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Simple mixture-phase diagram

5.8 Liquidliquid phase diagrams

Example 5.5 Interpreting a liquidliquid phase diagram
A mixture of 50 g of hexane (0.58 mol C6H14) and 50 g of nitrobenzene (0.41 mol
C6H5NO2) was prepared at 290 K. What are the compositions of the phases, and in
what proportions do they occur? To what temperature must the sample be heated in
order to obtain a single phase?

Self-test 5.7
Repeat the problem for 50 g of hexane and 100 g of nitrobenzene at 273 K.
Ans: [xN = 0.09 and 0.95 in ratio 1:1.3; 294 K]

Example 5.6 Interpreting a phase diagram

State the changes that occur when a mixture of composition xB = 0.95 (a1) in Fig.
5.50 is boiled and the vapour condensed.

Self-test 5.8 Repeat the discussion, beginning at the point xB = 0.4, T = 298 K

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Simple mixture-phase diagram

Physical Chemistry II
Chapter 5 Simple mixture
Exercise
5.22(a) At 90C, the vapour pressure of methylbenzene is 53.3 kPa and that of 1,2-dimethylbenzene is
20.0 kPa. What is the composition of a liquid mixture that boils at 90C when the pressure is 0.50 atm?
What is the composition of the vapour produced?

5.22(b) At 90C, the vapour pressure of

1,2-dimethylbenzene is 20 kPa and that of 1,3-dimethylbenzene is 18 kPa. What is the composition of a

liquid mixture that boils at 90C when the pressure is 19 kPa? What is the composition of the vapour
produced?

5.23(a) The vapour pressure of pure liquid A at 300 K is 76.7 kPa and that of pure liquid B is 52.0 kPa.
These two compounds form ideal liquid and gaseous mixtures. Consider the equilibrium composition
of a mixture in which the mole fraction of A in the vapour is 0.350. Calculate the total pressure of the
vapour and the composition of the liquid mixture.
5.23(b) The vapour pressure of pure liquid A at 293 K is 68.8 kPa and that of pure liquid B is 82.1 kPa.
These two compounds form ideal liquid and gaseous mixtures. Consider the equilibrium composition
of a mixture in which the mole fraction of A in the vapour is 0.612. Calculate the total pressure of the
vapour and the composition of the liquid mixture.

5.24(a) It is found that the boiling point of a binary solution of A and B with xA = 0.6589 is 88C. At
this temperature the vapour pressures of pure A and B are 127.6 kPa and 50.60 kPa, respectively. (a) Is
this solution ideal? (b) What is the initial composition of the vapour above the solution?

5.24(b) It is found that the boiling point of a binary solution of A and B with xA = 0.4217 is 96C. At
this temperature the vapour pressures of pure A and B are 110.1 kPa and 76.5 kPa, respectively. (a) Is
this solution ideal? (b) What is the initial composition of the vapour above the solution?

5.25(a) Dibromoethene (DE,

= 22.9 kPa at 358 K) and dibromopropene (DP,

= 17.1 kPa at 358 K) form a nearly ideal solution. If zDE = 0.60, what is (a) ptotal when the system
is all liquid, (b) the composition of the vapour when the system is still almost all liquid?

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Simple mixture-phase diagram

5.25(b) Benzene and toluene form nearly ideal solutions. Consider an equimolar solution of benzene
and toluene. At 20C the vapour pressures of pure benzene and toluene are 9.9 kPa and 2.9 kPa,
respectively. The solution is boiled by reducing the external pressure below the vapour pressure.
Calculate (a) the pressure when boiling begins, (b) the composition of each component in the vapour,
and (c) the vapour pressure when only a few drops of liquid remain. Assume that the rate of
vaporization is low enough for the temperature to remain constant at 20C.

5.26(a)

The following temperature/composition data were obtained for a mixture of octane (O)
and methylbenzene (M) at 1.00 atm, where x is the mole fraction in the liquid and y
the mole fraction in the vapour at equilibrium. The boiling points are 110.6C and
125.6C, for M and O, respectively. Plot the temperature/composition diagram for the
mixture. What is the composition of the vapour in equilibrium with the liquid of
composition (a) xM = 0.250 and (b) xO = 0.250?
5.26(b) The following temperature/composition data were obtained for a mixture of
two liquids A and B at 1.00 atm, where x is the mole fraction in the liquid and y the
mole fraction in the vapour at equilibrium.

The

boiling

points

are

124C

for

and

155C

for

B.

Plot

the

temperature/composition diagram for the mixture. What is the composition of the

vapour in equilibrium with the liquid of composition (a) xA = 0.50 and (b) xB = 0.33?

5.27(a) Methylethyl ether (A) and diborane, B2H6 (B), form a compound which melts
congruently at 133 K. The system exhibits two eutectics, one at 25 mol per cent B and
123 K and a second at 90 mol per cent B and 104 K. The melting points of pure A and
B are 131 K and 110 K, respectively. Sketch the phase diagram for this system.
Assume negligible solidsolid solubility.

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Simple mixture-phase diagram

5.27(b) Sketch the phase diagram of the system NH3/N2H4 given that the two
substances do not form a compound with each other, that NH3 freezes at 78C and
N2H4 freezes at +2C, and that a eutectic is formed when the mole fraction of N2H4 is
0.07 and that the eutectic melts at 80C.

5.28(a) Figure 5.64 shows the phase diagram for two partially miscible liquids, which
can be taken to be that for water (A) and 2-methyl-1-propanol (B). Describe what will
be observed when a mixture of composition xB = 0.8 is heated, at each stage giving
the number, composition, and relative amounts of the phases present.

Figure 5.64

5.28(b) Figure 5.65 is the phase diagram for silver and tin. Label the regions, and
describe what will be observed when liquids of compositions a and b are cooled to
200 K.

Figure 5.65

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Simple mixture-phase diagram

5.29(a) Indicate on the phase diagram in Fig. 5.66 the feature that denotes
incongruent melting. What is the composition of the eutectic mixture and at what
temperature does it melt?

Figure 5.66

5.29(b) Indicate on the phase diagram in Fig. 5.67 the feature that denotes
incongruent melting. What is the composition of the eutectic mixture and at what
temperature does it melt?

Figure 5.67

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Simple mixture-phase diagram

5.30(a) Sketch the cooling curves for the isopleths a and b in Fig. 5.66.

5.30(b) Sketch the cooling curves for the isopleths a and b in Fig. 5.67.

5.31(a) Use the phase diagram in Fig. 5.65 to state (a) the solubility of Ag in Sn at
800C and (b) the solubility of Ag3Sn in Ag at 460C, (c) the solubility of Ag3 Sn in
Ag at 300C.

5.31(b) Use the phase diagram in Fig. 5.66 to state (a) the solubility of B in A at
390C and (b) the solubility of AB2 in B at 300C.

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Simple mixture-phase diagram

5.32(a)

Figure 5.68

Figure 5.68 shows the experimentally determined phase diagrams for the nearly ideal solution of
hexane and heptane. (a) Label the regions of the diagrams as to which phases are present. (b) For a
solution containing 1 mol each of hexane and heptane molecules, estimate the vapour pressure at 70C
when vaporization on reduction of the external pressure just begins. (c) What is the vapour pressure of
the solution at 70C when just one drop of liquid remains. (d) Estimate from the figures the mole
fraction of hexane in the liquid and vapour phases for the conditions of part b. (e) What are the mole
fractions for the conditions of part c? (f) At 85C and 760 Torr, what are the amounts of substance in
the liquid and vapour phases when zheptane = 0.40? 5.32(b) Uranium tetrafluoride and zirconium
tetrafluoride melt at 1035C and 912C, respectively. They form a continuous series of solid solutions
with a minimum melting temperature of 765C and composition

x(ZrF4) = 0.77. At 900C, the liquid

solution of composition x(ZrF4) = 0.28 is in equilibrium with a solid solution of composition x(ZrF4) =
0.14. At 850C the two compositions are 0.87 and 0.90, respectively. Sketch the phase diagram for this
system and state what is observed when a liquid of composition x(ZrF4) = 0.40 is cooled slowly from
900C to 500C.

5.33(a) Methane (melting point 91 K) and tetrafluoromethane (melting point 89 K) do not form solid
solutions with each other, and as liquids they are only partially miscible. The upper critical temperature
of the liquid mixture is 94 K at x(CF4) = 0.43 and the eutectic temperature is 84 K at x(CF4) = 0.88. At
86 K, the phase in equilibrium with the tetrafluoromethane-rich solution changes from solid methane to

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Simple mixture-phase diagram

a methane-rich liquid. At that temperature, the two liquid solutions that are in mutual equilibrium have
the compositions x(CF4) = 0.10 and x(CF4) = 0.80. Sketch the phase diagram.

5.33(b) Describe the phase changes that take place when a liquid mixture of 4.0 mol B 2H6 (melting
point 131 K) and 1.0 mol CH3OCH3 (melting point 135 K) is cooled from 140 K to 90 K. These
substances form a compound (CH3)2OB2H6 that melts congruently at 133 K. The system exhibits one
eutectic at x(B2H6) = 0.25 and 123 K and another at x(B2H6) = 0.90 and 104 K.

5.34(a) Refer to the information in Exercise 33(a) and sketch the cooling curves for liquid mixtures in
which x(CF4) is (a) 0.10, (b) 0.30, (c) 0.50, (d) 0.80, and (e) 0.95.

5.34(b) Refer to the information in Exercise 33(b) and sketch the cooling curves for liquid mixtures in
which x(B2H6) is (a) 0.10, (b) 0.30, (c) 0.50, (d) 0.80, and (e) 0.95.

5.35(a) Hexane and perfluorohexane show partial miscibility below 22.70C. The critical concentration
at the upper critical temperature is x = 0.355, where x is the mole fraction of C6F14. At 22.0C the two
solutions in equilibrium have x = 0.24 and x = 0.48, respectively, and at 21.5C the mole fractions are
0.22 and 0.51. Sketch the phase diagram. Describe the phase changes that occur when perfluorohexane
is added to a fixed amount of hexane at (a) 23C, (b) 22C.

5.35(b) Two liquids, A and B, show partial miscibility below 52.4C. The critical concentration at the
upper critical temperature is x = 0.459, where x is the mole fraction of A. At 40.0C the two solutions
in equilibrium have x = 0.22 and x = 0.60, respectively, and at 42.5C the mole fractions are 0.24 and
0.48. Sketch the phase diagram. Describe the phase changes that occur when B is added to a fixed
amount of A at (a) 48C, (b) 52.4C.