Experiment 6: Simple and Fractional Distillation

Reading Assignment
Experiment 6 (pp. 51 -57) Technique 13, Parts A (pp. 694-702) Technique 14 (pp. 703-715) Technique 15 (pp. 715-732) Technique 22 (pp. 797-818)

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Experiment 6: Simple and Fractional Distillation

Work in pairs. Each pair will conduct both the simple and fractional distillations. There are three unknowns, A, B, and C. Perform the experiment as follows: Day One: Working in pairs, use simple distillation to separate the unknown (Experiment 6A). Day Two: Again, working in pairs, repeat the experiment using fractional distillation on the same unknown (Experiment 6A) Do not do Experiment 6B The products from each days distillation will be analyzed by gas chromatography.
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Key Point!
When conducting a distillation, the vapor should be richer in the lower boiling component than what you started with.

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Simple Distillation: Apparatus

Put in boiling stone!

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Correct Thermometer Placement

Thermometer must be below this level

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Your equipment has a built-in thermometer adapter, so your equipment will look a bit different. Look at the setup in the hood before you start assembling the equipment. Ask your instructor if you will be attaching the vacuum adapter! Some instructors will ask you to leave off this piece of glassware! There are wooden blocks that can be used to raise the apparatus. The wooden blocks are in the cupboard under the hood.

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Temperature Behavior During Distillation

A. Single pure component B. Two components of similar boiling points C. Two components with widely different boiling points
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Phase Diagram: Two Component Mixture of Liquids

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Questions based upon the previous slide:

a) What is the bp of pure A? b) What is the bp of pure B? c) What is the bp of a solution with the composition of 30 % B, assuming a simple distilllation apparatus? d) What is the composition of the vapor assuming a simple distillation apparatus? e) What is the composition of the distillate collected assuming a simple distillation apparatus? f) What does the tie-line, x-y represent? Hint: the upper curve is the vapor curve and the lower curve is the liquid curve. Composition of the vapor and liquid that are in equilibriuim with each other at 130 oC.
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Vapor-Liquid Composition Curve (Benzene vs. Toluene)

liquid

Vapor

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Questions based upon the previous slide:

a) What is the bp of pure toluene? b) What is the bp of pure benzene? c) What is the bp of a solution with the composition of 50 % benzene, assuming a simple distilllation apparatus? d) What is the composition of the distillate assuming a simple distillation apparatus? e) How many theoretical plates would be necessary for a fractional distillation starting with a 50 % benzene solution?

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When will simple distillation do a reasonable job of separating a mixture?

1) When the difference in boiling points is over 100o 2) When the there is a fairly small amount of impurity, say less than 10 %. 3) When one of the components will not distil because of a lack of volatility (i.e. sugar dissolved in water).

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Raoults Law

PTOTAL = PANA + PBNB

Moles A Moles A + Moles B

NA = Mole Fraction of A =

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Raoults law calculations

See Figure 15.6 on page 720 for example calculations.

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Fractional Distillation: Apparatus

Put in boiling stone

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Vaporization-Condensation
bp of pure A = 51 bp of pure B = 87

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Temperature vs. Volume: Fractional Distillation

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Fractional Distillation Phase Diagram

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How many theoretical plates are need to separate a mixture starting at L?

Looks like about 5 plates are needed to separate the mixture on the previous slide!
Count the tie-lines (horizontal lines) to come up with the 5 plates (labelled with arrows on the next slide)!
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Fractional Distillation Phase Diagram. The arrows indicate a theoretical plate!

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Theoretical Plates Required to Separate Mixtures based on BP

Boiling Point Difference 108 72 54 43 36 20 10 7 4 2 Theoretical Plates 1 2 3 4 5 10 20 30 50 100
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Microscale distillation: Hickman Head

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Azeotrope
Some mixtures of liquids, because of attractions or repulsions between the molecules, do not behave ideally These mixtures do not obey Raoults Law An azeotrope is a mixture with a fixed composition that cannot be altered by either simple or fractional distillation An azeotrope behaves as if it were a pure compound, and it distills from beginning to end at a constant temperature.
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Types of Azeotropes
There are two types of non-ideal behavior:
Minimum-boiling-point
Boiling point of the mixture is lower than the boiling point of either pure component

Maximum-boiling-point
Boiling point of the mixture is higher than the boiling point of either pure component

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Maximum Boiling-Point Azeotrope

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Observations with maximum boiling azeotrope

On the right side of the diagram: Compound B will distill (lowest bp). Once B has been removed, the azeotrope will distill (highest bp). On the left side of the diagram: Compound A will distill (lowest bp) Once A has been removed, the azeotrope will distill. (highest bp) The azeotrope acts like a pure compound

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Minimum Boiling-Point Azeotrope

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Observations with minimum boiling azeotrope

On the right side of the diagram: The azeotrope is the lower boiling compound, and it will be removed first. Pure ethanol will distill once the azeotrope has distilled. On the left side of the diagram: the azeotrope is the lower boiling compound, and it will distill first. Once the azeotrope has been removed, then pure water will distill. The azeotrope acts like a pure compound
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Dean-Stark Water Separator

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The Gas Chromatograph

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Gas Chromatography: Separation of a Mixture

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Gas Chromatogram

Highest b.p. Lowest b.p.

Retention time

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Triangulation of a Peak

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Sample Percentage Composition Calculation

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Gas Chromatography: Results

In a modern gas chromatography instrument, the results are displayed and analyzed using a computerized data station. It is no longer necessary to calculate peak areas by triangulation; this determination is made electronically. Our analysis will be conducted on a modern data station.
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Compounds in unknowns: boiling points. There will only be two components in each unknown
Hexanes (mixture of isomers) 68-70 oC Cyclohexane Heptane Toluene 80 oC 98 oC 110 oC

Mixture separates by distillation according to the boiling point. Compounds with the lower bp come off first! The same is true on the gas chromatographic column; the lower boiling compound comes off first!
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Gas Chromatography: Standards

Retention time

solvents

The x axis is in min.

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Notice: 1) hexane has the lowest retention time 2) toluene has the highest retention time The four compounds come off in the order of increasing boiling point.

Hexane is actually a mixture of three compounds. It is usually called hexanes

CH 3

hexane

cyclohexane

heptane

toluene

Increasing b.p.
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Preparing distillation samples for gas chromatography

After you have collected 1mL of distillate, then collect the next two drops in one of the special gas chromatography tubes. Add the solvent that is suggested by your instructor (methylene chloride or acetone). Screw on the cap and use a marking pen to put your initials on the tube. After 4.5 mL has been distilled, repeat the process indicated above. Charles Wandler will give a presentation in the lab on the instrument that we will use for gas chromatography. This includes a handout that tells you how to retrieve you data. The data will be available in the computer lab (CB 280). He will demonstrate where to put the tubes. He has a signup sheet and a carousel to put the samples in.

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How to identify the components in your unknown mixture

Use the retention time information from your gas chromatograms to provide a positive identification of each of the components in the mixture. Dont rely on the distillation plot to determine the composition of your mixture!
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Retention Times and Response Factors

Component Hexanes
(mixture of isomers)

Retention Time (min)

3.054 3.491 3.812 4.331

Response Factor
1.022 1.133 1.000 1.381

Cyclohexane Heptane Toluene

NOTE: These values are for illustration purposes. Your actual values will be different!
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First Fraction: Cyclohexane/Toluene Chromatogram

cyclohexane Solvents

toluene

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Data: Cyclohexane/Toluene First Fraction

solvents cyclohexane toluene ?

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Calculation of percentages from the data for fraction 1

area counts/response factor = adjusted area Cyclohexane area = 42795/1.133 = 32104 Toluene area = 18129/1.381 = 13127 Total area 45231
Note: this calculated area is different than that shown on the data sheet! Use this calculated area!

Percent cyclohexane = 32104/45231 x 100 = 71.0% Percent toluene = 13127/45231 x 100 = 29.0 %
Round off numbers so that the total equals 100%
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Second Fraction: Cyclohexane/Toluene Chromatogram

toluene

solvents

cyclohexane

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Data: Cyclohexane/Toluene Second Fraction

solvents cyclohexane toluene ?

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Calculation of percentages from the data for fraction 2

area counts/ response factor = adjusted area Cyclohexane area = 57546/1.133 = 43170 Toluene area = 191934/1.381 = 138981 Total area 182151
Note: this calculated area is different than that shown on the data sheet!

Percent cyclohexane = 43170/182151 x 100 = 23.7 % Percent toluene =138981/182151 x 100 = 76.3 %
Round off numbers so percentage = 100%
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First Fraction: Hexane/Heptane Chromatogram

solvents

heptane

hexanes

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Data: Hexane/Heptane First Fraction

solvents ? Three peaks for hexanes heptane

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Calculation of percentages from the data for fraction 1

area counts/response factor = adjusted area Hexanes area = 1251 + 60375 + 8147 = 69773/1.022 = 68271 Heptane area = 26374/ 1.000 = 26374 Total area =94645
Note: this calculated area is different than that shown on the data sheet! Use this calculated area!

Percent hexanes = 68271/94645 x 100 = 72.1 % Percent heptane = 26374/94645 x 100 = 27.9 %
Round off numbers so that the total equals 100%
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Second Fraction: Hexane/Heptane Chromatogram

heptane

solvents

hexanes

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Data: Hexane/Heptane Second Fraction

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