CHEN 623 Problems Page 1

OLD EXAMINATION PROBLEMS:

1. (1981.M.1) Consider a fluid with an equation of state given by: PV = ZRT where:
Z = 1+ B /V and B = 30.06 − 9246.2 / T − 0.2564 × 10 8 / T 2
(The units of B and T are cm3/mol and kelvins respectively.)
a. Calculate the heat capacity at constant volume, CV, for the real fluid at 300 K and 7 atmospheres. (Take CPig to
be 2.5R.)
b. Estimate the downstream temperature if this fluid expands through an insulated throttling valve from 300 K and
7 atmospheres to 6 atmospheres.

2. (1981.M.2) Prove that (∂T/∂P)H < (∂T/∂P)S. Is this always true?

3. (1982.I.1) Note: CP - CV = TVβ2BT .

a. Calculate (∂H/∂P)V in terms of observables for an ideal gas.
b. Show that (∂H/∂P)V = (CV/R){V(CP/CV) ) - b} for a fluid which obeys the equation of state: P(V-b) = RT.
c. Can (∂H/∂P)V = 0 for the fluid described in part b.). Explain your answer.

4. (1982.I.2) Consider two tanks separated by a vertical displacement h and connected by a pipe as shown below. The
upper tank initially contains mass m of a nonvolatile liquid at a temperature To. After the valve is opened, all the
liquid drains into the lower tank. Consider the following cases:
Case I: The connecting pipe and lower tank are thermally insulated from the surroundings.
Case II: The connecting pipe and lower tank are in thermal contact with the surroundings, which also are at tem-
perature T0.
a. Determine the final equilibrium temperature for each case in terms of m, g, h, C and T0 , where:
m = mass of liquid
g = acceleration due to gravity
C = liquid heat capacity
h = vertical separation of the tanks h
T0 = initial liquid temperature and the temperature of the surroundings.
(All of these variables may not be necessary to solve the problem.)
b. Which case will have the larger total entropy change of the universe? Give a brief intuitive
argument (expressed in complete sentences) to support your answer.
c. Calculate the total entropy change of the universe for each case in terms of the variables listed in part a, and
show that the relative difference between the two cases is approximately (gh/2CT0 ).

5. (1983.I) Consider a system consisting of two equal volumes. Initially, Volume B is evacuated and Volume A
contains N moles of a van der Waals fluid (with CVig = 2.5) at a temperature T0 and a pressure P0 . After the valve is
opened, the fluid expands into Volume B, and the entire volume (A+B) reaches thermal equilibrium. The van der
Waals equation of state is:
(P + a / V 2 )(V − b) = RT
a. Prove that CV = CVig for a van der Waals fluid.
b. Determine the final temperature of the fluid and the total entropy change of the universe if the system is isolated
from the surroundings. Express your answer in terms of T0 , N, and appropriate constants (e.g. a, b, R, VA, VB,
etc.). Does the temperature increase or decrease?
c. Determine the final temperature of the fluid and the total entropy change of the universe if the system reaches
thermal equilibrium with surroundings at 273.16 K.
d. Determine the final temperature of the fluid and the total entropy change of the universe if the expansion is re-
versible and adiabatic (i.e., volume B actually is an insulated piston and cylinder). How much work is done? Is
the energy transferred as work absorbed by or released from the system?
 CHEN 623 Problems Page 2

6. (1984.I) Consider a fluid which obeys the equation of state:

PV = RT exp(a / V ), where a = a0 + a1 / T and CVig = 1.4R
a. Derive an expression for [H (P,V ) − H ig (P,V )] / RT for this gas.
b. Derive an expression for the energy transferred as work if this gas is expanded isothermally, irreversibly and
adiabatically from V0 to 2V0 in a piston/cylinder arrangement.
c. Derive an expression for the entropy change of the universe during the process described in part b.).

7. (1985.I.1) The velocity of sound in a fluid is related to the volumetric properties by:
uS2 = − ( )( )
V2
M
∂P
∂V S

where M is the molecular weight of the fluid. Assuming that the perfect gas heat capacity for this fluid is given by
CVig / R = 2.5 , derive an expression that gives uS2 as a function of observables for a van der Waals gas, where
RT a
P= −
V −b V2
Show that your result reduces to
1.4RT
u s2 =
M
in the zero pressure (ideal gas) limit.

8. (1985.I.2) Show that the entropy of the universe must increase during any steady state flow process in which the
pressure decreases while no energy is transferred as either work or heat.

9. (1985.I.3) Derive expressions for the energy transferred as heat and the energy transferred as work during an iso–
thermal, reversible compression to one third the original volume of a gas which has an equation of state described by
⎛ B C⎞
PV = RT ⎜ 1+ + 2⎟
⎝ V V ⎠
Note that the virial coefficients B and C are functions of temperature but not volume or pressure.

10. (1988.I.1) Show that, at fixed composition, an extremum in CV with respect to volume at constant temperature [i.e.,
(∂CV/∂V)T = 0] occurs at any inflection point along an isochore (line of constant density).

11. (1988.I.2) In 1900, Berthelot proposed the following variation of the van der Waals equation:
⎛ a ⎞
⎜⎝ P + ⎟ (V − b ) = RT
TV 2 ⎠
a. Express [U(T,V) – Uig(T,V)] and [A(T,V) - Aig(T,V)] in terms of a, T, V, b and R for this fluid.
b. Is CV a monotonic function of density along an isotherm for a fluid which obeys this equation of state? Justify
your answer.

12. (1988.I.3) An insulated piston and cylinder assembly contains an ideal gas with a heat capacity at constant volume
equal to 1.5R (R is the gas constant). The piston, which is backed by a vacuum, initially is held in place by the
lower of two mechanical stops. When the lower mechanical stop is released, the piston rises until it encounters a
second mechanical stop. The volume after the expansion is 50% larger than the original volume, and the tempera-
ture drops to 75% of its initial value.
a. Determine the mass of the piston in terms of the acceleration due to gravity, g, the vertical displacement of the
piston between the two mechanical stops, z, the gas constant, R, the number of moles of gas present, n, and the
original temperature of the gas, T0.
b. Determine the total entropy change of the universe (in units of R) for this process. Is the process reversible or
irreversible?
 CHEN 623 Problems Page 3

c. Determine the minimum final temperature (given in terms of R and T0) allowed by the second law for the same
change in volume. . (Part c.) was not included in the original examination.)

13. (1989.I) Consider a gas that obeys the equation of state proposed by Kam (Phil. Mag., 37, 65 (1919)):
2a RT
P+ 2 =
(V + b ) V
where a and b are assumed to be independent of temperature.
a. Sketch the behavior of P as a function of V for -∞ < V < +∞.
b. Calculate the numerical value of the critical compressibility factor for this fluid.
c. Give expressions in terms of a, b, R and T0 for the entropy change of the universe per mole of fluid expanded
from V = 2b to V = 3b for each of the situations described below. In each case, the fluid and the surroundings
are at the same temperature, T0, at the beginning of the process.
1. Reversible expansion in a piston and cylinder arrangement which is thermally coupled to the surroundings.
(There is a vacuum behind the piston.)
2. Expansion from an internal chamber into the entire volume of a rigid box which is coupled thermally to the
surroundings.
3. Expansion through a throttling valve in a steady state flow process where, because the pipe is coupled therm-
ally to the surroundings, the fluid emerges at the same temperature as the surroundings.

14. (1990.I) Consider a fluid which obeys Berthelot's variation of the van der Waals equation:
⎛ a ⎞
⎜⎝ P + ⎟ (V − b ) = RT
TV 2 ⎠
a. Derive expressions which give the amounts of energy transferred as heat and as work per mole of fluid during a
reversible and isothermal expansion from V = 40b to V = 120b in a piston and cylinder arrangement.
b. Derive an expression for the total entropy change of the universe per mole of fluid during an irreversible and
isothermal expansion from V = 40b to V = 120b in which the amount of energy transferred as work is 50% of
the result calculated in part a.).
c. Derive an expression for the change in temperature which results from an adiabatic expansion of this fluid from
V = 40b to V = 120b in which no energy is transferred as work.
Note: All expressions should be given in terms of R, T, a and b. Assume that the ideal gas heat capacity for the
fluid is given by
CVig = 2.5R .

15. (1991.I.1) Derive an expression for the heat capacity at constant volume, CV , for a gas that obeys the Redlich-
Kwong equation of state:
RT a
P= − where CVig = 2.5R
V − b V (V − b ) T
This expression should contain no integrals, but (as necessary) only Turbine
numbers, the density (or specific volume), the temperature, the gas Shaft
constant and the parameters a and b. Work

16. (1991.I.2) One way to provide small amounts of electricity to power Exhaust to
instruments at remote sites is to use a small gas turbine and electric Compressed Atmosphere
generator supplied by a cylinder of compressed air as shown in the Gas
Cylinder
illustration at right. Assume that the air in the cylinder behaves as an
ideal gas and that the turbine operates isentropically. Use CPig = 3.5R for this gas.
a. Show that the temperature of the gas leaving the turbine is related to the turbine inlet temperature and
pressure and the outlet pressure by:
 CHEN 623 Problems Page 4

Tout = Tin ( Pout / Pin )

R/CVig

b. Derive an expression for the maximum amount of work which could be provided by the turbine during a
discharge of the compressed gas storage cylinder from an initial pressure, P0, to a final pressure, Pf , assuming
that the discharge occurs sufficiently slowly that the gas in the cylinder remains constant at ambient temperature,
T0. Acceptable parameters for the result are T0, P0, Pf , Patm (atmospheric pressure), R (the gas constant), and
Vcyl (the total internal volume of the compressed gas storage cylinder).
c. How much energy is absorbed as heat by the gas in the cylinder during the discharge from P0 to Pf ?
d. Would more or less energy be obtained if the discharge occurs sufficiently rapidly that the gas in the cylinder
does not experience any significant heat transfer (adiabatic process) during the discharge process? Why?
e. Derive an expression for the total entropy change of the universe during the process described in part b.).

17. (1992.I) Consider a fluid which obeys an equation of state proposed by Dieterici, Ann. Phys. 66, 826 (1898):
⎡ a ⎤
PV = RT exp ⎢
⎣ RTV ⎥⎦
where b, c and R are constants.
a. Does this equation of state have a critical point? If so, calculate the numerical value of Zc , and express this
equation in reduced form.
For parts b.), c.), d.) and e.), the result may be left as integral equations, but the expressions may contain only V, T,
b, c, R and CV (no partial derivatives are allowed).
b. Derive an expression for CV - CVig .
c. For an adiabatic expansion from V0 to 2V0 in a closed system for which no energy is transferred as work, give
expressions for:
1. The temperature change of the fluid;
2. The total entropy change of the universe (per mole of fluid).
d. For a reversible adiabatic expansion from V0 to 2V0 in a closed system, give expressions for:
1. The temperature change of the fluid;
2. The energy transferred as work (per mole of fluid).
e. For any isothermal expansion from V0 to 2V0 in a closed system, give expressions for:
1. The total energy transferred as heat and work (Q + W) per mole of fluid;
2. The total entropy change of the universe per mole of fluid for a given value W of energy transferred as work
per mole of fluid.

18. (1993.I.1) Consider a fluid which obeys the following equation of state:
⎛ a ⎞
⎜⎝ P + 4 ⎟⎠ (V − b ) = RT
V
For this fluid, CVig = 52 R , where R = 8.314 J/mol⋅ K=1.987 Btu/lbmol⋅°F=82.06 cm ⋅ atm/mol⋅ K
3

a. Show that CV = CVig for this fluid at all densities.

b. Derive an expression for the ratio (T2 / T1 ) which results from an adiabatic and reversible expansion of this fluid
from V1 to V2. This expression should contain no integrals and only V1, V2, a, b and R as necessary.
c. Derive an expression for the amount of energy transferred as heat during an irreversible expansion from (T1,V1)
to (T2,V2) in which no energy is transferred as work, where V2 = 3V1 and T2 = 0.90T1. This result should contain
no integrals and only T1 , V1 , a, T1, V1, a, b and R as necessary.
d. Derive an expression for the maximum amount of work which can be produced by a process which results in the
change of states defined in part b.), i.e., from (T1,V1) to (T2,V2) where the energy is exchanged as heat with a
reservoir at T3. Comment on the range of values allowed for T3. This result should contain no integrals and only
T1, T3, V1, a, b and R as necessary.
 CHEN 623 Problems Page 5

e. Derive an expression for the maximum amount of work which can be produced by a process which results in the
change of states defined in part c.), i.e., from (T1,V1) to (T2,V2) where the energy is exchanged as heat with a
reservoir at T3. Comment on the range of values allowed for T3. This result should contain no integrals and only
T1, T3, V1, a, b and R as necessary.

19. (1993.I.2) The Watson equation is a popular equation that is used to describe the variation of the heat of
vaporization with temperature:
0.38
ΔV H @T2 ⎡ 1− Tr 2 ⎤
=
ΔV H @T1 ⎢⎣ 1− Tr1 ⎥⎦
Using the Clapeyron equation (which relates the derivative of the vapor pressure with respect to temperature, the
heat of vaporization and the volume change upon vaporization, and the knowledge that near the critical temperature
d 2 P sat −θ
~ 1− Tr
dT 2
where θ is approximately 0.2, determine the critical exponent β* which the combination of the Clapeyron and
Watson equations require for the density difference:
β*
Δρ = ρ Lsat − ρVsat ~ 1− Tr

20. (1994.I.1) Consider a frictionless piston in an insulated cylinder which contains an ideal gas as shown below. The
piston is backed by a spring with force constant k so that the magnitude of the force acting upon the piston is kx (this
means that the force is zero when the piston is at the left wall). The piston initially is locked in place at the original
position, then the lock is released and the piston moves to the equilibrium position where the spring balances the
pressure force. The original position is illustrated with the solid piston, and the shaded piston shows the final
position The specified variables are the spring constant k, the initial piston position xo, the cross sectional area of
the piston A, the initial temperature To, and the initial pressure Po. The ideal gas heat capacity at constant volume
has the value 2.5 R, and it is independent of temperature.

xo
Vacuum
x
a. Show that the ratio of the final to the original temperature is given by

kxo ⎡⎛ x ⎞ ⎤
2
Tf
= 1− ⎢⎜ ⎟ − 1⎥
To 5APo ⎢⎝ xo ⎠ ⎥⎦
⎣
and the ratio of the initial to the final position is given by
x 1 5APo
= +
xo 6 6kxo
b. Derive an expression for the final pressures in terms of the specified variables listed in the problem statement
above.
c. For what values of the dimensionless group ( kx0 / AP0 ) will the piston move to the left, and for what values will
the piston move to the right? Give a brief explanation of the physical meaning of this variable.
d. Give an expression for the total entropy change of the universe for this process.
e. Give an expression for the final pressure and piston position which would result if the insulation were removed
and the process was carried out isothermally.
 CHEN 623 Problems Page 6

21. (1994.I.2) Show that ( ∂S / ∂V )U must always be positive and that ( ∂S / ∂P )H must always be negative.

22. (2000.I.1) Consider a shock absorber as shown in the drawing below. As the piston moves, the oil flows through
the small holes in the piston, producing a force which opposes the motion of the piston.

Oil

As the piston moves through a cycle from x0 to x0+3Δ and back to x0, the approximate force required to move the
piston as a function of position is

F0
Force

0
∆
Position

-F0

There are n moles of oil in the cylinder. Assume that the cylinder walls and the piston have negligible heat capacity.
The molar heat capacity of the oil is CP and the oil can be considered to be incompressible and have zero thermal
expansion. Initially, both the oil and the surroundings are at temperature T0.
a. Give an expression for the final temperature of the fluid at the completion of the cycle. Assume that no energy is
transferred as heat to the surroundings during the process.
b. Give an expression for the total entropy change of the universe during the process described in part a). What is
the irreversible feature of this process?
c. Give an expression for the total entropy change of the universe if the piston and cylinder remain in thermal
equilibrium with the surroundings during the process.

23. (2000.I.2) a. Derive an expression for (∂T/∂V)S for the Redlich-Kwong fluid:
RT a
P= −
V − b V (V + b ) T
b. The relationship between the temperature and volume for an adiabatic, reversible expansion of an ideal gas with
constant heat capacity is:
1−γ
T2 ⎛ V2 ⎞ CPig
= where γ =
T1 ⎜⎝ V1 ⎟⎠ CVig
Derive an expression that relates the temperature and volume for an adiabatic, reversible expansion of an ideal
gas for which the ideal gas heat capacity at constant volume is
CVig
= A + BT + CT 2 + DT −2
R
This expression may be implicit in temperature [i.e., f(T1,T2) = g(V1,V2)], but it should not contain integrals or
partial derivatives.
 CHEN 623 Problems Page 7

24. (2001.I.1) A Mollier diagram has enthalpy as the dependent variable (ordinate) and entropy as the independent
variable (abscissa). The slope of a line on a Mollier diagram is dH/dS. Based upon the compressibility factor form
of the equation of state (PV = ZRT),
a. derive an expression for the slope of an isobar (line of constant pressure) on a Mollier diagram;
b. derive an expression for the slope of an isotherm (line of constant temperature) on a Mollier diagram.
Note: Your answers should contain only P, V, T, Z and derivatives of Z as necessary.

25. (2001.I.2) Consider a fluid confined to a rigid (fixed volume) container. This fluid is described well by an equation
of state that is similar to, but not exactly the same, as the Redlich-Kwong equation:
RT a
P= −
V − b V ( V + b)
where a and b both are independent of temperature. The ideal gas heat capacity for this fluid obeys
Cvig = A + BT
a. Give an expression for the amount of energy (per mole of fluid) that must be transferred as heat to change the
temperature of the fluid from T1,V1 to T2,V2.
b. Give an expression for the total entropy change of the universe (per mole of fluid) if the energy is transferred as
heat from a reservoir at a fixed temperature of T3.
c. What conditions are required for T3? (Consider two cases: T2 > T1 and T2 < T1.)
⌠ dx 1 ⎛ a + bx ⎞
Mathematical note: ⎮⎮ = − ln ⎜ ⎟
⌡ x ( a + bx ) a ⎝ x ⎠

26. (2002.I) Consider a fluid that is described by an equation of state that has the same volume dependence as van der
Waals, but with the temperature dependence of Redlich-Kwong (a and b are independent of temperature):
RT a
P= −
V −b V2 T
The ideal gas heat capacity for this fluid is: CVig = 2.5R (1+ cT )

1 ⎡ 3Tr 9 ⎤
a. Show that the reduced form of this equation is Pr = ⎢ − ⎥
⎣ 3Vr − 1 8Vr Tr ⎦
2
Zc
b. Evaluate the numerical value of Zc. and give expressions for a and b in terms of R, Tc and Pc .
⎛ ∂C ⎞
c. Give an expression (containing only R, V, T, a, b and c as necessary) for ⎜ V ⎟ .
⎝ ∂V ⎠ T
d. Derive an expression for the entropy change of the fluid when it expands to five times its original volume (V2 =
5V1) in an isothermal expansion in which no energy is transferred as work. (This expression should contain only
a, b, c, R, T1 and V1 as necessary.)
e. Derive an expression for the amount of energy transferred as heat during the expansion specified in part d.).
(This expression should contain only a, b, c, R, T1 and V1 as necessary.)

27. (2014.I) Consider a fluid that is described by an equation of state with the same volume dependence as van der
Waals, but with the temperature dependence of Redlich-Kwong (a and b are independent of temperature):
RT a
P= − 2
V −b V T
The ideal gas heat capacity for this fluid is: CVig = 2.5R (1+ cT ) .
⎛ ∂C ⎞
a. Give an expression (containing only R, V, T, a, b and c as necessary) for ⎜ V ⎟ .
⎝ ∂V ⎠ T
 CHEN 623 Problems Page 8

b. Derive an expression for the entropy change of the fluid when it expands to four times its original volume (V2 =
4V1) in an isothermal expansion in which no energy is transferred as work. (This expression should contain only
a, b, c, R, T1 and V1 as necessary.)
c. Derive an expression for the amount of energy transferred as heat during the expansion specified in part b.).
(This expression should contain only a, b, c, R, T1 and V1 as necessary.)
d. Derive an expression for the energy transferred as work to or from the fluid if the fluid expands from V1 to V2 in
a mechanically reversible isothermal process. (This expression should contain only a, b, c, R, T1 and V1 as
necessary.)

28. (2015.I.1) An ideal gas is present in both volumes A and B (see drawing), which are
separated by a frictionless piston. Initially, the piston is held exactly in the middle by a stop. A B
The initial pressure in volume A is three times as large as that in volume B, and the
temperatures of volumes A and B and the surroundings all are equal at T. The piston then is
released and the system is allowed to come to equilibrium, both internally and with the surroundings.
a. Determine the fraction of the total volume of gas occupied by volume A when the system reaches equilibrium.
b. Determine the ratios of the equilibrium pressure to the initial pressures in volumes A and B respectively.
c. Determine the total entropy change of the universe for this process in terms of the gas constant, R, the total
volume, (VA+VB), and the total number of moles of gas (n = nA+nB).

RT a
29. (2015.I.2) For the Redlich-Kwong equation: P = −
V −b 1
T V (V + b )
2

a. Derive an expression that gives the compression factor, Z, in terms of density, ρ, temperature, T, and the
constants R, a, and b.
⎛ ∂G ⎞
b. Derive an expression that gives ⎜ in terms of V, T, R, a, and b.
⎝ ∂V ⎟⎠ T

30. (2016.I.1) Consider a frictionless piston in an un-insulated cylinder containing an ideal gas
that initially is at the same temperature as the surroundings. As shown, the piston is backed
by a spring with force constant k, and the magnitude of the force that the spring exerts on
the piston is k(x-L/4). The piston initially is located at x = L/2, where the force from the
spring balances the force from the gas pressure. Gas then leaks slowly past the piston until
the gas pressure is equal throughout the entire cylinder (i.e., there is no pressure difference across the piston). The
specified variables are the length (L) and cross sectional area (A) of the piston, the initial temperature (To) and the
initial pressure (Po). The ideal gas heat capacity at constant volume is 2.5R at all temperatures. The thickness of the
piston is very small compared to L. In terms of R, L, A, Po and To, give expressions for
a. the spring constant (k) and the number of moles of gas (n);
b. the final position of the piston (xf), and the final pressure of the gas (Pf);
c. the amount of energy transferred as heat (Q) during the process;
d. the total entropy change of the universe for this process.

31. (2016.I.1) P-H diagrams often are used for practical applications. The vertical axis on these diagrams is the
pressure and the horizontal axis is the enthalpy.
a. If both axes are linear, derive expressions that give the slope of the lines of constant entropy, temperature, and
volume in terms of the observables P, V, T, and CV (partial derivatives that involve only observables are
allowed).
b. In the usual version of the diagrams, the pressure axis is logarithmic and the enthalpy axis is linear. How can the
results from part a.) be used to calculate the slopes on the semilog plot?
 CHEN 623 Problems Page 9

32. (1982.II.1) Consider the equation of state: (P + a / V 4 )(V − b) = RT .

a. Show that: Z = 5VR / (5VR − 3) − 25 / (16TRVR3 )
b. Determine the numerical value of Zc.
c. Give an expression for Ur as a function of reduced temperature and reduced density. (This expression should not
contain any integrals.)

33. (1982.II.2) The Antoine equation often is used to describe vapor pressures: ln Pσ = A − B / (T + C ) .
For temperatures near the normal boiling point:
a. Derive an expression that gives the behavior of ∆Hvap as a function of temperature which is thermodynamically
consistent with the Antoine equation.
ΔH vap (T2 ) 2C
b. Show that, if C<<T1, T2:
ΔH (T1 )
vap
= 1+
T2T1
(T2 − T1 )

34. (1983.II.1) Consider a liquid where: GE/RT = Ax1x2 .

a. Determine the range of values for A within (-∞ < A < +∞) that allows two liquid phases to coexist in equilibrium.
b. Determine the range of values for A that allows azeotropic behavior if P1σ = 0.873 atm and P2σ = 0.530 atm.
c. Determine the total pressure and the composition of the vapor phase in equilibrium with the liquid if A = 5.24
and x1 = 0.327.

35. (1983.II.2) Derive expressions for the excess volume, excess Gibbs functions and the activity coefficients of each
component for a binary vapor phase mixture that obeys the equation of state:
BP
Z = 1+ , where B = y12 B11 + 2y1 y2 B12 + y22 B22 .
RT

36. (1984.II.1) Consider the behavior of fluids that obey the van der Waals equation of state:
P = RT / (V − b) − a / V 2 ,
where a and b are not functions of temperature or density.
a. Derive relations between the van der Waals parameters (a and b) and the second and third virial coefficients (B
and C) in the density form of the virial equation of state: Z = 1 + Bρ + Cρ2 + ...
b. Consider a partitioned box which contains two pure van der Waals fluids A and B at equal initial densities (ρ0)
and temperatures (T0). The partitioned volumes contain nA and nB moles of A and B respectively. Show that,
if the partition is removed and the fluids are mixed thoroughly, the energy which must be added to maintain the
system at a constant temperature is equal to (nA + nB )ρ0[yAaA + yBaB - aM ]. You may assume that mixture also
obeys van der Waals equation with a = aM and b = bM.

37. (1984.II.2) The following VLE data are available for an azeotropic mixture:
T/K Paz/bar x Aaz yAaz : PAσ / bar PBσ / bar

303 0.185 0.59 0.59 0.1308 0.0833

323 0.420 0.60 0.60 0.3176 0.1955
343 0.853 0.61 0.61 0.6715 0.4082

Calculate the heat of mixing and the entropy of mixing of the liquid phase at the azeotropic composition and 323 K.
You may assume that pressure effects may be neglected in the liquid phase and that the two-suffix Margules equa-
tion provides an adequate description of the liquid phase behavior.
 CHEN 623 Problems Page 10

38. (1985.II.1) Consider a ternary mixture where the excess Gibbs energy is given as a function of composition by:
G E / RT = A12 x1 x2 + A13 x1 x3 + A23 x2 x3
For this mixture,
a. Derive expressions for the activity coefficients for each component, both at finite concentration and at the
infinite dilution limit.
b. Derive an expression for the heat of mixing, assuming that the Aij are functions only of temperature.

39. (1985.II.2) A novel experimental technique for measuring the fugacity of hydrogen in mixtures is based upon the
ability of hydrogen to diffuse freely through palladium metal, while the metal is impervious to other fluids.
Assuming that the experiment operates in the pressure range where adequate descriptions of the compressibility
factor are provided by: Z = 1 + BP/RT, that a binary mixture containing hydrogen has achieved equilibrium across
a palladium membrane with pure hydrogen, and that the entire experiment is at a temperature T,
a. Derive an expression that gives f̂1 in terms of the equilibrium pressure of pure hydrogen (component 1 =
hydrogen).
b. Derive an expression that gives the interaction second virial coefficient for hydrogen and a second component,
B12, in terms of the pure fluid second virial coefficients, the temperature, the mixture composition, and the
equilibrium pressures of the mixture and of the pure hydrogen.

40. (1988.II.1) Consider a mixture of two liquids that obeys the following form of the Van Laar equation:
GE x1 x2
=
RT 3x1 + 8x2
at 350 K. The vapor pressures and second virial coefficients of the two fluids at 350 K are:
P1σ = 3.17 atm, P2σ = 1.74 atm, B1 = -185 cm3/mol, B2 = -330 cm3/mol
a. Determine the total pressure and the composition of the vapor over a liquid phase with equimolar composition
(x1 = 0.5 = x2).
b. Determine the numerical value of the Henry's constants for components 1 and 2.
c. Determine the relationship between the activity coefficients based upon pure liquid standard states and the activi-
ty coefficients based upon Henry's law standard states.

41. (1988.II.2) Consider a gaseous mixture for which the following form of the virial equation applies:
BP
Z = 1+ where B = ∑ ∑ xi x j Bij
RT i j

a. Show that the excess molar volume of a two component gas mixture is given by:
V E = x1 x2 (δ B12 ) where: δ B12 = [2B12 − B11 − B22 ]
b. Derive expressions for GE/RT, γ iV , and φiV in terms of δB12, {xi}, T and P.

42. (1989.II.1) Descriptions of excess properties for mixtures require the specification of reference states for each of the
pure materials. Two such specifications for standard states are based on the Lewis & Randall rule (reference state is
the pure substance at the same conditions as the mixture) and on Henry's law (in the limit of infinite dilution, the
fugacity of a substance in the mixture becomes directly proportional to the mole fraction of that substance). Con-
sider a mixture of two substances, A and B, where the excess Gibbs energy relative to standard states based on the
Lewis & Randall rule for both substances is given by a Van Laar form:
GE xA xB
=
RT 3.468x A + 1.908x B
a. Determine the numerical value of the activity coefficient of substance B at infinite dilution.
 CHEN 623 Problems Page 11

b. Derive an expression for the excess Gibbs function of this mixture relative to a Henry's law standard state for A
and a Lewis & Randall standard state for B. This expression should contain only xA, xB and numerical constants.

43. (1989.II.2) Determine the relations between the pressure residual Gibbs energy, GR(T,P) = G(T,P) - G*(T,P), as
defined earlier in the course (but calculated for the mixture) and the change of Gibbs energy upon mixing, ΔΜG, and
the excess Gibbs energy, GE , which are based upon ideal gas reference states at the same temperature and pressure.

44. (1989.II.3) A mixture of three substances A, B and C which participate in the reaction A <==> 2B + C is described
at 500 K by GE/RT = -10.62 xAxBxC . Determine the free energy change at 500 K per mole of reaction as written if
the equilibrium composition is xA = 0.32, xB = 0.49 and xC= 0.19.

45. (1990.II) Consider a mixture of A, B and A2B in equilibrium at 325.3 K and 5.863 atmospheres. Both vapor and
liquid phases are present and the vapor and liquid compositions are known (see table below). The species present
also undergo the reaction 2A + B <==> A2B. Assume that VlL ≈ 0 so that the Poynting correction can be ignored.
a. Calculate the numerical value of ∆rG° (in J/mol) relative to reference states of A, B, and A2B as ideal gases at
the same temperature and 1 atmosphere pressure. Do not assume ideal gases or ideal solutions; your result
should be accurate to at least three digits.
b. If the excess Gibbs function in the liquid phase is given by GE/RT = AxAxBxA2B , determine the numerical value
of A. Do not assume ideal gases or ideal solutions; your result should be accurate to at least three digits.
c. If one mole of the equilibrium vapor phase is reduced to 1 atm total pressure at 325.3 K, determine the ratio of
the final to the initial volume and the final composition. The mixture is a single phase vapor throughout this
entire process. You may assume ideal gas and ideal solution behavior for this problem.
Physical properties of interest:
Pisat/atm xi yi BAi /cm3 mol-1 BBi /cm3 mol-1 BA2Bi /cm3 mol-1
A 6.973 0.193 0.364 -10 -146 -18
B 4.782 0.268 0.293 -153 -25
A 2B 3.267 0.539 0.343 -452

46. (1991.II.1) The behavior of solvents near infinite dilution in polymers is important to the design of effective and
efficient devolatilization machinery. One method of measuring such vapor-liquid equilibrium behavior is to inject a
finite concentration of a solvent into the helium carrier gas stream of a gas chromatograph. This method (with
appropriate analysis of the chromatographic measurements) provides the mass fraction of solvent in a polymer
exposed to a vapor that contains a known fraction of the solvent of interest in helium, with the total pressure held
constant. Such chromatographic measurements have provided the following equilibrium data for a solvent in a
polymer at 325 K under a total pressure of 119.8 kPa:

Mole fraction solvent in vapor phase: yi : 0.040 0.080 0.140 0.280 0.690
Mass fraction solvent in polymer: wi : 0.0030 0.0060 0.0105 0.0210 0.0522

You may assume that the vapor phase behaves as an ideal solution, but not as an ideal gas.
a. Determine the Henry's constant for this system using weight fractions as the composition variable.
b. Derive an expression which gives the mass fraction activity coefficient (usually denoted as Ωι) for the solvent in
terms of the known variables. This expression should be based upon the pure liquid at its vapor pressure as a
reference state.
c. Calculate the numerical values of the mass fraction activity coefficient as defined in part b.) and the mass
fraction activity coefficient based upon a Henry's Law standard state, both at wi = 0.0210.
Solvent properties: Bsolvent = -743 cm3/mol; Bhelium= 9 cm3/mol; Psolvent
sat
= 256.4 kPa; Vsolvent
liquid
= 78.54 cm 3 / mol

47. (1991.II.2) For a liquid mixture that contains the reacting species A2B, AC, DC3 and D2B3, list the equations which
must be solved simultaneously to determine the equilibrium composition by minimization of the Gibbs free energy.
 CHEN 623 Problems Page 12

The forms of the elements in their standard states (as ideal gases at the same temperature and one atmosphere) are A,
B, C and D2. The free energies of formation are known for each of the four reacting species at the temperature of
interest. The excess Gibbs energy for the liquid (relative to the constituents as pure liquids at the same temperature
and pressure) is given by:
GE
= ∑ ∑ Aij xi x j (i, j = 1,2, 3, 4 )
RT i j

where the Aij are functions of temperature and pressure, but not composition. Recall that the function to be mini-
mized is F = G + Σλ k fk where the fk are the constraint equations which arise from the atom balances, the λκ are the
Lagrange multipliers, and G is the total Gibbs free energy for the mixture.

PV
48. (1992.II.1) Consider a fluid mixture that is described by Z= = ecP where: c = c(x,T)
RT
a. Derive an expression which gives Vi , the partial molar volume of substance i, in this mixture as a function of P,
pressure, T, temperature, c, exponential factor and ci , the partial molar exponential factor.
b. Derive an expression for in terms of P, T, c and ci .
c. Does this equation of state predict vapor-liquid equilibrium for a pure fluid?
d. What relation, if any, between c and the {ci}will describe an ideal solution?
⌠ ax 1 ax ⌠ eax
dx = ln x + ∑
∞
( ax )
n

Mathematical Notes: ⎮e
⎮ dx = e and ⎮
⎮
⌡ a ⌡ x n=1 n ⋅ n!

49. (1992.II.2) Consider a binary mixture containing substances A and B which have vapor pressures PAsat = 0.326 MPa
and PBsat = 0.131 MPa. If the excess Gibbs energy in the liquid phase for this mixture is represented adequately by
GE
= Cx A x B
RT
then only one experimental measurement is required to specify the model (by determining the numerical value of C).
You may assume that the vapor phase behaves like an ideal gas mixture and that the pressure dependence in the liq-
uid phase is negligible.
a. Determine the range of values for C for which an azeotrope (xA = yA) occurs in this mixture.
b. If γ A∞ = 3.291 , determine (1) the numerical value of γ B∞ and (2) the total pressure and composition of the
azeotrope for this system.

50. (1993.II.1) Consider a binary mixture of substances A and B, where the vapor pressures of A and B are 1.629 and
0.542 bar respectively. You may treat the vapor phase as an ideal gas and neglect all Poynting corrections. The
excess Gibbs energy for the liquid phase is given by:
GE
= ax A x B
RT
γ Aaz PBσ
a. Show that, if an azeotrope exists for this mixture, at the azeotropic composition: =
γ Baz PAσ
b. For the excess Gibbs energy form given above, determine the range of values of a which yields azeotropes for
this system.
c. For a > 2, liquid-liquid equilibrium occurs in this system. Noting that the Gibbs energy change upon mixing
ΔmG, is symmetric about xA = 0.5, show that the composition of one of the two liquid phases present is given by
1
xA =
1+ exp ⎡⎣ a (1− 2x A ) ⎤⎦
What is the composition of the second liquid phase?
 CHEN 623 Problems Page 13

d. For a = 2.134, calculate the azeotropic composition and the total pressure at the azeotrope, and the composition
at which liquid-liquid phase separation occurs. Is the azeotropic pressure a maximum or a minimum?

51. (1993.II.2) Consider the reaction A + B → AB , which occurs in the liquid phase at 1 bar and 475.0 K with a
standard free energy of reaction, relative to liquid standard states, of Δ r G° = 2,569 J/mol. You may treat the liquid
phase as an ideal solution and neglect the Poynting correction.
a. If an equimolar mixture of A and B (no AB) is fed in the liquid phase to a reactor at 475.0 K, determine the
equilibrium composition of the reactor effluent, and the percentage conversion.
b. Determine the equilibrium composition and the percentage conversion if the feed composition is xA = 0.25, xB =
0.25 and xC = 0.50, where C is an inert component which does not participate in the reaction.

52. (1994.II.1) At 210 K, carbon dioxide is below its triple point temperature so the solid sublimes directly to the vapor
with a vapor pressure of 3.27 bar. Methane is above its critical temperature, so if a second phase condenses from a
vapor mixture of carbon dioxide and methane, that second phase is essentially pure solid carbon dioxide. The
second virial coefficients at 210 K are -286 and -96 cm3/mol for carbon dioxide and methane respectively.
Assuming that Z = 1+BP/RT provides a good description of the vapor phase, that the vapor phase is an ideal
solution, that the condensed phase is pure carbon dioxide and that the Poynting correction for pure carbon dioxide
may be neglected, calculate the pressure at which the vapor phase in equilibrium with the solid at 210 K is
equimolar in composition (i.e., that the mole fractions of carbon dioxide and methane are both 0.5000.

53. (1994.II.2) Consider a mixture with the liquid phase described, based on Lewis-Randall reference states, by
E
GLR
= 0.136x1 x2
RT
The vapor pressures of substances 1 and 2 are 0.993 and 0.685 bar respectively, and the corrections for the vapor
phase nonidealities and the Poynting correction in the liquid may be neglected.
a. Calculate the Henry's constants H12 (for substance 1 in 2) and H21 (for substance 2 in 1).
b. Give an expression for the excess Gibbs energy based upon Henrys Law reference states for both substances 1
and 2.
c. Over what range of compositions is Henry's Law valid to within 1 % for substance 1? for substance 2?

54. (2000.II.1) The Wilson equation leads to the following expressions for the activity coefficients in a binary mixture:
⎡ Λ12 Λ 21 ⎤
ln γ 1 = − ln ( x1 + x2 Λ12 ) + x2 ⎢ − ⎥
⎣ x1 + x2 Λ12 x1Λ 21 + x2 ⎦
⎡ Λ12 Λ 21 ⎤
ln γ 2 = − ln ( x1Λ 21 + x2 ) − x1 ⎢ − ⎥
⎣ x1 + x2 Λ12 x1Λ 21 + x2 ⎦
Here Λ12 = 1.93 , Λ 21 = 2.62 , P1σ = 107 kPa , and P2σ = 93 kPa .
a. Determine the total pressure and vapor composition over a liquid mixture with composition x1 = 0.35 .
b. Determine the Henry's constant, Η 21 , for species 2 at infinite dilution in this mixture.

55. (2000.II.2) Calculate the derivative, ⎜ ( ) ⎟

⎛ ∂ nZ ⎞ RT a
, for the van der Waals equation, P = − .
⎝ ∂ni ⎠ T ,nV ,n V −b V2
j≠i

The result should be given in terms of R, T, V, a, b, ai and bi .

56. (2000.II.3) Determine the relation between the heat of vaporization (liquid → vapor), the heat of sublimation (solid
→ vapor) and the heat of fusion (solid → liquid) at the triple point for a pure material. No other variables should
appear in the expression.
 CHEN 623 Problems Page 14

57. (2001.II.1) Consider a semi-permeable membrane that allows species A to pass through it, but not species B. The
membrane separates pure A in the liquid phase from a liquid mixture of A and B. The vapor pressures and molar
volumes of the pure species are denoted by PA, PB, VA and VB
a. Derive an expression for the equilibrium pressure difference, ΔP, across the membrane at temperature, T, if the
liquid mixture is an ideal solution. (This pressure difference is called the osmotic pressure.)
b. In which direction will mass transfer occur if the if there is no pressure difference across the membrane? How
do you know this?
c. For non-ideal liquid solutions, derive an expression that gives the activity coefficient (Lewis-Randall reference
state) of A in the liquid mixture in terms of pure fluid properties, the equilibrium pressure difference, ΔP, and the
mole fraction of A in the liquid phase, xA.

RT a
58. (2001.II.2) Consider the Redlich-Kwong equation of state: P = −
V − b V ( V+ b ) T
a. Derive an expression for ln φ̂i based upon this equation of state. You do not need to perform the integration with
respect to volume.
b. Derive expressions for ai and bi for the following mixing rules: am = ∑ ∑ aik xi xk and bm = ∑ bi xi
i k i

59. (2002.II) Consider a reactor vessel that contains the following substances: A, AB, B2, and C. Three of the
substances participate in the reaction: 2A + B2 → 2AB, while C provides an inert liquid environment for the
reaction. At equilibrium, three phases are present in the reactor at 500 K and 2.79 bar: a solid phase that contains
only A; a liquid phase that contains all the substances with mole fractions of 0.00476 (A), 0.00135 (B2), 0.337 (AB)
and 0.657 (C); and a vapor phase that that contains mole fractions of 0.38 (AB) and 0.62 (B2). Also at 500 K, the
sublimation pressure (solid/vapor equilibrium) of A is 4.23×10-5 bars, the vapor pressures (liquid/vapor equilibrium)
of AB and C are 3.62 bar and 2.31×10-3 bar respectively, and B2 is well above its critical temperature. You may
assume that the Poynting corrections are negligible for all substances. You also may assume that the vapor phase is
an ideal gas for all calculations except for part d.).
a. Determine the standard free energy of the reaction at 500 K based upon the following standard states (standard
state pressure = 1 bar): A as a pure solid, AB as a pure liquid, and B2 as an ideal gas.
b. Estimate the Henry’s constants for A and B2 in the liquid phase.
c. Calculate the activity coefficient for AB in the liquid phase, based upon a Lewis-Randall (pure liquid) reference
state.
d. Determine the relative (percentage) difference between the standard free energy calculated by assuming an ideal
gas vapor and that caculated assuming that the vapor phase is an ideal solution with second virial coefficients of
–57.6 cm3/mol for B2 and –275.1 cm3/mol for AB. Use Z = 1+(BP/RT) as the equation of state for the vapor
phase.

60. (2014.II.1) For a liquid that is described by the following form of the van Laar equation
GE xA xB ⎧ A = a0 + a1T
= where ⎨
RT Ax A + Bx B ⎩ B = b0 + b1T
In this expression, a0, a1, b0 and b1 are numerical parameters.
a. Derive an expression for the excess entropy for this liquid.
b. Derive an expression for the enthalpy of mixing for this liquid.

61. (2014.II.2) Consider a gas that forms a dimer in the vapor phase according to the reaction 2A ( g ) → A2 ( g ) . For
this reaction, Δ r G° = 9.28 kJ/mol , based on standard states of an ideal gas at 1 bar and 450 K, for this. A reactor
vessel with a total volume of 3.15 liters is charged with 0.1015 mole of pure A that originally contains no A2. The
temperature of the vessel is 450 K. You may assume that the ideal gas equation of state provides an adequate
description of the PVT behavior.
a. Develop an expression for the pressure in the vessel as a function of the mole fraction of A2.
 CHEN 623 Problems Page 15

b. Calculate the pressure and the mole fraction of A2 of the gas after it reaches equilibrium.

62. (2015.II.1) Consider a ternary mixture with an excess Gibbs energy described by
GE
= AAB xA xB + AAC xA xC + ABC xB xC
RT
∞
Determine expressions for ln γB and ln γB .

63. (2015.II.2) A one liter container is filled with a substance A2B at 200 °C. The initial charge of A2B was pure, but
some A2B decomposes to form A2 and B, resulting in a final pressure in the vessel of 1.75 bar. At this temperature,
liquid B and liquid A2B have vapor pressures of 0.0024 bar and 15.1 bar respectively. The critical temperature of
substance A is well below 200 °C. The dimensionless standard Gibbs energy of formation (ΔfG°/RT) of A2B at 200
°C is -5.2, based upon standard states of A2 as a gas, A2B as a gas, and B as a liquid, all at 1 bar pressure.
a. Calculate the equilibrium mole fraction of A2 in the gas mixture, assuming that some B condenses as a pure
liquid.
b. Calculate the equilibrium mole fraction of A2 in the gas mixture, assuming that all B remains in the vapor phase.
c. Which scenario, a.) or b.), correctly describes this situation? Justify your answer.
d. Determine the dew pressure (that pressure at which the mixture would be entirely in the vapor phase, but
saturated with substance B).

64. (2016.II.1) Several vapor-liquid equilibrium measurements are shown in the table below, which shows the liquid
composition, vapor composition and total pressure values for binary mixtures of substances A and B.

xA 0.0000 0.0100 0.0200 0.0300 0.0400 1.0000

yA 0.0000 0.1092 0.1924 0.2578 0.3104 1.0000
P/bar 0.594 0.660 0.721 0.778 0.829 1.087

a. Determine the vapor pressures of substances A and B.

b. Determine the Henry’s constant for substance A in substance B.
c. Give an algebraic expression that relates the dimensionless excess Gibbs energy (GE/RT) based upon Lewis-
Randall reference states (pure liquid at same T, P as the mixture) to the measured values of xA, yA and P. List all
assumptions required to obtain this form.
d. Give an algebraic expression that relates the asymmetric dimensionless excess Gibbs energy (GE/RT)as, based
upon a Henry’s law reference state for substance A and a Lewis-Randall reference state for substance B, to the
Henry’s constant, H, and the measured values of xA, yA and P. List all assumptions required to obtain this form.

65. (2016.II.2) A gas A is bubbled through a nonvolatile liquid B, where the following reaction occurs:
A ( gas ) + B ( liq ) → AB ( liq )
The physical states indicated in parentheses are those that serve as the standard states for each substance when
calculating the standard Gibbs energy of reaction for this reaction. The following assumptions apply:
• The gas phase also contains an inert substance I that does not participate in the reaction.
• The gas phase will not condense at any pressure at the reaction temperature.
• Liquids B and AB both have very small vapor pressures, so their mole fractions in the vapor phase each are less
than 0.001.
• The mole fractions of A and I in the liquid phase each are less than 0.001.
The answers to the following questions should be given in terms of the mole fraction of A in the vapor phase, yA, the
mole fraction of AB in the liquid phase, xAB, the total pressure, P, the standard state pressure, P°, and the reaction
equilibrium constant, K.
a. Assuming that the liquid phase exhibits ideal solution behavior, derive an expression for the equilibrium mole
fraction of AB in the liquid phase.
CHEN 623 Problems Page 16

b. Assuming that the liquid phase is not an ideal solution, but that the dimensionless excess Gibbs function is
described by
GE
= Ax B x AB
RT
derive an expression for the equilibrium mole fraction of AB in the liquid phase. (This expression may be
implicit in xAB.)
 CHEN 623 Problems Page 17

66. (1981.F) Consider a system which contains both vapor and liquid phases at 350 K. This system contains three
components A, B, and C which participate in the reaction 2A + B <==> C.
a. Determine the maximum number of phases that could possibly be observed in an equilibrium mixture of A, B,
and C. (The system temperature is not restricted to 350 K for this portion of the problem.)
b. The total pressure (to 1% accuracy) and the vapor phase composition in the system at 350 K. (Note that the liq-
uid phase composition is included in the system specifications.)
c. The standard free energy of reaction in the liquid phase based on standard states of pure A, B and C as saturated
liquids at 350 K.
d. The standard free energy of reaction in the liquid phase based on standard states of pure A, B, and C as ideal
gases at one atmosphere pressure at 350 K. Is this value equal to the standard free energy of reaction in the
vapor phase at 350 K, based upon the same standard states? Justify your answer.
e. Show that the representation of GE for the liquid phase is consistent with the Gibbs-Duhem equation for constant
temperature and pressure ( ∑ xi dGiE = 0 ).

System Specifications:
Excess Gibbs energy for liquid phase: GE/RT = A xA xB xC
where: A = a (1 + bP)/T; a = 3500 K; b = 3×10-3 atm-1

A: B: C:
Liquid phase composition 0.40 0.35 0.25
Pure component vapor pressures (atm) 0.150 0.100 0.050
Pure second virial coefficient (cm /mol)
3 -500 -1000 1500
Pure component saturated liquid volumes (cm3/mol) 32 46 38

Cross second virial coefficients: BAB = -850 cm3/mol; BAC = -1180 cm3/mol; BBC = -1400 cm3/mol

67. (1982.F.1) Vapor pressure data are given below for a system consisting of a noncondensable gas A and a nonvolatile
liquid B. Determine for this system the activity coefficients of the gas based on the following standard states:
a. Pure A as an ideal gas at the same temperature and one atmosphere pressure.
b. Pure A as an ideal gas at the same temperature and pressure.
c. Henry's law.
P/atm: 0.682 0.933 1.408
x A: 0.0125 0.0171 0.0258

68. (1982.F.2) Derive an expression for the heat capacity at constant pressure of a single-phase binary mixture where
the excess Gibbs function is given by:
G E / RT = (a + bP + c / T )x1 x2 .
Your result should contain only ideal gas heat capacities for the pure materials, equation of state information (i.e., Z
or its derivatives) for the pure materials, and parameters from the excess Gibbs equation.

69. (1982.F.3) Determine the equilibrium composition for the reaction given below if the standard free energy of the
reaction (based upon pure liquid standard states) is 1.5 kcal/mol. The reaction 2A <==> B occurs in the liquid
phase (ideal solution) at 10 atmospheres and 400 K. The following physical properties information may be useful:

T = 400 K: A: B:
Vapor pressure (atm) 3.61 6.34
Second virial coefficient (cm3/mol) 418 249
Saturated liquid molar volume (cm3/mol) 35.1 43.4
Cross virial coefficient (cm3/mol) -328
 CHEN 623 Problems Page 18

70. (1983.F.1) Consider a gas F2G which has a free energy of formation as an ideal gas from the ideal gases F and G of
-5,000 cal/mol at 25 °C. An empty cylinder is filled to 5 atmospheres with pure F2G, then it is placed in a storage
area for one year. Assuming that the cylinder initially was clean, and that thermodynamic equilibrium has been
attained, estimate the maximum amounts of pure F and G that may contaminate the sample gas.

71. (1983.F.2) Consider a system containing hydrogen sulfide and water at 25 °C and 2 atmospheres. Both vapor and
liquid phases are present (the vapor phase may be treated as though it is pure hydrogen sulfide).
a. Calculate the mole fraction and the molality of H2S in the liquid phase.
b. Calculate Δ f GHo 2S .
c. Estimate the pH of the liquid solution. (Note: pH = -log10 [H+].)
d. Estimate γ± for H+, HS- using the Debye limiting law.
Pertinent Data: Δ f GHo 2S = -7,892 cal/mol
Henry's constant for H2S in H2O at 25˚C = 54,500 atm
H2S → H+ + HS- K1 = 5.7 x 10-8
HS - → H+ + S= K2 = 1.2 x 10-15

72. (1984.F.1) A vessel with an internal volume of 1.893 liters is controlled at 25.00 °C. A quantity of substance A
(0.1314 moles) is introduced into the container, which previously was empty. After equilibrium is obtained, the
pressure in the vessel is measured to be 1.526 atm. No liquid phase is present in the vessel.
a. Determine the apparent second virial coefficient for substance A (in cm3/mol), assuming that the virial series
given by: Z = 1 + Bρ applies to this situation.
b. If a reaction is involved which forms a dimer of A, (2A → A2 ), determine the free energy of formation for the
dimer reaction, assuming that Z ≈ 1 for this case.

73. (1984.F.2) According to Perry's Handbook, a saturated aqueous solution of barium carbonate contains 0.0023
grams of barium carbonate per 100 cm3 of solution at 25.0 °C and 1 atmosphere.
a. Calculate the apparent solubility product (γ± = 1) for barium carbonate in water.
b. Estimate the actual solubility product for this solution.

74. (1984.F.3) Consider a strong electrolyte MA2 in a galvanic cell. Upon electrolysis, pure M and pure A are
deposited at the respective electrodes. Both A and M are solids at the reaction temperature (25 °C), therefore we
take GA0 = 0 = GM0 . Electrode potential measurements for various molalities are as follows:
m /(mol/kg): 0.00010 0.00050 0.0010 0.0015 0.0020 0.500 1.50
E/volts: 0.899 0.879 0.870 0.866 0.862 0.804 0.792
a. Determine GoM++ + 2 GoA- for this electrolyte.
b. Calculate the mean activity coefficients at molalities of 0.5 and 1.5.

75. (1985.F.1) Consider vessel that contains two substances A and B which participate in the reaction 2A <=> B. The
reaction vessel contains both a vapor phase and a liquid phase which are in both chemical and physical equilibrium.
There are no other substances present in the reactor. At a temperature of 600 K, the vapor phase composition is 25
mole per cent A, 75 mole per cent B, while the liquid phase contains 40 mole per cent A and 60 mole per cent B.
The vapor pressures of A and B at 600 K are 1.58 and 2.78 atmospheres respectively. The total pressure in the ves-
sel is 2 atmospheres. You may assume that the vapor phase behaves as an ideal gas.
a. Calculate the standard Gibbs energy of reaction for this temperature and pressure, based upon ideal gas standard
states at the reaction temperature.
b. Calculate the excess Gibbs energy for the liquid phase based upon pure liquid reference states.
c. Calculate the standard Gibbs energy of reaction for this temperature and pressure, based upon pure liquid stan-
dard states.
 CHEN 623 Problems Page 19

76. (1985.F.2) The standard free energy of formation and the standard heat of formation for sulfur dioxide gas at a
temperature of 25 °C and a pressure of one atmosphere are -88.59 kcal/mol and -94.39 kcal/mol respectively, based
upon the elements in their standard states at the same temperature and pressure. Perry's Handbook provides the
following data for sulfur dioxide solubilities in aqueous solution at 0 °C :
wi (gm): 0.02 0.05 0.10 0.15 0.20 0.30 0.50 0.70
Pi (mm Hg): 0.25 0.6 1.2 1.9 2.8 5.1 9.9 15.2
wi (gm): 1.0 1.5 2.5 5.0 7.5 10 15 20
Pi(mm Hg): 23.3 38 69 148 228 308 474 646

where: wi = mass of SO2 dissolved per 100 gm of water

Pi = partial pressure of SO2 over solution.
a. Calculate the standard free energy of formation of gaseous sulfur dioxide at 0 °C and one atmosphere based upon
the elements in their standard states at the same temperature and pressure.
b. Calculate the standard free energy of formation of sulfur dioxide in aqueous solution at 0 °C and 1 atmosphere,
based upon the usual standard state of a hypothetical ideal solution of unit molality at the temperature and
pressure of the solution.
c. Calculate the activity coefficient of aqueous sulfur dioxide, based upon the standard state described in b.), when
the aqueous solution contains 50 grams of sulfur dioxide per kilogram of water at 0 °C and 1 atmosphere
pressure.

77. (1985.F.3) The surface tension of water at the normal boiling point is approximately 0.0589 N/m, the heat capacity
is approximately 4.2 kJ/kg K and the density is approximately 1000 kg/m3
a. Calculate the temperature change if 1 milligram of water, initially present as spherical liquid droplets all with
radii of 10-5cm at a temperature of 373 K, coalesce to form a single spherical droplet.
b. Calculate the temperature change if only three of the particles considered in a.) coalesce to form a single spheri-
cal droplet.
c. Consider the case where the spherical particles of liquid water have a distribution of radii described by
P(x) = ax exp{−(x − 1)2 } where: a = 2.34×1010
x = r/r0 (0 < x < ∞)
-5
r0 = 10 cm
Here P(x) gives the number of spherical particles with radius r. (The parameters have been chosen so that the
total amount of water present is approximately one milligram.)
i. Determine the radius at which the maximum number of droplets occurs, and the radius at which the
maximum mass of water is present.
ii. Determine the total surface area of all the droplets.
∞ Γ ( b+1
2 )
Useful mathematics information: Γ(n +1) = nΓ(n) = n!; Γ ( 12 ) = π ; ∫ x b eax dx =
2

b+1
0 2a 2

78. (1988.F.1) Consider two salts, A3B2 and AC2, the former of which is relatively insoluble (solubility product based
upon molalities = 1.473×10-8) and the latter extremely soluble (solubility product = 157) in water at 25°C. The
atomic weights of the constituent atoms are 45, 50 and 40 for A, B and C respectively. Both salts are very strong
electrolytes.
a. Determine the loading of A3B2 (in grams per 100 grams of water) at saturation at 25 °C, assuming that the solu-
tion is sufficiently dilute to be treated as an ideal solution.
b. If 5 grams of AC2 are added to 100 grams of a saturated solution of A3B2 at 25 °C, determine the mass of A3B2
that will precipitate and the final molalities of A++ and B---.
 CHEN 623 Problems Page 20

79. (1988.F.2) Consider a liquid mixture of two substances A and B which can be described by: GE/RT = 3.42x1x2
where the reference states for the excess Gibbs calculation are the pure liquids A and B at the same temperature and
pressure. The pressure may be considered to be sufficiently low that all Poynting corrections may safely be ignored.
This mixture divides into two liquid phases for mole fractions of substance A between 0.04169 and 0.95831. In
addition, substance A reacts to form B according to the reaction: 3A <==> B.
a. Develop one or more mathematical expressions which give the free energy change upon mixing, based upon the
pure liquid reference states, for the entire composition range, and which correctly takes into account the exis-
tence of the two liquid phase region. Sketch the behavior of the energy change upon mixing as a function of xA.
b. Determine the dimensionless free energy of the reaction (ΔrG/RT) if the equilibrium concentration is the
saturated phase with xA = 0.04169. Compare this value to that obtained when the other saturated phase is
considered.
c. Develop an expression for the total free energy of the mixture as a function of an extent of reaction variable,
ε = 1 - nA / nA0 ε = 1− nA / nA0 ,
the dimensionless free energy of the reaction and the initial numbers of moles of each compound present.
Assume that the overall composition is such that the system remains in the two-liquid-phase regime.

80. (1989.F.1) Consider a foam composed of bubbles all of radius 140 nm (1.4×10-7 m) imbedded in a continuous liquid
phase. The temperature is 310 K and the equilibrium vapor pressure, liquid molar volume, and surface tension of
the fluid are 2.36 bar, 65 cm3/mol, and 0.0106 N/m respectively. The bubbles occupy exactly half of the total
volume of the foam. (The gas constant is: R = 8.314 J/mol K.)
a. Calculate the pressure in the continuous (liquid) phase, recalling that the pressure difference between the two
phases is approximately 2σ/r.
b. Calculate the energy released per cubic meter of foam if the foam breaks (all bubbles coalesce into a bulk vapor
phase).

81. (1989.F.2) Solid-liquid equilibrium can be used to determine activity coefficients of solutes in liquid solutions.
Consider a pure nonelectrolyte solid in equilibrium with a liquid solution. (Nonelectrolyte means that the solid does
not dissociate into ions when it dissolves in the solution.)
a. Derive a relation between the activity coefficient of the solute in the solution (relative to the usual Lewis-Randall
reference states) and the fugacities of the solute as a pure liquid and as a pure solid (fiL and fis).
b. Derive an expression which can be used to calculate ( fi s / fi L ) from the pure solute vapor pressure, freezing
pressure and molar volume as a pure liquid.
c. The approach used in a.) and b.) is not convenient for most practical applications because most solutes are below
their triple point temperatures. Describe an alternate reference state and show how you would calculate a
numerical value for fi from physical properties (preferably those of the pure solute). Explicitly state all
assumptions that are required.

82. (1989.F.3) The statistical mechanics rule that describes the second virial coefficient for a binary mixture is
Bm = y12 B11 + 2y1 y2 B12 + y22 B22
where B11 and B22 are the second virial coefficients for pure fluids 1 and 2 respectively, and B12, the cross virial co-
efficient, contains information about the interactions between unlike molecules. For the pressure virial equation
truncated after the second virial coefficient, Z = 1 + BP/RT, derive the relationship which gives B12 in terms of B11
and B22 for an ideal solution (relative to the pure gases as real fluids).

83. (1990.F.1) Consider a membrane that is permeable to gas A but not to gas B. The membrane is elastic, with an
internal tension (equivalent to surface tension) which depends directly on the extent to which the surface is
stretched:
σ = k(A − A0 ) = 4π k(r 2 − r02 ) r ≥ r0
 CHEN 623 Problems Page 21

The membrane is surrounded by pure A at a pressure P0 and temperature T0, and it contains a mixture of A and B at
P and T0.
r02
a. Show that : P − Po = 8π k(r − ) for r ≥ ro .
r
b. The system is filled with a mixture of A and B to a pressure such that the radius of the sphere enclosed by the
membrane is 0.65 m. Molecules of A diffuse slowly through the membrane until equilibrium is achieved, at
which time the radius of the sphere enclosed by the membrane is 0.36 m. Calculate the initial and final composi-
tions of the mixture inside the membrane if P0 = 0.0978 MPa, T0= 298.62 K, r0 = 0.165 m, and k = 18,400 N/m3.
c. Calculate the total change in entropy of the universe for the change from the initial conditions of part b.) to the
equilibrium state.

84. (1990.F.2) Estimate the enthalpy and entropy of ionization for water at 20 °C based upon the following table
showing the behavior of the pH of water as a function of temperature. (pH = - log10[H+]):

t /°C: 0 10 20 30 40 50
pH: 7.47 7.27 7.08 6.92 6.77 6.63

85. (1990.F.3) The solubility products for silver chloride and silver carbonate at 25 °C are given in the table below.
Which of the following contains the most silver per unit volume: a saturated solution of silver chloride or a
saturated solution of silver carbonate? Calculate the mass of silver contained in a liter of each saturated solution.
Molecular Weight: Solubility Product:
Ag2CO3 275.77 1.56×10-10
AgCl 143.34 6.15×10-12

86. (1991.F.1) Soft drinks are carbonated by pressurization with carbon dioxide, which dissolves in the drink to an
appreciable extent. However, dissolved carbon dioxide forms carbonic acid, which dissociates to form bicarbonate
and carbonate ions and hydrogen ions (protons). This results in appreciable acidity on the part of the solution. In
addition, when the container is opened, the pressure on the liquid is reduced to atmospheric pressure, and the carbon
dioxide tends to leave the solution, especially if the mixture is agitated. Consider the case where the soft drink
(water) at 18 °C is pressurized to 4.86 bar with carbon dioxide in containers where two liters of liquid are present.
a. Calculate the volume of carbon dioxide at 25 °C and 1 atmosphere that would be released if all the dissolved gas
came out of solution.
b. Estimate the pH of the liquid at equilibrium with 4.86 bar of carbon dioxide at 18 °C. Note that the water-rich
liquid phase in a gas pipeline containing an equivalent partial pressure of carbon dioxide would have
approximately the acidity (e.g. a 10% carbon dioxide stream at 500 psia), thereby providing the potential for
serious corrosion problems.
Useful Information:
Carbon dioxide fugacity coefficients (pure fluid) and solubilities in water (from Perry's Handbook) at 18 °C:

P/atm: 25 50 75 100 150

wt CO2/wt H2O: 0.0386 0.0633 0.0669 0.0682 0.0707
φ CO2: 0.865 0.731 0.533 0.422 0.312

Molecular weights: Carbon dioxide: 44.01; water: 18.016

Vapor pressures at 18 °C: Carbon dioxide: 53.73 atm water: 0.020 atm
Dissociation reactions: H2CO3 → H+ + HCO3- K1 =4.3 × 10 -7 mol/L
HCO3- → H+ + CO3= K 2 =5.61× 10 -11 mol/L
pH = - log10 [H+] where [H+] denotes moles of hydrogen ion per liter of solution
 CHEN 623 Problems Page 22

87. (1991.F.2) Mercury porosimetry often is used to measure the size

distribution of pores with radii in the 1 to 10 nanometer range. In this
measurement, the volume of mercury forced into the sample is Hg Vacuum
measured as a function of temperature by measuring the volume r
displaced as the system is pressurized with a piston pump. Because Pore
mercury does not wet the surface of most materials, it is reasonable to
assume that the contact angle with the wall is approximately zero, i.e.,
r = radius of curvature of Hg surf
ace
that the wall is tangent to the curved surface of the liquid (see drawing = pore radius
below).
a. Calculate the pressures necessary to force mercury at 20 °C into
cylindrical pores of radius 0.1, 1.0 and 10 nanometers.
b. Calculate the pressures necessary to force water into the same pores treated in part a.). For what reasons is
mercury the fluid usually preferred for these measurements?
Useful Information: The Chemical Rubber Handbook lists the surface tension of mercury as 0.4803 and 0.4671
Pa·m at 0 and 60 °C respectively and of water as 0.07275 Pa·m at 20 °C.

88. (1992.F.1) The pressure in the vapor phase over a pure fluid contained in a pore (as shown below) is different from
the vapor pressure of the fluid. The angle, θ, between the liquid-vapor interface and the solid surface, which often is
referred to as the contact angle, provides a measure of the degree of wetting of the surface by the liquid. (Note that
the radius of curvature of the spherical liquid-vapor interface is not one half the diameter but is related to the
diameter through the contact angle.) Calculate the difference between the equilibrium pressure in the vapor over the
fluid in the pores and the bulk equilibrium vapor pressure of the fluid.

C o n ta c t a n gle
θ

D Vap o r
r

θ
Liq uid S olid S urf ac e
The properties of the pore and of the fluid are:
Vapor pressure (flat surface) = 0.1492 MPa Liquid molar volume = 76.9 cm3/mol
Second virial coefficient = -493 cm3/mol Surface tension = 0.0387 N/m
Pore diameter = 0.627 micrometers Temperature = 309.4 K
Contact angle = 54° Gas constant = 8.314 J/mol·K

89. (1992.F.2) Consider a mixture which involves the reaction: A + 2B → 2C. The equilibrium composition is
measured at two temperatures, 421.27 and 448.61 K, both at a pressure of 1.228 MPa. The compositions and other
pertinent physical properties data are shown below. Assuming that both the vapor and liquid phases may be treated
as ideal solutions, calculate the following:
a. The free energies of the reaction at 421.27 K relative to standard states of pre substances as liquids at pressures
of 0.1 MPa and 1.228 MPa.
b. The standard enthalpy and standard entropy of the reaction at 421.27 K relative to a standard state pressure of 0.1
MPa.
c. The bubble pressure of the liquid mixture at 421.27 K.
d. The equilibrium composition if the pressure of the mixture at 421.27 K is reduced to 0.0235 MPa. (The original
composition is that shown in the table below.)
 CHEN 623 Problems Page 23

Physical Properties:
A: B: C:
@421.27 K Liquid composition @ 1.228 MPa 0.4187 0.3126 0.2687
Liquid molar volume (cm3/mol) 98.67 84.71 105.62
Vapor pressure (MPa) 0.3082 0.2917 0.0965
Second virial coefficients (cm3/mol) -46.32 -192.1 -422

@ 448.61 K: Liquid composition @ 1.228 MPa 0.4245 0.3293 0.2462

Liquid molar volume (cm3/mol) 97.42 82.98 103.55
Vapor pressure (MPa) 0.4503 0.3352 0.1026
Second virial coefficients (cm3/mol) -34.23 -176.1 -402

90. (1993.F.1) The solubility product for Cu2S is 2.26×10-48. The atomic weights of copper and sulfur are 63.546 and
32.064 respectively.
a. Assuming ideal solutions behavior, determine the mass of Cu2S per 100 grams of water in a saturated solution.
b. Estimate the mean ionic activity coefficient in the saturated solution using extended Debye-Hückel theory.

91. (1993.F.2) Compare the pressure and composition in the vapor phase for a mist of fine droplets (r = 0.56 µm, σ =
0.043 Pa·m) with the pressure and vapor composition for equilibrium across a flat interface, all at 298.15 K.
Assume that the vapor phase is an ideal gas and the liquid phase is an ideal solution. Use the following physical
properties:
xi Pi sat Vi L

A 0.421 263.2 kPa 35.6 cm3/mol

B 0.579 108.4 kPa 42.1 cm3/mol

92. (1993.F.3) The fugacity of a substance in a mixture in the presence of a gravitational field is given by:
⎡ M gz ⎤
f̂i = f̂i no gravity exp ⎢ i ⎥
⎣ RT ⎦
dP M ave g
and the derivative of pressure with respect to height by: =
dz V
where g is the acceleration due to gravity, z is the vertical displacement relative to a reference level, Mi is the
molecular weight of substance i, Mave (= ∑xiMi) is the average molecular weight of the mixture, and V is the molar
volume of the mixture.
a. Give an expression for the fugacity of species i in the mixture as a function of vertical position relative to the
reference point. You may not neglect the Poynting Factor in this calculation.
b. Show that the gradient of composition with height is:
xiγ iL g ⎡ M V⎤
M − ave i ⎥
dxi RT ⎢⎣ i V ⎦
=
dz dγ i gz Vi ⎛ dM ave M ave dV ⎞
γ i + xi + xiγ i −
dxi RT V ⎜⎝ dxi V dxi ⎟⎠

c. For an ideal solution, assuming that last term in the denominator can be neglected, compute the numerical value
of the gradient of composition with height for a binary mixture where T = 301.6 K, g = 9.8 m/s2, and
xi Mi Vi L
A 0.376 43.12 59.3 cm3/mol
B 0.624 76.28 82.6 cm3/mol
 CHEN 623 Problems Page 24

93. (1994.F.1) Consider the reaction AB + 3C → AC3 + B , where A, B, and C are free elements. The physical
properties of substances A, B, C, AB and AC3 are given in Table 1. At a temperature of 325.4 K and a pressure of
1.615 bar, the equilibrium composition in the liquid phase is that given in Table 1. The free energy of formation of
compound AB is -1,352 J/mol, based upon the free elements A and B in their equilibrium states at the standard
conditions of 325.4 K and 1.000 bar. You may assume that the liquid and vapor mixtures are ideal solutions, but
you may not assume that any vapors are ideal gases.
a. Calculate the free energy of formation of compound AC3, based upon the free elements A and C in their
equilibrium states at the standard conditions.
b. Calculate the free energy of reaction for the reaction AB + 3C → AC 3 + B , based upon hypothetical ideal gas
standard states for all reactants and products at the reaction temperature, T, and 1 bar pressure.

94. (1994.F.2) Elements B and C in Problem 1 do not react when mixed. At a temperature of 325.4 K, the liquid phase
composition is xB = 0.419 and xC = 0.581.
a. Calculate the total pressure and the vapor composition for vapor-liquid equilibrium where the phases are
separated by a flat interface.
b. If the interfacial tension (surface tension) is 0.107 Pa·m, calculate the equilibrium pressure in the liquid phase
and the vapor phase composition in a foam consisting of bubbles with radii of 6.7×10−6 m.
Table 1994-1. Physical Properties of Materials for Problems 1994.F.1 and 1994.F.2
Substance A B C AB AC3
sat
Pi bar 47.2 4.356 0.631 0.229 0.0965
L 3
Vi cm /mol 23.2 38.4 57.6 69.1 78.2
3
Bi cm /mol 10.2 -32.6 -109.1 -219.4 -495.6
eq
x i 0 0.2977 0.4278 0.2155 0.0590

95. (1994.F.3) A strong electrolyte M3A generates the electrode potentials given in Table 2 as a function of
concentration of M3A when pure M and pure A as solids are present in the solution.
a. Determine the standard electrode potential E° for this reaction.
b. Estimate the mean ionic activity coefficient for M3A at unit molality.
Table 94.F.2. Data for Problem 94.F.3.
mM 3A / (mol/kg solvent) E/volts
−6
1.2 × 10 -0.837
1.57 × 10−5 -0.930
1.098 × 10−4 -1.001
1.331 × 10−3 -1.098
1.294 × 10−2 -1.196
0.0753 -1.282
0.1208 -1.306
0.533 -1.382
0.866 -1.406
1.035 -1.415
1.294 -1.425

96. (2000.F.1) Consider an ideal gas mixture subject to a gravitational field giving rise to an acceleration due to gravity,
g. The temperature of the gas, T, is uniform throughout.
⎡ gz ⎤
a. Show that the variation of pressure with respect to vertical position is P ( z ) = P ( 0 ) exp ⎢ − ∑y M ⎥i i
⎣ RT i ⎦
 CHEN 623 Problems Page 25

where P(0) is the pressure at z = 0, yi and Mi are the mole fraction and molecular weight respectively of
substance i,
b. Derive an expression for yi(z), the mole fraction as a function of vertical position, for this mixture, The result
should contain yi(0), the value at z = 0, and it should not contain P.

97. (2000.F.2) When a pure compound AB2 is fed as a gas to a reactor operating at equilibrium at 300 K and 1.68 bar,
20% of the compound decomposes according to AB2 → A + 2B.
a. Determine the percentage of AB2 which decomposes if the reactor feed contains 30% AB2 and 70% C, an inert
compound which does not participate in the reaction.
b. Determine the relative (percentage) difference between the free energy of reaction at 300 K based upon ideal gas
standard states at 1 bar, and the free energy based upon ideal gas standard states at 1 atm. (1 atm = 1.01325 bar).

98. (2000.F.3) Based upon the empirical extension of the Debye-Huckel limiting behavior
I
log10 γ ± = 0.509 z+ z−
1+ I
determine how many moles of a salt A2B must be added to 100 grams of water to obtain a solution with a mean
ionic activity coefficient of 2. You may assume that the salt dissociates completely.

99. (2001.F.1) The CRC Handbook of Chemistry and Physics contains a table titled “Lowering of Vapor Pressures by
Salts in Aqueous Solutions” that contains experimental data in the following format:
Pressure reduction: 0.5 1.0 2.0 etc.
Concentration: 12.0 23.7 45.1 etc.
In this table, the pressure units are millimeters of mercury and the concentration units are moles of salt per liter of
water. The data in the table are for a solution temperature of 100 °C, at which temperature the vapor pressure of
water is 760 mm Hg. The pressure reduction, ΔP, is
ΔP = Pwater
vapor
− Psolution
vapor

Derive an expression to be used to calculate the activity coefficient of water (based upon Lewis-Randall) from this
data and other physical properties as necessary. Assume that the salt, Mν + Aν − , is a strong electrolyte. Clearly state
any other assumptions that you make in the derivation.

100. (2001.F.2) Consider the case where a gas reacts with a solid to form a second gas: 2A ( g ) + B( s ) → A2 B( g )
At the reaction temperature, the dimensionless free energy of reaction, ΔrG°/RT, is 0.814, and the solid has a
sublimation pressure of 3.2×10-6 bar.
a. Beginning with an initial vapor composition of pure A and an excess of pure B, determine the equilibrium
composition of the vapor phase when the reaction occurs at a pressure of 1.81 bar.
b. For which species does the mole fraction in the vapor phase increase as the pressure increases?
c. Beginning with an excess of B and an initial vapor composition that is an equimolar mixture of A and C (an inert
vapor that does not participate in the reaction), determine the equilibrium vapor composition at 1.81 bar.

101. (2001.F.3) Determine the radius for which a bubble is in equilibrium with a liquid water + methane mixture at 35
°C and1 bar with x(CH4) = 0.0015. The Henry’s constant for methane in water at 35 °C is 4.9×104 bar, and the
surface tension for the interface is 0.070 N/m. You may assume that the gas in the bubble is pure methane.

102. (2002.F.1) The figure at right shows a droplet hanging from an open tube. Determine the
relationship between h, the height of the liquid in the tube, r, the radius of the droplet hanging
from the end of the tube, and physical properties of the fluid (e.g., density, vapor pressure. surface
tension, etc.). You may assume that atmospheric pressure, P0, acts upon the surface of the liquid
h
in the tube and upon the surface of the droplet. You also may assume that the effect of the
meniscus in the tube is negligible and that h >> r.
 CHEN 623 Problems Page 26

103. (2002.F.2) The saturation concentration of an aqueous solution of a strong electrolyte, BC3, is 4.63 g of electrolyte
per 100 grams of water. Determine the solubility product for this electrolyte. The molecular weights of B, C, and
water are 46.2, 61.9 and 18.0 respectively. You may not assume that this is an ideal solution, but you may assume
that the extended Debye limit law holds:
I
log10 γ ± = −0.50z+ z−
1+ I

104. (2002.F.3) One method of purifying water is a process known as reverse osmosis. A schematic diagram of a
reverse osmosis process is shown in the figure below. The key part of the equipment is a membrane (RO
Membrane) that is permeable to water but not to impurities such as ions. When the system is started up, the tank
initially is full of air at atmospheric pressure. When the discharge valve is closed, pure water begins to accumulate
in the storage tank. As water enters the tank, the air is compressed so that the pressure in the pure water system rises
until equilibrium is reached.

Air
Supply
Storage
Tank
Waste Pure Water
Discharge RO Membrane
Discharge

The impure water supply is at a pressure, Ps, and it contains a strong electrolyte, MaAb, at a weight fraction, χ. The
atmospheric pressure is P0 and the entire temperature is at T0.
a. Derive an expression that gives the mean molality, m±, of the feed solution.
b. Derive an expression that gives, at equilibrium, the fraction of the storage tank volume filled with water as a
function of Ps, χ, P0, T0, and other variables (e.g., vapor pressure, molar volume, molecular weight, gas constant,
etc.) as necessary.
∞ ∞
1 1
Math Notes: e x = ∑ x k ≅ 1+ x + 12 x 2 + 13 x 3 +! ; ln (1− x ) = − ∑ x k ≅ −x − 12 x 2 − 13 x 3 −!
k=0 k! k=0 k

105. (2014.F.1) Consider the capillary effect of a liquid in a tube as shown in the drawing at the right. θ
a.` Derive an expression for the height, h, to which the liquid rises in terms of the contact angle, θ,
the diameter of the tube, appropriate physical properties of the fluid and other physical
constants. State clearly what asumptions (if any) are made. h
b. Discuss the qualitative behavior as the contact angle varies from 0 (perfect wetting) to π
(perfectly non-wetting). Sketch the resulting situations for three cases: i.) 0° < θ < 90°; ii.)
θ = 90°; iii.) 90° < θ < 180°.

106. (2014.F.2) The fugacity of a polarizable fluid in the presence of an electric field is given by
⎡α E2 ⎤
f̂i field = f̂i no field exp ⎢ i ⎥
⎣ 2RT ⎦
where αι is the polarizability of substance i and E is the electric field strength. Derive an expression for the pressure
gradient induced in a pure polarizable fluid by the presence of a charged sphere as a function of r, where r is the
distance from the center of a sphere. Note that r is greater than the radius of the sphere. The field due to the
presence of the charged sphere is given by
Q ⎛ 1⎞
E= ⎜ ⎟ where Q is the total charge on the sphere and εo is the dielectric permitivity of free space.
4πε o (1+ α ) ⎝ r 2 ⎠
 CHEN 623 Problems Page 27

107. (2014.F.3) The solubility product (in water) of silver chloride (AgCl) is 1.77×10-10 (mol/kg solvent)2.
a. Estimate the equilibrium molalities of silver and chloride ions and the mean ionic activity coefficient for a
solution in equilibrium with solid silver chloride.
b. Estimate the equilibrium molalities of silver, sodium and chloride ions after an excess amount of solid silver
chloride is added to a solution originally containing 0.02 moles of dissolved sodium chloride (NaCl) per
kilogram water. You may assume that the solubility product of sodium chloride is much larger than that of silver
chloride.

108. (2015.F.1) Mercury manometers provide a simple method for accurately calibrating pressure transducers at
pressures below 2 bars. The best methods available for visual measurement of the height of the mercury column
provide a resolution of approximately 5 Pa (slightly over 0.001 in of Hg) in the pressure. Because mercury does not
wet clean glass, the contact angle at the mercury/glass/vapor interface is 180°, so that the radius of curvature of the
spherical mercury/vapor interface is equal to the radius of the glass tube. Assuming that the mercury/vapor interface
is spherical, determine the minimum diameter for the glass tube that assures that the pressure difference across the
interface is less than the resolution of the pressure measurement.
Physical properties of mercury: ρ = 13.6 g/cm3; σ = 0.47 Pa·m.

Note: The actual minimum diameter is less than that calculated under assumptions specified above, because the
surface is flattened by the effect of hydrostatic pressure head within the mercury.

109. (2015.F.2) A ideal gas sample with an average molecular weight of M is placed in a cylindrical shell container that
is rotated in a centrifuge. The sample container has an inner radius of ri and an outer radius of ro. The pressure at
the inner wall is Pi, the pressure at the outer wall is Po. The temperature, T, of the gas is constant throughout the
container, therefore the molar density, ρ, varies with position if the pressure varies with position. Determine the
difference in pressure between the inner and outer walls.
dP
The pressure gradient induced by rotation at an angular velocity of ω is: = M ρω 2 r
dr

110. (2015.F.3) A salt, MA2, which is a strong electrolyte, has a standard electrode potential, E°, of 0.913 volts.
Determine the actual electrode potential at 300 K for a 0.30 molal solution of this salt.

111. (2015.F.4) A tube with a cross-sectional area of 100 cm2 has a membrane at one end that is
permeable to water but not to ions. One liter of a 1 M solution of NaCl (MNaCl = 58.45 g/mol)
is placed in the tube, and it is inserted into a container of pure water as shown in the diagram.
The entire system is at a temperature of 300 K. Because water passes through the membrane,
the level of the liquid rises, and the salt solution is diluted. You may assume that the salt
solution is perfectly mixed, that the water in the solution may be described as an ideal solution
with respect to a Lewis-Randal reference state, and that the molar density of the solution is
always the same as the molar density of liquid water, which is 55.5 mol/liter.
a. Determine the vertical distance between the liquid levels when the system reaches steady
state.
b. Determine the entropy change of the universe resulting from the diffusion of 100 mol of water through the
membrane.

112. (2016.F.1) The fugacity of a polarizable fluid in the presence of an electric field is given by
⎡α E2 ⎤
f̂i field = f̂i no field exp ⎢ i ⎥
⎣ 2RT ⎦
where αι is the polarizability of substance i and E is the electric field strength. Derive an expression for the
composition gradient induced in a binary gaseous mixture of substances A and B near a charged cylindrical
conductor (e.g., an electrical transmission line) as a function of r, where r is the distance from the center of the
conductor. Note that r is greater than the radius of the conductor. The field due to the presence of the charged
conductor is given by
 CHEN 623 Problems Page 28

λ ⎛ 1⎞
E= ⎜ ⎟
2πε o (1+ α ) ⎝ r ⎠
where λ is the charge per unit length on the conductor, and εo is the dielectric permittivity of free space. The
following assumptions apply:
• The mixture of A and B is an ideal gas.
• The field does not induce a significant pressure gradient.
• The polarizability of the mixture is related to the individual polarizabilities by: α = x Aα A + x Bα B

113. (2016.F.2) One aspect of the environmental effect ascribed to increasing carbon dioxide content in air is the
increasing acidification of the ocean. Estimate the pH of the ocean for two atmospheric CO2 concentrations: 200
parts per million, and 500 parts per million. The following information may be helpful:
Molar density of water: 55.4 mol/liter
Henry’s constant for CO2 in water: 1,600 atm
Dissociation reactions: H 2CO 3 → H + + HCO −3 K1 = 4.3 × 10 -7 mol/L
HCO −3 → H + + CO =3 K 2 = 5.61× 10 -11 mol/L
pH = - log10 [H+] where [H+] denotes moles of hydrogen ion per liter of solution

114. (2016.F.3) Consider a membrane that is permeable to gas A but not to gas B. The membrane is elastic, with an
internal tension (equivalent to surface tension) which depends directly on the extent to which the surface is
stretched:
σ = k(A − A0 ) = 4π k(r 2 − r02 ) r ≥ r0
The membrane is surrounded by pure A at a pressure P0 and temperature T0, and it initially contains pure B at P and
T 0.
r02
a. Show that : P − Po = 8π k(r − ) for r ≥ ro .
r
b. The system is filled with pure B to a pressure such that the radius of the sphere enclosed by the membrane is 0.65
m. Molecules of A diffuse slowly through the membrane until equilibrium is achieved. Calculate final pressure,
radius and composition of the mixture inside the membrane if P0 = 0.0978 MPa, T0= 300 K, r0 = 0.165 m, and k
= 18,400 N/m3.
c. Derive an algebraic equation for the total change in entropy of the universe for the change from the initial
conditions of part b.) to the equilibrium state.
 CHEN 623 Problems Page 29

Other Problems:
115. (H01) Compressed gases are supplied to customers in cylinders containing 256 cubic feet of gas measured at 14.7
psia and 70 °F. The cylinder volume is such that when the appropriate amount of gas is in the container, the
pressure of an ideal gas at 70 °F would be 2500 psia. Therefore, when the cylinders reach the users, the cylinders
are guaranteed to be at a pressure of at least 2500 psia at 70 °F. A customer complains that when the cylinders were
received, they were not up to pressure. The supplier claims that this is impossible because all cylinders and valves
were checked for leakage, and it has been determined conclusively that leakage through the valves or out of the
cylinder in any other way does not exist. Furthermore, the supplier says that to be absolutely sure that the user
would receive full measure of gas, the cylinders were filled from a line in which the pressure never fell below 3,000
psia, with the temperature in the line always within 1 degree of 70 °F.
a. Do you think the user's complaint could be justified? If so, explain why.
b. Determine the minimum pressure at 70 °F that might actually be observed by the customer for cylinders
containing each of the following gases: helium, hydrogen and methane, assuming ideal gas behavior for each
each gas.
c. Determine the minimum pressure at 70 °F that might actually be observed by the customer for cylinders
containing each of the following gases: helium, hydrogen and methane, assuming real gas behavior for each
each gas.
d. Determine the number of pound moles present in the cyinder at 2,500 psia and 70 °F for each of the following
gases: helium, hydrogen and methane, assuming real gas behavior for each each gas.
Note: For parts c.) and d.), use the physical properties available at http://webbook.nist.gov/chemistry/fluid/

116. (H02) A steam supply line provides steam at 600 °F and 300 psia.
a. Determine the mass and the temperature of the steam in an insulated piston-cylinder arrangement if sufficient
steam is admitted to displace the piston by one cubic foot. The cylinder originally is empty, and the piston main-
tains a constant pressure of 100 psia as the steam is admitted to the cylinder.
b. Determine the mass and temperature of the steam admitted into a rigid tank from the supply line if sufficient
steam is admitted to obtain a final pressure of 100 psia. The tank originally was empty and the tank volume is
one cubic foot. Compare the results for the rigid tank and for the cylinder operating at constant pressure.

117. (H03) A 10 cubic foot insulated tank contains 1 pound of water at 100 °F. Steam at 600 °F and 600 psia is admitted
through a valve into the tank. Determine the temperature and pressure in the tank when the last drop of liquid disap-
pears.

118. (H04) Estimate the mass of carbon dioxide that must be added to the atmosphere to increase the concentration in the
atmosphere by 100 ppm. You may assume that the atmosphere is perfectly mixed, and at a temperature of 300 K
throughout.

119. (H05) Air stability is an important factor in calculating dispersion of pollutants into the environment. Air is
considered stable if the density decreases monotonically with height. If the temperature at the surface of the earth is
80 °F at sea level, determine the minimum temperatures (at intervals of 5000 feet up to 50,000 feet) which allow for
a stable atmosphere.

120. (H06) A plume of hot air exhausted from a chemical process will rise through the cooler surrounding air. As it
rises, it cools at a rate known as the adiabatic lapse rate. As the term implies, the cooling occurs without transfer of
heat to the surrounding air by conduction, convection or radiation. Assuming that no mixing of the plume with the
surrounding air occurs, explain why the plume cools and calculate the approximate temperature drop per one
thousand feet as the plume rises. You may assume that the initial temperature of the hot plume is 150 °F.
 CHEN 623 Problems Page 30

121. (H07) A system consisting of a gas contained in a piston cylinder device undergoes an irreversible process between
initial and final equilibrium states that causes its internal energy to increase by 30 Btu. During the process, the
system receives heat in the amount of 100 Btu from a heat reservoir at 1000 °R. The system then is restored to its
initial state by a reversible process during which the only heat transfer is between the system and the heat reservoir
at 1000 °R. The entropy change of the heat reservoir as a result of both processes is +0.01 Btu/°R. Calculate:
a. the work done by the system during the irreversible process;
b. the heat transferred (with respect to the system) during the reversible process;
c. the work done by the system during the reversible process.

122. (H08) Two solid bodies, A and B, with total heat capacities CA and CB (independent of temperature) and different
initial temperatures TA,0 and TB,0 exchange energy as heat with each other under isobaric conditions. Assume that no
energy is transferred as heat to the surroundings, and that there are no significant temperature gradients within the
each individual body.
a. Derive an expression for the total entropy change of the two bodies as a function of TA, the temperature of body
A.
b. Demonstrate that the process is irreversible by showing that the total entropy change is positive.
c. Calculate the equilibrium temperature of the system.

123. (H09) A power plant employs two adiabatic steam turbines in series. Steam enters the first turbine at 1100 °F and
950 psia, and discharges from the second turbine at 2 psia. The system was designed so that equal work is done by
the two turbines, and the design was based on an efficiency of 80 per cent compared with isentropic operation in
each turbine separately. If the turbines perform according to these design conditions, what is the temperature and
pressure of the steam between the turbines? What is the overall efficiency of the two turbines considered together,
compared with isentropic expansion from the initial state to the final pressure?

124. (H10) One mole of an ideal gas is compressed isothermally but irreversibly at 127 °C from 1 atm to 10 atm by a
piston in a cylinder. The heat removed from the gas during compression flows to a heat reservoir at 27 °C. The
actual work required is 20% greater than the reversible work for the same compression. Calculate the entropy
change of the gas, the entropy change of the reservoir, and the entropy change of the universe.

125. (H11) Two vessels, each with a volume of 1.0 cubic feet, are insulated from the surroundings and from each other,
but they are connected by an insulated valve and insulated lines. One compartment contains saturated steam at 200
psia, and the other compartment contains steam at the same temperature but at a pressure of 14.7 psia. The valve is
opened and the pressures in the two vessels are allowed to equalize.
a. Determine the states of the steam in each of the two vessels immediately after pressure equilibrium is achieved
in the system.
b. Determine the total change in entropy of the two vessels during this process.

126. (H12) Prove the following statements concerning the adiabats and isotherms of a particular body (which may be a
gas, a solid, or a liquid):
a. An isotherm and an adiabat cannot intersect more than once.
b. An isotherm and an adiabat cannot touch each other without intersecting.
c. Two adiabats cannot intersect.
d. In each infinitesimal portion of an isotherm, the heat absorbed by a body has the same sign for the same direction
of movement along the curve.

127. (H13) A test of a Hilsch vortex tube was reported as follows: Air entered at 75 psia and 19.3 °C. The warm air
leaving the tube had a temperature of 26.5 °C, and the cool air had a temperature of -21.8 °C, both at a pressure of 1
atm. The ratio of warm air to cold air was 5.39. Check these results to see whether they are possible. Assume air to
be an ideal gas, and the temperature of the surroundings to be the same as that of the inlet stream.
 CHEN 623 Problems Page 31

128. (H14) Which of the following processes will exhibit the largest changes in temperature when changes in pressure
occur?
a. An adiabatic expansion in which no work is done (injection or ejection work excluded).
b. A reversible adiabatic expansion.
Note: Consideration of derivatives of the form (∂T/∂P)x may prove useful.

129. (H15) Which of the following processes will produce more useful work? (In both cases, the process begins at the
same temperature and pressure and ends at the same pressure.)
a. A reversible adiabatic expansion of a gas contained in a piston and cylinder arrangement.
b. A reversible adiabatic expansion of the same gas in a steady state flow through a turboexpander.
Justify your answer.

130. (H16) The working relationships MATH-2 through MATH-5 were derived in class and are shown in the notes for
the case where there are only two independent variables. Derive the appropriate relations analogous to MATH-2
through MATH-5 for the case where an arbitrary number m of independent variables is involved, that is, for
f = f (x1 , x2 ,..., xm ).

131. (H17) Obtain expressions for the following derivatives in terms of P, V, T, CP , CV and S:
⎛ ∂T ⎞ ⎛ ∂ A⎞ ⎛∂H ⎞ ⎛∂H ⎞
a.) ⎜ ⎟ ; b.) ⎜ ⎟ ; c.) ⎜ ⎟ ; d.) ⎜
⎝ ∂V ⎠ T ⎝ ∂T ⎠ P ⎝ ∂T ⎠ S ⎝ ∂ G ⎟⎠ A

132. (H18) Derive expressions for CP − CV for each of the following equations of state:
a. PV = RT (ideal gas)
b. P(V-b) = RT (hard-core repulsion only)
c. ( P + a / V )V = RT
2
(attractive term only)

d. ( P + a / V )(V − b ) = RT
2
(van der Waals)
e. P = RT / (V − b) − aα / [V (V + b)] (Soave-Redlich-Kwong)
NOTE: For parts a) through d), the parameters a and b should be assumed to be constant. For part e), the
parameters a, b and α are given by:
a = 0.42747R 2Tc2 / Pc , b = 0.08664RTc / Pc and α = [1+ (0.48508 + 1.5517ω − 0.15613ω 2 )(1− Tr )]2

133. (H19) Derive expressions for the dimensionless pressure and density residual functions for the following equations
of state:
a. van der Waals: (P + a / V 2 )(V − b) = RT
b. Benedict-Webb-Rubin (BWR): PV / RT = 1+ B / V + C / V 2 + D / V 4 + E / V 5
where: B = B0 − A0 / RT − C0 / RT 3
C = b − a / RT + c exp[−γ / V 2 ] / RT 3
D = cγ exp[−γ / V 2 ] / RT 3
E = aα / RT
and a, b, c, γ, α, A0, B0, and C0 are constants.

134. (H20) Calculate U, H, A, G, S for steam at 5000 psia and 700 °F based on the following reference states:
a. Liquid phase of water at the triple point has U = 0 and S = 0.
b. Liquid phase of water at the triple point has H = 0 and S = 0.
c. Water as a hypothetical ideal gas at 25 °C and 1 atmosphere has H* = 0 and S* = 0.
 CHEN 623 Problems Page 32

135. (H21) The second and third virial coefficients for CO2 can be represented between 295 and 450 K by:
B = b0 + b1T −1 + b2T −2 and: C = c0 + c1T −1 + c2T −2
where: b0 = 23.0291 cm 3 / mol c0 = 1.841385 × 10 3 cm 6 / mol2
b1 = −2, 455.297 K cm 3 / mol c1 = −1.009178x10 6 K ⋅ cm 6 / mol2
b2 = −1.226275x10 7 K 2 cm 3 / mol c2 = 5.732103 × 10 8 K 2 cm 6 / mol2
For this form of the virial equation, calculate:
a. The density residuals at 130 °F at 15 and 800 psia;
b. Calculate Z, U, H, A, G, and S at 373 K and 5.0 MPa relative to reference states at:
i. 25 °C, 1 bar, ideal gas reference state;
ii. 25 °C, 1 bar, real fluid reference state;
iii. 60 °F, 1 atm, ideal gas reference state.

136. (H22) In 1900, Berthelot proposed the following equation of state: (P + a / TV 2 )(V − b) = RT
a. Express this in reduced form, giving the reduced pressure as a function of reduced temperature and reduced
density.
b. Determine the numerical value of the critical compressibility factor, Zc, for this equation of state.
c. Give expressions for the parameters a and b in terms of the critical temperature and pressure.

137. (H23) Consider the Peng-Robinson and the Soave modification of the Redlich-Kwong equations for carbon dioxide
at 250 and 500 K.
a. Sketch the behavior of P and of Z as a function of V for −∞ < V < +∞ for each equation at each temperature.
b. Determine the numerical values of V at the poles ( P → ∞ or P → −∞ ) for each equation at each temperature.
c. Determine the numerical values of V for each local extremum for each equation at each temperature.
d. Use each equation to calculate the vapor pressure of carbon dioxide at 250 K. Compare your results to the actual
value for carbon dioxide (Be sure to provide a bibliographic reference for the source of your actual vapor
pressure.)

138. (H24) Consider the Peng-Robinson and the Soave modifications of the Redlich-Kwong equation for propane at 300
and 550 K.
a. Sketch the behavior of P and of Z as a function of V for −∞ < V < +∞ for each equation at each temperature.
b. Determine all numerical values of V at which P → ∞ or P → −∞ for each equation at each temperature.
c. Determine the numerical values of V and P for each local extremum for each equation at each temperature.
d. Use each equation to calculate the vapor pressure of propane at 300 K. Compare your results to the actual value
for propane (Be sure to provide a bibliographic reference for the source of your actual vapor pressure.)

139. (H25) Calculate the reduced vapor pressure at a reduced temperature of 0.7 for a van der Waals fluid. Use this
value to calculate the value of Pitzer's acentric factor for such a fluid.

140. (H26) Show that the Soave modification of the Redlich-Kwong equation can be expressed in the form:
Z 3 − Z 2 + (A − B − B 2 )Z − AB = 0 ,
and the Peng-Robinson equation in the form: Z 3 − (1− B)Z 2 + (A − 2B − 3B 2 )Z − (AB − B 2 − B 3 ) = 0
Z = PV / RT , A = aP / (RT ) , and B = bP / RT
2
where, in both cases,
 CHEN 623 Problems Page 33

141. (H27) Derive the Modified Richmond Iteration formula for solving cubic equations:
Z n+1 = Z n − F(Z n ) / [F '(Z n ) − S(0.5F"(Z n ) − S)]
where S = F(Z n ) / F '(Z n ) . (This result is based upon a Taylor series expansion through third order and the obser-
vation that the third derivative of a cubic equation is always 6.)

142. (H28) For water at a temperature of 700 °F and pressures of 14.696, 150, 1500 and 3000 psia:
a. Calculate the compressibility factors and dimensionless residual U, H, A, G, S using the Soave-Redlich-Kwong
and Peng-Robinson equations of state and your favorite steam tables. Compare the results obtained by the three
methods.
b. Calculate Z, U, H, A, G, S, and V based on a reference state where So* = 0 = Ho* for water vapor as an ideal gas
at 25 °C and 1 atm, using the SRK and PR equations of state and the steam tables. Compare the results obtained
by the three methods.

143. (H29) Given that M = Σx j (M j + ln x j ) − Σx j ln[Σxk A jk ] , for some dimensionless molar property M of a multi-
component system, where the A's depend on T and P only, find an expression for the partial molar property M i .

A jk Akj x j xk
144. (H30) Given that: M = ∑ xi M i + 12 ∑ ∑
i j k A jk x j + Akj xk
for some dimensionless molar property M of a multicomponent system, where the A's depend on T and P only,
determine an expression for the partial molar property M i .

145. (H31) Consider a fluid mixture of three chemical species, A, B, and C, where the enthalpy of the mixture is given
(in dimensionless form) by:
H / RT = 50xA + 100xB + 150xC + xA xB xC (35xA + 30xB + 25xC )
For this mixture,
a. Derive expressions that give the dimensionless partial molar enthalpies of components A, B, and C as functions
of the mixture composition;
b. Determine the numerical values of the dimensionless enthalpies for pure components A, B, and C.
c. Derive expressions that give the dimensionless partial molar enthalpies at infinite dilution of each of the three
components as functions of the mole fractions of the other two components;
d. Give an expression for the dimensionless excess molar enthalpy of this mixture.

146. (H32) Derive expressions for the partial molar volume of components 1 and 2 in a ternary mixture for the equations
of state given below:
a.) PV = RT (1+ B / V + C / V 2 ) ; B = Σyi y j Bij ; C = Σyi y j yk Cijk

a = ∑ ∑ xi x j aij b = ∑ yi bi
RT a
b.) P = −
V −b T V (V + b ) i j i

147. (H33) Derive an expression for the partial molar volume of substance i in a fluid mixture which obeys the virial
equation of state truncated after the third term:
PV = RT (1+ B / V + C / V 2 )
The virial coefficients for the mixture are given by B = Σyi y j Bij and C = Σyi y j yk Cijk
The coefficients Bij and Cijk in these expressions are functions only of temperature.
 CHEN 623 Problems Page 34

148. (H34) Determine which of the following representations for the excess Gibbs energy of a binary mixture are
capable of representing liquid-liquid phase behavior:
a. Margules equations (How many suffixes are required?)
b. Wilson equation
c. Van Laar
d. NRTL
For those cases that involve liquid-liquid phase behavior, what range of parameters will cause such behavior?

149. (H35) Gaseous nitrogen peroxide consists of a mixture of NO2 and N2O4, which undergo the reversible reaction:
N 2O 4 ↔ 2NO 2 .
Chemical equilibrium between these components is established rapidly (i.e., if a step change in pressure or
temperature is imposed, it takes only about 0.1 to 0.2 microseconds for the system to react and to attain equilibrium
under the new conditions.). Ideal gas behavior may be assumed throughout this problem. The standard Gibbs
energy of reaction for the reaction (based on ideal gas standard states at the same temperature and a pressure of 1
bar) is given as a function of temperature by:
( )
∆ G˚/ J·mol−1 = 57, 330 − 176.72 (T / K )
The heat capacity for the frozen equilibrium mixture (i.e., no composition change with change in temperature) may
be approximated as:
( )
C p (frozen equilibrium) / J·g −1 ⋅ K −1 = 0.726 + 4.19 × 10 −4 (T / K)

a. It has been suggested that this gas mixture be employed as a heat transfer medium. To evaluate this proposal,
the heat capacity of the equilibrium mixture must be determined as a function of temperature. Calculate and plot
the effective heat capacity (∂H/∂T)p for the equilibrium mixture between 290 and 370 K at 1 bar. Compare this
result with the value for frozen equilibrium.
b. Estimate the change in temperature of a N2O4 + NO2 gas mixture as it is throttled across a valve. The valve is
well insulated and the flow rate is steady. The upstream temperature and pressure are 353 K and 5 bar. The
downstream pressure is 1 bar. What is the downstream temperature and composition?
c. Suppose that a NO2 + N2O4 mixture is expanded from a pressure and temperature P1, T1 to a lower pressure P2 in
an adiabatic reversible turbine.
i. Write a differential equation that expresses how the pressure, temperature, and fraction N2O4 dissociated vary
during the expansion. (Assume a basis of 1 mole N2O4 and let ε be the fraction dissociated.
ii. Show clearly how the adiabatic, reversible work may be calculated.
iiii. Repeat parts i.) and ii.) if the turbine were isothermal (at T1) and reversible.