (T 273.15)

H = H1 + H2 + H3

Question 5 :
3. G. In previous question, process was done under constant pressure and temperature,
so G = (G)P,T can be a criterion for the spontaneity of the process.