Problem Set 7

Solutions
Due 10-30-15
14 pts.
CHEM 3321 Problem Set 7: 14 pts Due: 10-30-15

1. ∆G for Change in P (2 pts)

Calculate the change in Gibbs energy of 35 g of ethanol (mass density 0.789 g cm−3 ) when
the pressure is increased isothermally from 1 atm to 3000. atm. Report your answer to 2
significant figures.

GIVEN: ASSUME incompressible fluid

m = 35 g ⇒ 2 Sig Figs
ρ = 0.789g cm−3
V = mρ = 0.78935g cm
g 3
−3 = 44.35995 cm = 4.435995 × 10
−5 3
m
isothermal, ∆T = 0, dT = 0
Pi = 1 atm Pf = 3000 atm
∆P = 2999 atm = 3.038737 × 108 P a

FIND: ∆G(P )
Start with the Fundamental equation for G
dG = −S dT + V dP
isothermal, so dT = 0
dG = +V dP
integrate
ZPf
∆G = + V dP
Pi
V is constant since we are assuming incompressible fluid
Therefore, V comes out of the integral
∆G = +V ∆P
= 4.435995 × 10−5 m3 × 3.038737 × 108 P a
= +1.347982 × 104 P a m3 = +1.347982 × 104 J
∆G = +1.3 × 104 J = +1.3 kJ

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CHEM 3321 Problem Set 7: 14 pts Due: 10-30-15

2. Gibbs-Helmholtz (3 pts)
◦
Calculate ∆r G (375 K) for the reaction 2 CO(g) + O2 (g) → 2 CO2 (g) from the value of
◦ ◦
∆r G (298 K), ∆r H (298 K) and the Gibbs-Helmholtz equation using the data below.
◦ ◦
compound ∆f G (kJ mol−1 ) ∆f H (kJ mol−1
CO(g) -137.17 -110.53
O2 (g) 0 0
CO2 (g) -394.36 -393.51

◦
GIVEN: ASSUME ∆r H is constant over the temperature range
Tf = 375 K
◦
FIND: ∆r G (375 K)
◦ ◦
First, compute ∆r G (298 K) and ∆r H (298 K)
◦ X ◦
∆r X = ν ∆f X
◦
∆r G (298 K) = [{2 (−394.36)} − {2 (−137.17) + 1 (0)}] kJ mol−1
= [−788.72 − −274.34] kJ mol−1
◦
∆r G (298 K) = −514.38 kJ mol−1
◦
∆r H (298 K) = [{2 (−393.51)} − {2 (−110.53) + 1 (0)}] kJ mol−1
= [−787.02 − −221.06] kJ mol−1
◦
∆r H (298 K) = −565.96 kJ mol−1

Use the Gibbs-Helmholtz equation

 
◦ Tf ◦ ◦ Tf
∆r G (Tf ) = ∆r G (298 K) + ∆r H (298 K) 1 − ◦
T◦ T
 
◦ 375 K −1

−1 375 K
∆r G (375 K) = −514.38 kJ mol + −565.96 kJ mol 1−
298 K 298 K
−1
= −647.2903 + +146.2380 kj mol
= −501.0523 kJ mol−1

◦
∆r G (375 K) = −501 kJ mol−1

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CHEM 3321 Problem Set 7: 14 pts Due: 10-30-15

3. Phase Diagram (2 pts)

Use the phase diagram below to state what would be observed when a sample of carbon
dioxide, initially at 1.0 atm and 298 K, is subjected to the following cycle: (a) isobaric
heating to 320. K, (b) isothermal compression to 100. atm, (c) isobaric cooling to 210. K, (d)
isothermal decompression to 1.0 atm, (e) isobaric heating to 298 K.

(a) Gas is heated above Tc , but the pressure is still well below Pc , therefore, the sample
remains a gas. There is NO phase transition.
(b) The pressure is increased above Pc and temperature remains above Tc . Therefore the gas
slowly becomes a supercritical fluid. There is NO phase transition.
(c) The temperature is lowered below Tc . Initially, the supercritical fluid will become a liquid
without a phase transition occurring. Then, as the sample is cooled further, the liquid
eventually becomes a solid in a phase transition.
(d) The pressure is lowered below the solid–gas coexistence curve. The solid sample sublimes
to gas around 3.5 atm. This IS a phase transition.
(e) The gas is heated to return to its original state. There is NO phase transition.

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CHEM 3321 Problem Set 7: 14 pts Due: 10-30-15

4. ∆f us H and ∆f us S (2 pts)
The molar volume of a certain solid is 161.0 cm3 mol−1 at 1.00 atm and 350.75 K, it’s melting
temperature. The molar volume of the liquid at this temperature and pressure is 163.3 cm3 mol−1 .
At 100. atm the melting temperature changes to 351.26 K. Calculate the enthalpy and entropy
of fusion of the solid.
GIVEN:
P = 1.00 atm = 101325 P a ⇒ 3 Sig Figs
T = 350.75 K
V sol = 161.0 cm3 mol−1
V liq = 163.3 cm3 mol−1
∆f us V = V liq − V sol = (163.3 − 161.0) cm3 mol−1 = 2.3 cm3 mol−1
= 2.3 × 10−6 m3 mol−1
Pf = 100 atm = 10132500 P a
Tf = 351.26 K
FIND: ∆f us S and ∆f us H at Pf and Tf
Start by rearranging the Claperyon equation
dP ∆f us S
=
dT ∆f us V
∆f us S
dP = dT
∆f us V
∆f us V can be assumed T independent
however, ∆f us S cannot be independent of T
∆f us H
instead, substitute ∆f us S =
T
because ∆f us H can be assumed to be T independent
∆f us H
dP = dT
T ∆f us V
integrate
ZPf ZTf
∆f us H
dP = dT
T ∆f us V
P T
∆f us V and ∆f us H come out of the integral, assumed T independent
ZPf ZTf
∆f us H 1
dP = dT
∆f us V T
P T

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CHEM 3321 Problem Set 7: 14 pts Due: 10-30-15

 
∆f us H Tf
∆P = ln
∆f us V T
solve for ∆f us H

∆P ∆f us V
∆f us H =  
T
ln Tf
(10132500 − 101325) P a × (2.3 × 10−6 m3 mol−1 )
=
ln 351.26 K
350.75 K
= +1.587898 × 104 J mol−1

∆f us H = +1.59 × 104 J mol−1 = +15.9 kJ mol−1

∆f us H
∆f us S =
Tf
1.587898 × 104 J mol−1
=
351.26 K
= +4.520578 × 101 J K −1 mol−1

∆f us S = +45.2 J K −1 mol−1

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CHEM 3321 Problem Set 7: 14 pts Due: 10-30-15

5. Ttrs (P ) (2 pts)
Calculate the melting point of ice under a pressure of 50. bar. Assume that the density of ice
under these conditions is approximately 0.92 g cm−3 and that of liquid water is 1.00 g cm−3 .
GIVEN:
P = 1 bar = 1 × 105 P a
T = 0◦ C = 273.15 K
Pf = 50 bar = 5.0 × 106 P a ⇒ 2 Sig Figs
∆P = 5.0 × 106 P a − 1 × 105 P a = 4.9 × 106 P a
ρice = 0.92 g cm−3 = 9.2 × 105 g m−3 ρwater = 1.00 g cm−3 = 1.00 × 106 g m−3
   
∆f us V = M ∆ ρ1 = 18.02 g mol−1 1.00×1016 g m−3 − 9.2×1015 g m−3
∆f us V = −1.566957 × 10−6 m3 mol−1
∆f us H = 6.008 × 103 J mol−1
FIND: Tf at Pf
∆ H
Substitute ∆f us S = fTus into the Clapeyron equation
ASSUME ∆f us H and ∆f us V are independent of T and integrate

∆f us H dT
dP =
∆f us V T
ZPf ZTf
∆f us H dT
dP =
∆f us V T
P T
∆f us H Tf
∆P = ln ( ) solve for Tf
∆f us V T
 
Tf ∆P ∆f us V
ln = exponentiate both sides
T ∆f us H
   
Tf ∆P ∆f us V
= exp
T ∆f us H
 
∆P ∆f us V
Tf = T exp
∆f us H
(4.9 × 106 P a) × (−1.566957 × 10−6 m3 mol−1 )
 
= 273.15 K exp
6.008 × 103 J mol−1
= 2.728011 × 102 K = 272.8 K

Tf = 2.7 × 102 K

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CHEM 3321 Problem Set 7: 14 pts Due: 10-30-15

6. Slope of Chemical Potential (3 pts)

Calculate the difference in slope of the chemical potential against pressure on either side of (a)
the normal freezing point of water and (b) the normal boiling point of water. The densities of
ice and water at 0◦ C are 0.917 g cm−3 and 1.000 g cm−3 , and those of water and water vapor
at 100.◦ C are 0.958 g cm−3 and 0.598 g dm−3 , respectively. By how much does the chemical
potential of water vapor exceed that of liquid water at 1.2 atm and 100.◦ C?

GIVEN:
MH2 O = 18.02 g mol−1 = 18.02 × 10−3 kg mol−1
0◦ C = 273.15 K
ρsol = 0.917 g cm−3 = 9.17 × 102 kg m−3
ρliq = 1.000 g cm−3 = 1.000 × 103 kg m−3
100◦ C = 373.15 K
ρliq = 0.958 g cm−3 = 9.58 × 102 kg m−3
ρvap = 0.598 g dm−3 = 0.598 kg m−3

FIND: Difference in slope of chemical potential, against pressure, on either side of the
(a) the solid–liquid phase and (b) the liquid–vapor phase, AND compute the difference
in chemical potential between liquid and vapor at 1.2 atm and 100◦ C.
The difference in the slope against pressure for two phases is just. . .

∂ µβ ∂ µα
− = V β − V α = ∆trs V
∂P T ∂P T
 
M 1 1
The other equation that you will need is V = ρ
and ∆trs V = M ρβ
− ρα

(a)
∂ µl ∂ µs
− = V l − V s = ∆trs V = ∆f us V
∂P T ∂P T
 
1 1
= M −
ρl ρs
 
−3 −1 1 1
= 18.02 × 10 kg mol −
1.00 × 103 kg m−3 9.17 × 102 kg m−3
= −1.631036 × 10−6 m3 mol−1

∂ µl ∂ µs
− = −1.63 × 10−6 m3 mol−1
∂P T ∂P T

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CHEM 3321 Problem Set 7: 14 pts Due: 10-30-15

(b)
∂ µg ∂ µl
− = V g − V l = ∆trs V = ∆vap V
∂P T ∂P T
 
1 1
= M −
ρg ρl
 
−3 −1 1 1
= 18.02 × 10 kg mol −
0.598 kg m−3 958 kg m−3
= +3.011497 × 10−2 m3 mol−1

∂ µg ∂ µl
− = +3.01 × 10−2 m3 mol−1
∂P T ∂P T
(c) Compute the difference of the chemical potential of vapor and liquid at 1.2 atm
and 100◦ C.
∂ µg ∂ µl
− = Vg −Vl
∂P T ∂P T
Since we are at a non-standard pressure, 1.2 atm, we have to integrate
first, multiply by dP


dµg − dµl = V g − V l dP
integrate
Z Z 1.2
Z atm 1.2
Z atm 1.2
Z atm


dµg − dµl = V g − V l dP = V g dP − V l dP
1.0 atm 1.0 atm 1.0 atm
assuming incompressible liquid, V l will come out of the integral
RT
assuming ideal gas, we substitute for V g
P
Z Z 1.2
Z atm 1.2
Z atm
RT
dµg − dµl = dP − V l dP
P
1.0 atm 1.0 atm
1.2 atm
µg − µl = R T ln − V l ∆P
1.0 atm
= 8.314510 J K −1 mol−1 × 373.15 K × ln 1.2
18.02 × 10−3 kg mol−1 101325 P a
− × (1.2 atm − 1.0 atm) ×
958 kg m−3 1 atm
2 −1
= +5.652796 × 10 J mol

µg − µl = +5.65 × 102 J mol−1

Since, µg is larger than µl this shows that the gas will spontaneously, and irreversibly
condense into liquid at 1.2 atm.