CHAPTER

6 Phase Equilibria

LAIDLER . MEISER . SANCTUARY

Physical Chemistry
Electronic Edition
Publisher: MCH Multimedia Inc.

Problems and Solutions

Chapter 6: Phase Equilibria Number of Components and Degrees of Freedom

Chapter 6
*problems with an asterisk are slightly more demanding
Number of Components and Degrees of Freedom
6.1. In Figure 6.1, in the region marked orthorhombic, how many degrees of freedom exist? How many components are present? How
many phases? How many phases exist in the region marked monoclinic?
Solution
6.2. What is the composition of the two-phase region in Figure 6.14? How many degrees of freedom exist in this region?
Solution
6.3. Determine the number of degrees of freedom for the following systems:
a. A solution of potassium chloride in water at the equilibrium pressure.
b. A solution of potassium chloride and sodium chloride at 298 K at 1 atm pressure.
c. Ice in a solution of water and alcohol.
Solution
6.4. How many components are present in a water solution of sodium acetate?
Solution
6.5. How many components are present in the system CaCO3–CaO–CO2?
Solution
6.6. How many components are present in the following system?
CO(g) + 3H2(g)  CH4(g) + H2O(g)

Solution

6-2
Chapter 6: Phase Equilibria Use of the Lever Rule; Distillation

6.7. A certain substance exists in two solid phases A and B and also in the liquid and gaseous states. Construct a P-T phase diagram
indicating the regions of stable existence for each phase from the following triple-point data:

T/K P/kPa Phase in Equilibrium

200 100 A, B, gas
300 300 A, B, liquid
400 400 B, liquid, gas
Solution
Use of the Lever Rule; Distillation
6.8. Answer the following questions, using the accompanying figure.

a. A liquid mixture consists of 33 g of component A and 99 g of component B. At what temperature would the mixture begin to
boil?
b. Under the conditions in (a), what is the composition of the vapor when boiling first occurs?
c. If the distillation is continued until the boiling point is raised by 5.0 °C, what would be the composition of the liquid left in the
still?

d. Under the conditions in (c), what are the composition and mass of the two components collected over the initial 5.0 °C interval?
Solution

6-3
Chapter 6: Phase Equilibria Use of the Lever Rule; Distillation

6.9. From the data of Figure 6.14, calculate the ratio of the mass of the water-rich layer to that of the nicotine-rich layer, for a 40 wt %
water–nicotine mixture at 350 K.
Solution
6.10. The ratio of the mass of chlorobenzene to that of water collected in a steam distillation is 1.93 when the mixture was boiled at
343.85 K and 56.434 kPa. If the vapor pressure of water at this temperature is 43.102 kPa, calculate the molar mass of
chlorobenzene.
Solution
6.11. a. Do the actual derivation of Eq. 6.11 from Eq. 6.8.
b. From Eq. 6.8 derive an expression that gives you the ratio of the mass of two volatile components, 1 and 2, in terms of their mole
fractions in the vapor and their molar masses.
Solution
6.12. Obtain an expression for the ratio of masses of the materials distilled in a steam distillation in terms of the molar masses and the
partial pressures of the two components.
Solution
6.13. Under atmospheric pressure 1 kg of pure naphthalene is to be prepared by steam distillation at 372.4 K. What mass of steam is
required to perform this purification? The vapor pressure of pure water at 372.4 K is 98.805 kPa.
Solution
6.14. The vapor pressure of water at 343.85 K is 43.102 kPa. A certain mixture of chlorobenzene and water boils at 343.85 K under a
reduced pressure of 56.434 kPa. What is the composition of the distillate?
Solution
6.15. Calculate the composition of the vapor in equilibrium at 323 K with a liquid solution of 0.600 mol fraction 2-methyl-1-propanol
(isobutyl alcohol) and 0.400 mol fraction 3-methyl-1-butanol (isoamyl alcohol). The vapor pressure of pure isobutyl alcohol is
7.46 kPa and that of pure isoamyl alcohol is 2.33 kPa both at 323 K.
Solution

6-4
Chapter 6: Phase Equilibria Construction of Phase Diagrams from Physical Data

6.16. The thermal expansion coefficient α = (1/V) (V/T ) P is often used when predicting changes in vapor pressure induced by
temperature changes. From the relation ρ = m/V, show that   – ( ln  /T ) P .

Solution
6.17. At 293.15 K the density of water is 0.998 234 g cm–3 and at 294.15 K it is 0.998 022 g cm–3 under 1 atm of pressure.
Estimate the value of α for water at 1 atm.
Solution
6.18. How many theoretical plates are required to separate the mixture shown in Fig. 6.7?
Solution
*6.19. A sealed reaction vessel is completely filled with liquid water at 293.15 K and 1.00 atm. If the temperature is raised exactly 6 K and
the walls of the vessel remain rigid, what is the pressure in the container if the average value of α = 2.85 × 10–4 K–1 and the
compressibility coefficient  [ – (1/V )(V/P )T ] is 4.49 × 10–5 atm–1?

Solution
Construction of Phase Diagrams from Physical Data
6.20. In Figure 6.16, a solution having composition p is cooled to just above the eutectic temperature (point s is about 0.18 xSi, and xe is
0.31 xSi); calculate the composition of the solid that separates and that of the liquid that remains.
Solution
*6.21. The melting points and heats of fusion of gold and silicon are

Au Si
T/K 1337 1683
∆fus H/J mol–1 12 677.5 39 622.5

For the data, calculate the solid-liquid equilibrium lines and estimate the eutectic composition graphically. Compare the result with the
values given by Figure 6.16.

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Chapter 6: Phase Equilibria Construction of Phase Diagrams from Physical Data

Solution
6.22. Use the following data to construct a phase diagram of the phenol–water system and answer the following questions (the
compositions are given in grams of phenol in 100 grams of solution):

t/ºC 20 25 30 35 40
Aqueous layer 8.40 8.71 8.92 9.34 9.78
Phenol layer 72.24 71.38 69.95 68.28 66.81

45 50 55 60 65 68.8
10.62 12.08 13.88 17.10 22.26 35.90
65.02 62.83 60.18 56.10 49.34 35.90

a. What will be the compositions of the layers formed from a solution of 30 g phenol and 70 g water maintained at 30 °C?
b. A solution of 20 g phenol and 80 g water is prepared at 70 °C. How many phases will be present?
c. At what temperature will two phases appear if the solution in part (b) is cooled gradually? What will be the compositions of the
two phases?
Solution

6-6
Chapter 6: Phase Equilibria Construction of Phase Diagrams from Physical Data

6.23. The following information is obtained from cooling curve data on the partial system Fe2O3–Y2O3 [J. W. Nielsen and E. F. Dearborn,
Phys. Chem. Solids, 5, 203(1958)]:

Composition of Temperature of Break/ºC Temperature of Halt/ºC

Melt/mol % Y2O3
0 1550
5 1540 1440
10 1515 1440
15 1450 1440
20 1520 1440
25 1560 1440
30 1620 1575/1440
40 1705 1575
50 1720

Sketch the simplest melting point diagram consistent with these data. Label the phase regions and give the composition of any
compounds formed.
Solution
6.24. The study of cooling curves for the thallium–gold system yields the following data. Construct the phase diagram and identify the
eutectic composition and temperature. Pure gold melts at 1063 °C and pure thallium melts at 302 °C. In each region, identify the
number of phases and the solid that separates out, if any.

Wt % Au 10 20 30 40 60 80 90
First break (ºC) 272 204 200 400 686 910 998
Eutectic halt (ºC) 128 128 128 128 128 128 128

[Data adapted from A. C. K. Smith, Applied Physical Chemistry Problems, London: McGraw-Hill, 1968, p. 13.]
Solution

6-7
Chapter 6: Phase Equilibria Construction of Phase Diagrams from Physical Data

6.25. a. From the following information, draw the binary phase diagram for the system FeO (mp. 1370 °C)–MnO (mp. 1785 °C). A
peritectic reaction occurs at 1430 °C between α solid solution containing 30 mass % MnO and solid solution containing 60 mass %
MnO. These are in equilibrium with melt that contains 15 mass % MnO. At 1200 °C the composition of α and β solution is 28 mass
% and 63 mass %, respectively.
b. Describe what happens as a liquid containing 28 mass % MnO is cooled to 1200 °C.
Solution
6.26. The following data for the magnesium–copper system is the result of analyzing cooling curves. Pure copper melts at 1085 °C while
pure magnesium melts at 659 °C. Two compounds are formed, one at 16.05 wt % Mg with a melting point of 800 °C, and the other
at 43.44 wt % Mg with a melting point of 583 °C, respectively. Construct the phase diagram from this information and identify the
compositions of the eutectics. [Data adapted from A. C. K. Smith, Applied Physical Chemistry Problems, London: McGraw-Hill,
1968, p. 14.]

Wt % Mg 5 10 15 20 30 35
First break (ºC) 900 702 785 765 636 565
Eutectic halt (ºC) 680 680 680 560 560 560

40 45 50 60 70 80 90
581 575 546 448 423 525 600
560 360 360 360 360 360 360

Solution
6.27. What are the empirical formulae of the compounds represented by the vertical lines formed in the magnesium–copper system
described in Problem 6.26?
Solution

6-8
Chapter 6: Phase Equilibria Construction of Phase Diagrams from Physical Data

6.28. A preliminary thermal analysis of the Fe–Au system showed two solid phases of composition 8.1 mol % Au and 25.5 mol % Au in
equilibrium at 1168 °C with liquid of composition 43 mol % Au. Construct the simplest melting point diagram consistent with this
information and label all the phase regions. Sketch the cooling curves for the composition 10 mol % Au, 30 mol % A, and 60 mol %
Au, and make them consistent with the fact that there is an α-γ phase transition in iron at 903 °C and that the γ-phase field extends to
45 mol % Au at this temperature. Iron melts at 1536 °C and gold at 1063 °C.
Solution
6.29. The aluminum–selenium system was determined from thermal analysis. Al2Se3 melts congruently at approximately 950 °C and
forms a eutectic both with aluminum and with selenium at a very low concentration of the alloying element and at a temperature
close to the melting point of the base elements. Draw a diagram from this information and give the composition of the phases.
Aluminum melts at 659.7 °C and selenium melts at approximately 217 °C.
Solution
*6.30. The metals Al and Ca form the compounds Al4Ca and Al2Ca. The solids Al, Ca, Al4Ca, and Al2Ca essentially are immiscible in each
other but are completely miscible as liquids. Maximum Ca solubility in Al is about 2% and occurs at 616 °C. Al melts at 659.7 °C
and Ca melts at 848 °C. Compound Al2Ca melts congruently at 1079 °C and gives a simple eutectic with Ca at 545°C. Compound
Al4Ca decomposes at 700 °C to give Al2Ca and a melt, the peritectic lying at 10 mol %. A monotectic exists at 616 °C. At
approximately 450 °C a transition occurs between α-Ca and β-Ca.
a. Draw the simplest phase diagram consistent with this information and label all phase regions.
b. Sketch cooling curves for melts of composition 15 mol % Ca and 80 mol % Ca.
Solution

6-9
Chapter 6: Phase Equilibria Construction of Phase Diagrams from Physical Data

*6.31. The extent of dehydration of a salt such as CuSO4 can often be followed by measuring the vapor pressure over the hydrated salt. The
system H2O–CuSO4 is shown in the accompanying figure as an example of such a system. Label the areas as to the phase(s) present.
Then describe the sequence of phase changes if a dilute solution of copper sulfate is dehydrated at 275 K, ending with anhydrous
copper sulfate. What would a vacuum gauge read starting with pure water during the dehydration process at 298.15 K? Sketch a plot
of P/Torr against CuSO4/wt %. Relevant data are:

The Vapor Pressure of CuSO4–H2O at 298.15 K P/Torr

Vapor + saturated solution + CuSO4 · 5H2O 16
Vapor CuSO4 · 5H2O + CuSO4 · 3H2O 7.85
Vapor + CuSO4 · 3H2O + CuSO4 · H2O 4.32
Vapor + CuSO4 · H2O + CuSO4 0.017
Vapor pressure of water 23.8

Solution

6-10
Chapter 6: Phase Equilibria Construction of Phase Diagrams from Physical Data

*6.32. The data in the accompanying table are approximate for the isobaric-isothermal system SnO2–CaO–MgO at 298.15 K and 1 atm.
Sketch a reasonable phase diagram in mol % with SnO2 at the apex of the triangle. Label all phase regions; the results are known as
composition triangles.

Material In Equilibrium with Solid Phases

SnO2 (MgO)2SnO2, CaOSnO2
(MgO)2SnO2 SnO2, (CaO)SnO2, MgO
MgO CaO, (CaO)2SnO2
CaO MgO, (CaO)2SnO2
(CaO)2SnO2 CaO, MgO, CaOSnO2
CaOSnO2 (CaO)2 SnO2, MgO, (MgO)2SnO2, SnO2

Solution
6.33. Sketch the P against T diagram for phosphorous from the following information. White phosphorous melts at 311 K and 0.2 Torr;
red phosphorous melts at 763 K and 43 atm. The white form is more dense than the liquid and the red form is less dense than the
liquid. The vapor pressure of the white form is everywhere greater than that of the red form. Label each area on the plot, and explain
which triple point(s) is (are) stable or metastable.
Solution
6.34. Giguère and Turrell, J. Am. Chem. Soc., 102, 5476(1980), describe three ionic hydrates formed between HF and H2O. Sketch the
H2O-HF phase diagram in mol % HF from the following information. HF · H2O melts at –35.2 °C, 2HF · H2O decomposes by a
peritectic reaction at –75 °C, and 4HF · H2O melts at –98.2 °C. HF melts at –83.1 °C. Label the composition of all regions. The
eutectic occurs at –111 °C with monotectics at –71 °C, –77 °C, and –102 °C.
Solution
6.35. In the system A–B a line of three-phase equilibrium occurs at 900 K as determined by thermal analysis. A second three-phase
equilibrium occurs at 500 K. Only one halt is observed for any one cooling curve. The compound AB2 is known and melts at 600 K.
If A melts at 1200 K and B at 700 K, sketch the simplest phase diagram consistent with the given data. Label each region.
Solution

6-11
Chapter 6: Phase Equilibria Data Derived from Phase Diagrams of Condensed Systems

Data Derived from Phase Diagrams of Condensed Systems

6.36. The following questions refer to Figure 6.28:
a. If liquid C were added to the system, what changes would occur if the system originally contained 80% salt A and 20% salt B?
b. What changes would occur if the system originally contained 50% salt A and 50% salt B upon the addition of liquid?
c. If liquid is added to an unsaturated solution of salt A and salt B in solution of composition lying at e, what changes would occur?
Solution
6.37. In the accompanying diagram, due to B. S. R. Sastry and F. A. Hammel, J. Am. Ceramic Soc., 42; 218(1959), identify the
composition of all the areas. Identify the phenomenon associated with each lettered position.

[[Diagram for Problem 6.37. Reprinted with permission of The American Ceramic Society, Post Office Box 6136, Westerville, OH 43086-
6136, Copyright © 1964 by the American Ceramic Society. All rights reserved.]]

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Chapter 6: Phase Equilibria Data Derived from Phase Diagrams of Condensed Systems

Solution

6.38. Describe what happens within the system Mn2O3–Al2O3 in Fig. 6.21 when a liquid of xA12 O3 = 0.2 is cooled from 2100 K to 1200 K.

Solution
6.39. The isobaric solubility diagram for the system acetic acid–toluene–water is shown in Figure 6.27. What phase(s) and their
composition(s) will be present if 0.2 mol of toluene is added to a system consisting of 0.5 mol of water and 0.3 mol of acetic acid?
Give the relative amounts of each phase.
Solution
6.40. A fictitious ternary system composed of liquids A, B, and C was constructed by adding the component B to various binary A–C
mixtures and noting the point at which complete miscibility occurred. The following are the mole-percents of A and B at which
complete miscibility was observed. Construct the phase diagram on a triangular graph paper.

xA(%) 10.0 20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0
xB(%) 20.0 27.0 30.0 28.0 26.0 22.0 17.0 12.0 7.0

Comment on the variation of the mutual solubility of A and C as B is added.

Solution

6-13
Chapter 6: Phase Equilibria Data Derived from Phase Diagrams of Condensed Systems

6.41. In organic chemistry it is a common procedure to separate a mixture of an organic liquid in water by adding a salt to it. This is
known as “salting out.” The ternary system K2CO3–H2O–CH3OH is typical. The system is distinguished by the appearance of the
two-liquid region abc.

a. Describe the phase(s) present in each region of the diagram.

b. What would occur as solid K2CO3 is added to a solution of H2O and CH3OH of composition x?
c. How can the organic-rich phase in (b) be separated?
d. How can K2CO3 be precipitated from a solution having composition y?
e. Describe in detail the sequence of events when a solution of composition F is evaporated.
Solution

6-14
Chapter 6: Phase Equilibria Essay Questions

Essay Questions
6.42. How is thermal analysis used to determine the liquid-solid equilibria and the eutectic temperature?
6.43. Explain what is meant by a metastable system.
6.44. Outline how isothermal distillation may be used to prepare a pure sample.
6.45. Detail the process by which a pure sample is obtained using a fractionating column.
6.46. What is the difference on a molecular level between a maximum and minimum boiling azeotrope? How do the plots of P against x
and T against x differ?
6.47. How would you distinguish between an azeotrope and a pure compound?
6.48. A synthetic chemist has prepared several zwitterionic compounds in a homogeneous series. With each compound a reproducible
melting point is determined using different samples from a fresh batch of material. If, however, the same sample is used in repeating
the determination, a progressively lower melting-point temperature is obtained. Explain what is happening.
SUGGESTED READING
A. Findlay, Phase Rule (revised and enlarged 9th ed., by A. N. Campbell and N. O. Smith), New York: Dover, 1951.
R. J. Forbes, A Short History of the Art of Distillation, Leiden: E. J. Brill, 1970.
J. H. Hildebrand, J. M. Prausnits, and R. L. Scott, Regular and Related Solutions, New York: Van Nostrand Reinhold, 1970.
W. Hume-Rothery, R. E. Smallman, and C. W. Haworth, The Structure of Metals and Alloys, The Metals and Metallurgy Trust of the
Institute of Metals and the Institution of Metallurgists, London, 1969.
R. G. Laughlin, The Aqueous Phase Behavior of Surfactants, New York: Academic Press, 1994.
C. S. Robinson and E. R. Gilliland, Fractional Distillation, New York: McGraw-Hill, 1950.
B. D. Smith, Design of Equilibrium Stage Processes, New York: McGraw-Hill, 1963.
Specifically on miscibility:
J. S. Walker and C. A. Vance. Scientific American, May 1987, p. 98.
Much of the literature has been reviewed and compiled in several areas. The following are convenient sources of much of the work.

6-15
Chapter 6: Phase Equilibria Suggested Reading

Azeotropic Data, Advances in Chemistry Series No. 35, American Chemical Society, Washington, DC, 1962.
R. P. Elliott, Constitution of Binary Alloys (1st Suppl.), New York: McGraw-Hill, 1965.
M. Hansen, Constitution of Binary Alloys (2nd ed.), New York: McGraw-Hill, 1958.
M. Hirata, S. One, and K. Nagahama, Computer Aided Data Book of Vapor-Liquid Equilibria, New York: Kodansha Limited, Elsevier,
Scientific Publishing Co., 1990.
E. M. Levin, R. Robbins, and H. F. McMurdie, Phase Diagrams for Ceramists, The American Ceramic Society, Inc., 1964; 1969
Supplement (Figures 2067–4149); E. M. Levin and H. F. McMurdie, 1975 Supplement (Figures 4150–4999). (Series through 1992.)
T. B. Massalski, Ed. Binary Alloy Phase Diagrams, ASM/NIST Data Program for Alloy Phase Diagrams, ASM International, Materials
Park, Ohio 44073. 2nd Ed., 1990, in three volumes.
W. G. Moffatt, Ed., The Handbook of Binary Phase Diagrams, Genium Publishing Corporation, Schenectady, NY: 1994. (In five volumes.)
G. Petzow and G. Effenberg, Eds., Ternary Alloys, A Comprehensive Compendium of Evaluated Constitutional Data and Phase Diagrams,
Materials Science; International Services GmbH and the Max Planck-Institut fur Metallforschung, Stuttgart, VCH Verlagsgesellschaft mbH,
Weinheim, Germany, 1992. (In five volumes.)
F. A. Shunk, Constitution of Binary Alloys (2nd Suppl.), New York: McGraw-Hill, 1969.
I. Wichterle, J. Linek, and E. Hala, Vapor-Liquid Equilibrium Data Bibliography, New York: Elsevier Science Publishers, 1985. Covers the
literature with four supplements to 1985.

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Chapter 6: Phase Equilibria Solutions

Solutions
6.1. In Figure 6.1, in the region marked orthorhombic, how many degrees of freedom exist? How many components are present? How
many phases? How many phases exist in the region marked monoclinic?
Solution:
The region marked orthorhombic is a single phase region. Since this is the phase diagram for pure sulfur, there is only one component.
From the phase rule, given by Eq. 6.2, f  c  p  2 , with c  1 and p  1 , f  1  1  2  2 . The two degrees of freedom are pressure and
temperature.
There is only one phase in the region marked monoclinic.

Back to Problem 6.1 Back to Top

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Chapter 6: Phase Equilibria Solutions

6.2. What is the composition of the two-phase region in Figure 6.14? How many degrees of freedom exist in this region?
Solution:
The compositions of the two phases at a particular temperature are:
i. Water saturated with nicotine
ii. Nicotine saturated with water
The number of degrees of freedom is given by Eq . 6.2,
f c p2
f  222
f 2

Back to Problem 6.2 Back to Top

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Chapter 6: Phase Equilibria Solutions

6.3. Determine the number of degrees of freedom for the following systems:
a. A solution of potassium chloride in water at the equilibrium pressure.
b. A solution of potassium chloride and sodium chloride at 298 K at 1 atm pressure.
c. Ice in a solution of water and alcohol.
Solution:
The number of degrees of freedom is given by Eq. 6.2,
f c p2

a. For KCl solution, c  2 since it completely dissociates into two ions in water, and p  1 since there is only one phase.

f  2 1 2
f 3

However, since equilibrium pressure has been specified, the degrees of freedom drops by one, and

f 2

b. For KCl and NaCl solution, c  3 since there are three ions present, K + , Cl- and Na + , and p  1 since there is only one phase.

f  3 1  2
f 4

However, since the restriction of constant pressure has been specified, the degrees of freedom drops by one, and

f 3

c. For ice, water and alcohol, c  2 since water and ice are considered one component. p  2 since there is a solid and a liquid phase.

f  222
f 2

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Chapter 6: Phase Equilibria Solutions

6.4. How many components are present in a water solution of sodium acetate?
Solution:
The system is given by

Ac  + H 2 O  OH  + HAc

Aqueous sodium acetate is a two-component system even though the above hydrolysis takes place, since the equilibrium constant defines
the concentration of OH- and HAc if the concentration of sodium acetate is given.

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Chapter 6: Phase Equilibria Solutions

6.5. How many components are present in the system CaCO3–CaO–CO2?

Solution:
There are three components in the system CaCO3–CaO–CO2. However, since a chemical reaction can take place in the given system, the
number of components is reduced by the number of equilibrium conditions, in this case 1. Therefore c  2 .

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Chapter 6: Phase Equilibria Solutions

6.6. How many components are present in the following system?

CO(g) + 3H2(g)  CH4(g) + H2O(g)

Solution:
There are four different gases, or components in the above system. However, since a chemical reaction can take place in the given system,
the number of components is reduced by the number of equilibrium conditions, in this case 1. Therefore c  3 .

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Chapter 6: Phase Equilibria Solutions

6.7. A certain substance exists in two solid phases A and B and also in the liquid and gaseous states. Construct a P-T phase diagram
indicating the regions of stable existence for each phase from the following triple-point data:

T/K P/kPa Phase in Equilibrium

200 100 A, B, gas
300 300 A, B, liquid
400 400 B, liquid, gas
Solution:

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Chapter 6: Phase Equilibria Solutions

6.8. Answer the following questions, using the accompanying figure.

a. A liquid mixture consists of 33 g of component A and 99 g of component B. At what temperature would the mixture begin to
boil?
b. Under the conditions in (a), what is the composition of the vapor when boiling first occurs?
c. If the distillation is continued until the boiling point is raised by 5.0 °C, what would be the composition of the liquid left in the
still?

d. Under the conditions in (c), what are the composition and mass of the two components collected over the initial 5.0 °C interval?
Solution:
a. To calculate the temperature at which the mixture would begin to boil, we need to find the weight percent of the component B.
mB
weight % B   100%
mA  mB
99 g
weight % B   100%
33 g  99 g
weight % B  75%

The temperature corresponding to 75% B is approximately 60 °C, where the mixture first begins to boil.

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Chapter 6: Phase Equilibria Solutions

T  60 C

b. The composition of the vapor is given by the intersection of the tie line at the vapor curve. In this case, the vapor has a composition of
approximately 88% B

weight % B  88%

c. The boiling temperature becomes 65.0 °C. The composition of the vapor is approximately 53% B

weight % B  53%

d. using the average composition of the distillates as the value halfway between the initial and final composition of the distillates, we obtain,
1
weight % B  88%  70% 
2
weight % B  79%

Let WR = mass of residue and WD = mass of distillate

Wtotal  WR  WD  132 g

Then, applying the condition that B is distributed through the residue and distillate, we obtain

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Chapter 6: Phase Equilibria Solutions

mB in residue  mB in distillate  99 g
0.53WR  0.79WD  99 g
0.53 132 g  WD   0.79WD  99 g
69.96 g  0.53WD  0.79WD  99 g
69.96 g  0.26WD  99 g
99 g  69.96 g
WD 
0.26
WD  111.692 307 7 g
WR  132 g  111.692 307 7 g
WR  20.307 692 31 g

The distillate is therefore 79% of the value of WD,

mB in distillate  0.79WD
mB in distillate  0.79 111.692 307 7 g 
mB in distillate  88.236 923 08 g
mB in distillate  88.2 g
mA in distillate  111.692 307 7 g  88.236 923 08 g
mA in distillate  23.455 384 62 g
mA in distillate  23.5 g

Back to Problem 6.8 Back to Top

6-26
Chapter 6: Phase Equilibria Solutions

6.9. From the data of Figure 6.14, calculate the ratio of the mass of the water-rich layer to that of the nicotine-rich layer, for a 40 wt %
water–nicotine mixture at 350 K.
Solution:
Given: Figure 6.14, 40wt % water  nicotine, T  350 K

mwater
Required:
mnicotine

From Figure 6.14, the composition at 350 K at equilibrium between the single-phase water-rich layer and the two-phase region is
approximately 10% nicotine. For the equilibrium value on the nicotine-rich side, the value is approximately 75% nicotine.
Using the lever rule, given by Eq. 6.16, we can solve for the ratio,

n1 y1 – xT pv
   
nv xT – x1 lp

mwater 75 – 40

mnicotine 40 –10
mwater 35

mnicotine 30
 
mwater
1.166 666 667
mnicotine
mwater
 1.2
mnicotine

Back to Problem 6.9 Back to Top

6-27
Chapter 6: Phase Equilibria Solutions

6.10. The ratio of the mass of chlorobenzene to that of water collected in a steam distillation is 1.93 when the mixture was boiled at
343.85 K and 56.434 kPa. If the vapor pressure of water at this temperature is 43.102 kPa, calculate the molar mass of
chlorobenzene.
Solution:
mchlorobenzene
Given:  1.93, T  343.85 K, P  56.434 kPa, Pwater  43.102 kPa
mwater

Required: M chlorobenzene

Using Eq. 6.21,

nA PA*

nB PB*

m
Using, n  we can rearrange and solve for M chlorobenzene ,
M
*
mchlorobenzene M water Pchlorobenzene
 *
mwater M chlorobenzene Pwater
*
mchlorobenzene M water Pwater
M chlorobenzene  *
mwater Pchlorobenzene
M water  2 1.007 94 g mol1   15.9994 g mol1 
M water  18.015 28 g mol1

The vapor pressure of pure chlorobenzene is obtained using Dalton’s law of partial pressures,

6-28
Chapter 6: Phase Equilibria Solutions

*
Pchlorobenzene  P  Pwater
*

*
Pchlorobenzene  56.434 kPa  43.102 kPa
*
Pchlorobenzene  13.332 kPa
43.102 kPa
M chlorobenzene  1.93 18.015 28 g mol1 
13.332 kPa
M chlorobenzene  112.408 834 g mol1
M chlorobenzene  112.41 g mol1

The actual molar mass of chlorobenzene, C6H5Cl is

M chlorobenzene  6 12.011 g mol1   5 1.007 94 g mol1    35.4527 g mol1 

M chlorobenzene  112.5584 g mol1

Back to Problem 6.10 Back to Top

6-29
Chapter 6: Phase Equilibria Solutions

6.11. a. Do the actual derivation of Eq. 6.11 from Eq. 6.8.

b. From Eq. 6.8 derive an expression that gives you the ratio of the mass of two volatile components, 1 and 2, in terms of their mole
fractions in the vapor and their molar masses.
Solution:
a. Equation 6.11 is given by

P1* P2*
P
P1*  ( P2* – P1* ) y1

We can manipulate Eq. 6.8 to obtain the same result.

P1
y1 
P
The total pressure is given by the sum of partial pressures of each of the components in a mixture, hence,

P  P1  P2

Raoult’s Law is given by Eq. 5.26, therefore we can use it solve for P

P1  x1 P1* ; P2  x2 P2*

P  P1  P2
P  x1 P1*  x2 P2*
P  x1 P1*  1  x1  P2*
P  x1 P1*  P2*  x1 P2*
P   P1*  P2*  x1  P2*

b. Using Eq. 6.8, we can obtain an expression for x1,

6-30
Chapter 6: Phase Equilibria Solutions

P1
y1 
P
x1P1*
y1 
P2*  x1  P1*  P2* 

Solving for x1 gives

x1P1*  y1 P2*  y1 x1  P1*  P2* 

x1  P1*  y1  P1*  P2*   y1 P2*

y1P2*
x1 
P1*  y1  P1*  P2* 

This expression may now be substituted back into Eq. 6.9 with the elimination of x1. The result is

y1 P2*
P   P1*  P2*   P2*
y1  P1  P2   P1
* * *

P

y1 P2*  P1*  P2*   P2* y1  P1*  P2*   P1* 
y1  P  P   P
1
*
2
*
1
*

y1 P2*  P1*  P2*   y1 P2*  P1*  P2*   P1* P2*

P
y1  P1*  P2*   P1*
 P1* P2*
P
y1  P1*  P2*   P1*

6-31
Chapter 6: Phase Equilibria Solutions

1
Multiplying by to remove the negative sign, we obtain,
1

P1* P2*
P
P1*  y1  P1*  P2* 

Which is the same equation as Eq. 6.11.

Back to Problem 6.11 Back to Top

6-32
Chapter 6: Phase Equilibria Solutions

6.12. Obtain an expression for the ratio of masses of the materials distilled in a steam distillation in terms of the molar masses and the
partial pressures of the two components.
Solution:
To solve this problem, we can use the expression for the composition of vapor, given by Eq. 6.21,

nA PA*

nB PB*

m
Using, n  we can rearrange and solve for the masses of the materials distilled
M

mA M B PA*

mB M A PB*
mA PA* M A

mB PB* M B

Back to Problem 6.12 Back to Top

6-33
Chapter 6: Phase Equilibria Solutions

6.13. Under atmospheric pressure 1 kg of pure naphthalene is to be prepared by steam distillation at 372.4 K. What mass of steam is
required to perform this purification? The vapor pressure of pure water at 372.4 K is 98.805 kPa.
Solution:

Given: P  101.325 kPa, mnaphthalene  1 kg, T  372.4 K, Pwater

*
 98.805 kPa

Required: msteam

To solve this problem, we can use the expression for the composition of vapor, given by Eq. 6.21,

nA PA*

nB PB*

m
Using, n  we can rearrange and solve for the masses of the materials distilled
M

mA M B PA*

mB M A PB*
mA PA* M A

mB PB* M B
*
Psteam M steam mnaphthalene
msteam  *
Pnaphthalene M naphthalene

The vapor pressure of pure naphthalene is obtained using Dalton’s law of partial pressures,
*
Pnaphthalene  P  Pwater
*

*
Pnaphthalene  101.325 kPa  98.805 kPa
*
Pnaphthalene  2.52 kPa
M steam  M H2O  2 1.007 94 g mol1   15.9994 g mol 1 
M steam  18.015 28 g mol1

6-34
Chapter 6: Phase Equilibria Solutions

The formula for naphthalene is C10H8, therefore the molar mass is

M naphthalene  10 12.011 g mol1   8 1.007 94 g mol1 

M naphthalene  128.173 52 g mol1

Solving for the mass of steam, we obtain

 98.805 kPa  18.015 28 g mol  1 kg 

1

msteam 
 2.52 kPa  128.173 52 g mol  1

msteam  5.510 809 449 kg

msteam  5.5108 kg

Back to Problem 6.13 Back to Top

6-35
Chapter 6: Phase Equilibria Solutions

6.14. The vapor pressure of water at 343.85 K is 43.102 kPa. A certain mixture of chlorobenzene and water boils at 343.85 K under a
reduced pressure of 56.434 kPa. What is the composition of the distillate?
Solution:

Given: T  343.85 K, Pwater

*
 43.102 kPa, P  56.434 kPa

mchlorobenzene
Required:
mwater

To solve this problem, we can use the expression for the composition of vapor, given by Eq. 6.21,

nA PA*

nB PB*

m
Using, n  we can rearrange and solve for the masses of the materials distilled
M

mA M B PA*

mB M A PB*
mA PA* M A

mB PB* M B
*
mchlorobenzene Pchlorobenzene M chlorobenzene
 *
mwater Pwater M water

The vapor pressure of pure chlorobenzene is obtained using Dalton’s law of partial pressures,
*
Pchlorobenzene  P  Pwater
*

*
Pchlorobenzene  56.434 kPa  43.102 kPa
*
Pchlorobenzene  13.332 kPa

The formula for chlorobenzene is C6H5Cl therefore the molar mass is

6-36
Chapter 6: Phase Equilibria Solutions

M chlorobenzene  6 12.011 g mol1   5 1.007 94 g mol1    35.4527 g mol1 

M chlorobenzene  112.5584 g mol1
M water  2 1.007 94 g mol1   15.9994 g mol1 
M water  18.015 28 g mol1

mchlorobenzene  13.332 kPa  112.5584 g mol1 


mwater  43.102 kPa  18.015 28 g mol1 
mchlorobenzene
1.932 567 968
mwater
mchlorobenzene
 1.9326
mwater

The sample contains 1.9326 g of chlorobenzene for each 1.000 g of water.

Back to Problem 6.14 Back to Top

 

6-37
Chapter 6: Phase Equilibria Solutions

6.15. Calculate the composition of the vapor in equilibrium at 323 K with a liquid solution of 0.600 mol fraction 2-methyl-1-propanol
(isobutyl alcohol) and 0.400 mol fraction 3-methyl-1-butanol (isoamyl alcohol). The vapor pressure of pure isobutyl alcohol is
7.46 kPa and that of pure isoamyl alcohol is 2.33 kPa both at 323 K.
Solution:

Given: T  323 K, xisobutyl alcohol  0.600, xisoamyl alcohol  0.400, Pisobutyl

*
alcohol  7.46 kPa, Pisoamyl alcohol  2.33 kPa
*

Required: yisoamyl alcohol , yisobutyl alcohol

To determine the composition of the vapor in equilibrium, we can use Eq. 6.18,

x1 P1*
y1 
x1 P1*  x2 P2*
xa Pa*
ya 
xa Pa*  xb Pb*

ya 
 0.600  7.46 kPa 
 0.600  7.46 kPa    0.400  2.33 kPa 
ya  0.827 662 721 9
ya  0.828
yb  1  ya
yb  1  0.827 662 721 9
yb  0.172 337 2781
yb  0.172

Back to Problem 6.15 Back to Top

6-38
Chapter 6: Phase Equilibria Solutions

6.16. The thermal expansion coefficient α = (1/V) (V/T ) P is often used when predicting changes in vapor pressure induced by
temperature changes. From the relation ρ = m/V, show that   – ( ln  /T ) P .

Solution:
To solve this problem, we first take the natural logarithm of the density expression to cast it into a more useful form.

m

V
m
ln   ln    ln m  ln V
V 

Taking the partial derivative with respect to T gives,

  ln    ln m   ln V 
    
 T  P T  T  P
  ln     ln V 
    
 T  P  T  P
  ln   1  V 
    
 T  P V  T  P

The thermal expansion coefficient is given by α = (1/V) (V/T ) P , hence,

  ln   1  V 
      
 T  P V  T  P
  ln  
   
 T  P

Back to Problem 6.16 Back to Top

6-39
Chapter 6: Phase Equilibria Solutions

6.17. At 293.15 K the density of water is 0.998 234 g cm–3 and at 294.15 K it is 0.998 022 g cm–3 under 1 atm of pressure.
Estimate the value of α for water at 1 atm.
Solution:

Given: T  293.15 K,  water  0.998234 g cm –3 , T  294.15 K,  water  0.998022 g cm –3 , P  1 atm

Required: α
To solve this problem, we can use the expression for α obtained in problem 6.16

1  V  1 V
   
V  T  P V T

We make the approximation since we are considering small changes in T and V.

m
Density is given by,   , and can be rearranged to solve for V. Therefore we obtain the expression,
V

1  V2  V1 
  
V1  T2  T1 
 m m

1   2 1 
  
m  T2  T1 
 
 

We can set m, the mass of water, equal to 1 gram and solve for α

6-40
Chapter 6: Phase Equilibria Solutions

 1g 1g 
  
0.998234 g cm –3  0.998022 g cm –3 0.998234 g cm –3 
  
1g  294.15 K  293.15 K 
 
 
  2.124 201 67 10 K 1
4

  2.1242 104 K 1

Back to Problem 6.17 Back to Top

6-41
Chapter 6: Phase Equilibria Solutions

6.18. How many theoretical plates are required to separate the mixture shown in Fig. 6.7?
Solution:
There are six full horizontal steps and two fractional steps in Figure 6.7. There are therefore approximately six theoretical plates required to
separate the mixture.

Back to Problem 6.18 Back to Top

6-42
Chapter 6: Phase Equilibria Solutions

6.19. A sealed reaction vessel is completely filled with liquid water at 293.15 K and 1.00 atm. If the temperature is raised exactly 6 K and
the walls of the vessel remain rigid, what is the pressure in the container if the average value of α = 2.85 × 10–4 K–1 and the
compressibility coefficient  [ – (1/V )(V/P)T ] is 4.49 × 10–5 atm–1?

Solution:

Given: T  293.15 K, P  1 atm, T  6 K,   2.85  10 –4 K –1 ,   4.49  10 –5 atm –1

Required: P
From chapter 3, Eq. 3.139 defines the expansion coefficient as
1  V 
    
V  T  P

To solve for P we rearrange the two expressions for  and  in the following manner,

 P   T   V 
From        1
 T V  V  P  P T
  1  V     P  
     V   
  V  T  P    V T 
  P 

  T V
Therefore
 2.85  104 K 1
P  T  6 K
 4.49  105 atm 1
P  38.084 632 52 atm
P  38.1 atm

Back to Problem 6.19 Back to Top

6-43
Chapter 6: Phase Equilibria Solutions

6.20. In Figure 6.16, a solution having composition p is cooled to just above the eutectic temperature (point s is about 0.18 xSi, and xe is
0.31 xSi); calculate the composition of the solid that separates and that of the liquid that remains.
Solution:

Given: Figure 6.16, xs  0.18 xSi , xe  0.31xSi

Required: p
Using the lever rule, given by Eq. 6.16, we can solve for the ratio,

msolid layer
p
msolid layer  mliquid layer
0.18
p
0.31
p  0.580 645161 3
p  0.58

This means that there is 58% solid and 42% liquid in the two-phase region. The overall composition of the liquid above the liquid line is xSi
= 0.31.
 

Back to Problem 6.20 Back to Top

6-44
Chapter 6: Phase Equilibria Solutions

6.21. The melting points and heats of fusion of gold and silicon are

Au Si
T/K 1337 1683
–1
∆fus H/J mol 12 677.5 39 622.5

For the data, calculate the solid-liquid equilibrium lines and estimate the eutectic composition graphically. Compare the result with the
values given by Figure 6.16.
Solution:
The temperature at which solid solvent is in equilibrium with liquid solvent, with mole fraction x1 is given by Eq. 5.115,

 fus H m  1 1 
ln x1  –
R  T f* T 
 

Values of x1 and T determined from this equation for each component give the desired liquidus lines in the regions near large values of x1.
Several values are:
x1 T (K) x1 T (K)
0.945 1650 0.969 1300
0.863 1600 0.924 1250
0.784 1550 0.879 1200
0.708 1500 0.783 1100
0.564 1400 0.681 1000

6-45
Chapter 6: Phase Equilibria Solutions

A plot is shown on which the points represent data points and the solid curves are experimental curves of Figure 6.16. The dotted lines
intersect at about xSi = 0.28, compared to the actual about xSi = 0.31. However, the eutectic temperature is approximately 400 K too high.
Back to Problem 6.21 Back to Top

6-46
Chapter 6: Phase Equilibria Solutions

6.22. Use the following data to construct a phase diagram of the phenol–water system and answer the following questions (the
compositions are given in grams of phenol in 100 grams of solution):

t/ºC 20 25 30 35 40
Aqueous layer 8.40 8.71 8.92 9.34 9.78
Phenol layer 72.24 71.38 69.95 68.28 66.81

45 50 55 60 65 68.8
10.62 12.08 13.88 17.10 22.26 35.90
65.02 62.83 60.18 56.10 49.34 35.90

a. What will be the compositions of the layers formed from a solution of 30 g phenol and 70 g water maintained at 30 °C?
b. A solution of 20 g phenol and 80 g water is prepared at 70 °C. How many phases will be present?
c. At what temperature will two phases appear if the solution in part (b) is cooled gradually? What will be the compositions of the
two phases?
Solution:

6-47
Chapter 6: Phase Equilibria Solutions

Graphing the data, we generate a phase diagram of the phenol-water system.

a. The tie lines drawn through the point (a) indicate that the two layers will have compositions of approximately 8.92% phenol by mass
in the aqueous layer, and 69.95% phenol by mass in the phenol layer at 30 °C.
b. The point (b) lies in the region of the diagram where only one phase is present.
c. Two phases appear at approximately 63.0 °C. The composition of the two layers will be 19.6% phenol by mass in the aqueous layer
and 52.5% phenol by mass in the phenol layer.

Back to Problem 6.22 Back to Top

6-48
Chapter 6: Phase Equilibria Solutions

6.23. The following information is obtained from cooling curve data on the partial system Fe2O3–Y2O3 [J. W. Nielsen and E. F. Dearborn,
Phys. Chem. Solids, 5, 203(1958)]:

Composition of Temperature of Break/ºC Temperature of Halt/ºC

Melt/mol % Y2O3
0 1550
5 1540 1440
10 1515 1440
15 1450 1440
20 1520 1440
25 1560 1440
30 1620 1575/1440
40 1705 1575
50 1720

Sketch the simplest melting point diagram consistent with these data. Label the phase regions and give the composition of any
compounds formed.
Solution:
Each halt corresponds to a line of three-phase equilibrium and each break to a boundary between a one- and two-phase region. At 50%
Y2O3, a compound is formed and may be written as Fe2O3• Y2O3 or YFeO3.

6-49
Chapter 6: Phase Equilibria Solutions

A compound unstable above 1575 °C is indicated between 30% and 40% Y2O3. This might be taken to be 2Fe2O3• Y2O3 at 33% Y2O3, but
actually, the formula is Y3 Fe5O12, corresponding to 3 Y2O3 + 5 Fe2O3 at 37% Y2O3.
Back to Problem 6.23 Back to Top

6-50
Chapter 6: Phase Equilibria Solutions

6.24. The study of cooling curves for the thallium–gold system yields the following data. Construct the phase diagram and identify the
eutectic composition and temperature. Pure gold melts at 1063 °C and pure thallium melts at 302 °C. In each region, identify the
number of phases and the solid that separates out, if any.

Wt % Au 10 20 30 40 60 80 90
First break (ºC) 272 204 200 400 686 910 998
Eutectic halt (ºC) 128 128 128 128 128 128 128

[Data adapted from A. C. K. Smith, Applied Physical Chemistry Problems, London: McGraw-Hill, 1968, p. 13.]
Solution:

By extending the smooth curves drawn through the given data points to the eutectic temperature, the composition of the eutectic is
identified as 26 wt. % Au.

Back to Problem 6.24 Back to Top

6-51
Chapter 6: Phase Equilibria Solutions

6.25. a. From the following information, draw the binary phase diagram for the system FeO (mp. 1370 °C)–MnO (mp. 1785 °C). A
peritectic reaction occurs at 1430 °C between α solid solution containing 30 mass % MnO and solid solution containing 60 mass %
MnO. These are in equilibrium with melt that contains 15 mass % MnO. At 1200 °C the composition of α and β solution is 28 mass
% and 63 mass %, respectively.
b. Describe what happens as a liquid containing 28 mass % MnO is cooled to 1200 °C.
Solution:
a.

b. As liquid of 28 mass % MnO cools, β first forms along with liquid. At 1430 °C, β converts to  and  + L remains only briefly at
the temperature is lowered about 50 °C, at which point all the liquid is reconverted to the  phase. The compositions are given by
the lever rule. As 1200 °C is approached, some β may again make an appearance.

Back to Problem 6.25 Back to Top

 

6-52
Chapter 6: Phase Equilibria Solutions

6.26. The following data for the magnesium–copper system is the result of analyzing cooling curves. Pure copper melts at 1085 °C while
pure magnesium melts at 659 °C. Two compounds are formed, one at 16.05 wt % Mg with a melting point of 800 °C, and the other
at 43.44 wt % Mg with a melting point of 583 °C, respectively. Construct the phase diagram from this information and identify the
compositions of the eutectics. [Data adapted from A. C. K. Smith, Applied Physical Chemistry Problems, London: McGraw-Hill,
1968, p. 14.]

Wt % Mg 5 10 15 20 30 35
First break (ºC) 900 702 785 765 636 565
Eutectic halt (ºC) 680 680 680 560 560 560

40 45 50 60 70 80 90
581 575 546 448 423 525 600
560 360 360 360 360 360 360

6-53
Chapter 6: Phase Equilibria Solutions

Solution:

From the graph, the first eutectic temperature, 680 °C, has a composition of 10.5 wt. % Mg, the second eutectic temperature, 560 °C, has a
composition of 35.0 wt. % Mg, while the third eutectic temperature, 360 °C has a composition of 65 wt. % Mg.

Back to Problem 6.26 Back to Top

6-54
Chapter 6: Phase Equilibria Solutions

6.27. What are the empirical formulae of the compounds represented by the vertical lines formed in the magnesium–copper system
described in Problem 6.26?
Solution:
Assuming that there are 100 g of the first compound, we have 16.05 g of Mg and 100 g  16.05 g  83.95 g Cu. The mole ratios of Mg : Cu
are,

nMg mMg M Cu

nCu mCu M Mg

nMg 16.05 g   63.546 g mol 

1


nCu 83.95 g   24.3050 g mol 
1

nMg
 0.499 858 324 7
nCu
nMg 1

nCu 2

Therefore the empirical formula of the first compound is MgCu2.

Assuming that there are 100 g of the second compound, we have 43.44 g of Mg and 100 g  43.44 g  56.56 g Cu. The mole ratios of Mg :
Cu are,

nMg mMg M Cu

nCu mCu M Mg

nMg  43.44 g   63.546 g mol 

1


nCu  56.56 g   24.3050 g mol 
1

nMg
 2.008 043 001
nCu
nMg
2
nCu

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Chapter 6: Phase Equilibria Solutions

Therefore the empirical formula of the second compound is Mg2Cu.

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Chapter 6: Phase Equilibria Solutions

6.28. A preliminary thermal analysis of the Fe–Au system showed two solid phases of composition 8.1 mol % Au and 25.5 mol % Au in
equilibrium at 1168 °C with liquid of composition 43 mol % Au. Construct the simplest melting point diagram consistent with this
information and label all the phase regions. Sketch the cooling curves for the composition 10 mol % Au, 30 mol % A, and 60 mol %
Au, and make them consistent with the fact that there is an α-γ phase transition in iron at 903 °C and that the γ-phase field extends to
45 mol % Au at this temperature. Iron melts at 1536 °C and gold at 1063 °C.
Solution:
The coexistence of the three phases is a clear indication of a peritectic-type diagram. A note of caution is in order here: In the range 0-
10mol% Au at 1430 °C to 1536 °C, still another phase, called δ exists. This would not be detected using only the compositions listed. One
must be careful to use enough composition to ensure that all phases are identified. Also, the equilibrium between liquid and γ is not a simple
curve and must be determined by careful experimentation.

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Chapter 6: Phase Equilibria Solutions

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Chapter 6: Phase Equilibria Solutions

6.29. The aluminum–selenium system was determined from thermal analysis. Al2Se3 melts congruently at approximately 950 °C and
forms a eutectic both with aluminum and with selenium at a very low concentration of the alloying element and at a temperature
close to the melting point of the base elements. Draw a diagram from this information and give the composition of the phases.
Aluminum melts at 659.7 °C and selenium melts at approximately 217 °C.
Solution:

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Chapter 6: Phase Equilibria Solutions

*6.30. The metals Al and Ca form the compounds Al4Ca and Al2Ca. The solids Al, Ca, Al4Ca, and Al2Ca essentially are immiscible in each
other but are completely miscible as liquids. Maximum Ca solubility in Al is about 2% and occurs at 616 °C. Al melts at 659.7 °C
and Ca melts at 848 °C. Compound Al2Ca melts congruently at 1079 °C and gives a simple eutectic with Ca at 545°C. Compound
Al4Ca decomposes at 700 °C to give Al2Ca and a melt, the peritectic lying at 10 mol %. A monotectic exists at 616 °C. At
approximately 450 °C a transition occurs between α-Ca and β-Ca.
a. Draw the simplest phase diagram consistent with this information and label all phase regions.
b. Sketch cooling curves for melts of composition 15 mol % Ca and 80 mol % Ca.
Solution:

a. The lower phase field of the -phase is less than 1%

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Chapter 6: Phase Equilibria Solutions

b.

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Chapter 6: Phase Equilibria Solutions

6.31. The extent of dehydration of a salt such as CuSO4 can often be followed by measuring the vapor pressure over the hydrated salt. The
system H2O–CuSO4 is shown in the accompanying figure as an example of such a system. Label the areas as to the phase(s) present.
Then describe the sequence of phase changes if a dilute solution of copper sulfate is dehydrated at 275 K, ending with anhydrous
copper sulfate. What would a vacuum gauge read starting with pure water during the dehydration process at 298.15 K? Sketch a plot
of P/Torr against CuSO4/wt %. Relevant data are:

The Vapor Pressure of CuSO4–H2O at 298.15 K P/Torr

Vapor + saturated solution + CuSO4 · 5H2O 16
Vapor CuSO4 · 5H2O + CuSO4 · 3H2O 7.85
Vapor + CuSO4 · 3H2O + CuSO4 · H2O 4.32
Vapor + CuSO4 · H2O + CuSO4 0.017
Vapor pressure of water 23.8

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Chapter 6: Phase Equilibria Solutions

Solution:

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Chapter 6: Phase Equilibria Solutions

In the upper figure, CuSO4 begins in a solution single-phase region. Pure CuSO4•5H2O precipitates out as the first phase boundary at a is
crossed. Water continues to be removed as more CuSO4•5H2O precipitates until only pure CuSO4•5H2O is present at b. In the next two-
phase region, CuSO4•5H2O dehydrates, forming progressively more CuSO4•3H2O, until all of the pentahydrate is gone at c. The process
repeats, the trihydrate forming the monohydrate, until only monohydrate is present at d. The monohydrate dehydrates until at e only pure
CuSO4 is present. 

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Chapter 6: Phase Equilibria Solutions

In the lower figure, the vapor pressure of water drops as the amount of CuSO4 increases, (according to Raoult’s Law), until the solution is
saturated with respect to the pentahydrate. The system is invariant since three phases, vapor, saturated solution and solid CuSO4•5H2O, are
present at the constant temperature of 298.15 K. As the concentration of CuSO4 increases, (water is removed), the pressure remains constant
until only CuSO4•5H2O is present. Removal of additional water causes some trihydrate to form, and the pressure drops. Again the system is
invariant; three phases are present, vapor CuSO4•5H2O, and CuSO4•3H2O. The process is continued as before at the other stages.

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Chapter 6: Phase Equilibria Solutions

6.32. The data in the accompanying table are approximate for the isobaric-isothermal system SnO2–CaO–MgO at 298.15 K and 1 atm.
Sketch a reasonable phase diagram in mol % with SnO2 at the apex of the triangle. Label all phase regions; the results are known as
composition triangles.

Material In Equilibrium with Solid Phases

SnO2 (MgO)2SnO2, CaOSnO2
(MgO)2SnO2 SnO2, (CaO)SnO2, MgO
MgO CaO, (CaO)2SnO2
CaO MgO, (CaO)2SnO2
(CaO)2SnO2 CaO, MgO, CaOSnO2
CaOSnO2 (CaO)2 SnO2, MgO, (MgO)2SnO2, SnO2

Solution:
The system SnO2–CaO–MgO is given by,

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Chapter 6: Phase Equilibria Solutions

6.33. Sketch the P against T diagram for phosphorous from the following information. White phosphorous melts at 311 K and 0.2 Torr;
red phosphorous melts at 763 K and 43 atm. The white form is more dense than the liquid and the red form is less dense than the
liquid. The vapor pressure of the white form is everywhere greater than that of the red form. Label each area on the plot, and explain
which triple point(s) is (are) stable or metastable.
Solution:

a. Stable triple point R (red phosphorus, solid), liquid (L), vapor (V).
b. Metastable triple point W (white phosphorus, solid), L, V. The vapor pressure of white phosphorus is greater than that of the red.
c. Stable triple point W, R, L. If we assumes that a solid cannot be superheated, the triple point W, R, L is totally unstable since it
probably lies above the melting point of the liquid.
 

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Chapter 6: Phase Equilibria Solutions

6.34. Giguère and Turrell, J. Am. Chem. Soc., 102, 5476(1980), describe three ionic hydrates formed between HF and H2O. Sketch the
H2O-HF phase diagram in mol % HF from the following information. HF · H2O melts at –35.2 °C, 2HF · H2O decomposes by a
peritectic reaction at –75 °C, and 4HF · H2O melts at –98.2 °C. HF melts at –83.1 °C. Label the composition of all regions. The
eutectic occurs at –111 °C with monotectics at –71 °C, –77 °C, and –102 °C.
Solution:

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Chapter 6: Phase Equilibria Solutions

6.35. In the system A–B a line of three-phase equilibrium occurs at 900 K as determined by thermal analysis. A second three-phase
equilibrium occurs at 500 K. Only one halt is observed for any one cooling curve. The compound AB2 is known and melts at 600 K.
If A melts at 1200 K and B at 700 K, sketch the simplest phase diagram consistent with the given data. Label each region.
Solution:
The 500 K equilibrium line probably contains a eutectic since the temperature is below the melting points of both AB2 and B. An unstable
compound is rules out because such a reaction would require cooling halts of both 900 K and 500 K. Instead, a peritectic reaction shown is
the simplest explanation.

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Chapter 6: Phase Equilibria Solutions

6.36. The following questions refer to Figure 6.28:

a. If liquid C were added to the system, what changes would occur if the system originally contained 80% salt A and 20% salt B?
b. What changes would occur if the system originally contained 50% salt A and 50% salt B upon the addition of liquid?
c. If liquid is added to an unsaturated solution of salt A and salt B in solution of composition lying at e, what changes would occur?
Solution:
a. As liquid C is added, the saturated liquid of composition b would be in equilibrium with the two solids A and B. At approximately
20% C, when the composition crosses the line bB , the solid A disappears and only solid B will be present in equilibrium with liquid
of composition b.
b. The two solid phases would not disappear until b is passed at approximately 50% liquid C.
c. Added liquid would cause dilution and the solid salt will no longer exist.

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Chapter 6: Phase Equilibria Solutions

6.37. In the accompanying diagram, due to B. S. R. Sastry and F. A. Hammel, J. Am. Ceramic Soc., 42; 218(1959), identify the
composition of all the areas. Identify the phenomenon associated with each lettered position.

[[Diagram for Problem 6.37. Reprinted with permission of The American Ceramic Society, Post Office Box 6136, Westerville, OH 43086-
6136, Copyright © 1964 by the American Ceramic Society. All rights reserved.]]

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Chapter 6: Phase Equilibria Solutions

Solution:

a. Peritectic point
b. Eutectic point
c. Melting point
d. Incongruent melting
e. Phase transition

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Chapter 6: Phase Equilibria Solutions

6.38. Describe what happens within the system Mn2O3–Al2O3 in Fig. 6.21 when a liquid of xA12O3 = 0.2 is cooled from 2100 K to 1200 K.

Solution:
At 2100 K, the mixture is in the liquid state. As the liquid is cooled, solid spinel first appears at about 1950 K in equilibrium with liquid. At
approximately 1875 K, all of the liquid converts to solid spinel, the composition of which varies according to the lever rule.
As the temperature falls to about 1400 K, a two-phase region appears that is Mn3O4+ spinel. Below about 1285 K, the spinel converts to
corundum and Mn3O4+ corundum coexist.

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Chapter 6: Phase Equilibria Solutions

6.39. The isobaric solubility diagram for the system acetic acid–toluene–water is shown in Figure 6.27. What phase(s) and their
composition(s) will be present if 0.2 mol of toluene is added to a system consisting of 0.5 mol of water and 0.3 mol of acetic acid?
Give the relative amounts of each phase.
Solution:

Given: Figure 6.27, ntoluene  0.2 mol, nwater  0.5 mol, nacetic acid  0.3 mol  

Required: phases, composition, relative amounts

Using the number of moles present, the composition of the system is 20% toluene, 50% water and 30% acetic acid.

The system point is practically on the pq tie line, and there are therefore two liquids present. The ends of this line, and thus the
concentrations of the two liquids are approximately,
a. 95.5% toluene, 4% acetic acid, 0.5% water
b. 1% toluene, 37% acetic acid, 62% water

To calculate the relative amounts of the two liquids, we can use the lever rule, given by Eq. 6.16,

n1 y1 – xT pv
   
nv xT – x1 lp

15.4 B
or 4B to 1A  
3.8 A

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Chapter 6: Phase Equilibria Solutions

6.40. A fictitious ternary system composed of liquids A, B, and C was constructed by adding the component B to various binary A–C
mixtures and noting the point at which complete miscibility occurred. The following are the mole-percents of A and B at which
complete miscibility was observed. Construct the phase diagram on a triangular graph paper.

xA(%) 10.0 20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0
xB(%) 20.0 27.0 30.0 28.0 26.0 22.0 17.0 12.0 7.0

Comment on the variation of the mutual solubility of A and C as B is added.

Solution:

It is clear from the phase diagram that A and C are only slightly soluble in each other in the absence of B. As B is added, two layers are
formed; one rich in A, and the other rich in C. As B is added, the mutual solubility of A and C increases until at 30 mole % in B, the three
liquids become miscible in all proportions.

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Chapter 6: Phase Equilibria Solutions

6.41. In organic chemistry it is a common procedure to separate a mixture of an organic liquid in water by adding a salt to it. This is
known as “salting out.” The ternary system K2CO3–H2O–CH3OH is typical. The system is distinguished by the appearance of the
two-liquid region abc.

a. Describe the phase(s) present in each region of the diagram.

b. What would occur as solid K2CO3 is added to a solution of H2O and CH3OH of composition x?
c. How can the organic-rich phase in (b) be separated?
d. How can K2CO3 be precipitated from a solution having composition y?
e. Describe in detail the sequence of events when a solution of composition F is evaporated.
Solution:

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Chapter 6: Phase Equilibria Solutions

a.
Region System
AEa K2CO3 in equilibrium with water-rich saturated solution
Aac K2CO3 in equilibrium with conjugate liquids a and c
abc Two conjugate liquids joined by tie lines
AcB K2CO3 in equilibrium with alcohol-rich saturated solution

b. The state of the system will move along a line joining x and A. Initially solution is formed; as more K2CO3 is added, two layers, a
and c form, and once beyond point z, K2CO3 ceases to dissolve so that solid K2CO3 and the two liquids a and c coexist.

c. As long as two liquids exist, liquid with composition in the region AcB is the alcohol-rich layer and may be separated from the
water-rich later by separatory funnel.

d. When water is added to an unsaturated solution of K2CO3 in alcohol, the state of the system moves along the line joining y and D.
Some K2CO3 will precipitate as the state moves into the ABc region and then redissolves as it moves into the solution region again.

e. On evaporation of F, the system composition follows a line drawn from the water corner through F to the Ac line. At the first
composition line, two liquids form and the compositions of the solutions of the solutions move toward a and c. When the system
composition reaches the ac line, K2CO3 begins to precipitate and is in equilibrium with the conjugate liquids a and c. Further
reduction of water moves the ratio of liquid a to liquid c in favor of c until the line Ac is crossed, at which time solid K2CO3 is in
equilibrium with a single solution.

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