Fractional Distillation

Hayley Williams, willi553@go.stockton.edu

CHEM 2125 007
February 20, 2018

Abstract
The purpose of this experiment was to identify two unknowns by separating a mixture using fractional
distillation. The process of fractional distillation was used to separate two components of a mixture based
on the differences in boiling points of the two. The mixture was heated and the unknowns separated,
lower boiling point first, through the process of evaporation and condensation into marked test tubes.
Once the unknowns were separated, a refractive index was measured using a refractometer to further
confirm the identity of the two compounds. The unknown mixture used in this experiment was unknown
#6, which was a mixture of methanol (lower BP) and 2-methyl-1-propanol (higher BP). Methanol has a
boiling point of 64.7C and a refractive index of 1.3292, while unknown A had an average boiling point
of 70.1C and a refractive index of 1.3341. Unknown A’s BP and RI came the closest to methanol’s BP
and RI, confirming that it was methanol. 2-methyl-1-propanol has a boiling point of 108C and a
refractive index of 1.3960, while unknown B had an average boiling point of 106.1C. These similar
values confirmed the identity of unknown B as 2-methyl-1-propanol. Boiling points and refractive indices
were used to match the unknowns with a known compound.
Purpose/Theory
The purpose of this experiment was to identify the components of a homogenous mixture using
fractional distillation. The identities of the unknowns were then confirmed by their boiling points and
refractive indices. The goal of fractional distillation is to separate a mixture into its pure components. All
liquids have different boiling points, making pure unknown compounds easily identifiable. Fractional
distillation uses the gap in boiling points to separate the compounds in a mixture by heating it slowly.
This causes the lower-boiling compound to evaporate to a vapor and then liquefy through the condenser,
while the higher-boiling compound continues to heat.
The process of fractional distillation is quite simple if executed properly. An unidentified liquid is
heated slowly to a boil in the “pot.” The component with the lower boiling point will boil first, causing
the vapor to travel up the fractioning column through the three-way adapter (head) where the thermometer
is placed. The thermometer records the temperature of the vapor while it passes through the head into the
west condenser where it cools and liquefies to be collected in a test tube (5mL at a time). Only the first
and third tubes are used and tested because the second tube contains a mixture of the two compounds.
This is because tube 2 contains an impure mixture of remaining unknown A and unknown B that has
begun to boil. The average head temperatures for tubes 1 and 3 represent the boiling points of each
unknown, which are then matched to boiling points of known compounds to determine the identities.
The difference between fractional distillation and simple distillation is the presence of a
fractioning column. This fractioning column separates the liquids more thoroughly due to the beads inside
(glass or plastic). These beads provide theoretical plates where the vapor can condense, re-evaporate, and
then re-condense. The purity of the distilled compounds can be determined by comparing the boiling
point to the closest boiling point of a known compound. Once the unknown has been identified, its boiling
point can be compared to the compound’s literature boiling point. The closer the boiling points, the purer
the compound. Refractometry can also be used to identify compounds. To use this method, a sample of a
distilled, pure unknown is placed in a refractometer where a refractive index is measured. This refractive
index can be matched to a known refractive index to identify each unknown.

Results/Discussion
Unknown #6 was correctly identified as a mixture of methanol (unknown A) and 2-methyl-1-
propanol (unknown B). The identities of the unknowns were found by using fractional distillation to
separate the two components from the mixture. The average boiling points were taken for the first 5mL
and the third 5mL sample of the distilled component. [Figure 1] The second 5mL sample was irrelevant
because it was a mixture, so the results would have been inaccurate. The average boiling point for the first
sample (unknown A) was 70.1C. This temperature fell between the boiling points of the two compounds,
methanol (64.7C) and 2-propanol (78.4C). Unknown A could not be accurately identified by solely its
boiling, but it was able to be identified by its refractive index. Unknown A’s refractive index was 1.3341,
which was much closer to the refractive index of methanol (1.3292) than that of 2-propanol (1.3770).
[Figure 2] Though the refractive indices were similar, unknown A’s boiling point did not closely match
its literature boiling point, indicating that it wasn’t completely pure. The average boiling point for the
third sample (unknown B) was 106.1C, which was close to the literature boiling point of 2-methyl-1-
propanol (108C). The refractive index was also taken to confirm unknown B’s identity. Unknown B had
a refractive index of 1.3945, almost matching that of 2-methyl-1-propanol (1.3960). [Figure 2] The
accuracy of unknown B’s boiling point and refractive index lead to the conclusion that the distilled
compound was very pure.
 Distillation Unknown #6 Identities
Volume Temp Average Unknown A Unknown B
(mL) (C) Temp
Identity methanol 2-methyl-1-prpopanol
(C)
1.0 68.5 Tube A: Average Boiling Point 70.1C 106.1C
1.5 69.0 70.1 Identity Lit. Boiling Point 64.7C 108C
(C)
2.0 69.2
Observed Refractive Index 1.3341 1.3945
2.5 69.9
Identity Lit. Refractive 1.3292 1.3960
3.0 70.1 Index
3.5 70.1 Figure 2: Unknown #6 Identities table
4.0 70.6
4.5 71.4
5.0 72.5
5.5 74.3 Mixed
6.0 76.1 Fraction
Boiling Points of Unknowns
6.5 77.4 –no 110
average 105
7.0 78.9
Head Temperature (℃)

needed 100
7.5 82.1
95
8.0 88.3 90
8.5 97.4 85
9.0 102.5 80
9.5 105.0 75
10.0 106.1 70
65
10.5 106.1 Tube B:
60
11.0 106.1 106.1
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
11.5 106.1
Volume (mL)
12.0 106.1
12.5 106.1
13.0 106.1 Figure 3: Boiling Points of Unknowns graph
13.5 106.1
14.0 106.1
14.5 106.1
15.0 106.1

Figure 1: Distillation table

Conclusions
Unknown #6 was a mixture of methanol and 2-methyl-1-propanol. Unknown A, which had the
lower boiling point (70.1C), was confirmed to be methanol. Fractional distillation, alone, was not enough
to determine its identity, but it helped to narrow the possibilities down to methanol (64.7C) and 2-
propanol (78.4C). The refractive indices of unknown A (1.3341) and methanol (1.3292) were similar
enough to conclude that unknown A was methanol. Unknown B, the higher boiling point (106.1C) was
determined, through fractional distillation, to be 2-methyl-1-propanol (108C) due to the similarity in
boiling points. The refractive index of unknown B (1.3945) was measured and compared to that of 2-
methyl-1-propanol (1.3960), further verifying the identity of unknown B. The source of error in
measuring the boiling point of unknown A was most likely due to contaminants in the fractioning column.
The presence of contaminates could have led to in inaccurate boiling point, which explains the higher
boiling point in this experiment.
References

https://blogs.stockton.edu/chem2/files/2016/05/TLClab_F16-1.pdf
th
Zubrick, James. The Organic Chem Lab Survival Manual, 9 ed.; Wiley: NJ, 2014.

Post-Lab Questions

1. A fractioning column is not used in simple distillation, but it is used in fractional distillation.

6. Yes, the temperature in the pot is higher than it is in the head. The vapor cools as it rises up the
fractioning column, then turns into a liquid at the three-way adapter. This is because it is further
away from the heat source.

10. The refractory indices for the three samples are 1.3928, 1.3756, and 1.3594 respectively.

11. a.) The boiling point for sample A is 140C. The boiling point for sample B is 70C.
b.) 140C would be 100% sample A and 0% sample B. 70C would be 100% sample B
and 0% sample A.
c.) If there were 3 theoretical plates, the composition of the original distillate would be
20% sample A and 80% sample B.
d.) Two theoretical plates would be needed to separate sample B from this mixture.

12. a.) Cindy performed simple distillation.

b.) Brad placed his thermometer too high in the 3-way adapter.
c.) Abby carried out a 30mL/10mL fractional distillation mixture.
d.) Doug carried out a 20mL/20mL fractional distillation mixture.