Separation of Ethyl Acetate and Butyl Acetate by Simple Distillation and Analysis of

Fractions by Gas-Liquid Chromatography

Riyushi Mahadik
February 13, 2014

O
H3C

O
O

CH3

Ethyl acetate (C4H8O2)

B.P. 77C, 88.11 g/mol

H3C

CH3

Butyl acetate (C6H12O2)

B.P. 126.3C, 116.16 g/mol

Methods and Background

The objective of this lab is to set up a simple distillation apparatus in order to separate a 1:1
mixture of ethyl acetate and butyl acetate. The goal was to analyze the fractions collected in
simple distillation through gas chromatography to determine the % composition of ethyl acetate
and butyl acetate in each fraction. And finally the last one was to create a graph of volume vs.
temperature from the simple distillation.
The boiling point of a substance is the temperature at which equilibrium vapor pressure of a
liquid equals to the atmospheric pressure. Boiling point is an important physical property of each
compound which determines the purity and identity of each compound.. It is process when
liquid bubbles and there is a spontaneous vaporization Compounds with higher equilibrium
vapor pressure have lower boiling points whereas compounds with lower equilibrium vapor
pressure have higher boiling points. More volatile liquids can readily vaporize at very low
temperatures and they have low boiling points. Relatively, volatile liquids have higher
equilibrium vapor pressure at low temperatures.

In this lab, two compounds will be examined. Their structures contain an ester group but due to
more number of carbon chains in butyl acetate than ethyl acetate , they differ in their boiling
points and equilibrium vapor pressures. The boiling point of ethyl acetate and butyl acetate is
77C and 126C respectively. Ethyl acetate is more volatile than butyl acetate.

The simple distillation apparatus has several parts that are still head, thermometer adapter,
thermometer, still pot(round bottom flask), west condenser , vacuum adapter. Keck clips, rubber
tubing, graduated cylinder, and beakers. They are all connected together which is shown in figure
1. Simple distillation is used to separate volatile liquid from non-volatile solute or separate two
volatile liquids when their boiling points difference is less than 50 C. In simple distillation, the
distillates are separated from less volatile substances that remain as pot residues after the
completion of distillation. Since ethyl acetate has lower boiling point, it will be evaporated first
in simple distillation. This process follows Raoult's law which says partial pressure is calculated
by multiplying the mole fraction and equilibrium vapor pressure.
During this process, three fractions will be collected depending upon the temperatures. The first
fraction remains close to the boiling point of ethyl acetate. The second fraction temperature
begins to increase and the third fraction stabilizes at or near the boiling point of butyl acetate..
These fractions are then used for gas chromatography.

Figure 1. Simple Distillation Apparatus

Gas chromatography is used to separate a mixture of two volatile liquids. Gas chromatography
separates the components of a mixture between two immiscible phases: mobile phase and
stationary phase. The mobile phase in gas chromatography is a gas which is called a carrier

gas; gases that include nitrogen and helium A stationary phase is a very high boiling, carbowax.
In gas chromatography, the components that get adsorbed to the mobile phase move through the
column more quickly, whereas those that show high affinity to the stationary phase migrate more
slowly. More volatile substances such as ethyl acetate in this lab would elute out from the
column faster and have lower retention time than less volatile substances such as butyl acetate
which have higher retention time. The time required for the compound to pass from the point of
injection to the detector is called as the retention time of the component. The retention time of a
component is not affected by the presence or absence of other mixture components. However,
experimental factors affect the retention time of a compound are nature of the stationary phase,
length of the column, temperature of the column, and flow rate of the carrier gas. Thus, for a
particular column, the retention time will be the same for a specific compound. In gas
chromatography, the columns efficiency increases with increasing length and decreasing
diameter. Increasing the length of the column increases the difference in retention time between
bands, whereas decreasing the diameter results in narrower bands. Fractions inserted into the gas
chromatography instrument are analyzed by observing the peaks on the graph. The first peak
observed in the graph is of a less polar compound, which has a short retention time. The second
peak observed in the graph is of a more polar compound, which has a larger retention time. Area
under peak is also calculated which is proportional to the moles of the compound eluted in the
column.

For this lab, the ideal % composition is calculated to figure out the % composition of each
compound in each fraction. However, the thermal conductivity of substances is slightly different.
So, a correction factor must be used in order to figure out the corrected % composition of
substances in a given fraction

Experimental Procedures
For The simple distillation, the apparatus was set up according to Figure 1. Attach a 100 mL still
pot equipped with a still head, west condenser (thick column), bend vacuum adapter,
thermometer, and thermometer adapter in a vertical position. Then, to ensure the stability, the
apparatus was clipped with Keck clips to prevent any leakage of vapor. A thermometer was
placed into the still head with the support of thermometer adapter. The thermometer was kept
below the entrance of the condenser to ensure the correct temperature of the vapors. Then, two
water rubber tubes were connected with west condenser, one allowing the water to enter in the
condenser and other one to drain the water out of the condenser. Graduated cylinder was by the
open end of bent vacuum adapter to collect three fractions. After everything was set up, the hot
plate was placed underneath the still pot, while 30 mL of 1:1 mixture of ethyl acetate and butyl
acetate was added to the still pot. The temperature was set to 45C. The vapors were collecting
more than 1 drop/ sec so the temperature was lowered to 0 C . Three fractions were transferred

in a beaker with a watch glass containing 10 mL, 10 mL, and 8 mL for fractions 1,2 and 3
respectively. The temperature was recorded for every 1 ml of liquid distilled.
All of the fractions were taken to run and analyzed by the gas chromatography instrument. The
graph indicating peaks and area of each fractions was printed out to further analyze.
Data Acquisition/Calculations:
I.

Equations
Boiling Point (mixture) B.P= Ptot= Patm
o Ptot- Total pressure above the liquid
o Patm- Atmospheric pressure

Dalton's Law:
Ptot = Px + Py + Pz..., where:
o Ptot = sum of all the partial pressure of the components in a mixture

Mole Fraction: Nx=nx/(nx+ny)

o Nx Mole fraction
o nx Moles of one compound in a compound
o nx+ny Total moles of compound

Ideal % Composition
Mol % (of compound A) =

Area of compound A
x 100
[(Area of compound A) + (Area of compound B)]

Correction % Composition
Mol % (of compound A) =
Area of compound A x Mf (A)
x 100
[
[(Area of compound A x Mf) +(Area of compound B x Mf)]

Part I: Simple Distillation

In Part I, three fractions were collected: 10mL of fraction one was collected between the
temperature range of 86.8-99 C, 10mL of second fraction was collected between 100-104 C
and 8mL of third fraction was collected between 118-129C. The table below illustrates the data
observed for the three fractions.

1. Ethyl Acetate:
Mole fraction = 0.89
Molecular Weight = 88 g/mol
Boiling Point = 77 C

2. Butyl Acetate:
Mole Fraction = 0.74
Molecular Weight = 116 g/mol
Boiling Point = 126 C
Fraction One:
Volume (mL)
1 mL
2 mL
3 mL
4 mL
5 mL
6 mL
7 mL
8 mL
9 mL
10 mL

Temperature C
86.8
88
90
91
93
94
95
98
98
99

Fraction Two:
Volume (mL)
11 mL
12 mL
13 mL
14 mL
15 mL
16 mL
17 mL
18 mL
19 mL
20 mL

Temperature C
100
101
103
103
104.5
106
108
110.5
113
114

Fraction Three:
Volume (mL)
21 mL
22 mL
23 mL
24 mL
25 mL
26 mL
27 mL
28 mL
29 mL

Temperature C
118
120
122
124
126
127
128
129
-

30 mL

Graph 1: Volume vs. Temperature for the simple distillation results:

Temperature (C) at Each Volume in Simple Distillation of 1:1 mixture of EtOAc/BuOAc (1 drop /sec)
130
120
110
Volume (ml) 100
90
80
0 5 10 15 20 25 30 35
Temperature (C)

The Volume vs. Temperature graph shows that in fraction one, the temperature is relatively
constant between 86.8-99 C. In fraction two, between 11-20mL, there is a sudden rise in
temperature. And in Fraction three between 21-28mL, the temperature again remained constant
around 120C.
Part II: Analysis of Distillation Fractions by GC
The peaks from the GC in the graph were analyzed and Mole percentages of the compound were
calculated. See attached copies of the three fractions from gas chromatography.
Ideal % Composition
Mol % (of compound A) =

Area of compound A

x 100

[(Area of compound A) + (Area of compound B)]

Correction % Composition
Mol % (of compound A) =

Area of compound A x Mf (A)

x 100

[(Area of compound A x Mf) + (Area of compound B x Mf)]

Table 1: Analyzing Fractions from Simple Distillation and Gas Chromatography

Fractions
Peaks
Area (s*mV)
Retention Time (s)

Fraction 1
Peak 1
Peak 2
3484
329.2
14
8
Ethyl
Butyl
Acetate
Acetate
91.3
8.63

Identity
Ideal % Composition
Corrected %
Composition
92.7
7.28
II.
Calculation for Mole percent ideal:

Fraction 2
Peak 1
Peak 2
2337
1154
14
11
Ethyl
Butyl
Acetate
Acetate
66.9
32.9
70.9

29.1

Fraction 3
Peak 1
Peak 2
240.7
3227
9
13
Ethyl
Butyl
Acetate
Acetate
6.9
93
8.23

Fraction one:
Peak one: Mol % = {(3484 s*mV)/ [(3484 s*mV) + (329.2 s*mV)]} x 100 = 91.3%
Peak two: Mol % = {(329.2 s*mV)/ [(3484 s*mV) + (329.2 s*mV)]} x 100 = 8.63 %
Fraction two:
Peak one: Mol % = {(2337 s*mV)/ [(2337 s*mV) + (1154 s*mV)]} x 100= 66.9%
Peak two: Mol % = {(1154 s*mV)/ [(2337 s*mV) + (1154 s*mV)]} x 100 = 32.9 %
Fraction three:
Peak one: Mol % = {(240.7 s*mV)/ [(240.7 s*mV) + (3227 s*mV)]} x 100 = 6.9%
Peak two: Mol % = {(3227 s*mV)/ [(240.7 s*mV) + (3227 s*mV)]} x 100 = 93%

Calculation for Mole percent corrected:

Fraction one:
Peak one: Mol % = {(3484 s*mV x 0.89)/ [(3484 s*mV x 0.89) + (329.2 s*mV x 0.74)]} x 100
= 92.7 %
Peak two: Mol % = {(329.2 s*mV x 0.74)/ [(3484 s*mV x 0.89) + (329.2 s*mV x 0.74)]} x 100
= 7.28 %
Fraction two:
Peak one: Mol % = {(2337 s*mV x 0.89)/ [(2337 s*mV x 0.89) + (1154 s*mV x 0.74)]} x 100
= 70.9%
Peak two: Mol % = {(1154 s*mV x 0.74)/ [(2337 s*mV x 0.89) + (1154 s*mV x 0.74)]} x 100

91.8

= 29.1 %
Fraction three:
Peak one: Mol % = {(240.7 s*mV x 0.89)/ [(240.7 s*mV x 0.89) + (3227 s*mV x 0.74)]} x 100
= 8.23%
Peak two: Mol % = {(3227 s*mV x 0.74)/ [(240.7 s*mV x 0.89) + (3227 s*mV x 0.74)]} x 100
= 91.8%
Conclusion

The objective of this lab was to separate a 1:1 mixture of ethyl acetate and butyl acetate using
simple distillation and then analyzing it by gas chromatography. For the first fraction, the
temperature it was collected was 86.8-99C which is close to the boiling point of ethyl acetate
(77C). This means the first fraction had higher moles of ethyl acetate than butyl acetate. This is
true because the results from gas chromatography graph of fraction on showed that the first peak
is ethyl acetate with shorter retention time and the second peak is butyl acetate with larger
retention time. In the first fraction, the mole percent of ethyl acetate was 92.7% which was much
larger than the mole percent of butyl acetate which was 7.28%. The second fraction was
collected at constant temperature of 100-114 C which indicates it contained about equal
proportions of both ethyl acetate and butyl acetate. From the peaks by GC, for fraction two, the
mole percent of ethyl acetate and butyl acetate were 70.9% and 29.1% respectively. The results
from gas chromatography graph of fraction two showed that the first peak is ethyl acetate with
shorter retention time and the second peak is butyl acetate with larger retention time. For the
third fraction, the temperature it was collected was 118-129C which is close to the boiling point
of butyl acetate (126.3C). This means the first fraction had larger portion of butyl acetate than
ethyl acetate. This is true because the results from gas chromatography graph of fraction on
showed that the first peak is ethyl acetate with shorter retention time and smaller area and the
second peak is butyl acetate with larger retention time and larger area. In the third fraction, the
mole percent of ethyl acetate was 8.23% which was much smaller than the mole percent of butyl
acetate which was 91.8%. Comparing the corrected data with the ideal data for the first fraction,
the simple distillation is efficient because there was no significant difference between the ideal
composition and the corrected composition.
Since butyl acetate has higher boiling point and is less volatile, it eluted out from the column last
and had a larger retention time. Comparing the corrected data percent composition with the ideal
data for the all of the fractions, the simple distillation is efficient because there was no significant
difference between the ideal composition and the corrected composition.
There have few of the challenges associated with this lab First most, setting up the distillation
apparatus was challenging because it wouldnt stand still at place until it was clipped. It was hard
to determine how to divide up the fractions after looking at the temperatures. The last part of
analyzing of the GC graphs was difficult because it was hard to understand how to use area and

what identity it stands for until after reading the text again, it was much clear. But finally, the
results obtained from this lab are very significant in determining successful separation of ethyl
acetate and butyl acetate. Ethyl acetate is more volatile and has a lower boiling point would elute
out first, whereas butyl acetate is less volatile and has a higher boiling point would elute out last.

Post lab Questions

Carbowax will be the most appropriate for separating a mixture of ethyl acetate and butyl acetate
because it is a polar stationary phase. Butyl acetate would elute out first because it is less polar
than ethyl acetate.
If the polarity of stationary phase increased, th retention time will increase.
Absorption is a process in which substance are dissolved. In adsorption, the substance adheres to
adsorbent.
In Gas Chromatography, the mobile phase passes in an oven.
If the rate of distillation would be increased, the temperature at each ml will be harder to
measure. Due to fast boiling rate, both compounds would get mixed together and difficult to
create fractions.
Reference
Gilbert, John C., and Stephen F. Martin. Experimental Organic Chemistry. Cengage Learning,
Massachusetts, 2011, 5th Ed, pp. 55-58, 127-132, 196-206.