Michigan State University

DEPARTMENT OF CHEMICAL ENGINEERING

ChE 321: Thermodynamics for Chemical Engineers Spring 2018

Exam 2A: April 4, 2018, Equation Sheet

1. (10) (T or F)
____ The UNIFAC model is based on local composition concepts.
____ Plotting ln(Prsat) (y-axis) vs. 1/Tr (x-axis) gives a line with a positive slope.
____ The compressibility factor Z for liquids is always ZL << 1.

2. (10) Estimate with minimum calculations the values of fugacity for hexane under the
following conditions. Include units. Your answer should be of the type provided by a
quick estimation.
(a) Hexane is a pure vapor at 65C and 346 mm Hg. The vapor pressure of hexane
at 65C is 675 mmHg.

(b) Hexane is in an ideal gas vapor mixture with acetone at 65C and 480 mmHg.
The mole fraction of hexane is yhexane = 0.4. The vapor pressures are Psathexane =
675 mmHg, Psatacetone = 1020 mmHg.

(c) Hexane is a pure liquid at 65C and 760 mmHg. The vapor pressure of hexane
at 65C is 675 mmHg.

1
3. (10) For the system 1-butanol (1) + 2-propanol (2) at 90C, the vapor pressures are
𝑃1𝑠𝑎𝑡 = 257 mmHg and 𝑃2𝑠𝑎𝑡 = 1026 mmHg. Using Raoult's law, estimate the dew
pressure and coexisting phase compositions for an overall composition of 70 mol%
butanol. Avoid unnecessary calculations. If an iterative solution is required, perform
the first iteration, and indicate clearly the specific steps needed to efficiently find the
answers.

4. A P-x-y diagram is shown below for the system A+B. From the diagram, mark the
answers to the following questions, label them as '(a)', ' (b)', etc., and provide
numerical values.

660

650

P
(mm Hg) 640

630

620
0 0.25 0.5 0.75 1

xA,yA

(a) (10) The dew pressure and coexisting phase compositions (use x for liquid, y for
vapor) and L/F for an overall composition zA = 0.5.

(b) (10) The phase compositions (use x for liquid, y for vapor) and calculated L/F for
an overall composition zA = 0.5 at 645 mm Hg.

2
5. The (1) + (2) system exhibits vapor liquid equilibria at 24.95 kPa and 50C. The
compositions of the coexisting phases are x1 = 0.36 and y1 = 0.62 and 𝑃1𝑠𝑎𝑡 = 69.4 kPa,
𝑃2𝑠𝑎𝑡 = 15.8 kPa.

(a) (5) Calculate GE/(RT) for the liquid phase at 50C and composition x1 = 0.36.
𝐸
Note:𝐺𝑖 /(𝑅𝑇) = ln 𝛾𝑖 .

(b) (10) Fit the two parameter Margules equation to the experimental data.

(c) (10) Use the results of part (b) to calculate the bubble pressure and coexisting
phase compositions for a mixture of overall composition at z1 = 0.8 at 50C. Avoid
unnecessary calculations. If an iterative solution is required, perform the first
iteration, and indicate clearly the specific steps needed to efficiently find the answers.

3
6. (10) The system (A) + (B) exhibits V + L phase equilibria and at a particular
temperature and pressure the coexisting compositions are yA = 0.6 and xA = 0.25.
Using Raoult’s law to model the system, what is PsatA/PsatB?

7. (15) Propane passes through an adiabatic expander with an efficiency of 85%. The
inlet conditions are 380 K and 5 MPa.

Continued on next page…

4
Several possible outlet states are given below (note that one state is on the next page).
(state 1)

(state 2)

Continued on next page…

5
(state 3)

Identify the correct outlet state, and calculate the work done by the expander in J/mol.

6
 Name _______________

Michigan State University

DEPARTMENT OF CHEMICAL ENGINEERING AND MATERIALS SCIENCE

ChE321: Thermodynamics for Chemical Engineers Spring 2017

Exam 2A: April 05, 2017, Equation sheet

1. (10) A binary system (A) + (B) of F total moles exists as V moles vapor and L moles
liquid, where the overall composition is 60 mol% (A) and the liquid composition is
47 mol% (A), and the vapor composition is 72 mol% (A). What is V/F?

2. Which of the following constraint(s) are NOT required to apply Raoult’s law: (I)
ideal gas in the vapor; (II) 𝑈 = ∑𝑥𝑖 𝑈𝑖 in liquid; (III) 𝐺 = ∑𝑥𝑖 𝐺𝑖 in liquid; (IV)
components similar in size; (V) components similar in functionality; (VI) 𝑆 = ∑𝑥𝑖 𝑆𝑖

3. (5) Pure hexane (C6) exists as V + L as shown. Pure heptane (C7) liquid is injected
into the vapor at constant temperature and pressure. After injection the overall
mixture is 10 mol% C7. What happens (circle the best answer)?
(a) All the C7 goes to L and the V is only C6.
(b) The vapor is mostly C6 with some C7.
(c) All the vapor condenses.
(d) All the liquid evaporates.
(e) None of the above. Explain V
C7
L
C6
4. (5) Select all that are true. This model is used frequently in polymer modeling.
___ Flory
___ van Laar
___ None of these models
___ Scatchard-Hildebrand
___ Flory-Huggins

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5. The system chloroform (1) + 1,4-dioxane (2) exists as V + L at 323.15K and P =

19.89 kPa with x1 = 0.2 and y1 = 0.3691. At this temperature 𝑃1𝑠𝑎𝑡 = 69.31 kPa and
𝑃2𝑠𝑎𝑡 =15.78 kPa. Vapor pressures can be estimated at other temperatures using
log10 𝑃1𝑠𝑎𝑡 = 6.2983 − 1432.1/𝑇(𝐾); log10 𝑃2𝑠𝑎𝑡 = 6.6074 − 1732.5/𝑇(𝐾);
(15) Fit the two-parameter Margules equation to this measurement.

(10) Determine the bubble temperature at 60 kPa and an overall composition of 40

mol% (1). If an iterative calculation is required, perform the first iteration and specify
values for the next iteration. If an iterative calculation is not required, provide the
bubble temperature and composition of the other phase.

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6. A fluid is described by the following equation of state:

𝑍 = 1 + (𝑎 + 𝑏/𝑇)𝜌
where a = 500 cm3/mol, b = -3.45E5 cm3K/mol and the ideal gas heat capacity is Cp
= 74.6 J/molK.
(a) (10) At 300K and 𝜌 = 4.5E-4 mol/cm3, what is P (MPa)?

(b) (10) For this equation of state, derive (𝑈 − 𝑈 𝑖𝑔 )/(𝑅𝑇) in the fully integrated
form. Leave the expression in terms of a, b, Z and 𝜌.

7. (10) For benzene at the state T2 = 290K and P2 = 0.1 MPa, the Peng-Robinson
equation gives a value of (S - Sig) = -93.8886 J/molK. For benzene at the state T1 =
480K and P1 = 1 MPa, the Peng-Robinson equation gives (S - Sig) = -2.1963 J/molK.
Cp is assumed to be constant and for benzene near these temperatures, Cp = 100
J/molK. Determine S for moving from state 1 to state 2.

8. Select the best answer. For the A + B system shown in the right,
a. (5) At 200 mmHg
___ boiling T of pure A < boiling T of pure B I
___ boiling T of pure A > boiling T of pure B 200 II
___ boiling T of pure A ≈ boiling T of pure B
___ can’t tell without Antoine coefficients P
b. (5) Liquid exists in which region(s) of the diagram? (mmHg) III
___ only I ___ II and III
___ only II ___ I and III
___ only III xA, yA
___ I and II

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9. Consider hexane at compressor inlet state I.

State I

(H-Hig) (J/mol)= -274.342 -27431.2

(U-Uig) (J/mol)= -177.63 -24286.7
(S-Sig) (J/molK)= -0.470365 -80.1804

a. (5) Is hexane one or two phases at the inlet state I? Use cell references or mark the
Matlab output to provide the inlet enthalpy. Explain.

b. (5) Hexane is compressed to 2 MPa in a reversible adiabatic compressor. Two

possible outlet states are shown below. What is the outlet temperature? Is the
outlet one or two phases? If the outlet is two phases, give the quality. Explain
your answer. If neither of the given alternatives is correct, explain how you would
find the reversible outlet state using cell references or Matlab selectors.

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(H-Hig) (J/mol)= -6581.11 -21031.6

(U-Uig) (J/mol)= -4656.07 -17545.3
(S-Sig) (J/molK)= -10.9282 -41.065

(H-Hig) (J/mol)= -5568.34 -19623.6

(U-Uig) (J/mol)= -3932.97 -16093.2
(S-Sig) (J/molK)= -8.78959 -38.0982

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 Name _______________

Michigan State University

DEPARTMENT OF CHEMICAL ENGINEERING AND MATERIALS SCIENCE

ChE321: Thermodynamics for Chemical Engineers Spring 2016

Exam 2A: April 08, 2015, Closed Book Portion (20 minutes)

1. (5) The fundamental relation for U is dU = TdS - PdV. The definition of Helmholtz
energy is A  U -TS. Derive the relation for dA.

2. At 320K pure component (1) is a liquid with a vapor pressure of 0.3 MPa and a
saturation fugacity coefficient of 0.85 and pure component (2) is a liquid with a vapor
pressure of 0.25 MPa and a saturation fugacity coefficient of 0.95.
(a) (5) Liquid components (1) and (2) are mixed at 0.8 MPa and 320K, such that x1 =
0.6 and x2 = 0.4. Provide the values of the component fugacities in the liquid mixture
if the mixture is assumed to follow Raoult’s Law.

(b) (5) Liquid components (1) and (2) are mixed at 0.8 MPa and 320K, such that x1 =
0.6 and x2 = 0.4. Provide the values of the component fugacities in the mixture if the
mixture is assumed to be an ideal solution of liquids, ignoring the Poynting
correction.

3. (10) ( T or F)
___ The compressibility factor Z for a real fluid is always less than unity
___ Plotting Z vs. Pr gives identical curves for all fluids at the same Tr.
___ Plotting ln(Pr) (y-axis) vs. 1/Tr (x-axis) gives almost a straight line with a negative
slope.

4. (10) A solution of 30 mol% hexane and 70 mol% ethanol exists in the vapor phase at
80 C and 0.1 MPa. The conditions are changed at constant pressure until the mixture
is totally condensed. What type of calculation should be performed to calculate the
conditions for complete condensation? (e.g. bubble temperature, dew temperature,
bubble pressure, dew temperature, isothermal flash?) For a complete answer, provide
constraint values needed for the calculation.

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5. (5) The Soave-Redlich-Kwong equation is 𝑍 = 1/(1 − 𝑏𝜌) − (𝑎/(𝑏𝑅𝑇))𝑏𝜌/(1 +

𝑏𝜌). The parameters are made dimensionless using A = aP/(RT)2 and B = bP/RT.
Rearrange the equation in the form Z 3  a2 Z 2  a1Z  a0  0 , where a2, a1, and a0 are
functions of A and B.

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 Name _______________

Michigan State University

DEPARTMENT OF CHEMICAL ENGINEERING

ChE 321: Thermodynamics for Chemical Engineers Spring 2016

Exam 2A. EQUATION SHEET PORTION

6. The equation of state for a simple fluid has been correlated to the equation
Z = 1 + aP/RT, where a = -2360 cm3/mol, and CP= 43 J/mol-K.

(a) (10) Derive the Helmholtz departure for the fluid and calculate the numerical
value (J/mol) at 300 K and 0.2 MPa.

7. (10) Indicate if each of the following equations is correct (T) or incorrect (F). Valid
work in the scratch area is required for full credit.

Expression Indicate T or F
𝜕𝐺 𝜕𝑇
(a) ( 𝜕𝑆 ) = −𝑆 (𝜕𝑆 ) + 𝑉
𝑃 𝑃

𝜕𝐺 𝑆𝑇 𝜕𝑇
(b) ( 𝜕𝑆 ) = − 𝐶 − 𝑉 (𝜕𝑉)
𝑉 𝑉 𝑃

𝜕𝐺 𝑉𝑇 𝜕𝑇
(c) (𝜕𝑇 ) = −𝑆 + 𝐶 (𝜕𝑉)
𝑆 𝑉 𝑃

Scratch area:

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1. The system methyl acetate (1) + hexane (2) forms an azeotrope at x1 = 0.667,
51.57oC, and 1 bar. The component vapor pressures at 51.57oC are P1sat = 0.833 bar,
P2sat = 0.5736 bar. Fit the two parameter Margules equation parameters.

(5) Pick which diagram represents the qualitative behavior that you expect for the
system based on the information given above.
The expected shape of the phase behavior is: _________
`

T T T T

x1 x1 x1 x1

(a) (b) (c) (d)

(5) Justify your choice:

2. (10) The system (1) + (2) can be modeled with Modified Raoult's law, using the one
parameter Margules equation, ln 1 = 1.6 x22, ln 2 = 1.6 x12. The vapor pressures are
log10P1sat = 8.4 - 1800 / (T + 230), log10P2sat = 7.3 - 1300 / (T + 170), where T is in
Celsius. Calculate the bubble pressure and coexisting phase compositions using
Modified Raoult's Law for a mixture that is overall 75 mol% (1) and 25 mol% (2) at
60 oC. If an iterative solution is required, perform the first iteration, and indicate
clearly the specific steps used to find the answers.

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3. The state below is the inlet to a throttle valve.

The outlet pressure is 0.05 MPa. Possible outlet states are shown below.
Case (a)

Case (b)

Case (c)

(5) Which of the above cases represents the outlet condition (with reasonable roundoff
error)? If none of the cases are reasonable, indicate.

(5) Justify your selection.

5 of 5
 Name _______________

Michigan State University

DEPARTMENT OF CHEMICAL ENGINEERING AND MATERIALS SCIENCE

ChE321: Thermodynamics for Chemical Engineers Spring 2015

Exam 2A: April 08, 2015, Closed Book Portion (25 minutes)

1. (5) The system (A) + (B) where PBsat > PAsat forms a maximum pressure azeotrope at
xA = 0.22. The system is in a piston-cylinder at xA = 1, where both vapor and liquid
coexist and V/F = 0.45. Some component B is injected into the system at constant T
and P until the overall composition is 10 mol% (A). What happens to the coexisting
phases? Be specific about the changes and compositions.

(5) (b) Discuss how/why KE and PE depend on density at a fixed pressure.

(5) (c) Besides temperature and pressure, what property(ies) are the same in both
phases when two binary phases are in phase equilibrium?

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2. We wish to use PreosProps.m to generate a n-pentane isotherm for a P-V chart at

375K between 0.1 MPa and 6 MPa. For n-pentane, Tc = 469.7K, Pc = 3.369,  =
0.249.

(a) (5) make a qualitative sketch of the shape you expect for the isotherm.
P(MPa)

V (cm3/mol)
(b) (10) Describe how you would use the GUI to generate the data you need to plot an
isotherm. Be specific about how you would find endpoints for any abrupt changes
in your isotherm, and how to interpret multiple values from the GUI such as those
above. Add a dot to your plot to indicate the approximate location of the state
given in the above GUI. Add values to the x- and y-axis for your dot.

2 of 5
 Name _______________

Michigan State University

DEPARTMENT OF CHEMICAL ENGINEERING AND MATERIALS SCIENCE

ChE321: Thermodynamics for Chemical Engineers Spring 2015

Exam 2A: April 08, 2015, Equation Sheet Provided (85 minutes)

ANTOINE CONSTANTS for log10(Psat(mmHg)) = A – B/(T(Celsuis) + C).

Component (1) Component (2)
A 7.2813 7.3205
B 1434.2 1465.2
C 254.2 264.3

3. Some experiments have shown that components (1) and (2) do not follow Raoult’s
Law. The following data are available from an experiment with component (1) +
component (2): x1 = 0.65, y1 = 0.586, T(oC) = 70, P = 842 mmHg.

(a) (10) Fit the two-parameter Margules equation to the data.

(b) (10) Using the two-parameter Margules equation, predict the bubble pressure and y1 at
70oC for a mixture where x1 = 0.3. If an iterative calculation is required, perform the
first iteration and specify values for the next iteration. If an iterative calculation is not
required, provide the bubble pressure and vapor composition.

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(c) (10) Based on your calculations, sketch the behavior you expect for the Pxy and
Txy diagrams. Make the Pxy semi-quantitative by labeling known quantities from
parts (a) and/or (b). The Txy can be left qualitative.

4. (10) A simple derivative manipulation is applied to each of the starting expressions in

the left column below. Some of the manipulations may involve errors. Indicate
whether the ending expression in each row is valid or invalid. Valid work in the
scratch area is necessary for full credit.
Starting Expression Ending Expression Indicate Valid or
Invalid
𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 𝜕𝑈 𝜕𝑉 𝜕𝑃
( ) = 𝐶𝑃 − 𝑃 ( ) ( )
𝜕𝑇 𝑃 𝜕𝑃 𝑇 𝜕𝑇 𝑉
𝜕𝑉 𝐶𝑉 𝜕𝑃
( ) − ( )
𝜕𝑇 𝑆 𝑇 𝜕𝑇 𝑉
Scratch area:

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5. (10) A mixture of (1) + (2) follow Raoult’s law. At 80oC, the vapor pressures are P1sat
= 1030 mmHg and P2sat = 620 mmHg. The mixture forms V + L phases at an overall
composition of 40 mol% component (1) and 750 mmHg. Write a Matlab function that
will find the V/F for this condition. For full credit, use an fzero call properly in your
code. Use programming syntax and variable names, not hand-written algebra or
pseudo-code. (If needed, syntax of a for loop: for i =firstvalue:lastvalue;
syntax for fzero: [varValueFinal] = fzero(@objName, varValueGuess))The
first statements are given.
function LOF
Psat = [1030 620]; %mmHg
P = 750; mmHg

𝑎
6. (10) A fluid follows the equation of state 𝑃𝑉 = 𝑅𝑇 − (𝑇) 𝑃 + 𝑏𝑃, where a = 385.2
cm3-K/mol and b = 15.23 cm3/mol. Derive the formula for the enthalpy departure of a
fluid that follows this equation of state. Possibly useful: ∫ (1/𝑥)𝑑𝑥 = ln 𝑥;
∫ (1/(𝑎𝑥 + 𝑏))𝑑𝑥 = (1/𝑎) ln(𝑎𝑥 + 𝑏) ;∫ (𝑥/(𝑎𝑥 + 𝑏))𝑑𝑥 = 𝑥/𝑎 −
(𝑏/𝑎^2)ln(𝑎𝑥 + 𝑏); ∫ (1/(𝑎𝑥 + 𝑏)2 )𝑑𝑥 = −1/(𝑎(𝑎𝑥 + 𝑏))

7. (10) Ideal gas state changes are given by Δ𝐻 𝑖𝑔 = ∫ 𝐶𝑃 𝑑𝑇, Δ𝑈 𝑖𝑔 = ∫ 𝐶𝑉 𝑑𝑇, Δ𝑆 𝑖𝑔 =

𝑇 𝑃
𝐶𝑃 ln 𝑇2 − 𝑅 ln 𝑃2 . For a fluid in at P1 = 1 MPa, T1 = 380K, the enthalpy departure is
1 1
-432 J/mol and Z = 0.75. At P2 = 0.15 MPa, T2 = 400 K, the enthalpy departure is
-120 J/mol and Z = 0.85. For the fluid, Cp = 77 J/mol-K and can be considered
temperature independent. Determine Δ𝐻 and Δ𝑈 in J/mol.

5 of 5
 Name _______________

Michigan State University

DEPARTMENT OF CHEMICAL ENGINEERING AND MATERIALS SCIENCE

ChE321: Thermodynamics for Chemical Engineers Spring 2014

Exam 2: April 02, 2014, Closed Book Portion (35 minutes)

Note: 1 bar = 0.1 MPa = 750 mmHg; 1 atm = 760 mmHg. R = 8.314 cm3MPa/mol-K

1. (5) The system (A) + (B) where PAsat > PBsat forms a maximum pressure azeotrope at
xA = 0.73. The system is in a piston-cylinder at the azeotropic conditions xA = 0.73,
where both vapor and liquid coexist and V/F = 0.45. More component A is injected
into the system at constant T and P. What happens to the coexisting phases? Be
specific about the changes.

(5) (b) dU = TdS – PdV; H = U + PV; G = H – TS. Derive the relation for dG.

(5) (c) Describe what is meant by the ‘combinatorial term’ and the ‘residual term’ in
UNIQUAC and UNIFAC.

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2. We wish to use PreosProps.m to generate an isobutane isotherm for a P-H chart at

280K between 0.1 MPa and 6 MPa. (The y-axis is usually a log scale, which is
shown linearly below using logarithms of values, so the shape should look the same
as P-H charts you have used.) For isobutane, Tc = 408.1K, Pc = 3.648,  = 0.177.

(a) (5) make a qualitative sketch of the shape you expect for the isotherm.
log P(MPa)

H(J/mol)
(b) (10) Describe how you would use the GUI to generate the data you need to plot an
isotherm. Be specific about how you would find endpoints for any abrupt changes
in your isotherm, and how to interpret multiple values from the GUI such as those
above. Add a dot to your plot to indicate the approximate location of the state
given in the above GUI. Add values to the x- and y-axis for your dot.

2 of 5
 Name _______________

Michigan State University

DEPARTMENT OF CHEMICAL ENGINEERING AND MATERIALS SCIENCE

ChE321: Thermodynamics for Chemical Engineers Spring 2014

Exam 2: April 02, 2014, Open Notes Portion (85 minutes)

ANTOINE CONSTANTS for log10(Psat(mmHg)) = A – B/(T(Celsuis) + C).

Component (1) Component (2)
A 7.2807 7.8103
B 1434.2 1420
C 246.5 191.15

NOTE: the same T of 80 oC is used throughout to minimize calculations.

3. Suppose component (1) and component (2) follow Raoult’s Law. The temperature is
80 oC.
a. (10) What is the dew pressure (mmHg) and liquid composition when y1 = 0.6?
What is x1 at the dew point?

b. (10) At 80 oC a mixture F that is 48 mol% component (1) is fed to a flash drum at

541.7 mmHg. The vapor composition is y1 = 0.60 and the liquid is x1 = 0.42.
What is the ratio of moles of vapor to moles of feed, V/F?

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4. Some experiments have shown that components (1) and (2) do not follow the results
predicted by problem 3. The following data are available from an experiment with the
system component (1) + component (2): x1 = 0.30, y1 = 0.567, T(oC) = 80, P = 694.3
mmHg.

(a) (10) Fit the two-parameter Margules equation to the data.

(b) (10) Using the two-parameter Margules equation, predict the bubble pressure and y1
at 80oC for a mixture where x1 = 0.6. If an iterative calculation is required, perform
the first iteration and specify values for the next iteration. If an iterative calculation is
not required, provide the bubble pressure and vapor composition.

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5. The virial equation can be written, Z = 1 + BP/(RT)

(a) (10) For methane, Tc = 190.6 K, Pc = 4.604,  = 0.011. What value is predicted for
the virial coefficient at 120K using the generalized virial coefficient correlation?

(b) (10) Write a Matlab function that will find the temperature where the virial
coefficient has a value of 100 cm3/mol. For full credit, use an fzero call properly in
your code. Use programming syntax and variable names, not hand-written algebra or
pseudo-code. (If needed, syntax of a for loop: for i =firstvalue:lastvalue;
syntax for fzero: [varValueFinal] = fzero(@objName, varValueGuess))The
first statements are given.
function virial
Tc = 190.6; %K
Pc = 4.604; %MPa
w = 0.011;

6. (10) A fluid follows the equation of state 1 / 1 , where a = 187

cm3/mol. Derive the formula for the fugacity of a fluid that follows this equation of
state. Possibly useful: 1\ ln ; 1/ 1/ ln
; / / / ^2 ln

5 of 5
 Name _______________

Michigan State University

DEPARTMENT OF CHEMICAL ENGINEERING AND MATERIALS SCIENCE

ChE321: Thermodynamics for Chemical Engineers Spring 2013

Exam 2: April 03, 2013, Closed Book Portion (40 minutes)

Note: 1 bar = 0.1 MPa = 750 mmHg; 1 atm = 760 mmHg. R = 8.314 cm3MPa/mol-K

1. (5) (a) Describe the easiest procedure (bubble, dew, flash, etc.) to create a complete
T-x-y diagram for a binary system at a specified P, where the activity coefficient
expression and parameters are known. Be specific about how each line on the
diagram is calculated.

(5) (b) The binary system A + B follows Raoult’s law, and at a specified temperature
PAsat > PBsat. The system is closed in a piston/cylinder. The system is equimolar and
initially at a low pressure where only vapor exists. The pressure is to be raised until
only a trace of vapor exists. What type of calculation (bubble, dew, flash) is best and
quickest to use to find this pressure? Explain your choice.

(5) (c) For the process described in 1(b), it is desired to create a qualitative plot of yA
and xA (both on y-axis) as a function of P (on x-axis) starting from the initial state
where everything is totally vapor to a state where everything is totally liquid. Sketch
the shape of the two curves/lines for each composition. Omit the lines for yA and xA
in the region where the respective phase does not exist.

xA, yA

0
P

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 Name _______________

2. (10) The van der Waals equation is Z = 1 /(1 − bρ ) − aρ / RT . The parameters are
made dimensionless using A = aP/(RT)2 and B = bP/RT. Rearrange the equation in the
form Z 3 + a 2 Z 2 + a1Z + a0 = 0 , where a2, a1, and a0 are functions of A and B.

3. (15) Ethane enters a reversible adiabatic expander at the following conditions. The
outlet of the expander is to be at 0.1 MPa.

Below are several possible outlet states. Calculate the work done by the expander
(J/mol) after selecting the correct outlet state. If none of the provided states is correct,
indicate how you would use the buttons/boxes on the GUI to find the outlet state.

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 Name _______________

State 2a State 2b

State 2c State 2d

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 Name _______________

Michigan State University

DEPARTMENT OF CHEMICAL ENGINEERING AND MATERIALS SCIENCE

ChE321: Thermodynamics for Chemical Engineers Spring 2013

Exam 2: April 03, 2013, Open Notes Portion (80 minutes)

Note: 1 bar = 0.1 MPa = 750 mmHg; 1 atm = 760 mmHg. R = 8.314 cm3MPa/mol-K

4. The following data are available from an experiment with the system n-pentane(1) +
acetone(2): x1 = 0.292, y1 = 0.614, T(oC) = 34.35, P=750 mmHg.
ANTOINE CONSTANTS for (a) (10) Fit the two-parameter van Laar
log10(Psat(mmHg)) = A – B/(T(oC) + C) equation to the data.
n-pentane acetone
A 6.85296 7.11714 (b) (10) Using the two-parameter van
B 1064.84 1210.6 Laar equation, predict the bubble
C 232.012 229.664 pressure at 34.35oC for a mixture where
x1 = 0.01.

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 Name _______________

(c) (15) Based on the parameters fitted above, provide Matlab code to solve for the
bubble temperature of a binary mixture with overall composition z1 = 0.8 at 760
mmHg. For full credit, your method must work, avoid unnecessary calculations, and
provide all constants. Half credit is for the logic and half credit is for Matlab syntax.
(If needed, syntax of a for loop: for i =firstvalue:lastvalue; syntax for fzero:
[varValueFinal] = fzero(@objName, varValueGuess)).

5. (10) Below is a plot for Z0 given by the Lee Kesler charts. We would like to generate
a predicted curve Z vs. Pr at Tr = 0.5 using the Peng-Robinson equation for methanol,
(Tc = 512.6 K, Pc = 8.096 MPa, ω = 0.566). Write a Matlab script to generate and plot
the line. The syntax of the PreosProps.m function line is
function [Z H S U phi info] = PreosProps(Tref, Pref, T, P, match).
Half the credit is for the logic and half credit is for the syntax. See problem 4 for
syntax hints. Also ‘match’ is a row vector of four zeros.

Tr = 0.5

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 Name _______________

6. A fluid is described by the following equation of state:

= 1 + /(1 − )
where a = −207 cm3/mol, and the ideal gas heat capacity is Cp = 65.3 J/molK.

(a) (10) Determine the fully integrated entropy departure function in terms of a, T, Z
and ρ. Hints: ∫ (1\ ) = ln ; ∫ 1/( + ) = (1/ ) ln( + )
;∫ /( + ) = / − ( / ^2)ln ( + )
(b) (5) At a pressure of 4 MPa and 400K, what is the molar volume (cm3/mol)?

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 Name _______________

Michigan State University

DEPARTMENT OF CHEMICAL ENGINEERING AND MATERIALS SCIENCE

ChE321: Thermodynamics for Chemical Engineers Spring 2012

Exam 2: April 11, 2012, Closed Book Portion

1. (5) Explain the differences in particle motions for the following types of simulations
at the same temperature and density: ideal gas particles, purely repulsive particles,
square-well particles.

(5) The van Laar and Scatchard-Hildebrand models are both derived from van der
Waals models. What did Scatchard-Hildebrand do differently than van Laar to make
the model less empirical?

(5) The acentric factor is a parameter used frequently in equations of state. Describe
the origin of the parameter.

2. (10) The van der Waals equation is Z  1 /(1  b )  a / RT . The parameters are
made dimensionless using A = aP/(RT)2 and B = bP/RT. Rearrange the equation in the
form Z 3  a 2 Z 2  a1Z  a0  0 , where a2, a1, and a0 are functions of A and B.

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 Name _______________

3. A P-x-y diagram is shown below for the system A+B at T = 85oC. From the diagram,
mark the answers to the following questions, label them as '(a)', ' (b)', etc., and
provide numerical values.

660

650

P
(mm Hg) 640

630

620
0 0.25 0.5 0.75 1

xA,yA
(a) (5) The dew pressure and coexisting phase compositions (use x for liquid, y for
vapor) and V/F for an overall composition zA = 0.5.

(b) (5) The phase compositions (use x for liquid, y for vapor) and calculated V/F for
an overall composition zA = 0.5 at 645 mm Hg.

(c) (5) Sketch the y-x diagram qualitatively for this system.

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 Name _______________

Michigan State University

DEPARTMENT OF CHEMICAL ENGINEERING AND MATERIALS SCIENCE

ChE321: Thermodynamics for Chemical Engineers Spring 2012

Exam 2: April 11, 2012, Open Book Portion

4. (15) Isobutanol is of interest as a fermentation product as a potential chemical

intermediate or biofuel. Literature studies (Udovenko, V.V.; Frid, Ts.B.; Zh. Fiz.
Khim. 1948, 22, 1135-1145) report the following data for methanol(1) +
isobutanol(2), T = 333.15, P = 45.66 kPa, x1 = 0.4, y1 = 0.827. Pure component vapor
pressures are P1sat = 82.66 kPa, P2sat = 12.8 kPa at 333.15K. Fit the two parameter
Margules equation.

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 Name _______________

(15) Based on the parameters fitted above, provide Matlab code to solve for the dew
pressure of a binary mixture with overall composition z1 = 0.8 at 333.15K. For full
credit, your method must work, avoid unnecessary calculations, and provide all
constants. Half credit is for the logic and half credit is for Matlab syntax. (If needed,
syntax of a for loop: for i =firstvalue:lastvalue; syntax for fzero:
[varValueFinal] = fzero(@objName, varValueGuess)).

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 Name _______________

5. A fluid is described by the following equation of state:

Z  1  (a  b / T )
where a = 500 cm /mol, b = -4.8E5 cm3K/mol and the ideal gas heat capacity is Cp =
3

79.3 J/molK.

(a) (10) Determine the internal energy departure function in terms of a, b, T, Z and .

(b) (5) At a density of 2E-4 mol/cm3 and 500K, what is the system pressure?

6. A curve for a binary (1) + (2) system is shown below.

0

-0.05

-0.1

-0.15
Gmix/RT

-0.2

-0.25

-0.3

-0.35
0 0.2 0.4 0.6 0.8 1
x1

(a) (5) Beginning with 1 mole of pure (1), how many moles of (2) can be added before
the system forms two liquid layers?

(b) (5) When two liquid layers form, what is the approximate LLE K1 for component 1?
Answers are accepted for either phase as the extract phase.

(c) (5) The student who generated the curve got confused about which Margules
parameters were used to generate the plot. The student thinks that values were A12 =
0.9 and A21 = 3.3. Is the plot consistent with these values? Explain using calculations.

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 Michigan State University

DEPARTMENT OF CHEMICAL ENGINEERING AND MATERIALS SCIENCE

ChE321: Thermodynamics for Chemical Engineers Spring 2011

Exam 2: April 13, 2011, Closed Book Portion

1. (5) Explain why the total kinetic energy of the sites of a molecule is different than the
kinetic energy of the center of mass.

(5) Explain why the temperature fluctuates in a simulation with attractive and
repulsive potential energy.

(5) Compare in magnitude the kinetic energy of a ethanol vapor molecule at 35oC and
103.1 mmHg (the vapor pressure) and a liquid molecule at 35oC and 103.1 mmHg.

2. VLE data for the system carbon tetrachloride (1) and 1,2-dichloroethane (2) are given
below at 760 mm Hg, as taken directly from the literature.1

x1 y1 T(oC) x1 y1 T(oC)
0. 0. 82.4a 0.506 0.557 75.78
0.040 0.141 81.59 0.880 0.831 75.71
0.091 0.185 80.39 0.900 0.848 75.86
0.097 0.202 80.27 0.923 0.875 75.95
0.185 0.310 78.73 0.960 0.907 76.20
0.370 0.473 76.62 1.0 1.0 76.7a

a. (5) Does an azeotrope exist? If an azeotrope exists, between which two of the
x1 entries in the table does the azeotrope exist? If an azeotrope does not exist,
explain why the data indicate that conclusion.

b. (5) To the right of the table above, sketch a schematic of what you think a P-x1-
y1 diagram would look like for this system.

1
Yound, H.D., Nelson, O.A., Ind. Eng. Chem. Anal. Ed. 4, 67 (1932), except for normal boiling points
marked with superscript a, from Perry’s 5th edition, p. 3-49ff.

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 c. (5)Does the system exhibit positive or negative deviations from Raoult’s law?
(you may neglect gas phase non-idealities). Justify your answer.

3. Antoine coefficients for ethanol (1) + 1-propanol (2) are provided below. The
Antoine equation is log10P(mmHg) = A – B/(T + C). This problem involves
setting up Matlab code for a bubble temperature calculation. The problem is
divided into two parts. If needed, the syntax for an fzero statement is
‘[varValueFinal] = fzero(@objName,varValueGuess).’ The syntax for a
function statement is ‘[result] = functname(input1,…)’

A B C
ethanol 8.1122 1592.864 226.184
1-propanol 8.37895 1788.02 227.438

(a) (5) Provide Matlab code that will establish vectors A, B, C to hold the Antoine
coefficients given above, and set the pressure P to 760 mmHg, and the binary
composition, represented by vector x to 70% ethanol.

(b) (10) Add to your code a procedure to find the bubble temperature at pressure P =
760 mmHg using Raoult’s law at the composition available in the vector x. Your
code statements should use valid Matab syntax. (Note: half the credit for this
section is for properly setting up the bubble temperature logic and half the credit
is for the Matlab programming).

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 Michigan State University

DEPARTMENT OF CHEMICAL ENGINEERING AND MATERIALS SCIENCE

ChE321: Thermodynamics for Chemical Engineers Spring 2011

Exam 2: April 13, 2011, Open Book Portion

4. VLE data for the system carbon tetrachloride (1) and 1,2-dichloroethane (2) are given
below at 760 mm Hg, as taken directly from the literature.2

x1 y1 T(oC) x1 y1 T(oC)
0. 0. 83.55a 0.506 0.557 75.78
0.040 0.141 81.59 0.880 0.831 75.71
0.091 0.185 80.39 0.900 0.848 75.86
0.097 0.202 80.27 0.923 0.875 75.95
0.185 0.310 78.73 0.960 0.907 76.20
0.370 0.473 76.62 1.0 1.0 76.65a

.(a) (10) Using only the data at x1 = 0.37, fit the van Laar equation. The vapor
pressures at 76.62 oC are P1sat = 757.5 mmHg and P2sat = 601.6 mmHg.

2
Yound, H.D., Nelson, O.A., Ind. Eng. Chem. Anal. Ed. 4, 67 (1932), except for normal boiling points
marked with superscript a, from NIST WebBook.

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(b) (10) Using the parameters fitted in part (a), set forth the procedure to determine
bubble pressure for a mixture of 60 mol% carbon tetrachloride at 80oC where the
vapor pressures are P1sat = 838.6 mmHg, P2sat = 672.1 mmHg. Avoid unecessary
calculations in your procedure. If an iterative calculation is required, perform the
first interation and specify values for the next iteration. If an iterative calculation
is not required, provide the bubble pressure and vapor composition.

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5. (10) The vapor pressure of n-pentane at 70oC is 0.261 MPa, where VsatL = 121
cm3/mol, VsatV = 9974 cm3/mol. Calculate the fugacity of n-pentane at 70oC and 2
MPa. Use the virial equation to represent vapor phase non-idealities.

6. (5) An equilmolar mixture of water (1) + MEK (2) exits a distillation column at 100
mol/h as vapor and is condensed into a decanter at 298K. LLE has been modeled for
the two components using UNIFAC in Example 14.3 and 14.5. What are the flow
rates of the two liquid streams exiting the decanter?

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7. The equation of state for a simple fluid has been correlated to the equation
Z = 1 + aP/RT, where a = -254 cm3/mol, and CP = 56 J/mol-K.

(a) (10) When the pressure is 5 MPa, what is the molar volume at 320K?
(b) (10) Evaluate the enthalpy departure for the fluid in terms of the EOS variables.

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