Distillation is the oldest method used for separating mixtures of liquids.

Distillation exploits the fact

that different liquids have different boiling points. When a mixture of liquids is heated, the liquid
with the lower (or lowest) boiling point vaporizes first. That vapor is routed through a condenser,
which cools the vapor and causes it to condense as a liquid; the liquid is then collected in a receiving
vessel. As the original liquid mixture continues being heated, eventually, some or all of the lower-
boiling liquid is driven off, leaving only the higher-boiling liquid or liquids in the distillation vessel.

I say “some or all” because distillation is an imperfect method for separating mixtures of liquids that
form azeotropes. An azeotrope, also called a constant boiling mixture, is a mixture of two or more
liquids at a specific ratio, whose composition cannot be altered by simple distillation. Every
azeotrope has a characteristic boiling point, which may be lower (a positive azeotrope or minimum-
boiling mixture) or higher (a negative azeotrope or maximum-boiling mixture) than the boiling points
of the individual liquids that make up the azeotrope.

For example, ethanol forms a positive azeotrope with water. The boiling point of a mixture of 95.6%
ethanol (by weight) with 4.4% water is 78.1 °C, which is lower than the boiling point of pure water
(100 °C) or pure ethanol (78.4 °C). Because the azeotropic mixture boils at a lower temperature, it’s
impossible to use simple distillation to produce ethanol at concentrations higher than 95.6%. (More
concentrated ethanol solutions can be produced by using drying agents such as anhydrous calcium
chloride that physically absorb the water from a 95.6% solution of ethanol. These solutions must be
stored and handled carefully, because otherwise they absorb water vapor from the air until they
reach the 95.6% azeotropic concentration.)

Ethanol also forms azeotropes with many other liquids, including some that are poisonous or taste
bad. This allows production of denatured ethanol, which is toxic, cannot be drunk and so can be sold
cheaply without cannibalizing sales of (and taxes on) much more expensive potable ethanol, such as
vodka and other distilled beverages.
High Boiling Point Azeotropes

Hydrochloric acid is one familiar example of a negative (high-boiling) azeotrope. Pure hydrogen
chloride has a boiling point of -84 °C and pure water a boiling point of 100 °C. A solution of 20.2%
hydrogen chloride (by weight) in water has a boiling point of 110 °C, higher than the boiling point of
either component. This means that boiling a solution of hydrochloric acid of any concentration
eventually produces a solution of exactly 20.2% hydrogen chloride by weight. If the starting solution
is more dilute, water is driven off until the solution reaches 20.2% concentration. If the starting
solution is more concentrated, hydrogen chloride gas is driven off until the solution reaches 20.2%
concentration.

In this laboratory, we’ll use distillation to increase the concentration of an ethanol solution. At 25 °C,
pure water has a density of 0.99704 g/mL and pure ethanol a density of 0.78522 g/mL. Solutions of
ethanol and water have densities between these figures. If you add the densities of the pure liquids
and divide by two, you get 0.89113 g/mL, which you might assume is the density of a 50/50 ethanol-
water mixture. As it turns out, that’s not true. Ethanol and water do not mix volumetrically; that is, if
you mix 100 mL of pure ethanol with 100 mL of pure water, you do not get 200 mL of solution, for
the same reason that dissolving 100 mL of sucrose in 100 mL of water does not yield 200 mL of
solution.

Nonetheless, it’s possible to determine the concentration of ethanol by measuring the density of the
solution and comparing that value to ethanol-water density tables available in the CRC handbook
and similar publications. We’ll measure the density of the starting solution and the resulting
distillate and compare those values to published values to determine the ethanol concentrations of
the two solutions.

All of the specialty lab equipment and chemicals needed for this and other

lab sessions are available individually from Maker Shed or other laboratory

supplies vendors. Maker Shed also offers customized laboratory kits at special

prices, including the Basic Laboratory Equipment Kit, the Laboratory Hardware Kit, the Volumetric
Glassware Kit, the Core Chemicals Kit, and the

Supplemental Chemicals Kit.

Ethanol solutions of 45% or greater concentration are flammable. Ethanol vapor is extremely
flammable. Handle the hot liquids used in this experiment with extreme care and have a fire
extinguisher handy. The distillate produced in this experiment is not safe to drink. Ethanol is
denatured with compounds that form azeotropes with ethanol, specifically to ensure that denatured
ethanol cannot be undenatured by distillation. Wear splash goggles, gloves, and protective clothing.

Substitutions and Modifications

If you do not have a balance, you can still do this experiment to observe the distillation process, but
you will not be able to determine the ethanol concentration of the distillate.

If you do not have a thermometer, plug the second hole in the stopper with a small piece of duct
tape or simply by dropping a disposable pipette into the hole. (Not much pressure is generated
because the ethanol vapor can escape from the flask through the glass and flexible tubing.)

If you do not have glycerol (sold in drugstores under that name, or as glycerin), you can use
vegetable oil or mineral oil to lubricate the stopper before you insert the thermometer and glass
tubing. If you use oil, wash the stopper thoroughly with soap or detergent as soon as possible after
you complete the experiment. Allowing any type of oil to remain in contact with the stopper for too
long can damage it.

Ethanol is sold in drugstores, sometimes by name, and sometimes as ethyl alcohol, ethyl rubbing
alcohol, or simply rubbing alcohol. (If the bottle is labeled as rubbing alcohol, make sure it’s ethanol
rather than isopropanol.) Most drugstore ethanol is 70% by volume (about 64.7% by weight), but
90% and 95% concentrations are also common. If you start with more concentrated ethanol, dilute it
with water to 70% before you begin the distillation.

A distillation is one of the most commonly used techniques to purify liquids (in some cases also
solids if their boiling points are not too high i.e., phenol, antimony(III) chloride). For instance, it is
used to refine alcohol from the fermentation process or to purify water (=distilled water) or separate
different hydrocarbons in raw oil (i.e., kerosine, gasolines, naphtha, etc.). In general, there are two
important processes involved in this technique.

1. Vaporization = phase transfer from liquid to vapor (gas)

2. Condensation = phase transfer from vapor to liquid

The vaporization process requires heat, which makes it endothermic (ΔH>0), while the condensation
process releases heat (=exothermic, ΔH<0). The entropy increases in the vaporization process
because the volume occupied from the vapor is much larger (~1000 times) compared to the liquid
(i.e., one mole of water is 18 mL of liquid but about 30600 mL at 100 °C as steam). The opposite
applies to the condensation process.

I. Simple Distillation (in micro-scale and macro-scale)

This type of distillation is carried out at a pressure of one atmosphere (1 atm). The mixture usually
only contains one volatile component i.e., salt solution, or two compounds that have boiling points
that are sufficiently far away from each other i.e., diethyl ether (b.p.=34.6 oC) and toluene (b.p.=111
oC). Since many organic compounds oxidize relatively easily in air, the boiling point should be below
150 oC to avoid thermal decomposition (i.e., oxidation) of the compound during the distillation.