University of Santo Tomas Physical Chemistry (CHE 311)

Faculty of Engineering 2nd Term AY 2014-2015

Department of Chemical Engineering PROBLEM SET (ANSWER KEY)

Name: Section: Date:

Topic Item numbers Raw Score & Percentage Module Grade
Second Law of Thermodynamics
and Phase Transition _____ / 100 ______% _____ /40

1.
2. Calculate the change in the molar entropy of a perfect gas when it is compressed isothermally
from a pressure of 1 bar to 10 bar.

Vf
∆ S=nR ln (entropy for gas expansion)
Vi
∆S V p
∆ S m= =R ln f =R ln i isothermal (Boyle’s Law)
n Vi pf
p J
∆ S m=R ln i =8.3145 ∗ln ¿ ¿ ¿
pf molK
3. Calculate the change in the standard molar entropy of hydrogen chloride, HCl, gas when it is
heated from a temperature of 20oC to 30oC. The standard molar constant-pressure heat capacity
of hydrogen chloride is 29.1 J/mol K.

Tf
∆ S=C ln (entropy when heating a substance)
Ti
Tf
∆ S m=C op ,m ln (molar entropy at standard pressure)
Ti

J (30+ 373.15 ) K J
∆ S m=29.1 ln =+ 0.976
mol K ( 20+ 273.15 ) K mol K
4. Calculate the standard molar entropy of vaporization of phosphorus trichloride, PCl 3, at its
boiling temperature, 74oC, given that the standard molar enthalpy of vaporization of
phosphorus trichloride is 30.5 kJ / mol.
∆ vap H o ( T b ) 30.5 x 103 kJ /mol J
∆ vap S o (T )= = =+78.9
Tb (74+ 273.15) K mol K
5. The boiling temperature of cyclohexane, C 6H12, is 354 K. Use Trouton’s rule to estimate the
enthalpy of vaporization of cyclohexane .
J J J kJ
∆ vap H o ( T b ) ≈ 85 ∗T b=≈ 85 ∗( 354 ) K =30.1 x 103 =30.1
mol K mol K mol mol
6. Calculate the change in entropy when exactly 1 mol of solid iodine, I 2, at a temperature of 360 K
is heated at constant pressure to produce liquid iodine at a temperature of 410 K. The constant
pressure molar heat capacity of solid iodine is 54.44 J/mol K and of liquid iodine is 80.67 J/mol K
 and of liquid iodine is 80.67 J/mol K. The melting temperature of iodine is 387 K, and the molar
enthalpy of fusion of iodine is 7.87 kJ/mol.

Answer:

Three steps: heating of solid iodine from360 K to 387 K, melting of solid iodine at 387 K and heating of
liquid iodine from 387 to 410 K.

∆ S m=∆ 360→ 387 S m +∆ fus Sm + ∆387→ 410 S m

Tf
∆ S=C ln (entropy when heating a substance)
Ti
Tf J 387 K J
∆ 360→ 387 S m=C❑p ,m ( I 2 , solid ) ln =54.44 ln =+3.94
Ti mol K 360 K mol K
For phase transition,

o ∆fus H o ( T ) 7.87 x 103 kJ / mol J

∆ fus S ( T )= = =+20.34
T 387 K mol K
Tf J 410 K J
∆ 387→ 410 Sm =C❑p ,m ( I 2 , liquid ) ln =80.67 ln =+4.66
Ti mol K 387 K mol K

J J J J
(
∆ S m= + 3.94
mol K
+20.34
mol K
+4.66
mol K
=+28.9 )
mol K
7.
8. At low temperature, the heat capacity of solid chlorine, Cl 2, follows the Debye T3 law,
C p ,m =a T 3 , with a=1.24 x 10-3 J/ mol K4. Estimate the molar entropy of solid chlorine at 10 K.

At low temperatures, the molar entropy of substances that obey the Debye T 3 law is
1 1 3 1 10−3 J ( 3 J
Sm ( T )= C p ,m ( T )= a T = 1.24 x 4
∗ 10 K ) =+ 0.413
3 3 3 mol K mol K

9. A
10.

∆ r S 0=∑ v S om ( products )−¿ ∑ v Som ( reactants ) ¿

11. A
G=H −TS
At constant temperature, ∆ G=∆ H−T ∆ S
∆ f G θ=∆f H θ−T ∆ f S θ

12. A
13. The expression ∆ G=∆ H−T ∆ S

kJ
14. Calculate ∆ r G ∈
o
( mol ) at T = 25 C for the combustion of methane:
o

C H 4 ( g ) +O 2 (g)→ C O2 ( g)+ H 2 O(l)

Use the following data thermodynamic data at this temperature:

C H4 ( g) C O2 (g) H 2 O( l)
kJ -74.81 -393.51 -285.83
∆f Ho ( mol )
J
∆ r S o=−242.98
mol K

C H 4 ( g ) +2 O2 ( g)→ C O2 (g)+2 H 2 O(l)

∆ r H 0=∑ ∆f H 0=∑ v H of ( products )−¿ ∑ v H of ( reactants ) ¿

kJ kJ
∑ ∆f H 0 ={( 2∗(−285.83 ) ) +(−393.51)}−{(−74.81 ) } mol =−890.36 mol
kJ
∆ r Go=∆r H o−T ∆r So = −890.36 { mol }
−¿

5
15. 1.00 mole of monoatomic ideal gas (C ¿ ¿ v , m= R)¿ is expanded adiabatically and
2
irreversibly from p1=3.00 atm and V 1=15.2 L by a sudden decrease in pressure to
p2=1.00 atm Calculate ∆ S .

P1 V 1 3.00 atm∗15.2 L
T 1= = =555.69 K
nR Latm
1.00 mole∗0.08206
molK
adiabatic :∆ U =W
C v ,m ( T 2−T 1 ) =− p2 ( V 2−V 1 ) irreversible work

Latm
1.00 mole∗0.08206 ∗T 2
nR T 2 molK
V 2= =
P2 1.00 atm

3 J ( V 2−15.2 L )∗101.325 kPa

∗8.314 ∗( T 2−555.69 K )=−1.00 atm
2 mol K 1 atm
 Latm

3
∗8.314
J
∗( T 2−555.69 K )=−1.00 atm
( 1.00 mole∗0.08206
1.00 atm
molK
∗T 2
)
−15.2 L ∗101.325 J

2 mol K 1 L atm

12.471T 2−6930=−8.31473 T 2+1540.14

T 2=407.5 K
∆ T =407.5 K −555.69 K=−148 K
Latm
1.00 mole∗0.08206 ∗407.5 K
molK
V 2= =33.44 L
1.00 atm

Step 1: expand at constant T1 from P1 to P2 (constant temperature expansion)

p1 J 3.00 atm J
∆ S1 =nR ln
[ ]p2
=1.00 mol∗8.314
molK
∗ln (
1.00 atm
=9.134
K )
Step 2: constant pressure cooling
T2
[ ]
∆ S2 =C p , m ln
T1

3 5
C p ,m =C v, m + R= R+ R= R
2 2
mol∗5 J 407.5 K J
∆ S2 =1.00
2
∗8.314
mol K
∗ln (
555.69 K
=−6.44
K )
J
∆ Stot =∆ S1 +∆ S2=+ 2.69
K
∆ S calculation requires two hypothetical reversible steps:
1) Constant pressure cooling
T2
∆ S1 =n C p ln
[ ]
T1

5 7
C p=C v + R= R+ R= R
2 2
mol∗7 J 255.4 K J
∆ S1 =0.320
2
∗8.314
mol K
∗ln (
298.0 K
=−1.43644
K)
2) Constant temperature, pressure decrease
 P1 J 2.00 atm J
∆ S2 =nR ln
[ ]
P2
=0.320 mol∗8.314
mol K
∗ln
1.00 atm (
=+1.8441
K )
J
∆ Stot =∆ S1 +∆ S2=0.40766
K

For Chapter 4

16. The vapour pressure of chloroform at 24.1 oC is 53.3 kPa. Assuming that Trouton’s rule applies,
calculate the temperature (oC) at which its vapour pressure is 70.0 kPa.
P2 ∆vap H 1 1
ln ( ) P1
=
R [
−
T1 T2 ]
We can get ∆ vap H , from Trouton’s rule where Tb is unknown at 101.325 kPa
J
85
∗T b
53.3 kPa mol K 1 1
ln (
101.325 kPa
= )
8.314
J
mol K
−
[
T b ( 24.1+273.15 ) K ]
0.0343943
−0.6424=10.224− ∗T b
K

T b=315.936 K

J
85 ∗315.936 K
ln ( 70.0 kPa
53.3 kPa )
=
mol K
8.314
J [ 1
−
1
( 24.1+ 273.15 ) K T 2 ]
mol K
T 2=304.9 K
T 2=31.7o C