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Chapter 6 Solutions

Engineering and Chemical Thermodynamics 2e

Milo Koretsky
Wyatt Tenhaeff

School of Chemical, Biological, and Environmental Engineering


Oregon State University

milo.koretsky@oregonstate.edu
6.1
At atmospheric pressure water boils at 100 oC – this is the state of the system when we put
the lid on. As the water boils, the pressure will increase as more vapor forms. If the
evaporation rate is constant, the number of moles entering the vapor is constant and the
pressure almost increases linearly with time (some effect from increase in T on P as well).
We are essentially moving along the liquid/vapor equilibrium line as water continues to boil,
but at a higher and higher pressure. The relation between T and P can be modeled by the
Clausius – Clapeyron equation:

P2sat ∆hvap 1 1
ln sat
=− −
P1 R T2 T1

T increases as the ln of P so less than linear. A sketch is shown below:


6.2

at less than 300K. Equilibrium is given when the molar Gibbs energy of the liquid and vapor are

equal:

g Av = g lA

Substituting in the definition of Gibbs energy

hAv − Ts Av = hAl − Ts lA

With attractive interactions in the vapor phase hiv would decrease relative to an ideal gas. That

would cause the Gibbs energy in the vapor to be less than that of the liquid and all the liquid

would evaporate. To return to phase equilibrium, the temperature needs to be lowered (to lessen

the effect of entropy). An alternative approach is to look at the Clapeyron equation and make an

argument about vv.


6.3

greater than 10 bar. Equilibrium is given when the molar Gibbs energy of the liquid and vapor

are equal:

g Av = g lA

Substituting in the definition of Gibbs energy

hAv − Ts Av = hAl − Ts lA

With attractive interactions in the vapor phase hiv would decrease relative to an ideal gas. That

would cause the Gibbs energy in the vapor to be less than that of the liquid and all the liquid

would evaporate. To return to phase equilibrium, the pressure needs to be raised (to lessen the

effect of entropy). An alternative approach is to look at the Clapeyron equation and make an

argument about vv.


6.4

(a) The quality is 0.1 so the system has 10% by mass vapor and 90% liquid. From the steam
tables:

m3 m3
vˆv = 0.039441 and v = 0.001286
ˆ l

kg kg

So the ratio is

V l 0.9 × vˆl
= = 0.003
V v 0.1× vˆv

Conclusion: eventhough the system has much more mass in the liquid – the volume is mostly
vapor.

(b) Before the valve is opened, the temperature is at the boiling point for steam at 5 MPa, which
is 264 oC. If the valve is opened to the atmosphere, the steam will leave the system decreasing
the pressure. This will lower the boiling point. Ultimately the system will reach equilibrium at 1
atm and 100 oC. If the heat transfer is really fast, it will follow the PT coexistence curve. If the
heat transfer is really slow, the temperature change may be negligible. In reality, it is probably
between these two extremes but closer to the slow heat transfer case.

4
Equilibrium
Pressure [Mpa]

From Steam Tables


3 Fast heat transfer Slow
heat
2
transfer

0
100 150 200 250 300
Temperature [C]
6.5
Starting with the Clapeyron equation
dP ∆h
=
dT ∆vT

Using the mathematical relation

d ln P d ln P dP 1 dP
= =
dT dP dT P dT

We can get
dP d ln P ∆h
=P =
dT dT ∆vT

Using two of the three assumptions for the Clausisus-Clapeyron equation (that the molar volume
of solid or liquid is insignificant compared to gas and that the gas can be assumed to be ideal) we
get the following:

d ln P ∆h
P =
dT RT
T
P
which simplifies and rearranges to
d ln P ∆h
=
dT RT 2

Finally
d ln P
∆h = RT 2
dT
and
15800
d (− − 0.76 ln T + 19.25)
∆h1 = T RT 2 = (15800 − 0.76T ) R
dT
15300
d (− − 1.26 ln T + 21.79)
∆h2 = T RT 2 = (15300 − 1.26T ) R
dT

Since vapors of a species have higher enthalpy than their liquids, and their liquids have higher
enthalpy than their solids, then ∆hsub should be larger than ∆hvap . The first one starts out higher
and decreases slower with temperature and will always be higher than the second one. Therefore
the first is sublimation and the second is evaporation.
6.6
(a) For a single component system:

µ = Gi = g i = g

From the fundamental property relation given by Equation 5.9:

dg = − sdT + vdP

We can identify a phase transition from the vertical line of the g vs. T plot, as indicated below.
Since this transition is vertical, i.e., the temperature is constant, the pressure must also be
constant. Thus, we can differentiate the Gibbs energy with respect to temperature at constant
pressure to get:

∂g
= −s
∂T P

Hence the slope of a plot of g (or T at any temperature must be the negative of the value
) vs.
of entropy on the plot for s vs. T. The resulting curve is sketched below.

(b) For a single component system the fundamental property relation, Equation 5.9, gives:

dg = − sdT + vdP
We can identify a phase transition from the vertical line of the g vs. P plot, as indicated below.
Since this transition is vertical, i.e., the pressure is constant, the temperature must also be
constant. Thus, we can differentiate the Gibbs energy with respect to pressure at constant
temperature to get:

∂g
=v
∂P T

Hence the slope of a plot of g vs. P must have a slope that matches the plot for v vs. T. Since the
molar volume of phase is about twice
The resulting curve is sketched below.
6.7
The ferrite phase has stronger bonds. At room temperature, iron is in the ferrite phase. The
heating to 912 ºC has the effect of increasing the entropy contribution to the Gibbs energy. At a
high enough temperature, the austenite phase becomes stable, so that its entropy must be greater
than the ferrite phase. If the entropy of the austenite phase is greater, the enthalpy of the ferrite
phase must be greater or else the austenite phase would be stable over the entire temperature
range. Hence, the ferrite phase has stronger bonds.
6.8
(a)
The freezing point occurs where there is a discontinuity in the g vs. T plot, as indicated below.
The liquid is at a temperature higher than the freezing point and the solid at lower temperature.
These are demarked below. The melting temperature is 250 K, which occurs at a value g = 3,000
[J/mol]

(b)
At constant pressure, the entropy can be found from Equation 5.14. For the solid we have:

∂g ∆g 1,000 J
s=− =− = = 10
∂T P ∆T 10 mol K

And for the liquid, we get:

∂g ∆g 2,000 J
s=− =− = = 40
∂T P ∆T 50 mol K

(c)
As we change pressure, we can see how the Gibbs energy changes at any given temperature by
Equation 5.14:
∂g
=v
∂P T

Assuming the molar volumes of the liquid and vapor stay constant over the temperature range around the
melting point, we see that the Gibbs energy of the liquid increases by 1.2 times the Gibbs energy of the
solid, since the molar volume of the liquid is 20% larger. The Gibbs energy of the new freezing point at
higher pressure is schematically drawn on the plot above. For convenience, we choose the solid to
increase by 1 unit on the plot. Thus, the liquid increases by 1.2 units. As the sketch shows, the freezing
point, where the two lines intersect, will shift to higher temperature.
6.9

Along the coexistence line, the Gibbs energy of solid must equal that of liquid – which leads to
the Clapeyron equation:

dP hil − his
= l
dT ( )
vi − vis T

Since solids are stabilized by bonds, hil > his and the numerator is always positive. In the
denominator T is also always positive. Therefore the slope of the coexistence line corresponds to
the relative magnitude of the molar volumes of the liquid. If the liquid volume is larger than the
solid volume, all terms are positive and the slope is positive. Conversely, species that expand
upon freezing the term is negative and the slope of the coexistence line is negative.
6.10

(a) The like interactions are stronger – when you replace A-A and B-B with A-B interactions the
enthalpy goes up, suggesting the A-B is less strong

(b) Increase. If they mix adiabatically, all the enthalpy stays in the system. Energy is released as the
stronger pure species interactions are replaced by weaker unlike interactions. This energy goes into
increasing the kinetic energy (speed) of the molecules, and the temperature goes up.

(c) Negative. For the final temperature to return to the initial temperature, energy must leave the system
via heat.
6.11

1 Tm 1 T=?
atm atm

Liquid Liquid
l
n1 n , n , n3l , n4l
l
1
l
2

Solid Solid
n1s n1s

Answer: T < Tm. For the case on the left:

g1s = g1l

or

h1s − Ts1s = h1l − Ts1l

Species 1 in the liquid mixture (right) has a higher entropy than pure 1 in the liquid (left). Thus, at Tm
the equivalent term on the right will be more negative, and the liquid will have a lower molar Gibbs
energy than the solid. This will cause all the solid to melt. To return to phase equilibrium, we must
lower the temperature.
6.12

T < Tb. For the case of pure species:

g1l = g1v

or

h1l − Ts1l = h1v − Ts1v

Species 1 in the vapor mixture has a higher entropy than pure 1 in the vapor. Thus, at Tb the
equivalent term on the right will be more negative, and the vapor will have a lower molar Gibbs
energy than the liquid. This will cause all the liquid to evaporate. To return to phase equilibrium, we
must lower the temperature.
6.13

T < Tm. For the case of pure species:

g1s = g1l

or

h1s − Ts1s = h1l − Ts1l

Species 1 in a liquid of species 2 has a higher entropy than pure 1 in the liquid. Thus, at Tm the
equivalent term on the right will be more negative, and the liquid will have a lower molar Gibbs
energy than the solid. This will cause all the solid to melt. To return to phase equilibrium, we must
lower the temperature.
6.14

The entropy of the liquid increases – so the melting temperature must decrease.
6.15
1 300 1 300
atm K atm K
Liquid
Liquid
l
n1 n1l , n2l , n3l , n4l

System I System II

(a) H1I = H1II If 1-1 and 1-2, 1-3, and 1-4 interactions are the same, there is no difference in species 1’s
contribution to the energy of the mixture vs. its pure species behavior.

(b) S1I < S1II More configurations in System II

(c) G1I > G1II From the definition of Gibbs energy and answers to part (a) and (b) above

(d) g1I = g1II gi just depends on T and P

(e) H1I = h1 < H1II Stronger interactions leads to lower partial molar enthalpy.
6.16
The following can be shown with the Gibbs-Duhem equation

0 = x1V1 + x 2V2

Differentiation with respect to x1:

dV1 dV
0 = x1 + x2 2
dx1 dx1

If the partial molar volume of species 1 is constant, the Gibbs-Duhem equation simplifies to

dV 2
0=
dx1

Therefore, the partial molar volume of species 2 is also constant.

Note that in this case, since the partial molar volume of species 1 is constant:

V1 = v1

and similarly for species 2:

` V2 = v2

Hence, the molar volume can be written:

v = x1V1 + x2V2 = x1v1 + x2v2

This is known as Amagat’s law.


6.17
(a)
The Clausius-Clapeyron equation:
vap
dPisat ∆hi dT Pisat ∆h vap 1 1
ln =− i −
sat = 2 or
101 [kPa] R T 373 [K]
Pi RT

so
vap
∆hi 1 1
Pisat = (101 [kPa])exp − −
R T 373 [K]

(b) and (c)


Using

kJ
∆h vap = 40.626
mol

we obtain the following table

Eqn 6.24 Steam %


T [K]
[kPa] Tables [kPa] Difference
273.156 0.84 0.6113 37.30%
278.15 1.16 0.87 33.02%
283.15 1.58 1.23 28.30%
288.15 2.13 1.71 24.51%
293.15 2.84 2.34 21.51%
298.15 3.76 3.17 18.62%
303.15 4.93 4.25 15.94%
308.15 6.40 5.63 13.68%
313.15 8.24 7.38 11.71%
318.15 10.54 9.59 9.86%
323.15 13.36 12.35 8.19%
328.15 16.82 15.76 6.75%
333.15 21.04 19.94 5.50%
338.15 26.13 25.03 4.40%
343.15 32.26 31.19 3.42%
348.15 39.58 38.58 2.58%
353.15 48.28 47.39 1.87%
358.15 58.56 57.84 1.25%
363.15 70.67 70.14 0.75%
368.15 84.84 84.55 0.34%
373.15 101.35 101.35 0.00%
The logarithmic trend is well-represented. However, at lower temperatures the Clausius-
kJ
Clapeyron equation is up to 37% off. The actual heat of vaporization changes from 2501.3
kg
kJ
at 0.01 oC to 2257.0 at 100 oC, a difference of around 10%.
kg

Eqn 6.24 [kPa]


Steam Tables [kPa]
1000
Pressure [kPa]

100
360 380 400 420 440 460 480

Temperature [K]

(d)

For 100 ºC to 200 ºC, we obtain the following table:

Eqn 6.24 Steam Tables %


T [K]
[kPa] [kPa] Difference
373.15 101.35 101.35 0.00%
378.15 120.51 120.82 0.26%
383.15 142.64 143.28 0.44%
388.15 168.11 169.06 0.56%
393.15 197.30 198.53 0.62%
398.15 230.63 232.1 0.63%
403.15 268.55 270.1 0.57%
408.15 311.54 313 0.47%
413.15 360.11 361.3 0.33%
418.15 414.82 415.5 0.16%
423.15 476.24 475.9 0.07%
428.15 545.00 543.1 0.35%
433.15 621.74 617.8 0.64%
438.15 707.16 700.5 0.95%
443.15 801.99 791.7 1.30%
448.15 906.98 892 1.68%
453.15 1022.93 1002.2 2.07%
458.15 1150.68 1122.7 2.49%
463.15 1291.10 1254.4 2.93%
468.15 1445.10 1397.8 3.38%
473.15 1613.62 1553.8 3.85%

Eqn 6.24 [kPa]


Steam Tables [kPa]
1000
Pressure [kPa]

100
360 380 400 420 440 460 480

Temperature [K]

Over this range the Clausius-Clapeyron equation represents the data well and is no more than 4
% off. The actual heat of vaporization changes from 2257.0 [kJ/kg ] at 100 oC to 1940.7 [kJ/kg ]
at 200 oC, a difference of around 15%.

(e)

The heat of vaporization can be corrected for temperature as follows

Tb T
∆hvap (T ) = ∫ c P
l
dT + ∆hvap (Tb ) + ∫ c Pv dT
T Tb
We can acquire heat capacity data from Appendix A.2, but to simplify the analysis, we will use
an average heat capacity for the vapor.

∆hvap (T ) = 75.4(373.15 − T ) + 40626 + 34.13(T − 373.15)

∆hvap (T ) = 56026 − 41.27T

Substitute this expression into the Clausius-Clapeyron equation

dPisat
=
(56026 − 41.27T ) dT
sat
Pi RT 2

Integrate:

1 1 1 T
Pisat = (101.35 kPa ) exp − 56026 − − 41.27 ln
R T 373.15 373.15

Now plot the data as before from 0.01 ºC to 200 ºC.

Eqn 6.24 Steam Tables %


T [K]
[kPa] [kPa] Difference
273.16 0.64 0.6113 4.95
278.15 0.91 0.87 4.96
283.15 1.28 1.23 4.24
288.15 1.78 1.71 3.88
293.15 2.43 2.34 3.86
298.15 3.29 3.17 3.65
303.15 4.39 4.25 3.35
308.15 5.81 5.63 3.17
313.15 7.60 7.38 3.03
318.15 9.86 9.59 2.78
323.15 12.66 12.35 2.51
328.15 16.12 15.76 2.28
333.15 20.35 19.94 2.06
338.15 25.49 25.03 1.84
343.15 31.68 31.19 1.58
348.15 39.10 38.58 1.34
353.15 47.91 47.39 1.09
358.15 58.32 57.84 0.82
363.15 70.54 70.14 0.57
368.15 84.80 84.55 0.29
373.15 101.35 101.35 0.00
378.15 120.46 120.82 0.30
383.15 142.40 143.28 0.61
388.15 167.48 169.06 0.94
393.15 196.00 198.53 1.28
398.15 228.29 232.1 1.64
403.15 264.70 270.1 2.00
408.15 305.56 313 2.38
413.15 351.26 361.3 2.78
418.15 402.16 415.5 3.21
423.15 458.64 475.9 3.63
428.15 521.10 543.1 4.05
433.15 589.92 617.8 4.51
438.15 665.51 700.5 4.99
443.15 748.27 791.7 5.49
448.15 838.59 892 5.99
453.15 936.89 1002.2 6.52
458.15 1043.55 1122.7 7.05
463.15 1158.98 1254.4 7.61
468.15 1283.56 1397.8 8.17
473.15 1417.67 1553.8 8.76

Eqn 6.24 [kPa]


Steam Tables [kPa]
500
Pressure [kPa]

50

0.5
260 310 360 410 460

Temperature [K]

The agreement between the two values at lower temperatures improves significantly at lower
temperatures, but actually worsens at higher temperatures. The agreement could potentially be
improved by not averaging the heat capacity.
6.18

We can find the required pressure by applying the Clapeyron equation:

T
dP ∆h fus
=
dT (
vs − v l T )
To use this equation we need an initial condition on the solid-liquid equilibrium line. We can
find the values using the triple point of water and then integrate to –5 oC. At the triple point,
0.01 ºC and 0.6113 kPa, Tables B.3 and B.1 give:

m3 kJ
vˆ s = 1.0908 ×10−3 and hˆ s = −333.4
kg kg
m3
vˆ l = 1.00 ×10−3 and hl = 0
kg

To calculate how the enthalpy of fusion changes with T we can use the following path:

liquid solid
T

∆h Tfus

273.16 T
∫ cPl dT ∫ cPs dT
T 273.16

T = 273.16 [K]

liquid kJ solid
∆hˆ fus = −333.4
kg
J
∆h fus = −6001.2
mol

273.16 T T
∆h Tfus = ∫ cPl dT + ∆h 273.16
fus + ∫ cPs dT = ∫ (cPs − cPl )dT + ∆h 273.16
fus
T 273.16 273.16

Using data in Appendix A:


∆h Tfus = −4.873R (T − 273.16) + ∆h 273.16
fus

which gives

273.16
dP −4.873R 1331R + ∆h fus
= +
dT (
v s − vl )
v s − vl T ( )
If we assume that (v s − v l )is independent of temperature and pressure, we can now separate
variables in the Clapeyron equation and integrate.

−4.873R 1331R + ∆h 273.16 T


P − Ptp = (T − Ttp )+ fus
ln
(vs − v l ) (vs − v l) Ttp

Solving this gives

P = 668 [bar]

Alternative:
If we also assumed that (h s − h l ) is independent of temperature and pressure, we get.

hs − hl T
P = Ptp + ln
(vs − v l ) Ttp

−333.4 ×10 3 [J/kg] 268.15 K


P = 611.3 [Pa] + ln
(1.0908 × 10−3 −1.00 × 10−3 [m3 /kg ]) 273.16 K
so
P = 680 [bar ]

a difference of 12 bar from above.


6.19
(a)
At 1 bar, the gas will act as an ideal gas.

J
8.314 (300 K )
RT mol ⋅ K m3
v= = = 0.0249
P 1 × 10 5 [Pa ] mol

The number of moles of vapor are found as follows (neglect molar volume of liquid)

vV
n = =
[ ]
0.001 m 3
v m3
0.0249
mol

n v = 0.0402 mol

(b)
At 21 bar, the gas will not behave ideally. Since we are assuming that the molar volume of
liquid is negligible and the heat of vaporization is independent of temperature, the Clapeyron
equation becomes

dP ∆h vap
= v
dT vT

The molar volume using pressure expansion of the virial equation is

vv =
(
RT 1 + B ' P
= RT
1)+ B'
P P

Substituting this expression into the Clapeyron equation yields

dP ∆h vap
=
dT 1
R + B' T 2
P

Separation of variables yields

P2 = 21 ×105 Par T2
1 ∆h vap dT
∫ + B dP = ∫
'
2
P1 =1 ×105 Pa
P R T1 =300 K T

and integration results in


P2 − ∆h vap 1 1
ln + B ' (P2 − P1 ) = −
P1 R T2 T1

We can substitute values for given quantities and constants to solve for T2.

T2 = 523.3 K

(c)
Using the virial equation,

3
1 J 1 −7 m
v v = RT + B ' = 8.314 (523.3 K ) + −1 × 10
P mol ⋅ K 21 × 10 5 Pa J
m3
v v = 0.00164
mol

We can assume the volume occupied by the liquid is negligible. Therefore,

nv =
V
=
[ ]
0.001 m 3
vv m3
0.00164
mol
n v = 0.61 [mol]
6.20
We can use the following computational path to solve for pressure at which graphite and
diamond are in equilibrium at 25 oC.

graphite diamond
P = 1 [atm]

J
∆g = 2866
mol

P 1
∆g1 = ∫ v graphdP ∆g 3 = ∫ v diam dP
1 P

graphite ∆g 2 = 0 diamond

Summing together the three steps we get:

J
∆g (1[atm]) = 2866 = ∆g1 + ∆g 2 + ∆g 3
mol

To find the change in Gibbs energy with pressure, we apply the fundamental property relation,
Equation 5.9. At constant temperature:

If the solid is assumed incompressible, we can integrate to get

∆g i = ∫ vi dP = vi ∆P

Thus the sum of Gibbs energy becomes


P 1
∆g (1[atm]) = 2866
J
mol
(
= ∫ v graph dP + 0 + ∫ v diam dP = v graph − v diam (P − 1) )
1 P

Solving

2866
J
mol
=
1

1
2.26 3.51
cm 3
g
12
g
mol 10
1
6
cm
m3
3
(P − 1.01× 105 [Pa ])
or

P = 1,514 [MPa] = 15,143 [bar]


6.21
From the Clausius-Clapeyron equation:

dP h lAl − h Al
s ∆hTfus
(I)
dT
=
(
v lAl − v Al
s
T
=
) (
v lAl − v Al
s
T )
T
where ∆h fus is the enthalpy of fusion at temperature T. We can get the molar volumes from the
densities:

kg
0.027
MW mol m3
v lAl = = = 1.17 × 10 − 5
ρl 2,300
kg mol
m3
and

kg
0.027 3
s MW mol −5 m
v Al = = = 1.00 × 10
ρs 2,700
kg mol
m3

so

m3
v lAl − v Al
s
= 1.7 × 10 −6
mol

T
We can use the following path to calculate for ∆h fus .

solid liquid
T
T
∆h fus

933 T
∫ cPs dT ∫ cPl dT
T 933

T = 933 [K]

solid J liquid
∆h fus = 10,711
mol
933.45 T
J
∆hTfus = ∫c Ps dT + 10,711 + ∫
l
cP dT
mol
T 933.45

J J
Using c Ps = 20.608 + 0.0138T l
and c P = 31.748 , we get:
mol K mol K

∆hTfus = 5,819.9 + 11.68T − 0.0069T 2

Back into Equation (I) gives:

5,819.9 + 11.68T − 0.0069T 2


dP =
(1.7 ×10 −6 )T dT

Integrating:

100 [bar] T
5,819.9 + 11.68T − 0.0069T 2
∫ dP = ∫ (1.7 ×10 − 6 )T dT
1 933.45 [K]

or

([100 − 1]×105 )(1.7 ×10 − 6 ) = 5819.9 ln 933T.45 (


+ 11.68(T − 993.45) − 0.00345 T 2 − 993.45 2 )
solving for T gives

T = 934.91 [K]
6.22
We can assume that silver acts as an ideal gas at 1500 K. We can also assume the molar volume
of the vapor is much greater than the molar volume of liquid. Therefore, we can use the
Clausius-Clapeyron equation

dP sat ∆h vap dT
=
P sat RT 2

This can be rearranged to show

dP sat ∆h vap P sat


=
dT RT 2

This relation assumes


1. vv>>vl
2. Silver acts as an ideal gas

We can differentiate the expression for pressure in the problem statement to obtain

dP sat 14260 0.458 − 14260


= 2
− exp − 0.458 ln (T ) + 12.23
dT T T T
dP sat 14260 0.458 sat
= − P
dT T2 T

Therefore,

14260 0.458 ∆h vap


− =
T2 T RT 2

Therefore,

∆h vap = R(14260 − 0.458T )

At 1500 K,

J
∆h vap = 8.314 [14260 − 0.458(1500 [K ])]
mol ⋅ K
kJ
∆h vap = 112.8
mol
6.23
Since the pressures are low, we can assume ideal gas behavior. We can also assume that the
molar volume of the vapor is much greater than the molar volume of liquid and the heat of
vaporization is independent of temperature. Therefore, we can rearrange the Clausius-Clayperon
equation to obtain

J 760 torr
− 8.314 ln
mol ⋅ K 400 torr
∆h vap =
1 1

353.25 K 333.75 K
kJ
∆h vap = 32.3
mol

This value is 7.7% smaller than the reported value.


6.24
The saturation pressure can be found using the Clausius-Clapeyron equation with the assumption
that the heat of vaporization is independent of temperature. First, we need to use the given data
for the 63.5 ºC and 78.4 ºC to find the heat of vaporization.

P2sat
− R ln J 760 torr
− 8.314 ln
P1sat mol ⋅ K 400 torr
∆h vap = =
1 1 1 1
− −
T2 T1 351.55 K 336.65 K
kJ
∆h vap = 42.39
mol

Now we can calculate the vapor pressure at 100 ºC.

kJ
vap − 42.39
− ∆h 1 1 mol 1 1
P3sat = P2sat exp − = (760 torr ) exp −
R T3 T2 kJ 373.15 K 351.55 K
0.008314
mol ⋅ K
P3sat = 1760 torr = 2.32 atm

In comparison, ThermoSolver gives a value of 2.23 atm, using the Antoine equation.
6.25
We can show using the Chain Rule that

gi T∂g i − g i ∂T

T
= T2 =
1 ∂g i g
− i
∂T ∂T T ∂T P T 2
P P

Using fundamental property relations, Equation 5.14 states

∂g i
= − si
∂T P

Therefore,

gi

T − Tsi − g i − Tsi − (hi − Tsi ) − hi
= = =
∂T T 2
T 2
T2
P
6.26

Let T1 = 922 K, T2 = 1,300 K

g 2 = h2 − T2 s 2
dh = c P dT
1,300 K
h2 − h1 = ∫ c P dT
922 K
J
h2 = h1 + c P (T2 − T1 ) = 39,116
mol
c
ds = P dT
T
T2 J
s2 = s1 + c P ln = 85.10
T1 mol K
J
g 2 = h2 − T2 s2 = −71,500
mol

Alternative solution using the result from Problem 6.25:

d gT h h + c (T − T1 )
=− T =− 1 P We must leave h as a function of T
dT T2 T2

g
T
h1 + c P (T − T1 )
2 1300 K
g
∫ d
T
=− ∫ T 2
dT
g 922 K
T 1

g g 1 1 T J
= + (h1 − c PT1 ) − − c P ln 2 = −55.01
T 2 T 1 T2 T1 T1 mol K

J
g 2 = −71,500
mol
6.27
A possible hypothetical solution path is presented below:

monoclinic orthorhombic

T = 298 [K]

∆g1 ∆g3

T = 368.3 [K]

monoclinic ∆g2 = 0 orthorhombic


From the diagram, we see that the Gibbs energy for steps one and three can be calculated as
follows:

368 K
∂g m
∆g1 = ∫
298 K
∂T
dT
P

and
298 K
∂g o
∆g 3 = ∫ ∂T dT
368 K P
respectively. We can apply Equation 5.14 from the thermodynamic web

∂g
= −s
∂T P
At 368 K, sulfur undergoes a phase transition, so

→o
∆g 3m68 K =0
m→o
Using these above relationships, the expression for ∆g 298 K becomes

368 K 298 K 368 K 298 K


∫ (13.8 + 0.066T )dT − ∫ (11 + 0.071T )dT
m→o m o
∆g 298 K =− ∫s dT + 0 − ∫s dT = −
298 K 368 K 298 K 368 K
m →o J
∆g 298 K = −79.5
mol
Therefore, the transition from the monoclinic to orthorhombic state occurs spontaneously. The
orthorhombic state is more stable.
6.28
At the phase transition, the following is true

g g
=
T Sr ( s ) T Sr (l )

Using the thermodynamic web, the following can be shown (see Problem 6.25)

∂(g / T ) −h
=
∂T P T
2

The enthalpies can be written as follows

T
h l (T ) = 49179 + ∫ 35.146 dT = 35.146T − 3540
1500 K
T
h s (T ) = 20285 + ∫ 37.656 dT = 37.656T − 16305.4
900 K

g
can also be calculated at 900 K for solid Sr and 1500 K for liquid Sr.
T

gl J
= −83.85
T mol ⋅ K
ref

gs J
= −68.68
T mol ⋅ K
ref

g
We can find at any temperature using the differential equation as follows
T
g ∂(g / T ) h
∫d T
=∫
∂T P
dT = − ∫
T2
dT

Substituting our expressions, we get

g l /T T
g 35.146T − 3540
∫ d
T
= ∫ −
T2
dT
− 83.85 1500 K
gl 3540
= −35.146 ln(T ) − + 176.04
T T

g s /T T
g 37.656T − 16305.4
∫ d
T
= ∫ −
T2
dT
− 68.68 900 K
s
g 16305.4
∴ = −37.646 ln(T ) − + 205.5
T T

gl gl
Set = and solve for T:
T T

T melt = 1059.8 K

The enthalpy of melting is defined as

( ) (
∆h fus = h s T melt − h l T melt )
Using the expressions developed above

kJ kJ kJ
∆h fus = 26.30 − 33.71 = −7.41
mol mol mol
6.29
At the phase transition, the temperature and Gibb’s energy of both phases must be equal.
Mathematically, this is equivalent to

g g
=
T SiO ( s ) T SiO (l )
2 2

Using the thermodynamic web, the following can be shown (see Problem 6.25)

∂(g / T ) −h
=
∂T P T
2

Using the definition of enthalpy, we can write the following

h(T ) T
∫ dh = ∫ c P dT
href Tref
T
∴ h(T ) − href = ∫ c P dT
Tref

The enthalpies can be written as follows

T
h (T ) = −738440 +
l
∫ 85.772 dT
2500 K

∫ [53.466 + 0.02706T − 1.27 × 10 ]


T
h s (T ) = −856840 + −5 2
T + 2.19 × 10 − 9 T 3 dT
1100 K

g
can also be calculated at 1100 K for solid SiO2 and 2500 K for liquid SiO2.
T

gl J
= −487.3
T mol ⋅ K
ref

gs J
= −903.5
T mol ⋅ K
ref
g
We can substitute our expressions for and h(T ) into the above differential equation and
T
separate variables to obtain

T
g l /T T
− 738440 + ∫ 85.772 dT
g 2500 K
∫ d
T
= ∫ −
T2
dT
− 487.3 2500 K

∫ [53.466 + 0.02706T − 1.27 × 10 ]


T
−5 2
g s /T
− 856840 + T + 2.19 × 10 − 9 T 3 dT
T
g 1100 K
∫ d
T
= ∫ −
T2
dT
− 903.5 1100 K

Integration provides

g l − 9.5268 × 10 9 − 85.772 ln(T ) + 1052.4T


= − 487.5
T T
g s − 1.82 × 10 −10 T 4 + 2.12 × 10 −6 T 3 − 0.01353T 2 − 927190.9 − 53.466T ln(T ) + 1230T
= − 903.5
T T

gl gs
If we plot − vs. T, we obtain the following:
T T
There are three solutions, but only the solution between 1100 K and 2500 K is physically
meaningful. If we magnify the plot near the middle solution, we find

T = 1983 K
The enthalpy of fusion is defined as

( ) (
∆h fus = h s T melt − h l T melt )
Using the expressions developed above

kJ kJ kJ
∆h fus = −792.5 − (− )782.78 = −9.72
mol mol mol
6.30
From the Clapeyron equation

sat
dPCS ∆h vap
=
( )
2

dT T vv − vl

Assuming:

v v >> v l

we get

sat
dPCS ∆h vap
2
= (I)
dT Tv v

The saturation pressure is given by:

4.7063 × 10 3
sat
ln PCS = 62.7839 − − 6.7794 ln T + 8.0194 × 10 − 3 T (II)
2 T

sat
= 4.48 ×10 [Pa]. Taking the derivative of Equation II
5
At T = 373 K, PCS
2

sat sat
d ln PCS 1 dPCS 4.7063 × 10 3 6.7794
2
= 2
= − + 8.0194 × 10 − 3 (III)
dT sat dT 2 T
PCS T
2

Plugging Equation III into Equation I,

4.7063 × 10 3 6.7794 ∆h vap


− + 8.0194 × 10 − 3 PCS
sat
=
T2 T 2
Tv v

vap kJ
Solving for vv using ∆hCS = 24.050 gives:
2 mol

−1
∆h vap 4.7063 × 10 3 6.7794 m3
v
v = − + 8.0194 × 10 −3 = 6.08 × 10 −3
sat
TPCS T2 T mol
2
Pv B
z= = 0.878 = 1 +
RT v
or
m3 cm 3
B = −7.4 × 10 − 4 = −740
mol mol

This value is about 50% higher than the reported value.

Alternative solution:

Following similar development as Problem 6.19:

sat
dPCS ∆h vap
2
=
dT
1
RT 2 + B'
sat
PCS
2

1 ' sat ∆h vap


sat + B dPCS 2
= 2 dT
PCS RT
2

We must be careful about the limits of integration. We need to pick a value of T close so
enthalpy of vaporization is not too different, but far enough away to avoid round off error. If we
sat
= 5.04 ×10 [Pa]. Integrating:
5
choose T = 378 K, Equation I gives PCS
2

4.48×10 5 [Pa] 373


1 ∆h vap
∫ sat + B
'
dP sat
CS2 = ∫ 2 dT
5 P
5.04×10 [Pa] CS2 378 RT

4.48 × 105 ∆h vap 1


ln
5.04 × 105 (
+ B' 4.48 ×10 5 − 5.04 × 105 = − ) R

1
373 378

Solving for B’ gives:

B' = −2.55 × 10−7 [Pa]

m3
Or B = B ' RT = −7.9 ×10−4
mol
6.31
First we need data. The appendices in Koretsky, and the NIST website
(http://webbook.nist.gov/chemistry/fluid/) are two sources:

Saturated water @ 100°C (both liquid and vapor present, in equilibrium)


Quantity Koretsky, Table B1 (p.508) NIST Website

ℎ𝑙 419.02 kJ/kg 419.17 kJ/kg
ℎ�𝑣 2676.0 kJ/kg 2675.6 kJ/kg
𝑠̂𝑙 1.3068 kJ/kg·K 1.3072 kJ/kg·K
𝑠̂𝑣 7.3548 kJ/kg·K 7.3541 kJ/kg·K

Water @ 100°C and 50kPa (this is in the superheated vapor phase)


Quantity Koretsky Table B4 (p.513) NIST Website
ℎ�𝑣 2682.5 kJ/kg 2682.4 kJ/kg
𝑠̂𝑣 7.6947 kJ/kg·K 7.6953 kJ/kg·K

A. Saturated water @ 100°C


Liquid phase:
g� 𝑙 = ℎ�𝑙 − 𝑑𝑠̂𝑙

kJ kJ kJ
g� 𝑙 = 419.02 kg
− (373.15 K) �1.3068 kg∙K
� = −68.61 kg

Vapor phase:
g� 𝑣 = ℎ�𝑣 − 𝑑𝑠̂𝑣

kJ kJ kJ
g� 𝑣 = 2676.0 kg
− (373.15 K) �7.3548 kg∙K
� = −68.44 kg

Since we are at the saturation point, we have both liquid and vapor present. Because both phases
are in equilibrium with each other, the Gibbs energies of the two phases should be equal:
g� 𝑙 = g� 𝑣

As shown above, the values are in fairly good agreement. However, the results obtained when
using NIST website data are somewhat closer:
kJ
g� 𝑙 = −68.612 kg

kJ
g� 𝑣 = −68.582 kg
This tells us that neither phase has a lower Gibbs energy, therefore neither phase is preferred
over the other. As a result, both phases coexist at equilibrium.

B. Water @ 100°C and 50 kPa


Here we have superheated water vapor, since the pressure is lower than that of saturated water at
the same temperature. Thus, the values we extract from Koretsky or NIST are for the vapor
phase only:
g� 𝑣 = ℎ�𝑣 − 𝑑𝑠̂𝑣

kJ kJ kJ
g� 𝑣 = 2682.5 kg
− (373.15 K) �7.6947 kg∙K
� = −188.77 kg

kJ
From the NIST data: g� 𝑣 = −189.10 kg

For the liquid phase, we can make the assumption that the change in pressure (100 kPa to 50
kPa) will not cause the values of enthalpy or entropy to change significantly from the saturation
value. Thus, we can just use the values at the saturation point, which gives us an result that is
identical to the liquid phase calculation in part (A):

g� 𝑙 = ℎ�𝑙 − 𝑑𝑠̂𝑙

kJ kJ kJ
g� 𝑙 = 419.02 kg
− (373.15 K) �1.3068 kg∙K
� = −68.61 kg

In comparing the two values, it is seen that the Gibbs energy of the vapor phase is quite a bit
lower than the liquid phase (about 120 kJ/kg less). This explains why we only see the vapor
phase when water is at 100°C and 50 kPa, since it has lower Gibbs energy and is therefore more
stable. This also tells us that any liquid water that might find itself at these conditions would
spontaneously vaporize.

This is consistent with Equation 6.3:

0 ≥ (𝑑𝐺𝑚 ) 𝑇,𝑃
6.32
1st printing – the triple point temperature of 225 K is missing
At the triple point

3000
PAsat = exp 12 − = 0.26 bar
225

Find enthalpy of vaporiwaion

d ln PAsat 3000 ∆hsub , A


= 2 =
dT T RT 2
J
h v − h s = 3000 R = 24,942
mol
And

J
h s − hl = −10,940
mol
So

J
h v − hl = 14, 000
mol
From the Clausius-Clapeyron equation:

h v − hl
d ln PAsat = dT
RT 2
Integrating
PAsat T
h v − hl

0.266
d ln PAsat = ∫225 RT 2 dT
So

1684
ln PAsat = 6.13 −
T
6.33
(a) There are many paths to solve this problem; one is shown below:

Calculate the molar volume of liquid and solid Ag from its density:
3
MW 1 m kg −5 m3
vs = s = 0.1079 = 1.028 ×10
ρ 10,500 kg mol mol

MW 1 m3 kg −5 m
3
vl = = 0.1079 = 1.160 ×10
ρl 9,300 kg mol mol
Find the melting temperature at 5,000 bar using the Clapeyron equation:
dP sil − sis 90.885 − 81.730 6 J
= l = = 6.90 ×10
dT v i − v is 1.160 ×10−5 −1.028 × 10−5 K m3
Hence, at 5,000 bar
1 [5,000 − 1] ×10
5
Tm
5,000
= Tm + 5 = 1,306 [K]
6.90 × 10
So we know that gl = gs at 1,306 K and 5,000 bar, so we can use the following path:
P = 5,000 bar
liquid T = 1400 K solid

gs − gl

∆g1 ∆g 3

P = 5,000 bar
T = 1306 K

liquid ∆g 2 = 0 solid

g s − g l = ∆g1 + ∆g 2 + ∆g 3
Starting with the differential definition of the Gibbs energy,

dg = −sdT + vdP = −sdT

1306
J
∆g1 = − ∫ s ldT = 8,515 mol
1400
1400
J
∆g 3 = − ∫ s s dT = −7653 mol
1306
s l J
g − g = 857
mol

(b) The liquid is stable at 5,000 bar and 1400 K since it has a lower Gibbs energy

(c) The entropy change can be found according to:

c
ds = P dT
T

T
sTl = s1234
l l
+ cP ln
1234

T
sTs = s1234 + B (T −1233)
s
+ Aln
1234

J J J
With c Pl = 33.472 and A = 22.963 ; B − 6.904 × 10 −3 ,
mol K mol K mol K 2

l T T
+ cPl ln
s
l s s1234 − s1234 + Aln + B(T −1233)
dP si − si 1234 1234
= = −5 −5
dT v il − v is 1.160 × 10 −1.028 × 10

dP =
( l
s1234 s
− s1234 )+ (cPl − A)ln
T
1234
− B(T −1233)
dT
−5
1.160 × 10 −1.028 × 10−5

J (l
Tm5000 s1234 s
− s1234)( )
+ cPl − A ln
T
− B(T −1233)
(5,000 −1) × 105 = ∫ 1234 dT
m3 1234 1.160 × 10−5 −1.028 × 10−5

Now solve the above implicit equation for Tm5000. Substituting values for the constants, and
expanding the integral, we find that the melting point that satisfies the relation is similar to the
estimate in part A:

Tm5000 = 1305.67 K

Now use this temperature to calculate the Gibbs energy changes of each step of the path:
1305.67 1305.67
T
∆g1 = − ∫ s dT = − ∫ + c Pl ln
l l
s1234 dT
1400 1400
1234
J
∆g1 = +8862.64
mol
Recall that ∆g2 = 0 (equilibrium phase change). Compute the final step:
1400 1400
T
∆g 3 = − ∫ s dT = − ∫ s1234
s s
+ Aln + B (T −1233) dT
Tm
1234
Tm

J
∆g 3 = −7985.70
mol

Using these values, compute the Gibbs energy of fusion at 1400K and 5000 bar:

g s − g l = ∆g1 + ∆g 2 + ∆g3

J
g s − g l = 877.14
mol

This value is somewhat higher than the “naïve” estimate we got in part A.
6.34
(a) We are given the enthalpies of sublimation and vaporization (which can be assumed to be
constant), and the temperature and pressure of these phase transitions. These data are
tabulated at the right.

Start by writing the Clausius-Clapyron equation for each of the two phase transitions. For
the pure species A phase transition from solid to vapor (sublimation), we write:

PTP ∆h 1 1
ln = − sub − (1)
Psub R TTP Tsub

and for the liquid-vapor transition,

Pvap ∆hvap 1 1
ln =− − (2)
PTP R Tvap TTP

Now, we have two equations, with two unknowns (PTP and TTP). We can combine
Equations 1 and 2 to get:

Pvap ∆hsub ∆hvap 1


R ln = − + ∆hvap − ∆hsub (3)
Psub Tsub Tsub TTP

Now solve for TTP in Equation 3:

∆hvap − ∆hsub
TTP =
P ∆h ∆h (4)
R ln vap + vap − sub
Psub Tsub Tsub

Substitution of the values from the table above into Equation 4 lets us find TTP :

J
( 28937 − 13921)
TTP = mol
J J
28937 13921
J 1 bar mol − mol
8.314 ln + (5)
mol ⋅ K 0.1 bar 250 K 200 K

∴TTP = 230 K
Now substitute the value of TTP into Equation 1, and solve for PTP :
∆hsub 1 1
PTP = Psub exp − −
R TTP Tsub
J
13921
mol 1 1
PTP = ( 0.1 bar ) exp − − (6)
J 230 K 200 K
8.314
mol ⋅ K

∴ PTP = 0.30 bar

Thus, the triple point for pure species A occurs at PTP = 0.30 bar and TTP = 230K.

∆hsub ,i = A + BT
∆hvap ,i = C + DT

Sublimation:
dP ∆hsub ,i
= dT
P RT 2
PT 1 TT A + BT
∫PS P dP = ∫TS RT 2 dT
PT 1 A TT 1 B TT 1
∫PS P dP = R ∫TS T 2 dT + R ∫TS T dT
P A 1 1 B T
ln T = − + ln T
PS R TT TS R TS

Vaporization:
P C 1 1 D T
ln T = − + ln T
PV R TT TV R TV
6.35
(a) Enthalpy of sublimation, assuming Δhsub is constant:
We can simply evaluate Δhsub using the Clausius-Clapeyron equation, integrating from state
1 to state 2

𝑃 ∆ℎ𝑠𝑢𝑏 1 1
𝑙𝑛 �𝑃2 � = − �𝑇 − 𝑇 �
1 𝑅 2 1

The above equation is based on 3 assumptions:


• Specific volume of the vapor is much greater than the specific volume of the solid
𝑣𝑚𝑠 ≪ 𝑣𝑚𝑣 or 𝑣𝑚𝑠 ≈ 0
• The vapor acts as an ideal gas
• Δhsub is constant with temperature
From this point, plug in the values given in the problem and solve for Δhsub.

𝑃 2 bar J
ln� 2 �∗𝑅 ln� �∗8.314
0.258 bar mol∙K
∆ℎ𝑠𝑢𝑏 = − =−
𝑃1
1 1 1 1
� − � � − �
𝑇2 𝑇1 350 K 250 K

kJ
∆ℎ𝑠𝑢𝑏 = 14.9 mol

(b) Enthalpy of sublimation, accounting for the temperature variation of Δhsub. A very useful
first step for this problem is to pick a path. A few possible paths are represented below:

Possible Path 1:
T=250K
∆hsub
T=250K, s T=250K, v

250𝐾 𝑇
∆ℎ1 = � 𝐶𝐶𝑠 𝑑𝑑 ∆ℎ2 = � 𝐶𝐶𝑣 𝑑𝑑
𝑇 250𝐾

T, s T, v
T
∆hsub

Possible Path 2:
T=350K
∆hsub
T=350K, s T=350K, v

350𝐾 𝑇
∆ℎ1 = � 𝐶𝐶𝑠 𝑑𝑑 ∆ℎ2 = � 𝐶𝐶𝑣 𝑑𝑑
𝑇 350𝐾

T, s T, v
T
∆hsub

Possible Path 3:
T=300K
∆hsub
T=300K, s T=300K, v

300𝐾 𝑇
∆ℎ1 = � 𝐶𝐶𝑠 𝑑𝑑 ∆ℎ2 = � 𝐶𝐶𝑣 𝑑𝑑
𝑇 300𝐾

T, s T, v
T
∆hsub

Let’s choose path 1 as an example. According to path 1, ∆hsubT is the summation of ∆h1,
∆hsubT=250K & ∆h2.
∆ℎ𝑠𝑢𝑏 𝑇 = ∆ℎ𝑠𝑢𝑏 𝑇=250𝐾 + ∆ℎ1 + ∆ℎ2
250𝐾 𝑑
∆ℎ𝑠𝑢𝑏 𝑇 = ∆ℎ𝑠𝑢𝑏 𝑇=250𝐾 + ∫𝑑 𝐶𝐶𝑠 𝑑𝑑 + ∫250𝐾 𝐶𝐶𝑣 𝑑𝑑

∆ℎ𝑠𝑢𝑏 𝑇 = ∆ℎ𝑠𝑢𝑏 𝑇=250𝐾 + 40(250 − 𝑑) + 40(𝑑 − 250) + 0.05(𝑑 2 − (250)2 )

The slashed out parts cancel each other out and we are left with a simplified equation for ∆hsubT.

J
∆ℎ𝑠𝑢𝑏 𝑇 = ∆ℎ𝑠𝑢𝑏 𝑇=250𝐾 + 0.05𝑑 2 − 3125 �mol�

Now we have an expression for ∆hsubT that is valid for any temperature. We can use this
information in the Clausius-Clapeyron equation now accounting for the temperature dependence
of ∆hsubT.
𝑑𝑃 �∆ℎ𝑠𝑢𝑏 𝑇=250𝐾 + 0.05𝑇 2 −3125�𝑑𝑇
=
𝑃 𝑅𝑇 2

When we integrate accordingly from T1 T2 and P1 P2, we get the following equation:

𝑃 1 1
ln �𝑃2 � ∗ 𝑅 = �−∆ℎ𝑠𝑢𝑏 𝑇=250𝐾 + 3125� �𝑇2 − 𝑇1� + 0.05(𝑑2 − 𝑑1)
1
The following assumptions are used to achieve the above equation:
• Specific volume of the vapor is much greater than the specific volume of the solid
𝑣𝑚𝑠 ≪ 𝑣𝑚𝑣 or 𝑣𝑚𝑠 ≈ 0
• The vapor acts as an ideal gas
Insert the given values for sublimation pressures and temperatures and solve for ∆hsubT=250K

∆ℎ𝑠𝑢𝑏 𝑇=250𝐾
kJ
= 13.6
mol

Now we can use the earlier developed path to find ∆hsubT=300K

kJ
∆ℎ𝑠𝑢𝑏 𝑇=300𝐾 = 13600 + 0.05(300)2 − 3125 = 15.0 mol
6.36
(a) Within the diamond phase. Gibbs energy is lower relative to the other phases of carbon.

(b) T ≈ 1200 [K], P ≈ 650 [kbar]

(c)
1 cm3 g cm3 m3
ν diamond = ⋅12 = 3.42 = 3.42 ×10−6
3.51 g mol mol mol
1 cm3 g cm3 m3
ν graphite = ⋅12 = 5.31 = 5.31×10 −6

2.26 g mol mol mol

T1 = 300 K, P1 = 25 kbar = 2.5×109 Pa

Since we assumed Δh to be constant,


Let T2 = 3000 K, P2 = 100 kbar = 1.0×1010 Pa

dP hd − hg
=
dT ( vd − vg ) T
hd − hg dT
dP = ⋅
vd − vg T
hd − hg T2
P2 − P1 = ⋅ ln
vd − vg T1
∆h 3000
75 ×108 Pa = 3
⋅ ln
m 300
( 3.42 − 5.31) ×10−6
mol
kJ
Δh = -6.20
mol

(d) Diamond has stronger bonds because Δh is negative, hg > hd.

(e) Set up a hypothetical path

Δh300K
g d

∫ cp,g dT ∫ cp,d dT
g d
ΔhT
∆hT = cp,g ( 300 − T ) + ∆h300K + cp,d (T − 300 )

Heat capacities,
J
c p , g = 8.5
mol ⋅ K
J
c p ,d = 6.1
mol ⋅ K

dP ∆hT 1
= ⋅
dT ∆v T
P2 T
1 2 2550 − 8.5T + ∆h300K + 6.1T − 1830
∫ dP = ∆v T∫
P1
T
dT
1

T
1 2 720 ∆h
∆P = ∫
∆v T1 T
− 2.4 + 300K dT
T

1 T T
= 720 ln 2 − 2.4 (T2 − T1 ) + ∆h300K ln 2
∆v T1 T1
∆P = 7.5 ×109 [ Pa ]
m3
∆v = −1.902 ×106
mol
T2
ln = 2.303
T1
T2 − T1 = 2700K

kJ
Δh 300K = -4.10
mol
6.37

dP ∆h vap
=
dT T ( viα − viβ )

RT
Assumptions: 1. Ideal gas: viv =
P
2. viv >> vil
3. constant ∆h vap

dP ∆h vap P
=
dT RT 2
P2 T2
dP ∆h vap dT
∫ P = T∫1 R T 2
P1

P2 ∆h vap 1 1
ln =− −
P1 R T2 T1
P2 −20,500 1 1
ln = −
1 atm 8.314 313 244
P2 = 9.1 atm
6.39
RT aP
P= −
v T

in terms of v we get
RT 2
v=
P(T + a )

Starting with the Clapeyron equation

dP ∆hvap
=
dT T (v v − vl )

we can assume that v v >> v l and substituting the equation of state in terms of v we get
dP ∆hvap P(T + a )
=
dT RT 3

Rearranging and integrating gives


20 1 ∆hvap 301.5 1 a ∆hvap
∫1 PdP = R ∫207.3 T 2 + T 3 dT → 3.0 = R (0.00166)
and finally
kJ
∆hvap = 15.0
mol
6.40
(a) Using the Gibbs-Helmholz equation gives:
g − gs
d d
T hd − hn (hd − hn )298 − (cP,d − cP,n )(298) (cP,d − cP,n )
=− 2 =− +
dT T T2 T

gd − gs
T
g − gs T (hd − hn )298 − (cP,d − cP,n )(298) (cP,d − cP,n )
∫ d d =− ∫ + dT
298 T T2 T
(gd −gs ) 298
298

298
(g d − g s )
gd − gs
T

298
[
= (hd − hn )
298
− (cP,d − cP,n )(298) ]T1 − 2981 − (c P,d − cP,n )ln
T
298

gd − gs = (gd − g s )
T
298
298 298
[
+ (hd − hn ) − (cP,d − cP,n )(298) 1−
T
298
]
− (cP,d − cP,n )T ln
T
298
T
gd − gs = (hd − hn ) − (sd − ss ) T + (cP,d − cP,n )(T − 298) − (cP,d − cP,n )T ln
298 298
298

(b) Alternative - Fundamental property relation to find an equation for gd-gn:

298 T
cP,n cP,d T
sd − sn = ∫ dT + (sd − sn ) + ∫ dT = (sd − sn ) + (cP,d − cP,n)ln
298 298
(1)
T T 298
T 298
Using the fundamental property relation and Equation (1) gives:
d (g d − gn ) T
= −(sd − sn ) = − (sd − sn ) + (cP,d − cP,n )ln
298
dT 298

gd −gn T
T
∫ d (g d − g n ) = − ∫ (sd − sn )298 + (cP,d − cP,n )ln 298 dT
298
(gd −gn ) 298

T
T
T + (cP,d − cP,n)T ln − (cP,d − cP,n )T
298 298
(g d − gn ) − (g d − g n ) = − (sd − sn )
298 298

T
g d − g n = (hd − hn ) − (s d − s s ) T − (c P ,d − c P ,n )T ln + (c P ,d − c P ,n )(T − 298)
298 298

298

For parts C, D & E, it is useful to make a plot of the g 𝑑 − g 𝑠 and interpret the plot.
6.41
Calculate vA, vB, v, VA, VB, and V from the ideal gas law:

RT
vA = = 0.05 m 3 / mol V A = n A v A = 0 .1 m 3
P
RT
vB = = 0.05 m 3 / mol V B = n B v B = 0.15 m 3
P
RT
v = = 0.05 m 3 / mol V = ntot v = 0.25 m 3
P

We calculate the partial molar volumes as follows

∂V ∂
VA = = (n A + n B ) RT =
RT
= 0.05 m 3 / mol
∂n A T , P, n ∂n A P P
B

∂V ∂
VB = = (n A + n B ) RT =
RT
= 0.05 m 3 / mol
∂n B T , P, n ∂n B P P
A

For remaining quantities

∆Vmix = n A (V A − v A ) + n B (V B − v B )
∆Vmix = 2(0.05 − 0.05) + 3(0.05 − 0.05) = 0

∆v mix = x A (V A − v A ) + x B (V B − v B )
∆v mix = 0
6.42
(a)
For a pure species property

v a = v( y a = 1)

Substitution yields

cm 3
v a = 100(1) + 80(0 ) + 2.5(1)(0 ) = 100
mol

(b)
From the definition:

∂V
Va =
∂na n ,T , P
b

We can find V by multiplying the given expression for molar volume by the total number of
moles.

y y n n
V = (na + nb ) 100 ya + 80 yb + 2.5 a b = 100na + 80nb + 2.5 a b
y a yb na + nb

Differentiating with respect to na we get,

∂ n n nb na nb
Va = 100na + 80nb + 2.5 a b = 100 + 2.5 − 2 .5
∂na na + nb n
b
na + nb (na + nb )2
so

Va = 100 + 2.5 yb (1 − ya ) = 100 + 2.5 yb2

To find the molar volume at infinite dilution, we can use the following relation

Va∞ = lim Va
ya →0

cm 3
∴Va∞ = 102.5
mol
(c)
Since species A contributes more to a mixture than to a pure species,

∆v mix > 0

Note: The Gibbs-Duhem equation says that species B also contributes more.
6.43 Calculate mole fractions:

n1 1 [mol]
y1 = = = 0.2 y 2 = 0.4 y3 = 0.4
ntot 5 [mol]

Calculate v.
Obtain an expression for v:

RT A
v= 1+ P2 ( y1 − y 2 ) + B
P RT RT

Substitute values:

cm 3 ⋅ atm
82.06 (500 [K ])
v=
mol ⋅ K
50 [atm]
[1 + (50 ) [− 9.0 ×10
2 −5
(0.2 − 0.4) + 3.0 × 10 − 5 ]]
cm 3
v = 919.0
mol

Calculate V.

V = ntot v
cm 3
V = (5 [mol]) 919.0
mol

V = 4595 cm 3[ ]
Calculate v1.
The value of v1 can be found by substituting y1=1 into the expression for v1.

cm 3 ⋅ atm
82.06 (500 [K ])
v1 =
mol ⋅ K
50 [atm]
[1 + (50 ) [− 9.0 ×10
2 −5
]
(1 − 0) + 3.0 × 10 − 5 ]
cm 3
v1 = 698
mol
Calculate v2.

cm 3 ⋅ atm
82.06 (500 [K ])
v2 =
mol ⋅ K
50 [atm]
[1 + (50 ) [− 9.0 ×10
2 −5
(0 − 1) + 3.0 × 10 − 5 ] ]
cm 3
v2 = 1067
mol

Calculate v3.

cm 3 ⋅ atm
82.06 (500 [K ])
v3 =
mol ⋅ K
50 [atm]
[1 + (50 ) [3.0 ×10 ]
2 −5

cm 3
v3 = 882
mol

Calculate V1 .
From the definition:

∂V ∂ (nv )
V1 = =
∂n1 n , n ,T , P ∂n1 n , n ,T , P
2 3 2 3

We can substitute the expression for V into this derivative and use the fact that
ntot = n1 + n2 + n3 to obtain

∂ RT A
V1 = (n1 + n2 + n3 ) + P 2 (n1 − n2 ) + B (n1 + n2 + n3 )
∂n1 P RT RT n 2 , n 3 ,T , P

Differentiating we get

RT A B
V1 = 1+ P2 +
P RT RT

Substitute values:
cm 3 ⋅ atm
82.06 (500 [K ])
V1 =
mol ⋅ K
50 [atm]
[1 + (50 ) [− 9 ×10
2 −5
]
+ 3 × 10 − 5 V1 = 697.5
cm 3
mol
6.44

(a)
By definition:

∂H
Ha ≡
∂na T , P , nb , n c

h = −5,000 xa − 3,000 xb − 2,200 xc − 500 xa xb xc [J/mol]

n = na + nb + nc

na nbnc
H = nh = −5,000na − 3,000nb − 2,200nc − 500
(na + nb + nc )2

∂H nbn c 2na nbnc


= −5,000 − 500 −
∂ na T ,P,nb ,nc (na + n b + nc )2 (na + nb + n c )3

∂H
Ha = = −5,000 − 500xb x c (1− 2xa ) [J/mol]
∂na T ,P,nb ,nc

(b)
1
xa = xb = xc =
3

Ha = −5,018.5 [J/mol]

(c)
xa = 1 , xb = xc = 0

Ha = −5,000 [J/mol]

(d)
xb = 1 , xa = xc = 0

Hb = hb = −3,000 [J/mol]
6.45
Let the subscript “1” designate CO2, and “2” designate propane. To calculate the partial molar
volumes, the following formulas will be used:

dv
V1 = v − y 2
dy 2
v = y1V1 + y 2V2

Expressions can’t be obtained for the molar volume with the van der Waals EOS; therefore, the
problem will be solved graphically. First, obtain an expression for the pressure that contains the
mole fractions of CO2 and propane:

a mix = y12 a1 + 2 y1 y 2 a1a 2 + y 22 a 2


bmix = y1b1 + y 2 b2

RT y12 a1 + 2 y1 y 2 a1a 2 + y 22 a 2
P= −
v − ( y1b1 + y 2 b2 ) v2

Solve for a and b using data from the appendices.

J ⋅ m3 mol
a1 = 0.366 b1 = 4.29 × 10 − 5
mol 2
m3
J ⋅ m3 mol
a 2 = 0.941 b2 = 9.06 × 10 − 5
mol 2 m3

Now we can create a spreadsheet with the following headings:

y1 y2 amix bmix v

The last column contains the molar volumes obtained by solving the van der Waals equation
with the spreadsheet’s solver function. After the table is completed, we create the following
graph.
v vs. y2

1.48E-03

1.46E-03

1.44E-03

1.42E-03
v (m 3 mol -1)

1.40E-03

1.38E-03

1.36E-03
y = -0.00008x 2 - 0.00008x + 0.00147
1.34E-03
R2 = 0.99946
1.32E-03

1.30E-03
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
y2 (Mole Fraction)

From the line of best fit, we find

v = −8 × 10 − 5 y 22 − 8 × 10 − 5 y 2 + 0.00147

Therefore,

dv
= −1.6 × 10 − 4 y 2 − 8 × 10 − 5
dy 2

and

(
V1 = v − y 2 − 1.6 × 10 −4 y 2 − 8 × 10 −5 )
We can find the partial molar volume of propane from the following relationship

v = y1V1 + y 2V2
v − y1V1
V2 =
y2

Tabulate the values of the partial molar volumes in the spreadsheet and create the following
graph
Partial Molar Volumes as a Function of Carbon Dioxide Mole
Fraction
0.0016
V1
V2
0.00155
mol -1)

0.0015
3
Partial Molar Volume (m

0.00145

0.0014

0.00135

0.0013

0.00125
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
y1 (CO2 mole fraction)
6.46
(a)
kJ
ga = 40
mol

dg
Ga = g − x b
dx b
dg
= 40 − 60 + RT (− ln xa − 1 + ln x b + 1) + 5x a − 5xb
dx b
Ga = −40xa − 60x b + RT (xa ln x a + x b ln xb ) + 5xa x b
− x b[40 − 60 + RT (− ln xa − 1 + ln x b + 1) + 5x a − 5xb ]

Ga = −40(xa + xb ) + RT (xa + xb ) ln x a + 5xb2

Ga = −40 + RT ln x a + 5xb2
8.314(300) kJ kJ
Ga = −40 + ln 0.2 + 5(0.64) = −40.8
1000 mol mol


Ga = −∞

∆Gmix = n(g − x a ga − xb gb )
g − (xa ga + x bgb ) = RT (x a ln xa + xb ln x b ) + 5x a xb

∆Gmix = nT [RT (x a ln xa + xb ln x b ) + 5xa x b ] = −2.2 kJ

(b)

∆gmix = ∆hmix + T∆smix

Assume the entropy of mixing is ideal:

∆hmix = 5x a xb > 0

so
∆h = ∆hmix + ∆hsensibleheat = 0

so
∆hsensibleheat < 0 and T goes down
6.47

To find V1 and V2 , we can read values directly from the graphs. Calculate mole fractions

1
x1 = = 0.2
5

At x1 = 0.2 ,

cm 3
V1 = 46.5
mol
cm 3
V2 = 69.8
mol

The following relationships are employed to calculate the molar volumes of pure species

v1 = lim V1
x1 →1
v 2 = lim V2 = lim V2
x 2 →1 x1 → 0

From the graph

cm 3
v1 = 50
mol
cm 3
v2 = 70
mol

Therefore,

[ ]
V1 = 50 cm 3
V2 = 280 [cm ] 3

To calculate the total volume, we can use

V = n1V1 + n2V2

Substituting the values, we find

V = 1(46.5) + 4(69.8) = 325.7 cm3[ ]


Therefore

V 325.7
v= =
ntot 1+ 4
cm 3
v = 65.14
mol

and the change in volume.

∆Vmix = V − (V1 + V2 ) = 325.7 − (50 + 280)

[ ]
∆Vmix = −4.3 cm3
6.48
(a)
Expression for ∆hmix :

∆hmix = ∑ X i H i −∑ X i hi =(X Cd H Cd + X Sn H Sn ) − ( X Cd hCd + X Sn hSn )

Multiply both sides by the total number of moles

∆H mix = (nCd H Cd + n Sn H Sn ) − (nCd hCd + n Sn hSn )

Therefore,

∂∆H mix
(∆H mix )Cd = = H Cd − hCd
∂nCd n ,T , P
Sn

(b)
We can show by repeating Part (a) for Sn that

(∆H mix )Sn = H Sn − hSn


and

(∆H mix )Cd = ∆hmix − X Sn d∆hmix


dX Sn

(∆H mix )Sn = ∆hmix − X Cd d∆hmix


dX Cd

Since,
∆hmix = 13000 X Cd X Sn

We get,

d∆hmix d
= [13000 X Cd X Sn ] = 13000( X Cd − X Sn )
dX Sn dX Sn

d∆hmix d
= [13000 X Cd X Sn ] = 13000( X Sn − X Cd )
dX Cd dX Cd

Therefore, for 3 moles of cadmium and 2 moles of tin at 500 ºC:


H Cd − hCd = (∆H mix )Cd = 13000 X Cd X Sn − X Sn13000( X Cd − X Sn ) = 13000 X Sn
2

J
H Cd − hCd = (∆H mix )Cd = 2080
mol

and
J
H Sn − hSn = (∆H mix )Sn = 13000 X Cd
2
= 4680
mol
(c)
Gibbs-Duhem equation:

nCd d (∆H mix )Cd + n Sn d (∆H mix )Sn = 0

Differentiate with respect to XCd:

d (∆H mix )Cd d (∆H mix )Sn


nCd + n Sn =0
dxCd dxCd

where

d (∆H mix )Cd


= 26000 X Sn = −26000 + 26000 X Cd
dX Cd
d (∆H mix )Sn
= 26000 X Cd
dX Sn

Therefore,

d (∆H mix )Cd d (∆H mix )Sn


nCd + nSn = xCd (ntot )(− 26000 + 26000 xCd ) + (1 − xCd )(ntot )26000 xCd
dxCd dxCd

Inspection of the above expression reveals that

d (∆H mix )Cd d (∆H mix )Sn


nCd + n Sn =0
dxCd dxCd

(d)
A graphical solution can be found using the tangent-slope method discussed on pages 285-287:

A plot of a line tangent to the enthalpy of mixing curve at XCd = 0.6, is given below:
Heat of mixin g in cadmium (Cd )-Tin (Sn) s ystem
6000

5400

4800

4200

3600
mol
J

data
3000
∆ hmix

2400

1800

1200

600

0
0 0 .2 0 .4 0 .6 0 .8 1

fit to: xCd


J
∆ hmix = 13, 000 xCd x Sn
mol

The intercepts give the respective partial molar quantities as follows:

J
H Cd − hCd ≅ 2050
mol
J
H Sn − hSn ≅ 4800
mol

The values using the graphical method are reasonably close to the analytical method.
6.49
Energy balance

∆H = 0 = nT ∆hmix + n1c p ,1 (Tout − Tin ) + n2 c p ,2 (Tout − Tin )

Find enthalpy of mixing for x2 – x1 = -0.5

J
∆hmix = Rx1 x2 −190.0 + 214.7 ( x2 − x1 ) − 419.4 ( x2 − x1 ) + 383.3 ( x2 − x1 ) − 235.4 ( x2 − x1 )
2 3 4
= −724
mol

Find Tout - Tin

∆hmix
(Tout − Tin ) = − = 8.5
y1c p ,1 + y2 c p ,2

So
Tout = 303 K
6.50
First draw a schematic of the process:

Stream A 1 = H2O
nA = 1 mol/s 2 = EtOH
x1 = 1; x 2 = 0 Q=0
TA = 298 K

Stream C
nC = 2 mol/s
Stream B xx11 == 0.75;
0.25; xx22 ==0.25
0.75
nB = 1 mol/s TC = ???
x1 = 0.5; x 2 = 0.5
TB = 298 K

Now refine the actual mechanisms of mixing. We need to “unmix” the mixture in Stream B into
pure components, and then mix those components with the pure water in Stream A. Below is a
diagram of the actual mechanism of mixing in the figure above. The yellow box represents the
“unmixing” step of ethanol/water to pure species.

Pure EtOH (n 2 = 0.5 mol/s)


“Unmix” Mix
H2O/EtOH H2O/EtOH
“Mix” H2O+H2O
−∆H mix,B Pure H 2 O Pure H 2 O ∆H mix,C
∆H mix, A
Stream B (n1 = 0.5 mol/s) (n1 = 1.5 mol/s) Stream C
nB = 1 mol/s nC = 2 mol/s
xx11 ==0.75; = 0.75
0.25;x2x=2 0.25
x1 = 0.5; x 2 = 0.5
TB = 298K Stream A TC = ???

nA = 1 mol/s
x1 = 1; x 2 = 0 1 = H2O
2 = EtOH
TA = 298K

Calculation of the enthalpy changes of mixing is fairly straightforward:

J
∆hmix , A = 0 [ ] (no enthalpy change for mixing of water with water)
mol A
For the mixtures, we will need to use the given relation to determine the enthalpy change of
mixing. First, look at what Δhmix,B would be if we were mixing (instead of unmixing) the ethanol
and water:

−190 + 214.7 ( x2, B − x1, B ) − 419.4 ( x2, B − x1, B ) +


2
J
∆hmix , B = Rx1, B x2, B [ ]
383.3 ( x2, B − x1, B ) − 235.4 ( x2, B − x1, B ) mol
3 4

J
∆hmix , B = −47.51R [ ]
mol B

And for the mixing of the pure ethanol and water into Stream C,

−190 + 214.7 ( x2,C − x1,C ) − 419.4 ( x2,C − x1,C ) +


2
J
∆hmix ,C = Rx1,C x2,C [ ]
383.3 ( x2,C − x1,C ) − 235.4 ( x2,C − x1,C ) mol
3 4

J
∆hmix ,C = −87.1R [ ]
mol C

The overall enthalpy change for the process then is:

∆H mix = ∆H mix , A + ( −∆H mix , B ) + ∆H mix ,C , where ∆H mix ,i = ni ∆hmix ,i

∆H mix = −126.69 R

Note that the mixing step for Stream B is “reversed” to account for the “unmixing” process.

Now write the energy balance for the components in this adiabatic process:

0 = ∆H = n1∆h1 + n2 ∆h2 + ∆H mix

Recall that we can write the molar enthalpy change of a stream as ∆h = nc p ∆T . Substituting this
into the above equation gives an expression with only Tc as an unknown (you can find liquid-
phase heat capacities in Appendix A).

0 = n1 cp ,1 (Tc − 298 ) + n2 cp ,2 (Tc − 298 ) + ∆H mix

Subsituting the known values for the constants and outlet molar flow rate into the above
equation, we find:

0 = 1.5 ( 9.069 R )(Tc − 298 ) + 0.5 (13.592 R )(Tc − 298 ) + ( −126.69 R )

Dividing through by R and solving for Tc provides the output temperature:


0 = 1.5 ( 9.069 )(Tc − 298 ) + 0.5 (13.592 )(Tc − 298 ) + ( −126.69 )

0 = 20.3995Tc − 6205.741

Tc = 304.2 K
6.51

∆g mix = RT [ xa ln xa + xb ln xb ] + 1000 xa xb
∆Gmix = ( na + nb ) ∆g mix
na nb nn
= RT na ln + nb ln + 1000 a b
na + nb na + nb na + nb

∂∆Gmix
( ∆G ) mix
a
=
∂na
= G a − ga
T , P , nb

na 1 1 nb nb na nb
= RT na ln + na − − + 1000 −
na + nb na na + nb na + nb na + nb ( na + nb )2

( ∆G ) mix
a
= RT ln xa + 1000 xb 2

(a) xa = 1, xb = 0 G a − ga = 0
J
(b) xa = 0.4, xb = 0.6 G a − g a = −1,910
mol
(c) xa = 0 G a − g a = −∞
6.52
(a)
We can write the extensive enthalpy change as:

∆𝐻𝑚𝑚𝑚 = 𝑛𝑇 ∆ℎ𝑚𝑚𝑚
where the total number of moles is 𝑛𝑇 = 𝑛1 + 𝑛2 = 5 [mol]. The molar enthalpy of mixing is
defined by the difference in the enthalpies of the pure starting species and the final mixture:

∆ℎ𝑚𝑚𝑚 = ℎ − (𝑥1 ℎ1 + 𝑥2 ℎ2 )

(Pure species 1 ⇒ x2 = 0) J
ℎ1 = 275 + 75𝑑 � �
mol

(Pure species 2 ⇒ x1 = 0) J
ℎ2 = 125 + 50𝑑 � �
mol
J
ℎ = 𝑥1 (275 + 75𝑑) + 𝑥2 (125 + 50𝑑) + 750𝑥1 𝑥2 � �
mol
Substituting these values into the expression for ∆ℎ𝑚𝑚𝑚 and simplifying, we find that:

J
∆ℎ𝑚𝑚𝑚 = 750𝑥1 𝑥2 � �
mol
For the mixture, it is easy to find that x1 = 0.4, and x2 = 0.6. Substituting into the above equation,

J J
∆ℎ𝑚𝑚𝑚 = 750(0.4)(0.6) � � = 180 � �
mol mol
Finally, calculating the extensive total enthalpy of the mixed solution,

∆𝐻𝑚𝑚𝑚 = 𝑛𝑇 ∆ℎ𝑚𝑚𝑚 = 900 J


(b)
Write the energy balance for the process (recall that it is adiabatic and at constant pressure, so
∆𝐻 = 0):

∆𝐻 = 0 = 𝑛𝐴̇ ℎ𝐴 + 𝑛𝐵̇ ℎ𝐵 − 𝑛̇ 𝑜𝑢𝑡 ℎ𝑜𝑢𝑡


Writing the terms individually from the information in part A, with the pure species in each
stream:

mol J 𝐽
𝑛𝐴̇ ℎ𝐴 = 2 � � (275 + 75𝑑𝑚𝑠 ) � � = 44500 � �
s mol 𝑠

mol J 𝐽
𝑛𝐵̇ ℎ𝐵 = 3 � � (125 + 50𝑑𝑚𝑠 ) � � = 44325 � �
s mol 𝑠
and for the outlet stream:

mol J
𝑛̇ 𝑜𝑢𝑡 ℎ𝑜𝑢𝑡 = 5 � � {0.4(275 + 75𝑑𝑜𝑢𝑡 ) + 0.6(125 + 50𝑑𝑜𝑢𝑡 ) + 750(0.4)(0.6)} � �
s mol

J
𝑛̇ 𝑜𝑢𝑡 ℎ𝑜𝑢𝑡 = 1825 + 300𝑑𝑜𝑢𝑡 � �
s
Substituting into the energy balance, 𝑛𝐴̇ ℎ𝐴 + 𝑛𝐵̇ ℎ𝐵 = 𝑛̇ 𝑜𝑢𝑡 ℎ𝑜𝑢𝑡
87000 = 300𝑑𝑜𝑢𝑡
𝑑𝑜𝑢𝑡 = 290K

(b) Alternate Method


Hypothetical Path:
∆𝐻𝑚𝑚𝑚
Tout

∆𝐻𝑠𝑠𝑠𝑠

∆𝐻 = 0

Tin

Pure 1, Mixed 1, 2
Pure 2

∆𝐻 = 0 = ∆𝐻𝑚𝑚𝑚 + ∆𝐻𝑠𝑠𝑠𝑠
∆𝐻𝑚𝑚𝑚 is calculated the same as in part (a) but with molar flow rate instead of just moles, so
𝐽
∆𝐻𝑚𝑚𝑚 = 900
𝑠
𝑇𝑜𝑢𝑡
∆𝐻𝑠𝑠𝑠𝑠 = � �𝑐𝑃,1 𝑛̇ 1 + 𝑐𝑃,2 𝑛̇ 2 � 𝑑𝑑
𝑇𝑖𝑛

𝑑ℎ𝑚
𝑐𝑃,𝑚 = � �
𝑑𝑑 𝑃
Using the given enthalpy expression, we can find cP1 and cP2

𝑑ℎ1 𝑑 J
� � = �275 + 75𝑑 � ��
𝑑𝑑 𝑃 𝑑𝑑 mol

J
𝑐𝑃,1 = 75 � �
mol∙K

𝑑ℎ2 𝑑 J
� � = �125 + 50𝑑 � ��
𝑑𝑑 𝑃 𝑑𝑑 mol

J
𝑐𝑃,2 = 50 � �
mol∙K
𝑇𝑜𝑢𝑡
𝐽
∆𝐻𝑠𝑠𝑠𝑠 = � �𝑐𝑃,1 𝑛̇ 1 + 𝑐𝑃,2 𝑛̇ 2 � 𝑑𝑑 = 300(𝑑𝑜𝑢𝑡 − 293) � �
𝑇𝑖𝑛 𝑠
If we return to the energy balance and use the expressions for ∆𝐻𝑚𝑚𝑚 and ∆𝐻𝑠𝑠𝑠𝑠

∆𝐻𝑚𝑚𝑚 = −∆𝐻𝑠𝑠𝑠𝑠

900 = −300(𝑑𝑜𝑢𝑡 − 293)

𝑑𝑜𝑢𝑡 = 290 K
6.53

V1 ≠ v1 except for pure Graphical Analysis of Molar Volume of Ethanol - Ethylene Glycol Mixtures

solutions (x1 = 1.0). Be 59.0

careful! 58.5 V1

58.0

0.8
57.5

A: For x1 = 0.8 : 57.0

v (cm /mol)
3 56.5

cm3
V1 ≈ 58.5 56.0

mol 55.5

55.0

54.5

54.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
x1 (ethanol)

Graphical Analysis of Molar Volume of Ethanol - Ethylene Glycol Mixtures

59.0

58.5

B: For x1 = 0.4 : 58.0


V1
1
57.5

57.0

cm3
v (cm /mol)

V1 ≈ 57.9 56.5
3

mol 0.4

56.0

55.5

55.0

54.5

54.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
x1 (ethanol)
C: For x1 → 0: Graphical Analysis of Molar Volume of Ethanol - Ethylene Glycol Mixtures

59.0

58.5
cm3
V1∞ ≈ 56.5 58.0
mol
57.5

57.0
v (cm /mol)


56.5 V1
3

56.0

0.0
55.5

55.0

54.5

54.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
x1 (ethanol)
6.54
(a) Before you fire up Excel, take a look at the equation. How will we fit the given data to it?

First, consider the pure-species “mixtures” at x1 = 0 and x1 = 1. Substitution of the data points
and compositions into the equation easily lets us find the values of the constants a and b.

• At x1 = 1 ⇒ x2 = 0, and thus, 58.591 = a + b ( 0 ) + c (1)( 0 ) = a


• At x1 = 0 ⇒ x2 = 1, and 55.828 = a + b (1) + c ( 0 )(1) = a + b = 58.591 + b

These two points give us a = 58.591 cm3/mol, and b = -2.763 cm3/mol.

How should we find the remaining unknown, c? One obvious answer is to choose a point from
the experimental (say, x1 = 0.5499) and solve for c. But, what if that point is a little off? Our
value for c will be off, too. Maybe we can get a better answer by finding c for each measured
point, and then taking the average to be the real c. But the best way is to use the least-squares
method and find the “best-fit” value for c.

In the least-squares method, we seek a value for the parameter, c, that minimizes the difference
between the observed value (vobs) and its calculated counterpart, vcalc. In order to prevent errors
of opposite-sign from canceling each other, and to emphasize large errors, we will minimize the
squares of these differences. That is, we are looking for a value of c that minimizes the sum of
the squares of the errors (s.s.e.) in:

s.s.e. = ∑ ( vobs − vcalc )


2

Minimizing a value is easy to accomplish with the Excel Solver add-in. First, set up a
spreadsheet as shown below, supplying a value of zero (or anything you want) for c :

x 1 (ethanol) x 2 (glycol) v exp (cm3/mol) v calc* (cm3/mol) (v e - v c ) 2


0 1 55.828 55.828 0.0000
0.1092 0.8908 55.902 56.130 0.0519 * v calc = a + bx 2 + cx 1x 2
0.2244 0.7756 56.06 56.448 0.1506
0.3321 0.6679 56.245 56.746 0.2506
0.4393 0.5607 56.513 57.042 0.2796
0.5499 0.4501 56.866 57.347 0.2317
0.6529 0.3471 57.178 57.632 0.2061 a = 58.591 (from x 1 = 1)
0.7818 0.2182 57.621 57.988 0.1348 b = -2.763 (from x 1 = 0)
0.8686 0.1314 58.004 58.228 0.0501 c = 0.000 (least-squares)
1 0 58.591 58.591 0.0000
Σ(v e - v c ) 2 = 1.3553

Now, use the Solver to minimize the sum of the squares of the error by changing the value of c.
x 1 (ethanol) x 2 (glycol) v exp (cm3/mol) v calc* (cm3/mol) (v e - v c ) 2
0 1 55.828 55.828 0.0000
0.1092 0.8908 55.902 55.925 0.0005 * v calc = a + bx 2 + cx 1x 2
0.2244 0.7756 56.06 56.081 0.0005
0.3321 0.6679 56.245 56.278 0.0011
0.4393 0.5607 56.513 56.523 0.0001
0.5499 0.4501 56.866 56.826 0.0016
0.6529 0.3471 57.178 57.154 0.0006 a = 58.591 (from x 1 = 1)
0.7818 0.2182 57.621 57.629 0.0001 b = -2.763 (from x 1 = 0)
0.8686 0.1314 58.004 57.987 0.0003 c = -2.107 (least-squares)
1 0 58.591 58.591 0.0000
Σ(v e - v c ) 2 = 0.0047

Notice that the sum of the squares of the errors does not go to zero. This tells us that there is
some scatter in our experimental data. Look at the error for the point x1 = 0.5499 – it’s a good
thing we didn’t choose to use the c computed only from it!

So, the “best-fit” equation to describe the molar volume of the mixture is:

cm3
v = 58.591 − 2.763 x2 − 2.107 x1 x2
mol

To find the partial molar volume of ethanol (species 1), we must rewrite the intensive v for the
mixture in terms of the extensive property V. First substitute xi = ni / nT,

n nn cm3
v = 58.591 − 2.763 2 − 2.107 1 2 2 ,
nT nT mol

then, multiply by the total number of moles to find the total volume, V :

n1n2 cm3
V = nT v = 58.591( n1 + n2 ) − 2.763n2 − 2.107
( n1 + n2 ) mol

Now evaluate the derivative with respect to n1 and simplify:

∂V n2 n1n2 n22
V1 ≡ = 58.591 − 2.107 + 2.107 = 58.591 − 2.107
∂n1 n1 + n2 ( n1 + n2 ) ( n1 + n2 )
2 2
T , P , n2

And, substituting for mole fractions,

V1 = 58.591 − 2.107 x22 = 58.591 − 2.107 (1 − x1 )


2

(b) Now, evaluate the equation for the partial molar volume of ethanol at each of the points:
cm3
V1, x1 =0.8 = 58.51
mol
cm3
V1, x1 =0.4 = 57.83
mol
cm3
V1, x1 =0.8 = 56.48
mol

(c) How do these values compare with the values from the graphical method?

Compute the relative error for each graphical method value vs. the best-fit analytical value. To
do this, we define the relative error as

observed - actual
error =
actual

Here, we assume that the “actual” value is the one calculated from the best-fit analytical method.

Performing the arithmetic, we find that the error is quite small, as would be expected.

58.5 − 58.51
errorx1 =0.8 = = −0.02%
58.51
57.9 − 57.83
errorx1 =0.4 = = +0.12%
57.83
56.5 − 56.48
errorx1 =0 = = +0.04%
56.48

Of course, the deviation of your values from the analytical solution is more a function of how
steady your eye and hand are, than a mathematical one. The extremely close tolerance in this
example is due to the fact that Excel was used to compute the tangent line intercepts at each
point. Errors of a few percent wouldn’t be unreasonable for a hand-drawn graph.
6.55
(a)

∆𝑣𝑚𝑚𝑚 = −13.1𝑥1 𝑥2 − 2.25𝑥12 𝑥2

∆𝑉𝑚𝑚𝑚 = 𝑛𝑇 ∆𝑣𝑚𝑚𝑚 = −13.1𝑛𝑇 𝑥1 𝑥2 − 2.25𝑛𝑇 𝑥12 𝑥2

−13.1n1n2 2.25n12 n2
∆Vmix = −
n1 + n2 (n1 + n2 ) 2

∂∆Vmix
∆Vmix ,1 = V1 − v1 =
∂n1 T , P ,n

−13.1n2 13.1n1n2 4.5n1n2 4.5n12 n2


V1 − v1 = + − +
n1 + n2 (n1 + n2 ) 2 (n1 + n2 ) 2 (n1 + n2 )3

13.1n22 4.5n1n22
V1 − v1 = − −
(n1 + n2 ) 2 (n1 + n2 )3

V1 − v1 = −13.1x22 − 4.5 x1 x22

V1 = v1 − 13.1x22 − 4.5 x1 x22

From the density and molecular weight of H2SO4:

V1 = 53.7 − 13.1x22 − 4.5 x1 x22

∂∆Vmix
∆Vmix ,2 = V2 − v2 =
∂n2 T , P ,n

−13.1n1 13.1n1n2 2.25n12 4.5n12 n2


V2 − v2 = + − +
n1 + n2 (n1 + n2 ) 2 (n1 + n2 ) 2 (n1 + n2 )3

𝑉�2 − 𝑣2 = −13.1𝑥1 + 13.1𝑥1 𝑥2 − 2.25𝑥12 + 4.5𝑥12 𝑥2

V2 = v2 − 13.1x12 + 2.25 x12 ( x2 − x1 )

From Steam Tables


cm3
𝑣
�2 = 1.003
g

V2 = 18 − 13.1x12 + 2.25 x12 ( x2 − x1 )

Plotting these expressions gives:

60
Partial Molar Volume (cm3/mol)

50

V1bar
40
V2bar
30

20

10

0
0 0.2 0.4 0.6 0.8 1
x1

(b)

cm3
V2 ∞ = 2.65
mol
(c)
When one molecule of water is placed in liquid sulfuric acid, it takes up almost no volume; it fits
between the sulfuric acid molecules.
6.56
(a)

Stream a
n = 2 mol/s
x1 = 0.5, x2 = 0.5
Outlet
T = 75°C, P = 1 bar
Q=0 n = 5 mol/s
Stream b x1 = 0.8, x2 = 0.2
n = 3 mol/s
x1 = 1.0
T = 20°C, P = 1 bar

J
h = 1500 x1 − 800 x2 + ( 25.0 x1 + 35.0 x2 − 11.86 x1 x2 ) T
mol

Write the energy balance for the process (recall that it is adiabatic and at constant pressure, so
∆H = 0 ):

∆H = 0 = nA hA + nB hB − nout hout

Writing the terms individually from the information in part A, with the pure species in each
stream:

mol J
nA hA = 2 (1500 × 0.5) − 800 × 0.5 + ( 25.0 × 0.5 + 35.0 × 0.5 − 11.86 × 0.52 ) × 348
s mol
J
= 21,116
s
mol J
nB hB = 3 (1500 × 0.5) + ( 25.0 × 0.5) × 293
s mol
J
= 26,475
s
nout hout = nA hA + nB hB
= 21116 + 26475
J
= 47,591
s
mol J
nout hout = 5 (1500 × 0.8) − 800 × 0.2 + ( 25.0 × 0.8 + 35.0 × 0.2 − 11.86 × 0.8 × 0.2 ) × Tout
s mol

Solve for Tout,

Tout = 325 K

(b)
h = 1500 x1 − 800 x2 + ( 25.0 x1 + 35.0 x2 − 11.86 x1 x2 ) T
n1 n2 n1 n2 n1 n2
h = 1500 − 800 + 25.0 + 35.0 − 11.86 × T
n1 + n2 n1 + n2 n1 + n2 n1 + n2 n1 + n2 n1 + n2
n1 n n n n n
H = nT 1500 − 800 2 + 25.0 1 + 35.0 2 − 11.86 1 × 2 T
nT nT nT nT nT nT
n1n2
= 1500n1 − 800n2 + 25.0n1 + 35.0n2 − 11.86 T
n1 + n2

∂H n1n2 n2
H1 = = 1500 + 25.0T − 11.86 − + T
∂n1 ( n1 + n2 ) n1 + n2
2

1 1
= 1500 + 25.0 × 348 − 11.86 − + × 348
22 2
J
= 9, 200
mol

(c)
∂H n1n2 n2
H1 = = 1500 + 25.0T − 11.86 − T
∂n1 ( n1 + n2 ) n1 + n2
2

lim H1∞ = 1500 + ( 25.0 − 11.86 ) T


x1 → 0

J
= 6,100
mol
6.57

0 = ∆𝐻𝑚𝑚𝑚 + 𝐶𝑝 (300 − 𝑑1 )𝑛̇ 1

Insert Mole Fractions and solve for T


𝑚𝑜𝑙 𝑚𝑜𝑙 𝑚𝑜𝑙
0 = −833(0.4)(0.6)5 + 50 (300 − 𝑑1 )2
𝑠 𝑗∙𝐾 𝑠

𝑑1 = 290 𝐾
6.58
(a)

J
Use equation: G1 = −500 + 2,500 ln x1 + 833 x22
mol

J
For g1 take the value as x1->1 g1 = −500
mol

Apply the Gibbs-Duhem equation:

dG1 dG2
x1 + x2 =0
dx1 dx1

From above:

dG1 2,500
= − 1, 666 x2
dx1 x1

Into Gibbs-Duhem equation:

2,500 dG2
x1 − 1, 666 x2 + x2 =0
x1 dx1
Rearranging

dG2 2,500 2,500


=− + 1, 666 x1 = − + 1, 666 x1
dx1 x2 1 − x1

Integrating
G2 = 2,500 ln (1 − x1 ) + 833 x12 + C = 2,500 ln ( x2 ) + 833 x12 + C

At x1 = 0, G2 = −800

G2 = −800 + 2,500 ln ( x2 ) + 833 x12

g = x1G1 + x2G2
= −500 x1 + x1 2,500 ln x1 + 833 x1 x22 − 800 x2 + x2 2,500 ln ( x2 ) + 833 x2 x12
= −500 x1 − 800 x2 + 2,500 ( x1 ln x1 + x2 ln x2 ) + 833 x1 x2
(b)

Lower – the 833x22 suggests an endothermic process.


6.59
(a)

𝑣 = 20𝑥1 + 50𝑥2 + 6𝑥1 𝑥2 2

𝑐𝑚3
𝑣1 (𝑥1 = 1) = 20
𝑚𝑜𝑙
𝑐𝑚3
𝑉1 = 𝑛1 𝑣1 = 40
𝑚𝑜𝑙

(b)
𝜕𝑉
𝑉�1 = � �
𝜕𝑛1 𝑇,𝑃,𝑠2

6𝑛1 𝑛2 2
𝑉 = 𝑛𝑇 𝑣 = 20𝑛1 + 50𝑛2 +
(𝑛1 + 𝑛2 )2

12𝑛2 3 6𝑛2 2
𝑉�1 = 20 + −
(𝑛1 + 𝑛2 )3 (𝑛1 + 𝑛2 )2

𝑉�1 = 20 + 12𝑥2 3 − 6𝑥2 2

(c)

4 3 4 2

𝑉1 = 20 + 12 � � − 6 � �
6 6
𝑐𝑚3
𝑉1 = 20.9
𝑚𝑜𝑙
6.60
(a)

𝑛𝑐𝑢 = 15748 𝑚𝑜𝑙


𝑛𝐴𝑔 = 18553 𝑚𝑜𝑙

𝑥𝐶𝑢 = 0.46
𝑗
∆𝐻𝑚𝑚𝑚 = −5116
𝑚𝑜𝑙
Now find the total energy

𝑄 = 𝑛𝑐𝑢 �𝐶𝐶𝐶𝑢,𝑆 ∆𝑑1 + ∆ℎ𝑓𝑢𝑠,𝐶𝑢 � + 𝑛𝐴𝑔 �𝐶𝐶𝐴𝑔,𝑆 ∆𝑑2 + ∆ℎ𝑓𝑢𝑠,𝐴𝑔 + 𝐶𝐶𝐴𝑔,𝐿 ∆𝑑3 � + 𝑛𝑇 ∆𝐻𝑚𝑚𝑚

𝑄 = 1.44 ∗ 109 𝐽

Use the power given to find time


𝑄
𝑡= = 12610 𝑠 = 3.5 ℎ𝑟𝑠
𝑃
6.61
(a)

cm3 g cm3
vEtOH = 1.27 × 46 = 58.4
g mol mol

At xEtOH = 0.6

cm3 g cm3
VH 2O = 0.95 × 18 = 17.1
g mol mol

cm3 g cm3
VEtOH = 1.24 × 46 = 57.0
g mol mol

So

cm3
v = xH 2OVH 2O + xEtOH VEtOH = 41.1
mol

∞ cm3 g cm3
VETOH = 1.195 × 46 = 55
g mol mol

cm3
∆vmix = v − xH 2O vH 2O + xEtOH vEtOH = −1.2
mol

∆Vmix = −6 cm3

(b)
The Gibbs-Duhem equation
6.62

𝑊𝐸𝑡𝑂ℎ
𝑀𝑊𝐸𝑡𝑂ℎ
XEtOH = 𝑊𝐸𝑡𝑂ℎ 𝑊
+ 𝐻2𝑂
𝑀𝑊𝐸𝑡𝑂ℎ 𝑀𝑊𝐻2𝑂

WEtOH XEtOH VEtOH [cm3 /mol] VH 2O [cm3 /mol]


1 0.96 0.9 57.9 15.6
2 0 0 18
3 0.56 0.33 54.7 17.75

𝑐𝑚3
𝑣3 = 𝑋𝐸𝑡𝑂ℎ 𝑉�𝐸𝑡𝑂𝐻 + 𝑋𝐻2𝑂 𝑉�𝐻2𝑂 = 30.1 𝑚𝑜𝑙

𝑉
𝑛3 = 𝑣 = 66.5 𝑚𝑜𝑙𝑒𝑠
3

𝑛3,𝐸𝑡𝑂𝐻 = 𝑥3,𝐸𝑡𝑂ℎ 𝑛 = 22.1 𝑚𝑜𝑙

𝑛3,𝐻2𝑂 = 𝑥3,𝐻2𝑂 𝑛 = 44.4 𝑚𝑜𝑙

𝑛1,𝐸𝑡𝑂𝐻 = 𝑛3,𝐸𝑡𝑂ℎ = 22.1 𝑚𝑜𝑙


𝑠1,𝐸𝑡𝑂𝐻
𝑛1 = = 24.45 𝑚𝑜𝑙
𝑚1,𝐸𝑡𝑂ℎ

𝑛1,𝐻2𝑂 = 𝑛1 − 𝑛1,𝐸𝑡𝑂𝐻 = 2.37 𝑚𝑜𝑙


Lab Alcohol

𝑉1 = 𝑛1,𝐻2𝑂 𝑉�1,𝐻2𝑂 + 𝑛1,𝐸𝑡𝑂𝐻 𝑉�1,𝐸𝑡𝑂𝐻 = 1317 𝑐𝑚3

Pure Water

𝑛2,𝐻2𝑂 = 𝑛3,𝐻2𝑂 − 𝑛1,𝐻2𝑂 = 42.0 𝑚𝑜𝑙

𝑐𝑚3
𝑣2 = 18 𝑚𝑜𝑙

𝑉2 = 𝑛2 𝑣2 = 756.5 𝑐𝑚3
6.63
(a)
Using the tangent intercept method
0

-100

-200

-300
∆gmix [J/mol]

-400 J
G1 − g1 = −460
-500
mol

-600

-700

-800

J -900
G2 − g 2 = −980
mol
-1000
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x1

J
G1l − g1 = −460
mol
J
G1l = −460 + g1
mol

From the steam tables, at 40 oC:


kJ
gˆ1 = hˆ1 − Tsˆ1 = −11.7
kg
J
g1 = −210.7
mol
J
G1l = −670.7
mol
(b)
At equilibrium
J
G1v = G1l = −670.7
mol
6.64

∆g mix = RT [ xa ln xa + xb ln xb ]b
∆Gmix = ( na + nb ) ∆g mix
na nb
= RT na ln + nb ln
na + nb na + nb

∂∆Gmix
( ∆G ) mix
a
=
∂na
= G a − ga
T , P , nb

na 1 1 nb
= RT na ln + na − −
na + nb na na + nb na + nb
G a − g a = RT ln xa
G a = RT ln xa + g a
(a) ya = 1, yb = 0
G a − ga = 0
kJ
G a = g a = −25
mol
kJ
g = g a = −25
mol
(b) ya = 0.5, yb = 0.5
kJ
G a = RT ln xa + g a = −26.7
mol
kJ
G b = RT ln xb + g b = −41.7
mol
kJ
g = ya G a + yb G b = −34.2
mol
(c) ya = 0
G a = −∞
kJ
g = gb = −40
mol
6.65
(a)
It will feel warm. Since the pure partial molar volumes are less than the pure species molar
volumes, the molecules get closer together, leading to greater attractive interactions. The
temperature goes up.

(b)

V1 = 175.8 cm3

cm3
v1 = 58.6
mol

cm3
v2 = 55.8
mol

V = n1V1 + n2 V2 = 230.04 cm3

V cm3
v= = 57.51
nT mol

∆Vmix = V − ( n1v1 + n2 v2 ) = −1.57 cm3

cm3
∆vmix = −0.4
mol

cm3
V1∞ = 56.519
mol
6.66
(a)
Let species 1 represent HCl and species 2 represent H2O. An expression for the enthalpy of the
solution is

h = x1h1 + x 2 h2 + ∆hmix

which can be written


~
h = x1h1 + x2 h2 + x1∆hs

Therefore,
~
H = n1h1 + n2 h2 + n1∆hs

To use the heat of solution data in Table 6.1, we need to determine the values of n1 and n2
consistent with the convention used in the table. As seen in Example 6.6,

n1 1
x1 = =
(n1 + n2 ) 1 + n
For this problem

x1 = 0.2

Therefore,

n1 = 1
n2 = n = 4

Now we can find expressions for the partial molar enthalpies.

∂H
H H 2O = H 2 =
∂n2 n ,T , P
1
~
d∆hs
H H 2 O = H 2 = h2 + n1
dn2
~
d∆hs
∴ H H 2 O − hH 2 O = H 2 − h2 = n1
dn2

Using the data in Table 6.1 for n = 4 ,


~ J
∆hs = −61,204
mol solute
J J
~ ~ ~ − 64049 − (− )56852
d∆hs ∆hs (n = 5) − ∆hs (n = 3) mol solute mol solute
≅ =
dn2 (5 [mol] − 3 [mol]) (5 [mol] − 3 [mol])
~
d∆hs J
= −3598.5
dn2 mol ⋅ mol solute

Therefore,

J J
H H 2 O − hH 2 O = (1 [mol solute]) − 3598.5 = −3599
mol ⋅ mol solute mol

Calculate H HCl − hHCl

H HCl − hHCl =
(
∆hmix − x H 2 O H H 2 O − hH 2 O ) = xHCl ∆h~s − xH O (H H O − hH O )
2 2 2

x HCl x HCl

J J
0.2 − 61204 − 0.8 − 3599
mol mol J
∴ H HCl − hHCl = = −46808
0.2 mol

(b)
For n1 = 2 and n2 = 80 ,

n1 + n2 82
n= −1 = − 1 = 40
n1 2

The new values for the number of moles consistent with Table 6.1

n1 = 1 [mol]
n2 = 40 [mol]

Using the data in the table for n = 40 ,


~ ~ ~
d∆hs ∆hs (n = 50 ) − ∆hs (n = 30 )

dn2 (50 [mol] − 30 [mol])
Interpolating the data in Table 6.1
~ J
∆hs (n = 30 ) = −72428
mol solute

Therefore,

J J
~ − 73729 − (− )72428
d∆hs mol solute mol solute J
≅ = −65.05 and
dn2 (50 [mol H 2O] − 30 [mol H 2O]) mol ⋅ mol solute

J J
H H 2 O − hH 2 O = (1 [mol solute]) − 65.05 = −65.05
mol ⋅ mol solute mol H 2 O
6.67
First perform an energy balance on the mixing process.

∆hmix = q

We can calculate ∆hmix using data from Table 6.1.

~
∆hmix = x HCl ∆hs

Calculate x HCl :

wHCl 0.30
(MW )HCl 36.46
x HCl = = = 0.175
wHCl w 0 . 30 0.70
+
H 2O
+
(MW )HCl (MW )H 2O 36.46 18.0148

Heats of data are tabulated for a solution containing one mole of the solute for various amounts
of water. Thus, we need to calculate how many moles of water must be added to HCl to obtain
the above mole fraction.

1 [mol HCl]
x HCl = ; where n is the number of moles of H2O
1 [mol HCl] + n
n = 4.71 [mol H 2 O ]

By interpolation of data from Table 6.1, we get

~ J
∆hs = −63224 (for n = 4.71 )
mol

Therefore,

J J
∆hmix = (0.175) − 63224 = −11064
mol mol

and

J
q = ∆hmix = −11064
mol
6.68
To calculate the enthalpy of mixing from Table 6.1, we must use the following expression
~
∆hmix = x H 2 SO 4 ∆hs

The mole fraction of sulfuric acid is

1
x H 2 SO 4 =
1+ n

where n is the number of moles of water.

Equation 6.24 states

(
∆hmix = −74.4 x H 2 SO 4 x H 2 O 1 − 0.561x H 2 SO
4
)
For n = 1 , x H 2 SO4 = 0.5 and x H 2 O = 0.5

~ J
Table 6.1: ∆hs = −31087
mol
J J
∴ hmix = 0.5 − 31087 = −15543.5
mol mol

Equation 6.24: ∆hmix = −74.4(0.5)(0.5)(1 − 0.561(0.5))


J
∆hmix = −13383
mol

The following table was made

∆hmix [kJ/mol] ∆hmix [kJ/mol]


n [mol H2O] x H 2 SO4 % Difference
(Table 6.1) (Eq. 6.47)
1 0.5 -15543.5 -13382.7 14.94
2 0.333333 -14978.7 -13441.6 10.82
3 0.25 -13001.8 -11993.5 8.07
4 0.2 -11414 -10568.4 7.69
5 0.166667 -10174.2 -9367.17 8.26
10 0.090909 -6367.27 -5835.17 8.72
20 0.047619 -3548.43 -3284.01 7.74
50 0.019608 -1497.22 -1414.49 5.68
100 0.009901 -762.238 -725.289 4.97
As you can see, the percent difference between the two methods decreases as the mole fraction
of sulfuric acid decreases. Although Equation 6.24 fit data at 21 ºC, while the Table 6.1
tabulates data taken at 25 ºC, we do not expect the temperature dependence to account for all the
observed difference. The table and equation come from different experimental data sets, and
also represent measurement uncertainty. Nevertheless, the agreement is reasonable.
6.69
To calculate the enthalpy of mixing from Table 6.1, we must use the following expression
~
∆hmix = x HCl ∆hs

The mole fraction of HCl is

1
x HCl =
1+ n

where n is the number of moles of water. The following table was made using these two
equations.

~ J J
n [mol H2O] x1 ∆hs ∆hmix
mol HCl mol
1 0.5 -26225 -13112.5
2 0.333 -48819 -16273
3 0.25 -56852 -14213
4 0.2 -61204 -12240.8
5 0.167 -64049 -10674.8
10 0.091 -69488 -6317.09
20 0.048 -71777 -3417.95
50 0.020 -73729 -1445.67
100 0.0099 -73848 -731.168
6.70
A schematic for the process is given below. The inlet streams are labeled “1” and “2” and the
exit stream “3”.
q

50 wt% NaOH 10 wt% NaOH


50 wt% H2O 90 wt% H2O

Stream 1 Stream 3

Stream 2 H2O

The energy balance for this process reduces to

Q = H 3 − H 2 − H1

We first convert from weight percentage to mole fraction. For stream 1,

wNaOH 0.50
(MW )NaOH 40
x NaOH ,1 = = = 0.311
wNaOH w 0 .50 0.50
+
H 2O
+
(MW )NaOH (MW )H 2O 40 18.0148

and for stream 3,

wNaOH 0.10
(MW )NaOH 40
x NaOH ,3 = = = 0.048
wNaOH w 0.10 0.90
+
H 2O
+
(MW )NaOH (MW )H 2O 40 18.0148

We now calculate the moles of water per mole of NaOH so that we can use Table 6.1:

1
x NaOH =
1 + nH 2 O

Therefore, for every mole of NaOH


n H 2 O,1 = 2.21
n H 2 O,3 = 19.8

Since enthalpy is a state function, we can choose any hypothetical path to calculate the change in
enthalpy. One such path is shown below. The box in our original schematic is depicted with
dashed lines below. We pick a basis of 1 mole NaOH. In step A, the inlet stream is separated
into its pure components. In step B, 17.6 additional moles of water are added to the pure water
stream. Finally the H2O and NaOH streams are remixed

The enthalpy change is found by adding each step

H 3 − H 2 − H 1 = ∆H A + ∆H B + ∆H C

Since ∆H B represents the mixing of water with water, ∆H B = 0 .

The enthalpies of mixing for steps A and C can be related to enthalpy of solution data from Table
6.1:

~ J
∆hs ,1 = −23906
mol NaOH
~ J
∆hs ,3 = −42858
mol NaOH

Note: The enthalpy of solution for Stream 1 is calculated by extrapolation. Generally,


extrapolation should be avoided, but it is necessary to complete this problem, and we are
not extrapolating very far.

For step A, we need the negative value of the heat of solution of stream 1. Thus for a basis of 1
mole NaOH:

∆H A = −(− 23906) [J ]
while for step C:

∆H C = −42858 [J ]

Now adding the enthalpies of each step per 1 mole of NaOH:

∆H = 23906 + 0 − 42858 = −18952 [J ]

To get the total heat that must be removed per mole of product solution, we divide by the number
of moles of product per mol of NaOH:

∆H J
q= = −910
n NaOH mol
6.71
The partial molar property can be written as follows:

∂nT K
K1 =
∂n1 T , P , n2 , n3

Applying the chain rule to the above relationship:

∂nT ∂k
K1 = k + nT
∂n1 T , P , n2 , n3
∂n1 T , P , n2 , n3

∂k
K1 = k + nT (1)
∂n1 T , P , n2 , n3

∂k
Now focus on nT . At constant T and P, we can write,
∂n1 T , P , n2 , n3

∂k ∂k ∂k
dk = dx1 + dx2 + dx3
∂x1 T , P, x , x ∂x2 T , P, x , x ∂x3 T , P, x , x
2 3 1 3 1 2

Therefore,

∂k ∂k ∂x1 ∂k ∂x2
= +
∂n1 T , P , n2 , n3
∂x1 T , P , x2 , x3
∂n1 T , P , n2 , n3
∂x2 T , P , x1 , x3
∂n1 T , P , n2 , n3
(2)
∂k ∂x3
+
∂x3 T , P , x1 , x2
∂n1 T , P , n2 , n3

but,

n1
x1 =
n1 + n2 + n3

so

∂x1 1 n1 1
= − = (1 − x1 ) (3)
∂n1 T , P , n2 , n3
n1 + n2 + n3 (n1 + n2 + n3 )2
nT

Similarly,
∂x2 n2 x2
=− =− (4)
∂n1 T , P , n2 , n3
(n1 + n2 + n3 ) 2
nT
and

∂x3 n3 x
=− =− 3 (5)
∂n1 T , P , n2 , n3
(n1 + n2 + n3 )2
nT

Substituting Equations 2, 3, 4, and 5 into the expression 1 for K1 and simplifying:

K1 = k +
∂k
(1 − x1 ) + ∂k (− x2 ) + ∂k (− x3 )
∂x1 T , P, x , x ∂x 2 T , P, x , x ∂x3 T , P, x , x
2 3 1 3 1 2

Utilize the fact that x1 + x 2 + x3 = 1

∂k ∂k ∂k ∂k
K1 = k + x 2 − + x3 − (6)
∂x1 T , P, x , x ∂x 2 T , P, x , x ∂x1 T , P, x , x ∂x3 T , P, x , x
2 3 1 3 2 3 1 2

When we hold species 3 constant:

∂k ∂k
dk = dx1 + dx 2
∂x1 T , P, x , x ∂x 2 T , P, x , x
2 3 1 3

∂k ∂k dx1 ∂k dx2
= +
∂x2 T , P , x3
∂x1 T , P , x2 , x3
dx2 ∂x2 T , P , x1 , x3
dx2

Thus,

∂k ∂k ∂k
=− + (7)
∂x2 T , P , x3
∂x1 T , P , x2 , x3
∂x2 T , P , x1 , x3

When we hold species 2 constant, a similar analysis shows:

∂k ∂k ∂k
=− + (8)
∂x3 T , P , x2
∂x1 T , P , x2 , x3
∂x3 T , P , x1 , x2

Substituting Equations 7 and 8 into Equation 6 gives


∂k ∂k
K1 = k − x2 − x3
∂x2 T , P , x3
∂x3 T , P , x2

Furthermore, the above analysis can be extended to m components. In general,

∂k
K i = k − ∑ xm
m≠i ∂xm T , P , x j ≠i ,m
6.72
The expression can be found by employing the Gibbs-Duhem equation:

0 = n1dV1 + n2 dV2

Differentiate with respect to x1 and then divide by the total number of moles:

dV1 dV dV dV
0 = x1 + x 2 2 = x1 1 + (1 − x1 ) 2
dx1 dx1 dx1 dx1

Differentiate the expression given in the problem statement.

dV1
= −5.28 + 5.28 x1
dx1

Substitution of this result into the Gibbs-Duhem equation and rearrangement yields

dV2 5.28 x12 − 5.28 x1


= = 5.28 x1
dx1 x1 − 1

Integrate:

cm 3
V2 = 2.64 x12 + C
mol

To determine C, we can use the density information given in the problem statement.

V2 (x 2 = 1) = V2 (x1 = 0 ) = C = v 2

where

1 1 cm 3
[ ]
C = v2 = = = 109.58
ρ2 0.768 g/cm 3 mol
MW2 84.16 [g/mol]

Therefore,

cm 3
V2 = 2.64 x12 + 109.58
mol
6.73
An expression for the enthalpy of the solution is

h = x1h1 + x 2 h2 + ∆hmix

which is equivalent to
~
h = x1h1 + x 2 h2 + x1∆hs

Multiplication by the total number of moles yields


~
H = n1h1 + n2 h2 + n1∆hs

To use the heat of solution data in Table 6.1, we need to determine the values of n1 and n2
consistent with the convention used in the table. As seen in Example 6.6,

n1 1
x1 = =
(n1 + n2 ) 1 + n
For this problem

x1 = 0.33

Therefore,

n1 = 1
n2 = n = 2

Now we can find expressions for the partial molar enthalpies.

∂H
H H 2O = H 2 =
∂n2 n ,T , P
1
~
d∆hs
H H 2 O = H 2 = h2 + n1
dn2
~
d∆hs
∴ H H 2 O − hH 2 O = H 2 − h2 = n1
dn2

Using the data in Table 6.1 for n = 2 ,


J J
~ ~ ~ − 2,787 − (− )812
d∆hs ∆hs (n = 3) − ∆hs (n = 1) mol solute mol solute
≅ =
dn2 (3 [mol] − 1 [mol]) (3 [mol H 2O] − 1 [mol H 2O])
~
d∆hs J
= −987.5
dn2 mol ⋅ mol solute

Therefore,

J J
H H 2 O − hH 2 O = (1 [mol solute]) − 987.5 = −987.5
mol ⋅ mol solute mol
Calculate the partial molar enthalpy:

J
H H 2 O = hH 2 O − 987.5
mol

From the saturated steam tables at 25 ºC:

kJ
hˆH 2 O = 104.87
kg
kJ
∴ hH 2 O = 1.89
mol

Now we can find the partial molar enthalpy

kJ J J
H H 2 O = 1.89 − 0.988 = 0.90
mol H 2 O mol H 2 O mol H 2 O
6.74
(a)
Calculate the mole fraction of sulfuric acid

w1 0.20
x1 =
(MW )1 = 98.078 = 0.044
w1 w2 0.20 0.80
+ +
(MW )1 (MW )2 98.078 18.0148

Calculate n to use in Table 6.1:

1
x1 = = 0.044
1+ n
n = 21.7 [mol H 2 O]

Interpolating from Table 6.1

~ J
∆hs = −74621
mol

Now calculate the heat transfer

~ J
q = ∆hmix = x1∆hs = (0.044 ) − 74621
mol
J
q = −3283
mol

(b)
Calculate the mole fraction of pure sulfuric acid. Consider a mixture of 20 kg of 18 M sulfuric
acid and 80 kg of water. Find the mass of sulfuric acid present.

mH 2 SO4 20 kg
VH 2 SO4 = = = 10.9 L
ρ H 2 SO4 1.84 [kg/L]
nH 2 SO4 = VM = (10.9 L )(18 mol/L) = 196.2 mol
( )
m H 2 SO4 = n H 2 SO4 MW H 2 SO4 = (196.2 mol)(0.098 kg/mol) = 19.2 kg

Since both the initial (i) and final (f) states contain mixtures, to get the enthalpy of mixing, we
need to calculate the relative differences follows:
~ ~
q = ∆hmix = x1, f ∆hs, f − x1,i ∆hs,i

calculate the mole fraction in the final state

w1 0.192
(MW )1 98.078
x1, f = = = 0.042
w1 w2 0.192 0.808
+ +
(MW )1 (MW )2 98.078 18.0148
Calculate n to use in Table 6.1:

1
x1, f = = 0.042
1+ n
n = 22.8 [mol H 2 O]

Interpolating from Table 6.1

~ J
∆hs, f = −74689
mol

For the initial 18 M sulfuric acid:

w1 0.192
(MW )1 98.078
x1,i = = = 0.81
w1 w2 0.192 0.008
+ +
(MW )1 (MW )2 98.078 18.0148
Calculate n to use in Table 6.1:

1
x1,i = = 0.81
1+ n
n = 0.23 [mol H 2 O]

We must extrapolate from Table 6.1. To do this we wish to extend the trend at low water
concentration. A plot of the data in Table 6.1 is useful. A semi-log plot follows:
0
3200 [J/mol]
-10000

enthalp of solution [J/mol solute]


-20000

-30000

-40000

-50000

-60000

-70000

-80000

-90000
0.1 1 10 100
n

~ J
∆hs,i = −3200
mol

Now calculate the heat transfer

~ ~ J J
q = ∆hmix = x1, f ∆hs, f − x1,i ∆hs,i = (0.042 ) − 74689 − (0.81) − 3200
mol mol
J
q = −710
mol

(c)
Calculate the mole fraction of sodium hydroxide

w1 0.20
x1 =
(MW )1 = 40 = 0.101
w1 w2 0.20 0.80
+ +
(MW )1 (MW )2 40 18.0148

Calculate the n value to use in Table 6.1:

1
x1 = = 0.101
1+ n
n = 8.9 [mol H 2 O]

Interpolating from Table 6.1

~ J
∆hs = −41458
mol
Now calculate the heat transfer

~ J
q = ∆hmix = x1∆hs = (0.101) − 41458
mol
J
q = −4187
mol

(d)
Calculate the mole fraction of ammonia

w1 0.20
x1 =
(MW )1 = 17.03 = 0.209
w1 w2 0.20 0.80
+ +
(MW )1 (MW )2 17.03 18.0148

Calculate the n value to use in Table 6.1:

1
x1 = = 0.209
1+ n
n = 3.78 [mol H 2 O]

Interpolating from Table 6.1

~ J
∆hs = −33153
mol

Now calculate the heat transfer

~ J
q = ∆hmix = x1∆hs = (0.209 ) − 33153
mol
J
q = −6929
mol
6.75
Let species 1 designate ethanol and species 2 designate water. We need to obtain an expression
for the molar volume, so first, convert the given the mass fractions and densities to mole
fractions and molar volumes.

w1

Mole fractions: x1 =
(MW )1
w1 w2
+
(MW )1 (MW )2

Specific molar volumes: v = vˆ(MW )mixture


where (MW )mixture = x1 (MW )1 + x 2 (MW )2

Using this set of equations, the following table was made.

Mole Frac. EtOH Mole Frac. H2O v (ml/mol)


0.000 1.000 18.05
0.042 0.958 19.54
0.089 0.911 21.18
0.144 0.856 23.11
0.207 0.793 25.47
0.281 0.719 28.34
0.370 0.630 31.85
0.477 0.523 36.19
0.610 0.390 41.65
0.779 0.221 48.73
1.000 0.000 58.36

The following graph plots the data. The trendline relates v to x1.

60.00

50.00

40.00
v (ml/mol)

v = 4.5491x12 + 35.918x1 + 17.957


30.00 R2 = 1

20.00

10.00

0.00
0.000 0.200 0.400 0.600 0.800 1.000

Mole Fraction EtOH (x1)


Now, we can calculate V1 .

∂V ∂ (nv )
V1 = =
∂n1 n , n ,T , P ∂n1 n , n ,T , P
2 3 2 3

We can substitute the trendline for V into this derivative and use the fact that ntot = n1 + n2 to
obtain

∂ n12
V1 = 4.5491 + 35.918n1 + 17.957(n1 + n2 )
∂n1 (n1 + n2 ) n 2 ,T , P

Differentiating we get

2n1 (n1 + n2 ) − n12 ml


V1 = 4.5491 + 53.875
(n1 + n2 ) 2 mol

( )
V1 = 4.5491 2 x1 − x12 + 53.875
ml
mol

Calculate V2 :

∂ n12
V2 = 4.5491 + 35.918n1 + 17.957(n1 + n2 )
∂n2 (n1 + n2 ) n1 ,T , P

Differentiating we get

− n12 ml
V2 = 4.5491 + 17.957
(n1 + n2 )2 mol
ml
V2 = −4.5491x12 + 17.957
mol

Plotting V1 and V2 vs. x1 we obtain


Partial Molar Volumes vs. EtOH Mole Fractions

60 20
EtOH Partial Molar Volume (ml/mol)

H2O Partial Molar Volume (ml/mol)


59 19
58 18
57 17
EtOH
56 16
H2O
55 15
54 14
53 13
52 12
0 0.5 1
Mole Fraction EtOH (x1)

(b)

( )
∆v mix = x H 2 O V H 2 O − v H 2 O + x EtOH (V EtOH − v EtOH )

From the data table in Part (a),

ml
v EtOH = v x1 =1 = 58.36
mol
ml
v H 2 O = v x1 = 0 = 18.05
mol

Using the expressions for partial molar volumes

( )
V1 = 4.5491 2(0.5) − (0.5)2 + 53.875 = 57.29
ml
mol
ml
V2 = −4.5491(0.5)2 + 17.957 = 16.82
mol

Therefore,

ml ml
∆v mix = (0.5) 16.82 − 18.05 + 0.5 57.29 − 58.36
mol mol
ml
∆vmix = −1.15
mol
6.76
We can use the density data given in the problem statement to determine the pure species
properties. For pure ethanol ( x1 = 1) :

MW1 46 [g/mol] cm 3
v1 =
ρ1
=
0.7857 g/cm 3 [
= 58.55
]
mol

V1 = n1v1 = (3 [mol]) 58.55


cm 3
mol
= 175.7 cm 3 [ ]
For pure formamide ( x1 = 0 ) :

MW2 45 [g/mol] cm 3
v2 =
ρ2
=
[
1.1314 g/cm 3 ] = 39.77
mol

V2 = n2 v 2 = (1 [mol]) 39.77
cm 3
mol
[ ]
= 39.77 cm 3

To calculate V and v, interpolate in the data table to obtain the density of the mixture when
x1 = 0.75 :

[
ρ = 0.8550 g/cm 3 ]
Therefore,

MW
v=
ρ
where
MW = 0.75(46 [g/mol]) + 0.25(45 [g/mol]) = 45.75 [g/mol]

Substitute numerical values:

v=
45.75 [g/mol]
[
0.8550 g/cm 3
] [
= 53.51 cm 3 /mol ]
V = nv = (4 [mol]) 53.51
cm 3
mol
[ ]
= 214.0 cm 3

Now, we can calculate the volume change of mixing:


[ ] [ ]
∆Vmix = V − V1 − V2 = 214 cm 3 − 175.7 cm 3 − 39.77 cm 3 [ ]
∆Vmix = −1.47 cm 3 [ ]
The intensive volume change of mixing:

∆v mix =
∆Vmix − 1.47 cm 3
=
[ ] [
= −0.368 cm 3 / mol ]
n 4

We can determine the partial molar volume of formamide:

dv ∆v
V2 = v − x1 ≈ v − x1
dx1 ∆x1

From the provided data table

45.8 45.7

∆v
= 0.8401 0.8701 = 19.50 cm 3 / mol
∆x1 0.8009 − 0.6986
[ ]
Therefore,

[ ] ( [ ])
V2 = 53.51 cm 3 / mol − 0.75 19.5 cm 3 / mol = 38.89 cm 3 / mol[ ]
Now calculate the partial molar volume of ethanol:

V = n1V1 + n2V2

∴V1 =
[ ] ( [
214.0 cm 3 − (1 [mol]) 38.89 cm 3 /mol ])
= 58.37 cm 3 / mol [ ]
3 [mol]
6.77
Using the definition of G, the Gibbs energy of mixing of an ideal gas can be rewritten in terms of
the enthalpy of mixing and the entropy of mixing:

∆g mix
ideal gas
= ∆hmix
ideal gas
− T∆smix
ideal gas

Since an ideal gas exerts no intermolecular interactions,

ideal gas
∆hmix =0

and

ideal gas
∆smix = − R( xa ln xa + xb ln xb )

so

ideal gas
∆g mix = RT ( xa ln xa + xb ln xb )

To find the partial molar Gibbs energy of mixing of species a:

∂ (n∆g mix )
(∆Gmix )a = ∂na T , P , nb

Applying the expression above

na nb
n∆g mix = RT na ln + nb ln = RT [na ln na + nb ln nb − (na + nb )ln (na + nb )]
na + nb na + nb
where the mathematical relation of logarithms was used. Thus,

∂ (n∆g mix ) (n + nb ) = RT ln x
(∆Gmix )a = ∂na
n
= RT ln na + a + 0 − ln (na + nb ) − a
na (na + nb ) a
T , P , nb
at infinite dilution xa goes to zero, and the ln term blows up,

(∆Gmix )∞a = µ a∞ − g a = −∞
As chemical engineers, we are often interested in the limiting case of infinite dilution. We see
that even for ideal gas mixtures the chemical potential in this limit is not mathematically well-
.behaved, In Chapter 7, we will develop a different function, the fugacity, which behaves better.
6.78
At equilibrium

l v
µH O
= µH O
2 2

or
G Hl O = G Hv O
2 2

Since the water in the liquid phase is pure

GHl 2O = g Hl 2O = hHl 2O − Ts Hl 2O

The enthalpy and entropy of liquids are not sensitive to pressure changes. We can use data from
the saturated steam tables at 25 ºC to determine the Gibbs energy.

l
gˆ H = 104.87 [kJ/kg ] − (298.15 K )(0.3673 [kJ/kg ⋅ K ])
2O
l
gˆ H = −4.640 [kJ/kg ]
2O

gHl
2 O
( l
= MWH 2 O gˆ H
2O
)( )
= (0.0180148 [kg/mol])(− 4.640 [kJ/kg ]) = 0.0836 [kJ/mol]
Therefore,

v
µH l
= gH = 83.6 [J/mol]
2O 2O

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