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Milo Koretsky

Wyatt Tenhaeff

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

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

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

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

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

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]

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

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

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

∂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

g1s = g1l

or

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

g1l = g1v

or

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

g1s = g1l

or

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.

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

(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

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

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

V1 = v1

` V2 = v2

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]

Using

kJ

∆h vap = 40.626

mol

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

Steam Tables [kPa]

1000

Pressure [kPa]

100

360 380 400 420 440 460 480

Temperature [K]

(d)

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%

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)

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.

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

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

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

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

∆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.

P − Ptp = (T − Ttp )+ fus

ln

(vs − v l ) (vs − v l) Ttp

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

P = 611.3 [Pa] + ln

(1.0908 × 10−3 −1.00 × 10−3 [m3 /kg ]) 273.16 K

so

P = 680 [bar ]

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

vv =

(

RT 1 + B ' P

= RT

1)+ B'

P P

dP ∆h vap

=

dT 1

R + B' T 2

P

P2 = 21 ×105 Par T2

1 ∆h vap dT

∫ + B dP = ∫

'

2

P1 =1 ×105 Pa

P R T1 =300 K T

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

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

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:

∆g i = ∫ vi dP = vi ∆P

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

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

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

+ 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

=

dT RT 2

1. vv>>vl

2. Silver acts as an ideal gas

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

= 2

− exp − 0.458 ln (T ) + 12.23

dT T T T

dP sat 14260 0.458 sat

= − P

dT T2 T

Therefore,

− =

T2 T RT 2

Therefore,

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

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

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

∂g i

= − si

∂T P

Therefore,

gi

∂

T − Tsi − g i − Tsi − (hi − Tsi ) − hi

= = =

∂T T 2

T 2

T2

P

6.26

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

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]

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

∫ (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

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

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

( ) (

∆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

h(T ) T

∫ dh = ∫ c P dT

href Tref

T

∴ h(T ) − href = ∫ c P dT

Tref

T

h (T ) = −738440 +

l

∫ 85.772 dT

2500 K

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

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

= − 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

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

− + 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

Alternative solution:

sat

dPCS ∆h vap

2

=

dT

1

RT 2 + B'

sat

PCS

2

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

1 ∆h vap

∫ sat + B

'

dP sat

CS2 = ∫ 2 dT

5 P

5.04×10 [Pa] CS2 378 RT

ln

5.04 × 105 (

+ B' 4.48 ×10 5 − 5.04 × 105 = − ) R

−

1

373 378

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:

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

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

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.

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.

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

= 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,

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

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

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:

R ln = − + ∆hvap − ∆hsub (3)

Psub Tsub Tsub TTP

∆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

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

• 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

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

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.

(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

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

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 )

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

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

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

∂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

∆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

∂ 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

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

n = na + nb + nc

na nbnc

H = nh = −5,000na − 3,000nb − 2,200nc − 500

(na + nb + nc )2

= −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:

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

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

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)

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 + 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

(b)

∆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

cm 3

v1 = 50

mol

cm 3

v2 = 70

mol

Therefore,

[ ]

V1 = 50 cm 3

V2 = 280 [cm ] 3

V = n1V1 + n2V2

Therefore

V 325.7

v= =

ntot 1+ 4

cm 3

v = 65.14

mol

[ ]

∆Vmix = −4.3 cm3

6.48

(a)

Expression for ∆hmix :

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

and

dX Sn

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

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 + n Sn =0

dxCd dxCd

where

= 26000 X Sn = −26000 + 26000 X Cd

dX Cd

d (∆H mix )Sn

= 26000 X Cd

dX Sn

Therefore,

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

dxCd dxCd

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

J

∆ hmix = 13, 000 xCd x Sn

mol

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

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

∆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.

“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

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:

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,

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

∆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:

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).

Subsituting the known values for the constants and outlet molar flow rate into the above

equation, we find:

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,

(b)

Write the energy balance for the process (recall that it is adiabatic and at constant pressure, so

∆𝐻 = 0):

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

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

𝑑𝑜𝑢𝑡 = 290 K

6.53

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

careful! 58.5 V1

58.0

0.8

57.5

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)

59.0

58.5

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

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:

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 :

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

∂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

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)

−13.1n1n2 2.25n12 n2

∆Vmix = −

n1 + n2 (n1 + n2 ) 2

∂∆Vmix

∆Vmix ,1 = V1 − v1 =

∂n1 T , P ,n

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

∂∆Vmix

∆Vmix ,2 = V2 − v2 =

∂n2 T , P ,n

V2 − v2 = + − +

n1 + n2 (n1 + n2 ) 2 (n1 + n2 ) 2 (n1 + n2 )3

cm3

𝑣

�2 = 1.003

g

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

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

x1 → 0

J

= 6,100

mol

6.57

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

dG1 dG2

x1 + x2 =0

dx1 dx1

From above:

dG1 2,500

= − 1, 666 x2

dx1 x1

2,500 dG2

x1 − 1, 666 x2 + x2 =0

x1 dx1

Rearranging

=− + 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

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)

6.59

(a)

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

(c)

4 3 4 2

�

𝑉1 = 20 + 12 � � − 6 � �

6 6

𝑐𝑚3

𝑉1 = 20.9

𝑚𝑜𝑙

6.60

(a)

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

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

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

𝑠1,𝐸𝑡𝑂𝐻

𝑛1 = = 24.45 𝑚𝑜𝑙

𝑚1,𝐸𝑡𝑂ℎ

Lab Alcohol

Pure Water

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

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 cm3

v= = 57.51

nT mol

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

~

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

∂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

~ 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

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]

~ ~ ~

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

~

∆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 ]

~ 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

1

x H 2 SO 4 =

1+ n

(

∆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

J

∆hmix = −13383

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

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% H2O 90 wt% H2O

Stream 1 Stream 3

Stream 2 H2O

Q = H 3 − H 2 − H1

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

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

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

H 3 − H 2 − H 1 = ∆H A + ∆H B + ∆H C

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

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 ]

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

∂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

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

∂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

∂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

∂k ∂k ∂k

=− + (8)

∂x3 T , P , x2

∂x1 T , P , x2 , x3

∂x3 T , P , x1 , x2

∂k ∂k

K1 = k − x2 − x3

∂x2 T , P , x3

∂x3 T , P , x2

∂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

dV1

= −5.28 + 5.28 x1

dx1

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

= = 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

~

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

∂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

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

kJ

hˆH 2 O = 104.87

kg

kJ

∴ hH 2 O = 1.89

mol

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

1

x1 = = 0.044

1+ n

n = 21.7 [mol H 2 O]

~ J

∆hs = −74621

mol

~ 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

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]

~ J

∆hs, f = −74689

mol

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

-20000

-30000

-40000

-50000

-60000

-70000

-80000

-90000

0.1 1 10 100

n

~ J

∆hs,i = −3200

mol

~ ~ 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

1

x1 = = 0.101

1+ n

n = 8.9 [mol H 2 O]

~ 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

1

x1 = = 0.209

1+ n

n = 3.78 [mol H 2 O]

~ J

∆hs = −33153

mol

~ 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

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

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)

30.00 R2 = 1

20.00

10.00

0.00

0.000 0.200 0.400 0.600 0.800 1.000

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

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

Partial Molar Volumes vs. EtOH Mole Fractions

60 20

EtOH 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 )

ml

v EtOH = v x1 =1 = 58.36

mol

ml

v H 2 O = v x1 = 0 = 18.05

mol

( )

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

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]

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

[ ] [ ]

∆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

dv ∆v

V2 = v − x1 ≈ v − x1

dx1 ∆x1

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

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 )

∂ (n∆g mix )

(∆Gmix )a = ∂na T , P , nb

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

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