Aust. J. Ed. Chem.

, 2009, 70,

Distillation: integration of a historical perspective

Marco Lagi1 and Rebecca S. Chase2
1
Dept. Nuclear Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts, USA
02139 E-mail: [email protected]
2
Lesley University, Cambridge, Massachusetts, USA 02138

Abstract
We present here a possible introductory lecture of the distillation technique, different from what is commonly seen in
classrooms. A rigorous thermodynamical approach to distillation could be put side by side with a historical one, where
the student can see the unfolding of the primal worldview into the modern perspective. We believe that this method,
where the old is redeemed to complement the new, can provide a deeper understanding of, and more interest in, this
fundamental separation process.

Introduction: of distillation [2,3], and about the distillation theory

Distillation is the first separation technique ever developed as well [4,5]. But in this paper, we shall try to sketch a
and still one of the most popular in a wide variety of short introductory lesson that both provides the basis
contexts, from state-of-the-art organic chemistry labs to of distillation and follows its evolution. We believe,
processing plants, from farms to abbeys. It was estimated as previously noted [6], that such an approach is more
in 1994 that 4·104 distillation columns were scattered interesting to students and that it can provide them with
throughout the USA, consuming about 7% of the entire a deeper understanding of 1) how the first chemists
energy demand of the country [1]. Although distillation looked at matter, and 2) the distillation technique itself.
has a low thermodynamic efficiency (around 10%), it is The lesson has four sections: A) Principle, B) Theory, C)
widely used because of the simplicity of its principle: Practice and D) Application of distillation.
when a liquid mixture is heated, its vapor has usually
a different composition from the liquid the remains. A The Principle of Distillation
Mankind has long made use of this knowledge - moralists Vapor pressure (also known as vapor tension), is the
would say often for its own damage. pressure of a vapor in equilibrium with its liquid. All
liquids have a tendency to evaporate (volatility), and all
Every undergraduate student in chemistry or chemical gases have a tendency to condense back into their liquid
engineering knows the definition of distillation: a method form. For a liquid i at any given temperature T, there
of separation based on relative vapor pressures. They learn is a pressure Pi at which the gas of that substance is in
the distillation theory through the Clausius-Clapeyron dynamic equilibrium with its liquid.
equation, the Raoult’s law and the Trouton’s rule. They
are taught how to determine the number of plates required
to separate a 1:1 mixture of n-hexane and n-heptane, and
how to set up a vacuum distillation apparatus.

But only a very few of them are also given a historical

perspective of this method. The lack of this perspective
is characteristic of the majority of chemistry classes,
in contrast to other scientific subjects where more
time is devoted to the evolution of the discussed topic.
The reason can probably be found in the roots of this
ancient technique, developed and brought to perfection
over hundreds of years by the ancestors of the chemists,
alchemists. The modern conception of this proto-science
is often negative, and chemistry teachers prefer not to
include references to it in their courses. But alchemy
is actually the first approach to the study of matter
undertaken by man, the primal genuine attempt to look
at the chemical and physical transformations occurring
in Nature. Students are usually interested in the naïve
alchemic approach since, like the early alchemists, they
are dazed by the novelty of the physical and chemical Figure 1. Conceptual evolution of the distillation technique.
transformations of substances. a) Aristotelian (simple boiler),
b) Alexandrian (boiler + alembic),
c) Medieval (boiler + alembic + condenser),
It is easy to find exhaustive monographs about the history d) Modern (boiler + alembic + condenser + column).

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 Aust. J. Ed. Chem., 2009, 70,

This equilibrium can be represented as [7] The effect was the trickling down (destillatio in Latin)
of the purified liquid in the alembic. Distillation was
Molecules liquid ! Molecules vapor officially born.

As T increases, the equilibrium is shifted to the right When the gas in equilibrium with the liquid mixture reaches
and the vapor pressure Pi increases exponentially. The the vapor pressure, further evaporation is precluded. This
dependence of Pi from T is given by the Clausius- limitation was overcome by the introduction of a water
Clapeyron equation, jacket surrounding the side tube. This device condenses
the B-rich gas phase, subtracting it from equilibrium and
increasing the efficiency of the process (Fig. 1c). The
(1) condenser, introduced by medieval alchemists around the
13th century, was necessary to obtain reasonable yields
where Pi0 is a known pressure at a known temperature T0, of products containing high alcohol contents. This is a
6H is the heat of vaporization of the liquid and R is the great advantage of distillation over the other separation
gas constant. methods: the only required energy is in the form of heat,
which can be be easily removed with the condenser. The
The boiling point Ti is defined as the temperature when
separation process can be controlled solely by the heat
Pi= Pext . Usually, Pi0 and T0 are taken from the normal
supply.
boiling point, so that Pi0 = 1 atm and T0 = Ti. Pi is therefore
an indication of a liquid’s evaporation rate: a substance lthough chemical engineers have made distillation more
with a high vapor pressure at room temperature is often efficient during the last century, the essence of the still
referred to as volatile. apparatus has survived mostly unchanged.
The goal of a distillation is to separate a volatile liquid In this section we learned that, in principle, a liquid
from a non-volatile substance or, more frequently, the mixture can be separated into its components. What to do
separation of two or more liquids with different vapor to accomplish this is the subject of the next section.
tensions [8]. For the sake of simplicity, throughout the
paper we will refer to the distillation as the separation by B The Theory of Distillation
means of heat of a mixture of two liquids A and B, where Alchemists had a very clear idea of what distillation was:
B is more volatile than A (i.e. PB > PA). “distilling is nothing other than purifying the gross from
the subtle” [10]. The purification would make incorruptible
Two requirements for distillation can be derived from the
the corruptible [11]. As with all alchemic processes, a
previous definition: 1) the process needs a heat source
correspondence to the inner self can be drawn; today we
to force the liquid mixture into the gas phase, 2) the gas
still use the verb to distill to mean “to extract the essential
phase (enriched in B) has to be condensed back to the
meaning of something”. Distillation was subdivided into
liquid phase in order to obtain a separation of the two
ascension (evaporation) and descension (condensation).
components.
These processes were powerfully symbolized by a bird
The first requirement (evaporation) was already known by flying upwards or downwards (Fig 2, left panel), or by
ancient Greeks. Aristotle mentions in his Meteorologica two dragons, one winged, seizing each other’s tails (Fig.
that pure water may be obtained from seawater through 2, right panel).
evaporation. However, he does not write of any practical
Therefore, distillation was an art at its very beginning,
method to condense the vapor and take advantage of
with deep correspondence to man’s unconscious: fire
this phenomenon. Nowadays we call this process open
somehow could remove unnecessary and leave essence.
evaporation of the mixture [9] (Fig. 1a).
But around two centuries ago, a radical shift took place
in how man looked at matter. The works of Boyle and
Lavoisier were shaping the birth of a new science,
chemistry. In the following years, a parallel revolution
occurred in the development of distillation, when
quantitative rationalizations of the process in mathematical
models improved dramatically the efficiency of this
separation technique [12,13]. Boyle himself is considered
to be the first to have performed the first analytical
distillation [14]
Figure 2. Symbolic representation of the phase transitions
involved in the alchemical distillation. Left: Avicenna and the We can trace the origins of the theory of distillation back
Eagle, in M. Maier “Symbola aurea mensae”, 1617 (Franckfurt). to the question François-Marie Raoult was trying to
Right: Two dragons, from A. Eleazar “Uraltes chymisches Werck” answer at the end of the 19th century [15]: what happens
1735 (Erfurt).
to the vapor pressures of A and B when they are mixed?
The second requirement (condensation) was fulfilled
Figure 3. Graphic representation of Raoult’s Law. The total
around the 1st century A.D. by the Alexandrian chemists, pressure in the case of pure components is equal to the partial
who added to the boiler (main vessel) an alembic pressure of the component i, Pi0. Yi is the molar fraction in the
(secondary vessel) connected by a side tube (see Fig. 1b). gas phase.

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 Aust. J. Ed. Chem., 2009, 70,

only after this step could the performances of the

experimental apparatus have been dramatically improved.
Indeed, looking at Fig. 5 it is clear that there is no hope
to separate A and B with a distillation if they have the
same volatility (_ = 1), because the gas phase has the
same composition as the liquid phase (azeotrope). But if
_ is larger than 1, and we condense the B-rich gas phase,
we obtain a new mixture of A and B but with a higher
concentration of B. Therefore, the larger _ is the easier
the separation.
What if we want to distill a mixture with _ ~ 1? Sometimes
revolutions are born from relatively small issues. In 1807,
when England organized a blockade against Europe,
Raoult realized that for an ideal solution at a given Napoleon was forced to open a competition to produce
temperature, white sugar from beets, since his noblemen were not
(2) particularly fond of brown sugar! Extracting sugar
with alcohol instead of water looked promising, but the
where PM is the vapor pressure of the mixture and xi the solvent had to be purified afterwards [4]. The Frenchman
molar fraction of the component i (xA + xB = 1). Again, the Cellier-Blumenthal had an idea: continuously repeat the
mixture boils at the temperature TM when PM = Pext . procedure after the first evaporation-condensation cycle to
Raoult’s law implies that the total pressure decreases further increase xB in the mixture. The alchemist Libavius,
linearly from PB to PA as the concentration of B in A who had lived 200 years before Cellier-Blumenthal, had
decreases (Fig. 2). This is intuitive: the more of B in the known that the alcohol content could be increased with a
mixture, the more the mixture will behave like pure B. second distillation step [16], but he didn’t extrapolate the
One of the non trivial consequences of this law is that concept to n distillation steps. Thanks to this improvement,
even if PA = 0, the total pressure is smaller than the vapor nowadays large-scale industrial distillations can be
pressure of pure B (PM < PB), as one can see comparing undertaken even if _ ~ 1.05 [9]. In conclusion, the effect
Fig. 4a with Fig. 4c. If we define the relative volatility _ of the noblemen’s pickiness was the development of the
of the solution as first distillation column (Fig 1d).

(3) When the distillation is such a multi-stage process, it is

called fractional distillation or rectification (from the
and the molar fraction of B in the vapor phase YB as Latin expression “recte facere” = improve). Each of these
repetitions in a rectification process is called a theoretical
(4) plate (equilibrium stage between gas and liquid), and a
then, combining Eq. 2, 3 and 4 we have path composed of several plates is shown in Fig. 6 as an
example.
(5) The larger _ is, the smaller the number of plates n
necessary to achieve the desired concentration of B.
Now we can plot YB vs xB for different values of _ (Fig. 5
upper panel). As one can see, when we heat a liquid mixture
1) the gas phase is enriched in the most volatile component,
2) the enrichment increases with _. These conclusions
may seem obvious at first sight, but they actually imply
that Raoult’s law was the first theoretical justification of
distillation since its birth, 2000 years before.

Figure 4. Vapor-liquid equilibria in 3 different cases: molecules

of A are represented in gray, B in red. a) Pure A, the liquid phase
evaporates until PA is reached. b) Mixture A + B, if PB > PA the
concentration of B is bigger in the gas phase than in the liquid
phase. c) Even if PB = 0, P < PA according to the Raoult’s law.

We notice here that even though distillation had been

practiced for centuries before its theoretical formulation,

7
 Aust. J. Ed. Chem., 2009, 70,
Figure 5. temperature-mole fraction diagram in Fig. 6, Eq. 9 is the
Upper panel: Molar fraction of component B in the gas phase
upper line.
DV D IXQFWLRQ RI LWV PRODU IUDFWLRQ LQ VROXWLRQ 7KH ¿YH FXUYHV
are plotted for different _ values (_ = 1, 3, 5, 10, 30), and YB is
normalized for the total pressure in equilibrium with the mixture,
PM =1. Lower panel: Concentration of a liquid mixture with _ = 3
from xB = 0.2 to xB = 0.86. The separation requires 3 plates: each (9)
plate is composed of an evaporation step (solid vertical arrows)
and a condensation step (horizontal dashed arrows).

After a little algebra, one can demonstrate that the two

quantities at PM = Patm = 1 are in fact inversely related
according to
(6)

where xBi and xBf are the initial and final concentrations
of B, respectively. If n , it should be rounded to the next
higher integer.
In this section we learned what to do to separate an ideal
bicomponent liquid mixture. How to do it is the subject
of the next section.

C The Practice of Distillation

As we saw schematically in Section A, the still apparatus
Figure 6. Temperature-molar fraction diagram. The cycle 1-2-
for a simple distillation is composed of a heat source, a 3-4 represents one distillation (theoretical plate). The horizontal
boiler, a condenser and a receiving flask (the alchemic dashed arrows are sometimes called liquid-vapor tie-lines.
alembic). The thermodynamic conditions are chosen so
that the constituent to be separated (B in our case) enters One distillation cycle is represented by the path 1-2-3-4 in
the second phase in the receiving flask. The rule of thumb Fig. 6. Starting from a mixture of B = 20% and A = 80%
is to use this method when the boiling temperatures of at room temperature (1), if we heat the mixture it will
A and B differ by at least 60 K (TA > TB + 60 K). An reach its boiling point TM (2) with the same composition.
important addition to the alchemic setup is therefore a Its vapor has composition (3), and when we lower the
thermometer, to check the temperature of the boiling temperature it condenses reaching (4). As expected, the
mixture: T will stay constant while the mixture is boiling new liquid in (4) is richer in the lower-boiling component
at TM and B evaporates, then it will raise towards TA. At B. This is the result of a simple distillation, n = 1.
this point, the distillation plate can be considered over.
As we learned in Section B though, the required n
One could ask a similar question to the one seen in Section is usually bigger than 1. So at least one more thing is
B: what happens to the boiling points of A and B when necessary for a high-efficiency distillation: an appropriate
they are mixed? To answer this, we can consider that the column, that includes as many theoretical plates as are
mole fraction of liquid A is given by rearranging Raoult’s necessary for the separation. To be more specific, the
law (Eq. 2), column must realize n − 1 plates, since the last plate is the
head of the apparatus. The whole setup is shown in Fig.
(7) 7. As the vapor travels up the column, it cools, condenses
into liquid, and then it vaporizes again after it comes into
Substituting the Clausius-Clapeyron equation (Eq. 1) in
contact with hotter vapor rising from below. We want to
Eq. 7 for both A and B at their normal boiling point, we
stress here that there are two reasons why they are called
get
theoretical plates: 1) in practice one needs more plates
than the calculated n, since the efficiency of each plate
is less than 1 [17]; 2) distillations can be carried out on
bubble-plate columns, composed of several horizontal
(8)
glass plates. A discrete distillation occurs at each plate,
but the concept can be extended to columns without
This equation is valid in general for every temperature, physical plates. A plate is in fact realized by any physical
and in particular for the boiling point of the mixture. We device that provides good contact between the vapor and
can get a similar equation for the mole fraction of vapor the liquid phases: the simplest column that one can think
B, YB, substituting Eq. 8 in Eq. 4, of is therefore just a glass tube. Each plate will occur at
the interface between vapor and the liquid droplets that
When the mixture boils, PM = 1 atm and the only variables
condense on the column. This is the open tube column,
in Eq. 8 and 9 are the boiling temperature and the fraction
and it is displayed in Fig. 8a.
of B. Therefore while Eq. 8 is the bottom line of the

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 Aust. J. Ed. Chem., 2009, 70,
Furthermore, all the various distillation methods
discussed can be performed in continuous (ongoing
separation in which a mixture is continuously fed into the
process without interruption) or batch mode (where the
mixture is added at the beginning, distillate fractions are
taken out sequentially and the remaining bottom fraction
is removed at the end).
In this section we learned that there are 4 main classes of
distillations (simple, fractional, vacuum and steam) that
can be performed in two modes (continuous and batch).
Distillation comes in many forms. Why to do it is the
subject of the next section.

Figure 7. Schematic illustration of a modern organic chemistry

lab setup for a fractional distillation.

Henri Vigreux, a French chef and glassblower, realized

around 1920 that the separation can be enhanced by
increasing the surface area of the glass of the column [18].
A Vigreux column has, therefore, a series of downward
pointing indentations (Fig. 8b): in this way, the number of
plates can be increased roughly up to a factor 5. The next
step to increase the surface area was taken by Clement by
adding a filler (glass balls) to the column of an alcohol
still: a packed column is therefore packed with small inert
objects (Fig. 8c). Now n can be up to 20 times larger than Figure 8. Representation of 3 different columns for distillation
an open tube column of the same length. When a column LQ RUGHU RI HI¿FLHQF\ D 2SHQ WXEH VXUURXQGHG E\ D YDFXXP
is added to the apparatus, simple distillation becomes chamber b) Vigreux column, c) Packed column.
fractional distillation. If the fractionating column is
ideally efficient, the vapor that reaches the distilling head D The Application of Distillation
at the top of the column will be composed entirely of B: As we will see in this section, distillation has a fundamental
Vigreux columns can be used if TA > TB + 25 K, packed role in our society. Without it, we could not move cars or
columns even if TA > TB + 1 K. planes, separate nitrogen from oxygen on a large scale
or even enjoy a cognac. This is a short list of the most
The heating bath allows for the uniform distribution of important uses of distillation: many more applications
heat to the liquid: usually oil or water is used, implying of this technique could be named, in a wide variety of
that the boiling point of the mixture must be TM < 420 K. fields.
If this condition is not satisfied, A or B may decompose
before reaching the boiling point, so TM must somehow The first uses of distillation were alchemic: mercury, nitric
be decreased. Lavoisier had shown the spontaneous acid, sal-ammoniac, acetic acid and sulphur, together with
evaporation of ether in vacuum and Philippe Lebon worked many other substances (including urine!), were purified
on this idea in 1796 to conceive vacuum distillation [19]. through distillation. Today, the “purification” concept
Applying a partial vacuum to the apparatus decreases the is still applied to solvents, after they have been used in
temperature at which TM = Pext, and therefore the boiling laboratory or industrial extractions.
point of the mixture. In other words, in these conditions Dioscorides [3] writes around the 1st century that sailors
molecules require less energy to leave the surface of the used to evaporate seawater and condense it into sponges
liquid. to get fresh water. Strangely enough, evaporation is still,
In 1800, the great scientist and inventor Sir Benjamin at present, the most valid alternative to get desalination
Thomson, Count Rumford used open steam as a heating of seawater [22].
agent [20], creating steam distillation. This process is still It was probably around the 11th century that it was
very useful if one wants to separate essences or flavor oils first used in Italy to increase the alcohol percentage of
from plant material (leaves or seeds). In this case, B can aqueous mixtures, derived from the fermentation of plant
be distilled from the mixture at a temperature well below extracts rich in carbohydrates. Fermentation usually stops
TB since it is not soluble in A (water), and can exert its own when the yeast dies in its own 15% ethanol solution,
full vapor pressure TB (Raoult’s law cannot apply). B does so the concentration had to be increased by distillation.
not have to be a liquid at room temperature: caffeine (a The results were the spirits, or waters of life. Depending
solid) can be steam distilled from green tea, for example on where and from what they were produced, they had
[21]. different names: brandy from fruit, grappa from pomace,
vodka from grain or potatoes, rum from molasses,

9
 Aust. J. Ed. Chem., 2009, 70,
whiskey from grain mash, shochu from rice, tequila Conclusions
from the cactus blue agave and so forth [23]. This field In this paper, we presented a possible introductory
of application (which was initially practiced by monks, lecture on distillation that includes on the one hand its
and later became the first industrial application of the thermodynamical basis, and on the other continuous
distillation) has greatly influenced the development of the links to the conceptual evolution of this method over the
still apparatus. As a side note, due to the formation of centuries. We would like to stress that a similar approach
an azeotrope, ethanol-water mixture cannot be distilled to can be used for many other topics: from the symbols of
get pure ethanol (the azeotrope is at xethanol = 0.95, xwater = chemical elements to the familiarization of glassware
0.05), but this obstacle can be removed by adding small in a chemical laboratory, from the concept of acid to
amounts of benzene. the transmutation of elements in high-energy colliders.
According to our experience, such an integration seems
Pure nitrogen, oxygen and argon are obtained by to be an important step if one wants to give the students a
rectification of air. To separate air by rectification, part of complete understanding of the concepts and the techniques
it must be liquefied and this can only be achieved below they will use for the rest of their professional lives.
its critical point (Tc = 132.5K , Pc = 37.7 bar) [24]. N2
is then used for ammonia synthesis, as an inert gas and References
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Apparate” 1893 (Berlin)
Figure 9. Schematic representation of a fractional distillation of 13 E. Sorel “La Rectification de l’alcool” 1894 (Paris)
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of the column. From top to bottom, the average boiling point of 15 F.-M. Raoult Comptes Rendus 1887, 104, 1430-3
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GHQVLW\ )UDFWLRQV DUH XVXDOO\ LGHQWL¿HG ZLWK WKH QXPEHU RI 17 R.H. Perry and D.W. Green “Perry’s Chemical Engineers’
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scientifiques et industriels” Dunod, 1920 (Paris)
Nowadays, the most common (and one of the most 19 P. Lebon “Distillation au moyen du vide et du froid“ (French
recently developed) application of distillation is by far the patent of Sep. 11, 1796)
separation of petroleum into its components [26]. Crude 20 B. T. Rumford “Essays, Political, Economical and Philosophical”
1802, 3 (London)
oils are complex mixtures of hydrocarbons with a wide 21 J. W. Zubrick “Organic Chem Lab Survival Manual” 1992 John
variety of properties, hence they have to be separated for Wiley & Sons (New York)
industrial or commercial applications. Different fractions 22 H. Weingärtner1, E. U. Franck, et al. “Water” in Ullmann’s
are collected at different heights of the distillation Encyclopedia of Industrial Chemistry, 2009, John Wiley & Sons
23 D. C. Watson “Spirits” in Ullmann’s Encyclopedia of Industrial
tower (see Fig. 9): gas fuels on top (collectively known Chemistry, 2009, John Wiley & Sons
as liquefied petroleum gas, LPG), then naphtha, motor 24 R. F. Barron, “Cryogenic Technology” in Ullmann’s Encyclopedia
gasolines, kerosene, diesel oils, lubricating oils, fuel oils of Industrial Chemistry, 2009, John Wiley & Sons
and residues at the bottom (asphaltenes). 25 M. J. Kirschner “Oxygen” in Ullmann’s Encyclopedia of Industrial
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Finally, the concept of distillation can also be applied to 26 W. W. Irion, and O. S. Neuwirth, “Oil Refining” in Ullmann’s
dry materials: wood can be “distilled”, for example. In this Encyclopedia of Industrial Chemistry, 2009, John Wiley & Sons
destructive process that now involves chemical reactions,
wood decomposes to leave charcoal as a residue and
methanol and terpenes as distillate. Methanol is in fact
also known as wood alcohol.

10