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Simple & Fractional Distillation

Experiment Simple & Fractional Distillation

Evaluation of the relative effectiveness of Simple &


Fractional Distillation to separate mixtures of organic
compounds based on differences in Boiling Point

Determination of Mole % from Distillate Volume Data, Gas


Chromatography, and Refractive Index

Text References

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Slayden

p. 39-41, 43-46, 47

Pavia
- Tech 14.1 - 14.3;
Distillation)

p. 719 729 (Simple

Pavia
- Tech 15.1 - 15.6;
distillation)

p. 729 740 (Fractional

Pavia
- Tech 22.1 22.12; p. 817 836 (Gas
Chromatography)

Pavia

- Tech 24;

p. 845 850 (Refractive Index)


1

Simple & Fractional Distillation

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Overview

A mixture of Ethyl Acetate and Butyl Acetate


(unknown mole %) will be subjected to both a
Simple Distillation and a Fractional Distillation
(using a Vigreux Fractionation Column)

Each distillation will result in three (3) vials


(fractions) of distillate representing 3
temperature ranges
(0-95oC; 95 -105oC; and 105-130oC)

Volume recovery of total distillate as well as


volume recovery of the distillate fractions will be
computed

Fractions 1 & 2 will be combined mathematically


and assumed to be Ethyl Acetate

Fraction 3 will be assumed to be Butyl Acetate


2

Simple & Fractional Distillation

Overview (cont)
From the volumes and respective densities, the mass,
moles, mole fraction, and mole % will be computed.
Gas Chromatograms of the 6 distillate vials (3 from Simple
Distillation & 3 from Fractional Distillation) plus the original
unfractionated mixture will be obtained
Mole % of the components in each fraction will be
computed based on the relationship between peak area
(readjusted for non-linear thermal response) and mole
content
If directed by instructor, Mole % values will also be
determined from a standard Regression Curve relating
Refractive Index of known mixtures of Ethyl & Butyl Acetate
to the measured Refractive Index values of the distillate
fractions
Distillation results and mole % values will be used to
evaluate the relative effectiveness of component
separation by Simple Distillation vs Fractional Distillation

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Simple & Fractional Distillation

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Vapor Pressure / Boiling Point

According to Kinetic Theory, the molecules in a liquid are


in a constant state of thermal motion and some of these
molecules are moving fast enough to escape from the
liquid forming a vapor above the liquid. This vapor exerts
a pressure on the surface of the liquid, i.e., Vapor Pressure

Vapor Pressure The pressure of the vapor coexisting with


a confined liquid or solid, i.e., the pressure in an
evacuated container containing a liquid at constant
temperature after the liquid and escaping molecules near
the surface of the liquid the vapor - reach equilibrium

The Vapor Pressure of a liquid increases, generally


exponentially, with temperature

Boiling Point As a liquid is heated, the vapor pressure of


the liquid increases to the point at which it just equals the
applied pressure - usually atmospheric pressure. The
liquid now begins to bubble (boil)

Simple & Fractional Distillation

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Vapor Pressure / Boiling Point


Boiling Point
The normal boiling point (also called the atmospheric
boiling point or the atmospheric pressure boiling
point) of a liquid is the temperature at which the
vapor pressure of the liquid is equal to the
atmospheric pressure.
At that temperature, the vapor pressure of the liquid
becomes sufficient to overcome atmospheric
pressure and allow bubbles of vapor to form inside
the bulk of the liquid
The standard boiling point is now (as of 1982) defined
by IUPAC as the temperature at which boiling occurs
under a pressure of 1 bar
1 bar = 105 Pascals = 0.98692 atmospheres (atm)
= 14.5038 psi (pounds per square inch)
= 29.53 in Hg (inches of mercury) = 750.06 mm
5

Simple & Fractional Distillation

Distillation / Boiling Point Measurement


Note: The temperature range you obtain for your
boiling
point may be inaccurate for three (3) reasons
1. The atmospheric pressure in the lab may not be:
1 bar (0.98692 atm)
2. The thermometers used in the lab may not
reflect the actual temperature
3. The thermal inefficiency of the glassware used for
the boiling point determination may result in a
lower than expected measured value by as much
as 2 5oC
You should take this potential temperature differential
into account when you compare your measured
results with the list of possible unknowns in lab
manual tables

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Simple & Fractional Distillation

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Vapor Pressure / Boiling Point (Cont)

Different liquid compounds or mixtures of liquids have


different vapor pressures at a given temperature

Liquids with high vapor pressures (Volatile


compounds) require relatively little energy (heat) to
increase the vapor pressure to match the applied
(atmospheric) pressure, and thus, boil, i.e. they have
low boiling points

Liquids with low vapor pressures require considerably


more energy to increase the vapor pressure to the
point where it matches the applied pressure, thus,
they have relatively high boiling points

The individual compounds in a mixture each exert its


own pressure partial pressure

The sum of the partial pressures equals to the total


vapor pressure of the solution
7

Simple & Fractional Distillation

Raoults Law

In a solution of two miscible liquids (A & B) the partial


pressure of component A (PA) in the solution equals
the partial pressure of pure A (PAo) times its mole
fraction (NA)
Partial Pressure of A in solution = PA = (PAo) x (NA)
Partial Pressure of B in solution = PB = (PBo) x (NB)

When the total pressure (sum of the partial pressures) is


equal to or greater than the applied pressure, normally
Atmospheric Pressure (760 mm Hg), the solution boils
Ptotal = PA + PB = PAo NA + PBo NB

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If the sum of the two partial pressures of the two


compounds in a mixture is less than the applied
pressure, the mixture will not boil. The solution must be
heated until the combined vapor pressure equals the
applied pressure
8

Simple & Fractional Distillation

Raoults Law (Cont)

Example
Consider a solution at 100 oC where NA = 0.5 and NB = 0.5

What is the Partial Pressure of A in the solution if the Vapor


Pressure of Pure A at 100 oC is 1020 mm Hg?
Ans: PA = PoANA = (1020) * (0.5) = 510 mm Hg

What is the Partial Pressure of B in the solution if the Vapor


Pressure of Pure B at 100 oC is 500 mm Hg?
Ans: PB = PoBNB = (500) * (0.5) = 250 mm Hg

Would the solution boil at atmospheric pressure (760 mm


Hg)?
Ans: Yes Ptotal = PA + PB = (510 + 250) = 760 mm Hg

What is the composition of the Vapor at the Boiling Point?


Ans: The mole fraction of each would be:
NA (vapor) = PA / Ptotal= 510/760 = 0.67
NB (Vapor) = PB / Ptotal= 250/760 = 0.33

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Simple & Fractional Distillation

Distillation

Process of vaporizing a liquid, condensing the


vapor, and collecting the condensate in another
container

Uses of Distillation

Separating liquids with different boiling points

Purifying a liquid.

Distillation Methods

Simple

Vacuum (at reduced pressure)

Fractional

Steam

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10

Simple & Fractional Distillation

Distillation (Cont)

Pure Substance

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Temperature remains constant during


distillation process so long as both vapor and
liquid are present

Miscible Liquid Mixture

Temperature increases throughout process


because composition of vapor changes
continuously

Composition of vapor in equilibrium with the


heated liquid is different from the
composition of the liquid
11

Simple & Fractional Distillation

Simple Distillation
Single Vaporization / Condensation cycle of a mixture
that produces a distillate that is always impure at any
temperature range between the range of boiling points
of the components
Therefore, it is impossible to completely separate the
components in a mixture with Simple Distillation
Relatively pure substances can be obtained from a
mixture with Simple Distillation if the boiling points of
the components differ by a large amount (>100oC)
If a small increment of the initial distillate is separated
and redistilled and this process is repeated many
times, effectively producing multiple sequential
Vaporization/ Condensation Cycles, an increasingly
pure solution can be attained. This would be a very
tedious process involving a large number of distillations

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12

Simple & Fractional Distillation

Fractional Distillation

Accomplishes the same thing as Multiple Simple


Sequential Vaporization / Condensation Cycles, by
inserting a Fractionating Column (a Vigreux Column)
between the Distillation Flask and the Distillation Head

The Fractionating Column, of which there are many


types containing a variety of packing materials, subjects
the mixture to many Vaporization/Condensation Cycles
as the material moves up the column toward the
Distillation Head, which is attached to the Condenser

With each cycle within the column, the composition of


the vapor is progressively enriched in the lower boiling
liquid

This process continues until most of the lower boiling


compound is removed from the original mixture and
condensed in the receiving flask

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13

Simple & Fractional Distillation

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Fractional Distillation (Cont)

When the lower boiling liquid is effectively


removed from the original mixture, the
temperature rises and a second fraction
containing some of both compounds is
produced

As the temperature approaches the boiling


point of the higher boiling point compound, the
distillate condensing into the third receiving
flask is increasingly pure in the higher boiling
point compound

14

Simple & Fractional Distillation


Fractional Distillation (Cont)
As the distillation proceeds, the
composition of the liquid and the vapor
are continuously changing
The Horizontal and Vertical Lines represent
the processes that occur during a
fractional distillation.
Each Horizontal Line (L3V3, L2,V2), etc.,
represents both the vaporization step of a
given vaporization/condensation step and
the composition of the vapor in equilibrium
with the liquid at a given temperature.
Examples:
At 53oC with a liquid composition of 80% A
and 20% B (L4V4 on the diagram), the vapor
would have 95% A and 5% B when
equilibrium has been established between
the liquid and the vapor.

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At 63oC with a 50/50 liquid mixture of A&B


(L3V3 on the diagram), the vapor would
have a composition of 80% A & 20% B at
equilibrium.

15

Simple & Fractional Distillation

Column Efficiency - How pure can you get!!

A common measure of the efficiency of a


Fractionation Column is given by its number of
Theoretical Plates

One Theoretical Plate is equivalent to a Simple


Distillation, i.e., one Vaporization / Condensation
Cycle

The smaller the boiling point difference, the


greater the number of theoretical plates a
Boiling Point
fractionating
columnNumber of
Difference
Theoretical
Plates
must have
to achieve
separation
of mixtures
108
54
20
7
4
2

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1
3
10
30
50
100
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Simple & Fractional Distillation


Distillation Equipment Setup
Note: Equipment used in distillation experiment is expensive
Use care to avoid breakage
ASK BEFORE YOU ACT!!
Equipment

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Heating Block (or sand bath) & Heating Plate

50 mL round bottom Distilling Flask (with boiling chip)

Distillation Head

Thermometer & Thermometer Adapter

Vigreux Fractionation Column (second group only)

Aluminum foil for Vigreux Column & Distillation Head

Water Jacket Condenser (with rubber tubing for water)

Receiving containers 2 10 mL graduated cylinders &


6 labeled vials with sealing caps
17

Simple & Fractional Distillation

Distillation Equipment Setup (Cont)

Use 2 ring stands to support apparatus.

Attach clamp to Ring Stand & the Condenser

Attach clamp to other Ring Stand & Distillation


Head

Use Blue Plastic Clamp to secure Water Jacket


Condenser to neck of Distillation Head

Use Blue Plastic Clamp to secure Distillation Head (or


Vigreaux Column) to Distillation Flask

Insert thermometer through adapter so that the bulb


is positioned inch below opening to the Condenser

NOTE: Wrap the Distillation Head, Vigreux Column, and


Distillation Flask in Aluminum foil to improve heat
insulation
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18

Simple & Fractional Distillation


Typical Distillation Setup

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19

Simple & Fractional Distillation

Elements of The Experiment

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Two Distillations

Simple Distillation

Fractional Distillation with Vigreux Column

Work in groups of 4 (2 groups of 2 each)

First group

- Simple Distillation

Second group - Fractional Distillation

Each group of 4 will share data, but reports will


be written independently

Each report must contain all of the raw data


from the group, i.e., from both distillations
20

Simple & Fractional Distillation

Elements of The Experiment (Cont)

Simple and Fractional distillations


Note: Can be setup as a single (1) procedure
Note: In Procedure Description make note of addition of
the Vigreux column used in the Fractional Distillation

Construct Barchart of incremental volumes (y-axes) vs


temperature ranges (x-axes)

For both Simple Distillation & Fractional Distillation:

Determine Total volume recovered

Compute Percent volume recovered

Total Volume in temperature ranges


0 95

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C; 95 105 oC; 105 130 oC

Compute % volume recovered in each fraction


21

Simple & Fractional Distillation

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Combine the volumes from the 1st & 2nd fractions


and refer to it as Fraction A

Assume the combined 1st & 2nd fractions (fraction


A) is Ethyl Acetate and the 3rd fraction (fraction B)
is Butyl Acetate

Determine the mass of each compound in fraction


A and in fraction B from their respective volumes
and density

Compute the Moles of each compound in fraction A


and fraction B

Determine the total moles in each fraction

Compute mole fraction

Compute mole %
22

Simple & Fractional Distillation

Data Collection

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Place 20 mL of mixture in a 50 mL round bottom flask


Set Hot Plate setting to about 5
Use 10 mL graduated cylinder to collect distillate
Collect distillate in 5 degree increments recording the
incremental volume collected in the 5 degree interval
Note: 1st increment is from 0oC 65oC
Continue to collect incremental volumes in 5 degree
increments, until temperature reaches 95oC
Transfer the total volume collected in the graduated
cylinder up to 95oC to the first labeled vial
Continue to collect distillate in 5 degree increments
from 95oC to 105oC
Transfer the total volume collected between
95oC - 105oC into the second labeled vial

23

Simple & Fractional Distillation

Data Collection (Cont)

Increase temperature setting of Hot Plate

Continue to collect 5 degree volume increments in


the graduated cylinder until 1 mL remains in the
flask
Note: DO NOT DISTILL TO DRYNESS

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Turn off heat

Allow liquid in Distillation Head & Vigreux column to


cool and drain into the Distillation Flask (Pot
Residue)

Transfer the Pot Residue to the graduated cylinder

Determine the volume of Pot Residue

Transfer the contents of the graduated cylinder to


the third labeled vial
24

Simple & Fractional Distillation

Data Collection (Cont)


Suggested Table Template For Distillation Data
Temp Range
0-65 oC
65-70 oC
70-75 oC

Vial #1

75-80 oC
80-85 oC
85-90 oC
90-95 oC

Vial #2

95-100 oC
100-105 C
o

105-110 oC
110-115 oC

Vial #3

115-120 oC
120-125 oC
125-130 oC
Pot Residue
Initial Volume

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Total Volume
Recovered

Simple

Fractional

Volume (mL)

Volume (mL)

Incremental Volumes
For each 5 oC temperature interval, record
the volume of distillate collected in that
temperature range.
Cumulative Volumes for the 0 95 oC, 95
105 oC, and the 105 - 130 oC fractions, can
be computed by summing the incremental
volumes for each fraction.
Pot Residue
Pot Residue is the volume of undistilled
sample remaining in the Distillation Flask
after the Hot Plate is turned off.
Allow the apparatus to cool down; then
transfer the remaining liquid in the
Distillation Flask to the Graduated
Cylinder.
The Pot Residue becomes part of the final
increment of Distillate.
25

Simple & Fractional Distillation

Results

NOTE:
The following data analysis scheme is to
be applied
separately to both the Simple and
Fractional data
First Vial - All the distillate up to 95 oC
(Mainly Ethyl Acetate B.P. - 77.1 oC)
Second Vial - All the distillate collected between
95-105oC
Third Vial - All distillate above 105 oC
(Mainly Butyl Acetate B.P. 126.1oC)
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26

Simple & Fractional Distillation

Results (Cont)
1. Calculate the total volume of distillate

recovered

2. Calculate the % Recovery of the distillate

(Total Final Volume / Initial Volume) x 100


3. Use Excel to plot a bar chart of temperature

increments on the x-axis and volume


increments on the y-axis

Note: First increment is 0 65oC


Draw perpendicular lines to the 95 & 110
degree marks on the x-axis
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27

Simple & Fractional Distillation

Example BarChart
1st
Fraction

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2nd
Fraction

3rd
Fraction

28

Simple & Fractional Distillation

Results (Cont)
4. Calculate the total volume to the left of the

95 oC line
(1st fraction)
Calculate the total volume in the zone between
95 & 105 oC (2nd fraction)
Calculate the total volume to the right of the
105 oC line (3rd fraction)
5. Calculate volume percent composition of each of
the three (3) fractions
Vol % 1st fraction = Vol 1st fraction / Total Vol
Rcvd x 100
Vol % 2nd fraction = Vol 2nd fraction / Total Vol
Rcvd x 100
Vol % 3rd fraction = Vol 3rd fraction / Total Vol
Rcvd x 100
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29

Simple & Fractional Distillation


6. Compute Masses of Ethyl & Butyl Acetate

Combine Fractions 1 & 2 and assume it is Ethyl


Acetate
Assume Fraction 3 is Butyl Acetate
Compute the Mass of Ethyl Acetate and Butyl
Acetate from the Volumes and Densities of the two
new fractions
7. Compute the Moles of compound in each fraction

Density

Moles

Mass
Volume

Mass Density x Volume

Mass
grams

grams
Mol Wgt
mole

8. Compute the Total Moles in the two fractions


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30

Simple & Fractional Distillation

Results (Cont)
9. Compute the Mole Fraction of each fraction
10. Compute the Mole % of each fraction
Mole Fraction

Moles A
NA
Moles A Moles B

Mole Fraction

NB

Moles B
Moles A Moles B

NA NB 1

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Mole Percentage

NA% NA x 100

Mole Percentage

NB% NB x 100
31

Simple & Fractional Distillation

Example calculations

Mixture Example (1000 mL 60% / 40% by Volume)

Ethyl Acetate (600 mL)

Den 0.895 g/mL


Mol Wgt 88.11 g/mole

Butyl Acetate (400 mL)

Den

0.882 g/mL

Mol Wgt 116.16 g/mole

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Compute moles from volume, density, molecular weight

Ethyl Acetate

600 mL0.895 g / mL
= 6.095 moles
88.11 g / mole

Butyl Acetate

400 mL0.882 g / mL
= 3.037 moles
116.16 g / mole

Mole Fraction

Total Moles = 9.132

Ethyl Acetate

6.095 / 9.132 = 0.667 x 100 = 66.7%

Butyl Acetate

3.037 / 9.132 = 0.333 x 100 = 33.3%

32

Simple & Fractional Distillation

Mole Percent of Distillates by Gas Chromatography

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Refer to Website notes on the Gas


Chromatography of Acetates Experiment

Refer to Gas Chromatogram of the Equimolar


Mixture

Use the TRx/Tri thermal response correction


factor for the Ethyl Acetate & Butyl Acetate
peaks to adjust the distillate fraction peak areas

Obtain a Gas Chromatogram of the Standard


Mixture (A or B), whichever you used in the
Simple & Fractional Distillation experiment

Obtain Gas Chromatograms of each of the 3


vials you collected from the Simple Distillation
and each of the 3 vials collected from the
Fractional Distillation
33

Simple & Fractional Distillation

Mole Percent of Distillates by Gas Chromatography (cont)

Compute the Peak Areas using Triangulation method


Note: There are two peaks on each Chromatogram

Adjust

the peak areas for non-linear thermal response

NOTE: Use TRs/Tri correction factor from the equimolar


mixture used in the GC Acetates experiment

Compute adjusted areas by multiplying measured areas


from distillate fraction chromatograms the by the
equimolar mixture TRs/Tri correction factor
Compute

total area for peaks on each chromatogram

Compute

the Mole Fraction

Compute

Mole Percent

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34

Simple & Fractional Distillation

Mole Percent by Refractive Index


Note: Add to Experiment only if directed by
Instructor

Obtain

temperature corrected Refractive Index


values for the Unknown mixture (A or B) and the 6
simple & fractional distillation vials
Use

MS Excel to create a standard regression


curve from the known Refractive Index (y-axis) and
Mole % Ethyl Acetate (x-axis) values in the table
Mole%
Mole % Measure
Correcte
below
Temperature
Ref
Solutions of
Known Mole %
and Refractive
Index

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d
R.I.

d
R.I.

Ethyl
Acetate

Butyl
Acetate

100

1.3714

21.7

1.3722

60

40

1.3813

21.7

1.3821

50

50

1.3839

21.7

1.3848

40

60

1.3856

21.7

1.3864

100

1.3932

21.7

1.3941

(oC)

(20oC
1.3723

1.3941
35

Simple & Fractional Distillation

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Mole % by Refractive Index (cont)

Open MS Excel

From previous slide enter Mole % Ethyl


Acetate values into column A of spread sheet

Enter Corrected Ref. Index values into


column B

Select data in columns A & B

Select Format Cells from Task Bar

Select Number and 4 decimal places

Select Insert from Task Bar

Select Scatter Plot (2 clicks) to plot the data


36

Simple & Fractional Distillation

Mole % by Refractive Index (cont)

Add a trend (regression) line and regression


equation to the plot

Click on a data point in the plot

Select Add a Trend Line

Select

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Linear

Display Equation on Chart

Display R-Square value on Chart

Select and move Regression Equation to


upper left corner
37

Simple & Fractional Distillation

Mole % by Refractive Index (cont)

Select Axis Titles

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Select Horizontal Axis Title

Select Title Below Axis

Enter text - Mole % Ethyl Acetate

Select Chart Title

Select Above Chart

Enter text - Refractive Index(corr) vs.


Mole % Ethyl Acetate

Select and move chart labels as appropriate

38

Simple & Fractional Distillation

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Mole % by Refractive Index

39

Simple & Fractional Distillation

Mole % Analysis by Refractive Index (cont)

The Mole % values of the unknown mixtures are


determined either:

Directly from the Regression Curve by selecting


the mole % value relative to its equivalent
Refractive Index value

Computed from the regression equation

Rearrange the equation as follows to compute


your Mole % values
y = - 0.00022 x + 1.3949

x (Mole %) = (1.3949 y (Measured R.I.) / 0.00022


Ex. Measured R.I. 1.3850
X = (1.3949 - 1.3850) / 0.00022
X = 45% Ethyl Acetate (55% Butyl Acetate)
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40

Report Preparation

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The Report (Combined with GC Distillates Report)

Scan Chromatograms and insert files into


report

Only one (1) procedure is required for the


Distillation Equipment setup, simple
distillation, fractional distillation. Use one table
to report results

The Description for each procedure involving a


computation must include the computational
logic behind the equation used and the
equation setup with suitable definition of the
variables

The Summary section restates the results in


paragraph form
41

Report Preparation
The Report (Cont)

Each procedure that produces data includes both


Simple Distillation results and Fractional
Distillation results

For comparison purposes each Simple result


should be paired with its equivalent Fractional
result

For example: The total volume recovered for the


Simple Distillation was 17.6 ml (88.0%), while
the total volume recovered from the Fractional
Distillation was 18.3 mL (91.5%)

Create separate procedures for the computation


of mass, moles, mole fraction, mole %

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42

Report Preparation

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Analysis & Conclusion Section


Discuss the effectiveness of component
separation by Simple & Fractional Distillation
based on:
Analysis of the bar chart of the incremental &
fractional volumes, including the significance of
the amounts in the 2nd fraction (95oC 105oC)
Mole % values from the computed mass (from
volume and density) of the fractional volumes
Mole % from peak areas obtained from Gas
Chromatography
Compare the results for the original
undistilled A or B mixture and the distillate
fractions
Mole % from Refractive Index
43