Simple&Fractionaldist

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
04/21/16
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
04/21/16
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
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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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)
04/21/16
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
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
04/21/16
04/21/16
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
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
04/21/16
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
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
04/21/16
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
Distillation (Cont)
Pure Substance
04/21/16
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 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
04/21/16
12
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
04/21/16
13
04/21/16
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

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
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
04/21/16
1
3
10
30
50
100
16

Distillation Equipment Setup
Note: Equipment used in distillation experiment is expensive
Use care to avoid breakage
ASK BEFORE YOU ACT!!
Equipment
04/21/16
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
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
04/21/16
18

Typical Distillation Setup
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19
Elements of The Experiment
04/21/16
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
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
04/21/16
C; 95 105 oC; 105 130 oC
Compute % volume recovered in each fraction

21
04/21/16
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
Data Collection
04/21/16
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
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
04/21/16
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
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
04/21/16
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
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)
04/21/16
26
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
04/21/16
27
Example BarChart
1st
Fraction
04/21/16
2nd
Fraction
3rd
Fraction
28
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
04/21/16
29

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

04/21/16
30
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
04/21/16
Mole Percentage
NA% NA x 100
Mole Percentage
NB% NB x 100
31
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
04/21/16
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
Mole Percent of Distillates by Gas Chromatography
04/21/16
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
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
04/21/16
34
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
04/21/16
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
04/21/16
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
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
04/21/16
Linear
Display Equation on Chart
Display R-Square value on Chart
Select and move Regression Equation to

upper left corner
37
Select Axis Titles
04/21/16
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
04/21/16
Mole % by Refractive Index
39
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)
04/21/16
40
Report Preparation
04/21/16
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 %
04/21/16
42
Report Preparation
04/21/16
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

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Simple & Fractional Distillation

Experiment Simple & Fractional Distillation

Evaluation of the relative effectiveness of Simple &

Determination of Mole % from Distillate Volume Data, Gas

p. 719 729 (Simple

p. 729 740 (Fractional

p. 845 850 (Refractive Index)