MSE 260. 1st Mid-Semester Exam; Solutions.

R = 8314 J/deg.mole = 0082 L.atm/deg.mole

1. (14 points)
1 mole of solid Cu at 1300K is dropped into a well-insulated large heat reservoir that is
maintained at a temperature of 500K.
Calculate the total entropy change of the universe (system and heat reservoir).
Data: CpCu = 22.64 + 6.28x10-3T J/mol.K

Suniverse = SCu + Sheat res.

500
SCu = (nCp/T)dT = 22.64ln(500/1300) + 6.28x10-3(500-1300)
1300
SCu = -21.63 5.02 = -26.65 J/deg

Sheat res.= -HCu/500

500
HCu = nCpdT = 22.64(500-1300) + 6.28x10-3/2(5002 13002) = -22,633.6 J
1300
Sheat res.= +22633.6/500 = 45.27 J/deg

Therefore; Suniverse = -26.65 + 45.27 = 18.62 J/deg

2. (36 points)
A rigid container is divided into two compartments each with volume V. One
compartment contains 4 moles of Ne at 4 atmospheres. The second compartment contains 6
moles of He. The entire system is at 298K.
The partition between the two compartments is removed, the volume of the complete
system is reduced to V, and the system is heated at constant volume to 596K. Calculate:
(a) the change in entropy of the system
(b) the change in free energy of the system
Data: Assume that neon and helium are ideal gases with Cv = 1.5R, Cp = 2.5R.
S298K,Ne(g) = 160 J/deg.mol, S298K,He(g) = 120 J/deg.mol
(a) the change in entropy of the system, 14 points

There are several ways to solve this; heres one

4 mol Ne
4 atm
298K

6 mol He
6 atm
298K;

4 mol Ne
+ 6 mol He
596K

(1) Remove partition

& reduce volume to V at 298K

(2) heat at const. V to 596K

4 mol Ne
+6 mol. He
298K

(1) Remove partition and reduce volume to V at const T.

Initial pressures: 4 moles Ne @ 4atm; 6 moles He @ 6atm.
After removal of partition and reduction in vol. to V, total pressure of 10 mol @
298K = 10 atm
Partial pressures @ 298K in V: pNe = 4/10(10) = 4atm; pHe = (6/10)(10) = 6atm
S1 = 4Rln(4/4) + 6Rln(6/6) = 0
(2) heat 10 moles gas from 298K to 596K at constant volume.
596
S2 =
10(Cv/T)dT = 10(3R/2)ln(596/298) = 86.44 J/deg
298
Total entropy change system = 0 + 86.44 = 86.44 J/deg.

(b) the change in free energy of the system; 22 points

There are also several ways to do this. What we cannot do is the following: use
G =H TS and then calculate H plug in S from above. Why? Because T is
changing. G = H-TS; therefore G = H (TS) we must know the total
entropies not just the change.
Correct way: change in free energy, G = Gfinal Ginitial = G596 G298
G596 = H596 (596)S596; G298 = H298 298S298
G = (H596-H298) {596S596 298S298)
because T is changing we need to know the absolute values of S.
First lets deal with H598-H298: because enthalpy only depends on T for ideal gases
then the enthalpy change is the change in enthalpy corresponding to the heating of
4 moles Ne + 6 moles He (= 10 moles ideal gas) from 298 to 596.
596
H598-H298 = 10(5R/2)dT = 61,939.3 J
298
(also note H298 for this system = 0 as they are elements but this doesnt enter into
the calculation)

Now we need Sinitial (S298) and Sfinal (S596); because we already calculated the
change in entropy in part (a), then:
S596 = S298 + S = S298 + 86.44 J/deg
S298 = 4(SNe at 298 and 4 atm) + 6(SHe at 298 and 6 atm.)
We are given S298 values these correspond to the molar entropies at 1 atm. We
must correct for the gases not being at 1 atm.
S298 = 4[SNe,298 + Rln(1/4)] + 6(SHe,298 Rln(1/6)]
S298 = 4[160 + Rln(1/4)] + 6(120 + Rln(1/6)] = 1224.5 J/deg
Therefore: S596 = 1224.5 + 86.44 = 1310.9 J/deg
So: G = G596 G298 = 61,939.3 (596(1310.9) 298(1224.5) = - 354,456.1J

3. (32 points)
2.5 moles of solid CO2 at 200K are introduced into a rigid (constant volume), evacuated
(completely empty), 41 liter container maintained at 200K by a surrounding heat reservoir.
Calculate:
(a)
the final equilibrium state of the system - include the pressure and number of moles of
each phase present.
(b)
the change in the entropy of the universe (system plus heat reservoir) that results from
the process.
Data: lnp(CO2,s) = -3116/T + 1601 atm.
At the triple point for CO2 T = 217K and P = 5.21 atm
Assume CO2 vapor behaves as an ideal gas.

(a) Calculate the final equilibrium state of the system - include the pressure
and number of moles of each phase present. 12 points.
At 200K; lnp(CO2,s) = -3116/200 + 1601 atm: p(CO2,s) = 1.537 atm.
This would be the pressure of CO2 vapor IF we had solid-vapor eqbm.
Is there enough CO2 to give this pressure?
For p(CO2,s) = 1.537atm need nCO2 = {[(1.537)(41)]/[(0.082)(200)]} = 3.84 mol.
Not enough; therefore all CO2 will sublime to vapor:
Final state: 2.5 mol. CO2 vapor at p = {[(2.5)(0.082)(200)]/(41)} = 1 atm.
(b) Calculate the change in the entropy of the universe (system plus heat
reservoir) that results from the process. 20 points.
System:
2.5 moles solid CO2 @ 200K

2.5 moles CO2 vapor @ 1 atm and 200K

Because these two states cannot coexist at eqbm at this T, this is an irreversible
change, therefore we must construct a reversible path to calculate S. This must
include a step where the solid and vapor could be at eqbm the most obvious one
is @ 200K when the solid could coexist with its vapor IF the vapor was at
1.537atm.
Reversible Path:
2.5 moles solid CO2 @ 200K
(1)

2.5 moles CO2 vapor @ 1 atm and 200K

(2)

2.5 moles CO2 vapor at p = 1.537atm

for (1) S1 = 2.5(Hsublimation/T)

Need Hsublimation: (dlnp(s))/dT = Hsub/RT2 = +3116/T2 ; Hsub = 25906.4J.
S1 = 2.5(25906.4)/(200) = 323.8 J/deg.
For (2) S2 = (2.5)R ln(1.537/1) = 8.9 J/deg
Therefore, SCO2 = 323.8 + 8.9 = 332.7 J/deg.
Heat reservoir:
Sheat.res. = -HCO2/T = 2.5(25906.4)/(200) = -323.8 J/deg
Suniverse = 332.7 323.8 = + 8.9 J/deg.
4. (18 points)
3 moles of Argon gas at 400K and 4 atmospheres are adiabatically expanded to 1 atmosphere.
During the expansion 4650 joules of work are performed by the gas.
Assuming argon gas is ideal with Cv = 3R/2, calculate:
(a)
the change in internal energy of argon
(b)
the change in enthalpy of argon
(c)
the change in entropy of argon

(a)

the change in internal energy of argon; 4 points

U = q-w = 0 4650 = - 4650 J.

(b)

the change in enthalpy of argon; 7 points

need the final temperature

T
U = -4650 = 3(3R/2)dT = 9R/2(T-400); T = 275.7K
400
275.7
therefore: H = 3(5R/2)dT = -7750.7 J.
400
[Note: because for an ideal gas Cp/Cv = 5/3 then H/U = 5/3 & H = 5/3(U) = 7750.7J]

(c)

the change in entropy of argon; 7 points

3 moles,400K @ 4atm 3 moles, 275.7K @ 1 atm

Choose reversible path; combination of isobaric and isothermal.
275.7
S = 3Rln(4/1) +
3Cp/TdT = 3Rln4 + 3(5R/2)ln(275.7/400) = 11.37 J/deg
400