2.

A review of the history of laboratory distillation

Not only i t is interesting to study the development of a chemical operation through

the centuries from a historical point of view, but it is often found that valuable
pointers for research are obtained from parallels between old and present-day methods.
As an introduction to a special field of chemical technology, such as distillation, a
historical review gives the reader an appreciation of how the human mind has always
sought for new ways of achieving better processes and more efficient apparatus with
the facilities available at the time.
Schelenz [I], Gildemeister [2] and von Rechenberg [3] have considered much
historical material concerning the development of distillation for their discussions of
the preparation of essential oils. Underwood [a] presente a brief outline of the evo-
lution of distillation technique up to the 19th century, and in his excellent book
Forbes [5] tells the history of the art of distillation from its beginnings to the death
of Cellier-Blumenthal.The latter, a French engineer who died in Brussels in 1840, was
one of the most talented column designers of the early 19th century. Further histori-
cal details can be found scattered in the various accounts of the history of alchemy
and chemistry. Of the more recent publications, the history of science and technology
of Forbes and Dijksterhuis [6] may be mentioned. In two volumes, the evolution of
technology, astronomy, mathematics, chemistry, and, in particular detail, of physics
is presented in an easily comprehensibleway. The development of distillation methods
is described in some detail in Bittel’s [16] paper on the history of multiplicative
separating niethods. W. Schneider [7] has published a lexicon of alchemistic and
pharmaceutical symbols which helps to understand ancient writings.
In the book of Strube [15] the main strands of development are described.
Distillation is dealt with according to its significance and its history from the 3rd
mntury A. D. is illustrated by numerous pictures.
The present review has been written, not with the object of providing complete
historical details or etymological derivations, but rather of giving a clear account
of the steps by which laboratory methods and apparatus (not omitting those for
semi-technical use) have developed to their present forms.
Distillation is an art that m a practised long before the Christian era by the
ancient Egyptians and was cultivated and protected as secret science by temple
priests. It also appears to have been carried out in early times in India, Persia and
China. Schelenz [I] is of the opinion that the discovery of distillation must be ascribed
to the Persians, who employed the art for the preparation of rose water. Another
view Rhared by v. Lippmann [8-lo] is that the principle of distillation found its
origin in the carbonization of wood, since descending distillation is referred to in the
“Ebers ppy-ru~~’’ of about 1500 B.C., so that the process would be almost 3500 vears
 2. A review of t,he history of laboratory distillation 21

old. It should he noted in this connection that the word distillation was a t that time
a collective tern1 for all separating processes then known; the word may be trans-
lated as “separation drop by drop’’ and in alchemistic speech denoted the separation
of more or less subtle (or “fine’)) elements from each other. The concept of distillation
also covered operations such as filtration, crystallization, extraction and the ex-
pression of oil.
We shall here deal only with the history of distillation in the present meaning of
the term : the separation of bodies by evaporation and condensation of the vapour.
I n this connection it should be observed that by the foregoing definition descending
distillation is a true distillative operation.

Fig. 1
Alembic on furnace, surrounded by magic
signs. From a treatise on t h e making of
gold by t h e Egyptian alchemist Cleopatra
(2nd century A.D.)

The earliest uses of distillation were the preparation of rose oil and other ethereal
oils, distilled water for sailors (Aristoteles mentions how fresh water can he matie
from salt water) and a large number of alchemical mixtures and draughts. Fig. I
shows a so-called alembic (helmet) on a furnace, surrounded by the magic inscriptions
which in early ages played such a large part in the process of distillation. The illu-
stration is taken from a treatise on the preparation of gold dating from the second
century A.D., by the Egyptian woman alcheniist Cleopatra. A typical apparatus of
this period is shown in the next figure (2a). It is a glass still on a sand or water bath,
an arrangement still in use today, as demonstrated by the adjoining illustration of a
mercury still (2b). The four separate parts - the heating bath, the still (curcurbita),
the head (alembic) and the receiver (receptacula) - have remained in use as compo-
nents to this day. It is interesting to note that the collar for collecting the distillate
is also still found in a number of modern forms of equipment. The material employed
for the apparatus in antiquity was chiefly glass, a ceramic compound or copper.
From about 1300 A.D. onwards the methods of distillation may be divided into
two basic types:
per ascensum = “rising distillation”, per descenszm = “descending distillation”.
22 2. A review of the &tory of laboratory dietilation

The deanding procedure (l9g. 38) sank into oblivion after about 1800, although
it is the best method for certain types of separation. We find the pciuciple again in a
water still of thr year 1952, where it is chosen to enswe an economical use of heat
(we Fig. 3b).

Fig. 2a)
Glass dist,illation apparatus with sand or water bath (2nd century -4.D.)
Fig. 2 b)
Variiiim d i l l for merriiry with collecting collar for the distillate (20th century)

Fig. 3a)
Dry distillation of bark and herbs “per
deacensrni” (1 300 A.D.)
Fig. 3 b)
Water still of Blome according to the
“per desc,ernaacni” principle (20th
b) century)
 2. A review of the history of laboratory distillation 23

Soon after the invention of printing a series of verygraphic descriptions of distilla-

tion were published, showing the state of development at the end of the middle ages.
The most important of these were the following:
1483, Schrick: Verzeichnis der ausgeprannten Wasser (Account of the hurnt -out
watefs) ;
1500, Brunswig: Das Buch der rechten Kunst zu destillieren die eintzige Ding (Book
of the true art of distilling the sole things);
1507, Brunswig: Das Buch der wahren Kunst zu destillieren (Book of the true art of
distilling) ;
1528, Ulstad : Coelum philosophorum (The philosopher’s heaven) ;
1536, Rpff: Neu gross Destillierbuch wohl begrundeter kiinstlicher Uestillation (Kew
large distilling book of well-founded artificial distillation).
After the 16th century a large variety of methods of heating the stills is observed.
Heating is carried out by air bath, water bath, sand or ash bath and also with the a d
of wax candles. The furnaces are provided with fuel hoppers, in order to permit of
working without interruption. Very strange systems of heating are also encountered.

Fig. 4a)
Separate heating furnace for wooden
distilling apparatus, with condensing coil
(17th century)
Fig. 4 b)
Separate boiler for continuous industrial
plant (20th century) b)
24 2. -4review of the history of laboratory distillation

such aa those utilizing the heat of fermentation of bread dough or pressed-out fruit.
In hot climates heat was occasionally obtained from burning mirrors and it is of
inbrmt to find that the same method of heating is covered by a patent in the year
1943. In industrial installations it is often necessary to separate the heating from the
actual still (Fig,4b). This arrangement had already been described by Ghuber
(lSOa-l668), aa shown in Fig. 4a. For obtaining larger amounts of distillate it' was
customaq-, even in the 16th century, to operate several &ills simultaneously on a
furnace, which was often arranged in terraces (Fig. 5 ) . The first attempts at heat

Fig. 5
Distilling furnace in terraces. The
fire is in the rentre of the cone; at
the sides there are draught
channels for temperatureregulation.
The earthenware fans support the
alembics (air bath heating) (16th
century)

Fig. 6a)
Semi-terhnical or labolatory distilling apparatus with serpentine air or water
condenser (16th century)
Pig. Bb)
Coil condenser (Dimroth) with standard joints (20th century)
 2. A review of the history of laboratory distillation 25

insulation, using clay mixed with animal hair, are due to Lully (1415). I n the 16th
century the advantages of heating in stages were recognized and steam distillation
was already practised. The use of steam as heat carrier first became general, how-
ever, around the year 1800.
For condensing the vapour, air-cooling was the only method available up to
about 1300. Long vapour tubes were necessary t o obtain the required effect. Later
these were led through a barrel or trough filled with water. Finally it was found that
the best form of condenser was a coil (Fig. 6a), a type stillvery common today (Fig. 6b).

Fig. 7a)
Distilling apparatus ot thcb
Pharmacopoeia Medico-
Chylmica. Large Turk’s-he,itl
still and still with helm.
using air cooling, on f u i -
naces. Zig-zag ascending
tube. Receiver with a d j n s t -
able support (1709)
Fig. 7 b)
Distilling apparatus with coil
(Jantzen; 20th centurj )

In the 16th century continuous condensation by water followed. The concentrating

effect of a long vapour riser and of partial condensation (Fig. 7a) were also recognized
(1648). The modern coiinterpart is illustrated in Fig. 7h. The countercurrent principle
in condensation was introduced by Pissonnier in 1770, the same principle fonnrl
today in the well-known Liebig condensers (Fig. 8b), which dat,e back to Dariot
(1533-1594; see Fig. 8a).
The development of distillation technique from the 16th to the 19th centiirj-
kept pace with the general improvement in equipment construction. By the middle
of the 16th century it was known that metal stills are subject to corrosion, whereupon
glass and ceramics came to be the preferred materials. Kunkel (1638-1703) was the
first to use glass as a general laboratory material, as is done t o this day. Fig. 9 showb
the large variety of still heads emploj-eda t that time. Micro-forms were a1read;v in use.
The appearance of an alchemical laboratory of about 1700 is illustrated by Fig. 10,
representing the apothecary’s laboratory of the Capuchin monastery in Paris. The
large nuinher of distilling devices proves that they were among the most frequentlj-
used laboratory apparatus. Up to the 18th century laboratory stills were almost
26 2. A review of the history of laboratory distillation

). b)
Fig. 8a)
Dsriot’s condenser with continuous c o u n t e r c m n t cooling (16th century)
Pig. 8b)
Liebig condenser using countercurrent principle (19th century)

Fig. 9
Still heads after Andreas Libao, about 1600
Alembic with long beak m) Tin head with beak-shaped
Alembic with short beak end
Blind alembics n) Head with extension tube
Alembic of tin 0 ) Alembic with cooler
Sublimation heads p) Dwarftypes
Blind alembics with tube q) Blind beaked alembic
Bell-shaped alembic r) Triple blind alembic
Tiara a) Triple beaked a,lembic
Fig. 10
Apothecary’s laboratory of the Capuchin monastery in Paris (about 1700)

Fig. 11
Boyle’s apparatus for vaciiiim distillation (1627- 1691)

a) C)

Fig. 12
Semi-technical distillation equipment in the 19th century
a) Germany, b) China, c) Bulgaria
n

Fig. 13
Continuous distillation appa-
ratus of Cellier-Blnmenthal
(1813)

Fig. 1Pa)
Bubble-cap colamn of Chtiui-
ponnois (1854)
Fig. 14b)
Glass plate column of Briiun
with 20 actiial t,rays and
vacuum jacket (1931)
 2. A review of the history of laboratory distillation 39

exact copies of those utilized in early antiquity, but towards the middle of the 18th
century chemists like Baum6 and Woulff began to create new forms. Systematic
experiments on distillation were first performed by the physicist Boyle in England
(1627-1691)) who even carried out experiments in vacuum and under pressure
(Fig. 11).By the middle of the 18th century a few standard types of equipment had
evolved, which were used in all countries (Fig. 12). The diameter was about 45 t o
75 cni and the height 90 to 120 cm. I n the 19th century there were considerable
developments,particularly as a result of the activity of French constructors concerned
with the alcohol industry. After several stages of development (Adam, Berard, Perrier)
a continuous still was patented in 1813 by Cellier-Blumenthal; in its basic features
it corresponded to modern apparatus (Fig. 13). Stills for vacuum distillation were
built in 1828 by Tritton, and the sieve-plate column of Coffey (1830) constituted

el fl 4 hl i)

Fig. 15
Stages of evolution of the bubble-cap column
a) Distillation flask with vapour side-tube g) Spray-plate column of Le Bel-Henniger
b ) Claisen flask (1875)
c) Still heads without and with bulbs h) Rectifier of Young and Thomas (1889)
d) Ball head according t o Wurtz (1854) i) Baum’s plate column (1910)
e) Sieve-plate head of Linnemann (1871) k) Bubble-cap column of Bruun (1951)
f ) Sieve-plate head of Glinsky (1875)
30 2. A review of the history of laboratory distillation

anot,her advance. The principle of bubble-cap plates was introduced in 1864 by

Champonnois for industrial installations (Fig.14a). This process is basically that used
in large-scale tinits up to the present day, together with packed columns. The lat'ter
were introduced by Ilges, who first utilized spheres as packing material in 1873.
Reviewing what has heensaid above, we realize that the hasic principles of distilla-
tion were already known in antiquity and in the middle ages, in spite of the simple
equipment then availahle. Vntil the middle of the 19th century, laboratory and semi-

Fig. 16e)
Von Rechenberg's V U C U I I ~distillation apparatus (1920) with Hempel column and Bertrend
receiver
Fig. 16h)
Elsner's rectifier for normal pressurg and vacuum (1920)

technical apparatus differ in their dimensions only. It was not until the tempestuous
development of organic chemistry around t,he middle of the 19th cent,ury that distilla-
t ion equipment evolved entirely designed for experiments in the laboratory. Noted
chemists, between this time and 1900, such as Claisen, Dimroth, Glinsky, Hempel,
1,t. BPI, IAehig, Mitscherlich, Mohr and Wurt,z, evolved apparatus for laboratory
(lintillation practice. Retorts were wed as stills and as receivers; the distillation flask
with air-cooled side tube developed, by way of the Claisen flask and the Wurtz ball
head, into t,he spray-plate column. The still heads of Linnemann, Glinsky and Le Bel-
Henniger are precursors of the hubble-cap column [ l l ] (Figs. 14b and 15). The
cdunin packed with glass beads was introduced into t.he laborat,orv in 1881 hy
Herlipel.
 2. A review of the history of laboratory distillation 31

Toward3 the end of the 19th century came the need to compare the many still heads
thus available as regards efficiency. Kreis, Young and Friedrichs [12] carried out
measurements in this field, and also studied condensers. Besides the Liebig condenser,
that of Diniroth (Fig. 6b) became of importance; a specially effective condenser for
low-boiling substances, designed by Mitscherlich, led to the construction of similar
types.
During the period between 1900 and 1920 numerous pieces of apparatus at
present still in use were developed: for instance the Jantxen column (Fig. 7 b), and
the Raschig and Prym rings for column packing (1916 and 1919, respectively). Heating
systems wer? improved, whilst pressure controllers for work in vacuum were evolved.
Fig. 16a shows an apparatus used for vacuum distillation by the well-known specialist
von Rechenberg [3] between 1900 and 1920, which, like Elsner’s rectifier (Fig. 16b),
illustrates the stage of development a t the end of this period.
It was not, however, until Jantzen [13] and his pupils had systeniatically in-
vestigated the physical fundamentals of the distillation process that the numerous
clevelopinents after 1920 could take place. This later phase is still too recent to allow
11s to consider it historically. Ever and again we find, however, that multiple threads
lead us hack from our present complicated apparatus and methods to long-vanished
times when t,he fundament a1 principles of our modern knowledge were first recognized
and elaborated [ 141.