Problems Set: Theory on Distillation, Raoult’s Law & Gas Chromatography

Learning Objectives: By the end of this practice problems set, students should be able to interpret simple
distillation phase diagram for ideal mixture. In addition, students should be able to calculate %
composition based on GC data, understand the effect of different parameters that may affect GC elution
outcome and the application of Raoult’s law and Dalton’s law to determine vapor pressure at a given
temperature.

1. Substances A and B are two miscible liquids that behave as an ideal mixture. Use the following liquid-
vapor phase diagram for a mixture of A and B to answer questions (i) – (iii).
The diagram is for atmospheric pressure = 760 torr.

(i) What are the boiling points of the pure liquids A and B?

b.p. A = ____________ b.p. B = ____________

(ii) What is the boiling point of a solution that is a mixture of 50 mole % A and 50 mole % B?

b.p. mixture = ____________

(iii) What is the composition of the vapor in equilibrium with a solution that is a mixture of 50 mole % A and 50
mole % B at the temperature determined in part (ii)?

Mole % A (vapor) = ___________ Mole % B (vapor) = ___________

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2. What is the vapor pressure (in mmHg) of a solution of 4.40 g of Br2 in 101.0 g of CCl4 at 300 K? The vapor
pressure of pure bromine at 300 K (or around 27oC) is 229 mmHg and the vapor pressure of CCl4 is 124 mmHg.

Molar masses: Br2 = 159.808g/mol CCl4 = 153.823g/mol

3. Using a gas chromatograph equipped with a column containing a non-polar stationary phase, the following
chromatogram was obtained for a mixture of ethyl acetate (bp 77oC), toluene (bp 111oC), and heptane (bp 98oC).
You may assume the three compounds have similar polarity.

a. Label/identify each of the peaks in the chromatogram below.

b. Sketch the chromatogram of this mixture that would result if the temperature of the column were higher
than it was in (a). You do not need to consider the shape of the signal in your answer.
c. Sketch the chromatogram of this mixtuer that would result if the length of the column were doubled
compared with the column in part (a). You do not need to consider the shape of the signal in your
answer.
d. Sketch the chromatogram of this mixture that would result if the helium carrier gas flow were doubled
compared to the column in part (a). You do not need to consider the shape of the signal in your answer.

Note: For parts (b) – (d), we are holding all other conditions on the GC constant.

4. A mixture of A, B, and C gives three peaks in the GC with relative areas (in cm2) of 1.0 : 5.5 : 7.8. What is the
percent composition of each compound?

5. Use the vapor pressure curve at a particular temperature for a solution of two volatile liquids of A and B as
shown below to complete the following series of statements by circling one of the underlined choices in each set of
choices. Dash lines are from Raoult’s law prediction. Solid black curves are the actual vapor pressure curves.
• The solution is ideal / non-ideal, and exhibits PB
positive / negative / no deviation from Raoult’s law.
PA
• The intermolecular forces in the solution
(attractions to each other) are stronger / weaker
than those in pure liquids (attractions to
themselves).
• Liquid A is more / less volatile than Liquid B.
1 XA 0

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6. Both hexane and octane are non-polar hydrocarbon compounds. Hexane and octane form an ideal solution.
Sketch the liquid-vapor phase diagram for binary component system of hexane and octane based on the following
data. Label the axes and the phases in each area. Show the data points clearly on the sketch based on the
information provided above.

• Hexane (b.p. = 68oC)

• Octane (b.p. = 125oC)
• A solution containing 30% hexane has a boiling point of around 97oC. At 97oC, the first drop of the
distillate for this mixture has a composition of 60% hexane and 40% octane.
• A solution containing 90% hexane has a boiling point of around 70oC. At 70oC, the first drop of the
distillate for this mixture has a composition of 98% hexane and 2% octane.

Based on the phase diagram you sketched, indicate the temperature at which a 60% octane solution should begin to
boil. Assuming complete condensation, what is the composition of the vapor in equilibrium with the solution at
this same temperature?

140
T
E
M
P
E 120
R
A
T
U
100
R
E
O
C
80

60

0 0.2 0.4 0.6 0.8 1.0

MOLE FRACTION OF HEXANE

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 Answer Key

1. (i) b.p. A = 40oC b.p. B = 80oC

(ii) b.p. mixture = approximately 53oC

(iii) Mole % A (vapor) = approximately 74% Mole % B (vapor) = approximately 26%

Note: Your % values may differ slightly from the answer but they should agree to within ±5%.

2. (i) Calculate moles, then mole fraction of each substance:

Br2 ⇒ 4.40 g / 159.808 g/mol = 0.0275 mol

CCl4 ⇒ 101.0 g / 153.823 g/mol = 0.6566 mol

Total mole = 0.6841

χBr2 ⇒ 0.0275 mol / 0.6841 mol = 0.0402 (or 0.0403)

χCCl4 ⇒ 0.6566 mol / 0.6841 mol = 0.9598

(ii) Calculate total pressure (Dalton’s Law and Raoult’s Law)

Ptotal = P(Br2) + P(CCl4) = P°Br2 χBr2 + P°CCl4 χCCl4

x = (229 mmHg) (0.0402) + (124 mmHg) (0.9598)

x = 9.21 + 119 = 128mmHg

3. (a)
ethyl acetate
heptane toluene

(b) Shorter retention times, less separation

(c) Retention times should double, same order of separation, the difference in retention times between
adjacent signals should also double
(d) Shorter retention times, less separation

4. A: 7.0%, B: 38%, C: 55%

% Component = Individual Area ÷ Total Area of ALL Components

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5.
Use the vapor pressure curve at a particular temperature for a solution of two volatile liquids of A
and B as shown below to complete the following series of statements. (Circle one of the underlined
choices in each set of choices)
• The solution is ideal / non-ideal, and exhibits PB
positive / negative / no deviation from Raoult’s law.
PA
• The intermolecular forces in the solution
(attractions to each other) are stronger / weaker
than those in pure liquids (attractions to
themselves).
• Liquid A is more / less volatile than Liquid B. 1 XA 0

Explanation: The BLUE dash line corresponds to the SUM of the vapor pressure lines of PA (i.e. the
orange line) and PB (i.e. the yellow line) obtained from simply using Raoult’s law:
PA = PoA ×XA PB = PoB ×XB
This is why both the orange dash line and the yellow dash line are simply a linear function due to the
simplicity of Raoult’s law (for ideal solution). For a given fixed temperature, PoA and PoB have specific
values. The x-axis of the graph corresponds to the mole fraction of A (i.e. XA). However, XA + XB MUST
add up to 1 (or 100%). The dash lines correspond to what we call IDEAL SOLUTIONS.

The solid black curves correspond to the actual vapor pressure for A and B in the mixture. The top curve
is the TOTAL vapor pressure of the mixture at a particular temperature. The bottom two solid black
curves correspond to the individual vapor pressure curve of A and B. As you can see, all the solid black
curves are located BELOW the ideal lines (i.e. the dash lines). Therefore, the deviation from Raoult’s law
is NEGATIVE. You can also notice that a negative deviation from Raoult’s law means that there is a
STRONGER attractive forces that exist between A and B in the mixture. This is why at any given mole
fraction, the overall vapor pressure of the mixture is LOWER than the ideal solution (except for pure
component)! Finally, the lower the vapor pressure, the less volatile the solution is (i.e. higher boiling
point). Since pure liquid A has a LOWER vapor pressure than pure liquid B (i.e. PA vs. PB), liquid A is
less volatile (higher boiling point) than liquid B.

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6.

The BLUE dots shown on the graph correspond to the information provided in the question.

A 60% octane solution will begin to boil at around 90oC (refer to the tie line shown below). The composition of
the vapor in equilibrium with the solution contains about 70% hexane and 30% octane.

Your answer may vary slightly from the answer key depending on how you sketch the phase diagram.

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