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Separation of Liquids by Fractional Distillation and Analysis by Gas Chromatography


Riyushi Mahadik
February 20, 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 fractional 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
fractional distillation through gas chromatography to determine the % composition of ethyl
acetate and butyl acetate in each fraction. Finally the last one was to create a graph of volume vs.
temperature from the fraction distillation and compare it to the graph of simple distillation to
determine which technique is effective in separating the components of a mixture.
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. The importance of boiling points is crucial in fractional distillation to
separating the components of a mixture. The liquid boiling in a closed system increases the
number of gas molecules until the rate of the molecules entering the gas phase and liquid phase
equal out. And reach the dynamic equilibrium. This process of molecules in gas phase in a rapid
motion collides against the walls of the vessel exerting pressure. The pressure is called
equilibrium vapor pressure which is dependent on the temperature. As the temperature increases,
the vapor pressure above the boiling liquid increases. Whereas when a liquid is boiled in an open
system, the vapor above the liquid is mixed with air and the total pressure. This process is

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denoted by Daltons Law of partial pressures, Ptotal = Psample + Pair. So, the total pressure above the
liquid is calculated by adding the partial pressure of each component The partial pressure of the
sample is equal to its equilibrium vapor pressure at a given temperature. At a higher temperature,
the rate of evaporation increases and the equilibrium vapor pressure equals the total pressure
which is referred to as the boiling point of the liquid.
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.
But the impurities in a nonvolatile liquid decrease the vapor pressure at a given temperature. This
relationship od vapor pressure and volatile components in a liquid is denoted by Raoults law,
PX=PXNX where PX is the partial pressure of component X, PX is the vapor pressure of pure X at
a given temperature, and NX is the mole fraction of each component. The mole fraction of each
component X and Y in mixture is calculated from equation, NX= PX/ (PX+PY+). Thus, this
relationship between temperature, composition of the liquid and the vapor phase is important in
determining which component will be distilled first.
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.
Fractional distillation separates two or more volatile components present in the mixture. As
shown in Figure 1, the liquid mixture is placed in a still pot along with a stir bar and the
distillation flask is clamped. The Hempel column or distillation column with raschig rings is then
attached. Then the west condenser with two water tubes is attached to the column. Sometimes
the vapor from the still pot rises up the column and some of it condenses in the column to the
still pot. If the temperature of the lower part of the column is higher than the temperature of the
upper part of the column, the condensate will be partially revaporized as it flows down the
column. The uncondensed vapor along with that produced by revaporization of the condensate in
the column rises higher and higher in the column and undergoes a repeated series of
condensation and revaporization. This cycle of condensation and vaporization is equivalent to
performing simple distillation and is termed as theoretical plates in the column. The number of
theoretical plates determines the efficiency and separating power in fractional distillation. The
height equivalent to a theoretical plate (HETP) is the vertical length of the column which
increase the efficiency of theoretical plate. The number of theoretical plates increases as the
surface area and the length of the vertical column increases. 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.
In Part I of fractional distillation, three fractions were collected: 13mL of fraction one was
collected between the temperature range of 75-76.5 C, 3mL of second fraction was collected
between 93-122 C and 6mL of third fraction was collected between 122-122.1C. The table
below illustrates the data observed for the three fractions. In the second part of gas
chromatography analysis, the first fraction produced 100 % of ethyl acetate and the third fraction

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produced 100% of butyl acetate. Whereas in second fraction there were both components of
mixture found.

Figure 1. Simple Distillation and Fractional 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

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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 fractional distillation, the apparatus was set up according to Figure 1. Attach a 100 mL
still pot equipped with a Hempel column with raschig rings, 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. Also, to keep the whole apparatus from bending another stand was used. Along with
that to avoid the air flow in the Hempel column two balloons were used to secure the holes in the
column. 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 less than 1 drop/ sec so the temperature was increased to 55C. 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.
For the gas chromatography instrument, 5 micro liters of the liquid samples were taken into
syringes and were inserted into GC instrument individually in port A of carbowax. All of the
fractions were taken to run and analyzed by the gas chromatography instrument. The graph
indicating peaks and area of each fraction 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

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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: Fractional Distillation


In Part I, three fractions were collected: 13mL of fraction one was collected between the
temperature range of 75-76.5 C, 3mL of second fraction was collected between 93-122 C and
6mL of third fraction was collected between 122-122.1C. 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) Temperature C
1 mL
75
2 mL
75
3 mL
75
4 mL
75.1
5 mL
75.5
6 mL
75.6
7 mL
75.8
8 mL
75.8
9 mL
75.8
10 mL
75.8
11 mL
75.8
12 mL
76.5
13 mL
93
Fraction Two:
Volume (mL) Temperature C
14 mL
119
15 mL
122
16 mL
122

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Fraction Three:
Volume (mL) Temperature C
17 mL
122.1
18 mL
122.1
19 mL
122.1
20 mL
122.1
21 mL
120
22 mL
122

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

x 100

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 Fractional Distillation and Gas Chromatography
Fractions
Fraction 1
Fraction 2
Fraction 3
Peaks
Peak 1
Peak 2
Peak 1
Peak 2
Peak 1
Peak 2
Area (s*mV)
5766
1371
4254
5844
Retention Time (s)
25
15
24.5
39
Ethyl
Butyl
Ethyl
Butyl
Ethyl
Butyl
Identity
Acetate
Acetate
Acetate
Acetate
Acetate
Acetate
Ideal % Composition
100
0
24.4
75.6
0
100
Corrected %
Composition
100
0
27.9
72.1
0
100
Table 2: Analyzing Fractions from Simple Distillation and Gas Chromatography
Fractions
Fraction 1
Fraction 2
Fraction 3
Peaks
Peak 1
Peak 2
Peak 1
Peak 2
Peak 1
Peak 2
Area (s*mV)
3484
329.2
2337
1154
240.7
3227
Retention Time (s)
14
8
14
11
9
13
Ethyl
Butyl
Ethyl
Butyl
Ethyl
Butyl
Identity
Acetate
Acetate
Acetate
Acetate
Acetate
Acetate
Ideal % Composition
91.3
8.63
66.9
32.9
6.9
93
Corrected %
92.7
7.28
70.9
29.1
8.23
91.8

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Composition

Table 3: Comparison of Simple Distillation and Fractional Distillation


Simple Distillation
Fractional Distillation
Volume (mL) of Fraction 1

10

13

Volume (mL) of Fraction 2

10

Volume (mL) of Fraction 3

10

Mol % EtOAc in Fraction 1

92.7

100

Mol % BuOAc in Fraction 1

7.28

Mol % EtOAc in Fraction 2

70.9

27.9

Mol % BuOAc in Fraction 2

29.1

72.1

Mol % EtOAc in Fraction 3

8.23

Mol % BuOAc in Fraction 3

91.8

100

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Graph 1. Temperature (C) at Each Volume in Fractional Distillation of 1:1 mixture of EtOAc/BuOAc (1 drop /sec)
130
120
110
100
Volume (ml) 90
80
70
60
0 1 2 3 4 5 6 7 8 9 1011121314151617181920212223
Temperature (C)

The Volume vs. Temperature graph shows that in fraction one, the temperature is relatively
constant between 75-76.5 C. In fraction two, between 13-15mL, there is a sudden rise in
temperature. And in Fraction three between 17-22mL, the temperature again remained constant
around 122.1C.

Graph 2. 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

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.

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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)]
I.

Calculation for Mole percent ideal:

Fraction one:
Peak one: Mol % = {(5766 s*mV)/ [(5766 s*mV) + (0 s*mV)]} x 100 = 100%
Peak two: Mol % = {(0 s*mV)/ [(5766 s*mV) + (0 s*mV)]} x 100 = 0 %
Fraction two:
Peak one: Mol % = {(1371 s*mV)/ [(1371 s*mV) + (4254 s*mV)]} x 100= 24.4%
Peak two: Mol % = {(4254 s*mV)/ [(1371 s*mV) + (4254 s*mV)]} x 100 = 75.6 %
Fraction three:
Peak one: Mol % = {(0 s*mV)/ [(0 s*mV) + (5844 s*mV)]} x 100 = 0%
Peak two: Mol % = {(5844 s*mV)/ [(0 s*mV) + (5844 s*mV)]} x 100 = 100%
Calculation for Mole percent corrected:
Fraction one:
Peak one: Mol % = {(5766 s*mV x 0.89)/ [(5766 s*mV x 0.89) + (0 s*mV x 0.74)]} x 100
= 100 %
Peak two: Mol % = {(0 s*mV x 0.74)/ [(5766 s*mV x 0.89) + (0 s*mV x 0.74)]} x 100
= 0%
Fraction two:
Peak one: Mol % = {(1371 s*mV x 0.89)/ [(1371 s*mV x 0.89) + (4254 s*mV x 0.74)]} x 100
= 27.9%
Peak two: Mol % = {(4254 s*mV x 0.74)/ [(1371 s*mV x 0.89) + (4254 s*mV x 0.74)]} x 100
= 72.1 %
Fraction three:
Peak one: Mol % = {(0 s*mV x 0.89)/ [(0 s*mV x 0.89) + (5844 s*mV x 0.74)]} x 100
= 0%
Peak two: Mol % = {(5844 s*mV x 0.74)/ [(0 s*mV x 0.89) + (5844 s*mV x 0.74)]} x 100
= 100%
Conclusion

The objective of this lab was to separate a 1:1 mixture of ethyl acetate and butyl acetate using
fractional distillation and then analyzing it by gas chromatography. For the first fraction, the

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temperature it was collected was 75-75.1C 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 there was
only one of ethyl acetate with shorter retention time and no second peak of butyl acetate. In the
first fraction, the mole percent of ethyl acetate was 100% whereas there was not any amount of
butyl acetate being at 0%. The second fraction was collected at rapid increasing temperature of
93-122 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 27.9% and 72.1% 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 122-122.1C which is close to the boiling point of butyl acetate (126.3C). This
means the third fraction had larger portion of butyl acetate than ethyl acetate. This is true because
the results from gas chromatography graph of fraction on didnt show the first peak is ethyl
acetate with shorter retention time rather the second peak of butyl acetate with larger retention
time and larger area was seen. In the third fraction, the mole percent of ethyl acetate was 0%
which was much smaller than the mole percent of butyl acetate which was 100%. Comparing the
corrected data with the ideal data for all the fraction, the fractional 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.
After analyzing the volume vs. temperature graphs of simple distillation and fractional
distillation, it would conclude that the fractional distillation separates the liquids more efficiently
than simple distillation. From the observations and graphs, the first fraction collected in simple
distillation didnt have constant temperature if compared to fractional distillation. Similarly there
was sharp rise in temperature of second fraction for fractional distillation. At the same time, in
fraction second the graph of simple distillation the temperature increased gradually over a larger
volume. Similar pattern was seen in third fraction where the temperature remained constant for a
long period of time in fractional distillation indicating the boiling point of Butyl acetate. Whereas
in simple distillation the temperature took significant amount of time to make the temperature
constant. Overall, as the comparison the fractional distillation yielded 100 % of ethyl acetate in
first fraction in compare to simple distillation having both mixtures yielding in the first fraction.
For the third fraction, the simple distillation again yielded both components of mixture rather
fractional distillation produced 100% of butyl acetate. Thus, in conclusion fractional distillation
separated the mixture of two volatile compounds better than simple distillation because it
contained more theoretical plates which increased efficiency of the process of separation.
The downfall of simple distillation data in compare to simple distillation is that it didnt
determine the correct boiling points of ethyl acetate and butyl acetate in the GC analysis. The
third fraction was collected between 114-129C which is not close to the boiling point of butyl
acetate (126C). Whereas, in fractional distillation, the third fraction was collected between 122122.1C which was relatively not close to the boiling point of butyl acetate. There might be other
impurities in the simple distillation that could led to decrease the efficiency or other error that
could cause the glitches in the temperature in the experiment. There have few of the challenges
associated with this lab First most, setting up the distillation apparatus was challenging because

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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. Then the process of distillation was too slow and it
started distillation less than 1 drop/sec, so the temperature was manipulated several times to
collect effective data. 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.
Reference
Gilbert, John C., and Stephen F. Martin. Experimental Organic Chemistry. Cengage Learning,
Massachusetts, 2011, 5th Ed, pp. 58-59, 127-129, 135-140.