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An Experimental Comparison of the East Asian,

Hellenistic, and Indian (Gandhran) Stills in
Relation to the Distillation of Ethanol and Acetic
Acid

Anthony R. Butler & Joseph Needham

To cite this article: Anthony R. Butler & Joseph Needham (1980) An Experimental Comparison of
the East Asian, Hellenistic, and Indian (Gandhran) Stills in Relation to the Distillation of Ethanol
and Acetic Acid, Ambix, 27:2, 69-76, DOI: 10.1179/amb.1980.27.2.69

To link to this article: http://dx.doi.org/10.1179/amb.1980.27.2.69

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AMBIX, Vol. 27, Part 2, July 1980

AN EXPERIMENTAL COMPARISON OF THE EAST ASIAN,

HELLENISTIC, AND INDIAN (GANDHARAN) STILLS IN RELATION
TO THE DISTILLATION OF ETHANOL AND ACETIC ACID

By ANTHONYR. BUTLER*and JOSEPHNEEDHAMt

TECHNIQUES
for the distillation of wine to give strong spirituous liquor were developed in
several civilisations. Although the aim was the same, the construction of the still differed.
The evolution of Western stills has been treated by Berthelot1 and Taylor2, and Needham3
has described the development of stills in Asia. What has not, to our knowledge, been
considered previously is the efficiencyof each type of still. This has relevance to a previous
discussion concerning who first discovered strong distilled alcohol and where.4
We can distinguish four basic forms of the simple still. They are described and illus-
strated in more detail in Needham, 33 and are as follows:

(I) The "Mongolian" still, where the distillate falls from the concave roof of the still
into a central catchbowl;
(2) The IIChinese" still, which is similar to the Mongolian still except that a side-tube
leads from the catchbowl to the outside, so that the distillate can be continuously
removed;
(3) The llHellenistic" still, where condensation occurs on the walls of the still,
collects in a circular trough, and is removed continuously by a side tube;
(4) The llGandharan" or "Indian" still, which is really a retort; condensation occurs
in a cooled receiver.

We constructed glass working models of these stills (Figures 1,2, and 3). The external
dimensions of the stills in Figures Ib and 2b are identical so as to permit precise comparison.
The apparatus illustrated in Figure Ib can function both as a Mongolian and a Chinese still.
With tap B closed (and tap A open to prevent formation of high pressures during distilla-
tion) collection of distillate continues until the catchbowi is full. When tap B is kept open,
and tap A closed, the distillate can be removed continuously. The liquid to be distilled
was, in all cases, contained in a 100 ml round bottom flask, attached to the still by a ground
glass joint. Heating was effected by an electric mantle with a rheostat at a fixed setting.
Where water cooling was applied, the same volume of water (Soml) was used in all cases.
A number of experiments involving the distillation of aqueous ethanol or aqueous acetic
acid was performed to test the efficiences of the different stills. The ethanol "and acetic
acid contents of the distillate were measured by densitometry and by titration respectively.
The results of these experiments are now reported.
When water cooled, the Chinese, Hellenistic, and Gandharan stills are all efficient in
that little material remains unrecovered after distillation. When So ml of a pure low
boiling liquid (acetone, b.p. 56) were distilled the volume of liquid condensed was, in all
cases, in excess of 45 ml. In terms of the efficient use of coolant this compares well with
a modern Liebig condenser, where water flows in counter-current over the condensing
surface. During these experiments one fact became obvious. Distillation with a Chinese

=Ie Department of Chemistry, The University, St. Andrews, Fife, Scotland, to whom correspondence
should be addressed.
t East Asian History of Science Library, 16 Brooklands Avenue, Cambridge, England.
 ANTHONY R. BUTLER AND JOSEPH NEEDHAM

A
c

Figure I: (a) Chinese or Mongolian still; (b) glass model

still is much slower than with either a Gandharan or Hellenistic still. With the first any
distillate which condenses on thewalls, rather than the upper surface, of the still runs back
into the distilling flask. With the Hellenistic still all that condenses is collected. This
may have given the Chinese still something of the character of a reflux condenser.

~~

Figure 2: (a) Hellenistic still; (b) glass model

 AN EXPERIMENTAL COMPARISON OF STILLS 71

Figure 3: (a) Gandharan still; (b) glass model

The preparation of strong spirituous liquor from a fermenting broth, which contains
only dilute ethanol, depends upon the ability of the still to effect fractionation or separation
of the two components. Aqueous ethanol (46% wt/wt ethanol, 50 ml) was distilled and
the distillate collected as a series of 5 ml aliquots. The ethanolie content of each aliquot
from the Chinese, Hellenistic, and Gandharan stills is shown in Table 1. All three stills

TABLE I

Distillation of 50 ml of 46% aqueous ethanol using various -stills.

Ethanol content of aliquot (% wt/wt)

Aliquot Chinese Hellenistic Gandharan

ml still still still
0-5 84 83 82
5-10 83 82 81
10-15 81 81 79
15-20 78 78 78
20-25 74 75 76
25-30 58 67 69
30-35 14 24- 23

show similar behaviour. The first 500/0 of distillate contains a high concentration of ethanol
(almost twice that in the original mixture) but, after this amount has been collected, there
is a sudden decrease in the ethanol content. In fact, nearly all the ethanol in the original
mixture is contained in the first 50% of the distillate.
There are two points of special interest in the results displayed in Table T. First, the
composition of the distillate does not vary eontinously, with the first aliquot containing
mainly lower boiling component (i.e., ethanol, b.p. 76) and then a gradual increase in the
amount of higher boiling component (i.e., water) in each aliquot as the distillation goes on.
This matter will be discussed in more detail later. Secondly, results for the three stills are
very similar. In spite of very different condensing procedures fractionation is the same
72 ANTHONY R. BUTLER AND JOSEPH NEEDHAM

in each of them. The removal of the last traces of water from ethanol by distillation, even
using the most sophisticated equipment, is impossible owing to formation of an azeotrope.
Recovery of 82-84% aqueous ethanol by simple distillation is a reasonable accomplish-
ment.
A special apprehension concerning the !vIongolianstill was that ascending hot vapours
around the catchbowl might "distil out" of the distillate the lower boiling component.
However, this was found not to be the case. The composition of the liquid in the catch-
bowl was unchanged after it had been allowed to equilibrate for IS minutes after filling.
The use of 46% aqueous ethanol is not a good simulation of the preparation of strong
spirituous liquor from a fermentation broth as the latter contains only a low concentration
of ethanol (ca. 10%). Fermentation ceases if the ethanol content is higher than that. We
examined, therefore, what happens when dilute aqueous ethanol (75% wt/wt, 50 ml) was
distilled. With a Chinese, Hellenistic, and Gandharan still the first 5 ml of distillate was
collected, and was found to contain the following concentration of ethanol: Chinese (59%),
Hellenistic (60%), Gandharan (S8eyo)' In view of the simplicity of the apparatus this
eight fold increase in the ethanol concentration on distillation is quite remarkable. A
second distillation of the material would produce, of course, concentrated ethanol. It is
clear, then, thatthe preparation of strong spirituous liquor was, from a technological point
of view, a rather simple matter and no civilisation had a distillatiOll apparatus which gave
it an advantage.
It has been suggested5 that the introduction of water cooling was a critical factor in the
development of alcohol distillation. As water keeps the condensing surface cool it ob-
viously allows more liquid to be distilled in one batch, but we found it had no effect on
fractionating' efficiences. The Chinese, Hellenistic, and Gandharan stills \vere used,
without water cooling, to distil 7'5 wt/wt aqueous ethanol. The first 5 ml of distillate
contained 53, 60, and 58% ethanol respectively, similar to the results obtained with water
cooling. To collect only 5 ml of distillate may appear wasteful but this contains most of the
ethanol present in the original liquid.
The separation of ethanol from dilute aqueous solution by distillation \vas thus simple,
but we must consider whether this is the case also for other mixtures of liquids. The
preparation of concentrated acetic acid from vinegar is a matter of some interest in connec-
tion with certain Chinese alchemical recipes for bringing minerals into solution contained
in the sixth century text San-shih-li'u-Shui Fa6,3b. It should be possible to remove the
lower boiling component (i.e. water) and leave the acetic acid (b.p. 118) behind. The
Chinese still with water cooling was quite ineffective in achieving this separation. Dilute
acetic acid (10% wtjwt, 50 ml) was placed in the distilling flask and 40 ml of distillate
collected. The concentration of acid in the distillate was slightly less than that in the
original mixture (8'5%), and the liquid remaining was 165eyoacetic acid. Thus, the separa-
tion achieved was dramatically less than that with aqueous ethanol. We must seek a
reason for this.
It has been suggested that addition of water to acetic acid results in formation of ortho-
acetic acid CH3C(OH)37 and this makes separation by distillation impossible. Hydration
of the carbonyl group certainly occurs with acetaldehyde.8 We examined this possibility
by carbon-I3 n.m.r. spectroscopy. The changes in chemical shift for the methyl and
carbonyl carbon atoms of acetic acid as water is added are given in Table 2. The very
small changes in the chemical shift of the carbonyl group indicate that no addition of water
 AN EXPERIMENTAL COMPARISON OF STILLS 73

TABLE 2

Carbon-I3 n.m.r. spectra of acetic acid-water mixtures

Mole fraction Chemical shift p.p.m.

acetic acid CH3 CO
1'00 2287 179.89
0,67 22'43 179'05
0'50 22'72 178.81
0'33 2281 178'67
0'20 2289 178.70

to the carbonyl group occurs. In fact, the changes in chemical shift are unexpectedly small
in view of the possibility of hydrogen bonding of water molecules to the carbonyl oxygen. 9
However, it is known that acetic acid, in both solution and vapour, exists as the dimer.10
Hydrogen bonding between acid molecules is so strong that addition of water can have little
effect upon the structure of acetic acid in solution.

80
Benzene- Chloroform

75

00
Q.)
~
...,:J
x
"E70
"t-
o
ci.
.d

Inole fraction.benzene
I I I
02 04 06
[.Figure 4: Boiling point-composition diagram for a chloroform-benzene mixture
74 ANTHONY R. BUTLER AND JOSEPH NEEDHAM

It is instructive to compare the distillation of an acetic-water mixture with that of a

mixture of two regular organic liquids (chloroform and benzene). The datall,12 for these
two systems are displayed in Figures 4 and 5. Let us consider first the chloroform-benzene
mixture (Figure 4). The vapour of the mixture boiling at 70 contains 0'15 mole fraction

Acetic Acid-Water
115

vapour~

105

mole fraction acetic acid

100 ,. t J J , r
02 0-4 0-6 0-8 10
Figure 5: Boiling point-composition diagram for an acetic acid-water mixture

benzene (i.e., 085 mole fraction chloroform) while the remaining liquid contains 0'26 mole
fraction benzene. The enrichment of the vapour in the lower boiling component (chloro-
form, b.p. 62) is thus not great, although the separation of the boiling points is reasonable
(benzene, b.p. 80). It is thus not possible to separate benzene and chloroform by a simple,
single distillation. Repeated distillation is required and there are fractionation columns
which effect this. The b.p. curve for an acetic acid-water mixture (Figure 5) is similar to
that of a benzene-chloroform mixture and it is equally difficult to effect the separation of the
two components. Both these mixtures are normal and it is not necessary to propose
hydrate formation with acetic acid to explain why distillation does not lead to separation.
 AN EXPERIMENTAL COMPARISON OF STILLS 75

The above considerations become more significant when one considers the b.p. diagram
for an ethanol-water mixture13 (Figure 6). For a mixture boiling at 86 the vapour contains
a 0'52 mole fraction of water (i.e., 0'48 mole fraction of ethanol) while the remaining liquid
at this temperature has O'go mole fraction of \vater (only oro mole fraction of ethanol).

Ethanol- Water

95
vapour~

,,
liquid
80
mole fraction water

02 04 06 os 10
Figure 6: Boiling point-composition diagram for an ethanol-water mixture

Thus, very substantial separation of ethanol and water isachieved in a single distillation.
An ethanol-\vater mixture is different from most other liquid mixtures in this respect.
The reason for this probably involves the type of hydrogen bonding occurring in an ethanol-
.water mixture. The anomolous properties of ethanol-water mixtures have been described
in detail by Franks and Ives.14 Were it not for the unusual properties of this mixture,
strong spirituous liquor, brandy, whisky, gin or mao-tai would not have been discovered
before the development of modern distillation techniques. This fact is probably not
without significance in the history of mankind. The ease of separation of ethanol and
\vater by distillation means that the type of still used \vas not crucial. However, the
experimental work here reported suggests that no one of them was markedly superior to
the others in fractionating ability.

Acknowledgement
Mr. C. Smith, University of St. Andrews, is thanked for constructions of the glass stills.

REFERENCES
1. M. Berthelot, La Chimie au Moyen Age, Impr. Nat., Paris, 1893. Photo. repro Zeller, Osnabruck,
Philo, Amsterdam, 1967.
2. F. Sherwood Taylor, Annals of Science, 5, 185, 1945.
 ANTHONY R. BUTLER AND JOSEPH NEEDHAM

3. J.Needham, Scie'ttce and Civilisation in China, Vol. 5, Part 4, C.U.P., in press, (a) p. 63 (b) p. 167.
{. Lu Gwei-Djen, J. Needham, and D. Needham, Ambix, 19,69, 1972.
5. E. O. von Lippmann, Zeitschr. f. angewandte Chemie, 25, 1680, 1912.
6. Ts'ao T'ien-Ch'in, Ho Ping-Yii, and J. Needham, Ambix, 7, 122, 1959.
7. McGraw Hill Encyclopedia of Science and Technology, {thed., New York, 1977, i, p. 37.
8. R. P. Bell, M. H. Rand, and K. M. A. Wynne-Jones, Transactions Faraday Society, 52, 1093, 1956.
9. A. R. Butler, J. Chem. Soc. Perkin II, 959,1976.
10. F. H. MacDougall and D. R. Blumer, J. Amer. Chem. Soc., 55, 2236, 1933.
II. G. Povarnina and V. Markova, J. Russian Physico-Chel1tical Society, 55, 381, 1924.
12. D. Tyrer, J. Chern. Soc., 101, 110{, 1912.
13. P. N. Evans, Industrial and Engineering Chemistry, 8, 260, 1916.
14. F. Franks andD. J. G. Ives, Quarterly Reviews, 20, I, 1966.