Professional Documents
Culture Documents
SoapProductionandUseinAntiquity-Konkol Rasmussen
SoapProductionandUseinAntiquity-Konkol Rasmussen
SoapProductionandUseinAntiquity-Konkol Rasmussen
net/publication/282650616
CITATIONS READS
9 6,626
2 authors:
Some of the authors of this publication are also working on these related projects:
Low Band Gap Conjugated Polymers and Re-evaluation of the Donor-Acceptor Approach View project
History of Early Glass Technology and its impact on the Chemical Sciences View project
All content following this page was uploaded by Kristine L Konkol on 16 November 2019.
kristine.konkol@ndsu.edu; seth.rasmussen@ndsu.edu
Chemistry of Soap
The principal method for soap production is the combination of a
triglyceride and an alkali salt, in a reaction known as saponification, as shown in
Figure 1 (3,4). Soap can also be manufactured from the neutralization of a fatty
acid such as stearic acid with an alkali metal salt such as sodium hydroxide.
However, because the isolation of the fatty acid would first require the
hydrolysis of the triglyceride to the fatty acid, with subsequent removal of the
glycerin (5), it would not have been a viable method of production throughout
antiquity.
Triglycerides are found in fats, such as tallow and lard, as well as various
oils. Common oils include palm, palm kernel, coconut, and olive oils, where
palm oil is extracted from the pulp of the palm fruit and palm kernel oil is
extracted from the inner kernel of the palm fruit. Triglycerides that are semi-
solid or solid at room temperature are classified as fats, and are primarily found
The nature of the fatty acid with which the alkali is combined can affect the
consistency of the soap formed. For example, sodium salts of lower molecular
weight fatty acids have no soap-like properties, dissociating into ions and
dissolving in water as true molecular solutions (8). With soaps made from caproic
acid (C6 carbon chain), there is a faint trace of soap-like properties with a slight
foaming occurring in cold solutions. As the chain length increases, the soap becomes
harder in consistency and more insoluble, with lauric acid (C12) producing a soap
that is very soluble, lathering freely in cold water, while stearic acid (C18) produces a
slightly soluble soap in cold water (8).
Fats and oils were historically obtained from a variety of different sources,
where locally available materials were primarily used so there was minimal
trade over long distances. The main carcass fats produced industrially today are
tallow (beef and mutton) and lard (pork), which are used for human food, animal
feed, and as source material in the oleochemical industry, the majority of which
is used in the production of soap and other surface-active compounds (6). The
first fats were probably obtained through rendering, since this is a relatively easy
operation that only involves simmering of the fatty animal tissue. Animal fats
are relatively easy to render because the cell walls and membranes in animal
Figure 2. Salsola kali and Salicornia herbacea L. [Botanical Prints from Flora
Batava by J. Kops – 1807 and Flora von Deutschland by O. W. Thomé – 1885]
Origins of Soap
Investigation of the etymology of the word soap could potentially provide
some indication of its historical development. The word soap originates from the
Proto-Indo-European root *seib, meaning to pour out, drip, or trickle (23). The
romance language words for soap are from the late Latin sapo, mentioned in the
writings of Pliny (24), which is a Germanic loan-word. Keeping in mind that in
many languages the pronunciation of certain letters is interchangeable,
translations of the word soap are quite similar and are cognates of one another
(Table 2) (22,25). Ezov, the classical Hebrew name for a plant used for ritualistic
cleansing in the Bible, translates to hyssop in English (26). A connection could
be made between the plant used for cleansing purposes and soap, which has the
identical consonants as hyssop. In more ancient civilizations, the concept of soap
was not always recognized with its own distinct word. For example, the
Soap in Mesopotamia
Mesopotamia is a geographical region in the Near East, referring to the land
lying between the Euphrates and Tigris rivers (33). The name is based on a term
local to the area, given in the time of Alexander the Great (326 – 323 BCE),
which corresponds to modern-day Iraq, and to a lesser extent Kuwait, Iran,
Turkey, and Syria (Figure 5). The ancient city-states of Mesopotamia, and the
civilizations that spawned them, are among the earliest known non-nomadic
agrarian societies. Mesopotamia included Sumer, as well as the Akkadian,
Babylonian and Assyrian empires (4th – 1st millennia BCE). Of the ancient
civilizations, it is the Mesopotamians that have had a large volume of their
records survive to the modern day, because they wrote on the durable writing
material of clay tablets, their primary form of record keeping (34). These texts
provide a rich record of their daily life, including their accounts and usage of
soap.
Many peoples of the ancient Near East dedicated a great deal of attention to
the concept of cleanliness. In an almanac from the Mesopotamian settlement of
Assur, a man is cautioned not to enter a laundry, and thus cleanse his garments
or himself, on the sixth and seventh days of the month of Teshrit, this being in a
month of penance (35). Simple detergents that were commonly used in ancient
Mesopotamia to cleanse were alkalis, clays, earths, and resins, although the
alkalis, such as those leached from the ashes of plants, were most common (22).
A Sumerian tablet found in the Hittite capital of Boghazkoi discusses the use of
soda for cleansing the body (22,36):
With water I bathed myself. With soda I cleansed myself. With soda
from a shiny basin I purified myself. With pure oil from the basin I
beautified myself. With the dress of heavenly kingship I clothed
myself.
May the tamarisk, whereof the tops grow high, cleanse me; may the
date palm, which faces every wind, free me; may the mastakal plant,
So that he makes pure with water, so that he cleanses with potash, (?)
and so he intermixes the pure oil with potash.
In a text from a later period, during the reign of Nabonidus of Babylon (556 –
539 BCE), a recipe for soap is given which specifies the oil source (14):
In this recipe, uḫulu designates the potash or soda plant source (40). Unlike
previous recipes, which indicate that the purpose of the soap is to clean cloth,
soap at this time is being used for cleaning the stones by the servants.
Soap was found to be of value as a medicament very early, and soap is
mainly mentioned in connection with medical writings in Mesopotamian
records. Mesopotamians utilized the concepts of diagnosis and prognosis of
illness, creating herbal remedies to treat the afflictions (43). Medicine was
usually composed of a pharmacological ointment that contained oil, plant
matter, and various other substances, which was applied to the affected area of
the body. In an Assyrian medical prescription from the 7 th century BCE, castor
oil and horned alkali (Salicornia plant) are used, together with other drugs, as a
mouth cleanser, in enemas, and to wash the head (35,44). Sulfur ointments,
variants of which are used in modern times for the treatment of skin disorders
such as acne, scabies, and dandruff, were also known in Mesopotamia. One
sulfur ointment for the eyes involves using saltpeter, iron sulfate, Salicornia
alkali, fir turpentine, niter, Lepidium, sulfur, ox-fat, and other substances
(35,44). Another recipe from Mesopotamia directs (35):
Take turpentine, sulfur, horned alkali and put in water, then oil and
spittle are poured thereon forming an ointment.
Sift and knead together – all in one – turtle shell, the sprouting (?)
naga-plant (a plant used to obtain soda and other alkalies), salt, (and)
mustard; wash (the sick spot) with quality beer (and) hot water; scrub
(the sick spot) with all of it (the kneaded mixture); after scrubbing, rub
with vegetable oil (and) cover (?) with pulverized fir.
Although little direction is given as to what part of the body this remedy was
supposed to cure, this set of prescriptions was preceded by the passage directing
arrangement of rushes over the hands and feet of the sick man, so it is possible it
was to be applied in the same area (43). As the first recipe includes salt, this
could suggest that “salting out” was practiced in antiquity, although there is no
direct evidence of such. The process of salting out involves the precipitation of
soap from the solution of glycerin, excess water, and impurities, thus making a
hard soap (22). This is typically accomplished by adding salt (e.g. NaCl) to the
soap solution, rendering the soap insoluble because of the large amount of
electrolyte in solution (3). Otherwise, without filtration, the soap produced
would most likely be soft and liquid in consistency because of the impurities.
Also, from the recipes above, and other medical writings, it is quite possible that
the Sumerians were familiar with resin soaps (compounds of soda or potash
combined with coniferous resins i.e. pulverized fir/tree sap) (22).
As with all of these medical formulations, the efficacy was questionable,
and they may have done more harm than good. Nevertheless, hundreds, if not
thousands, of tablets containing medical prescriptions survive from
Mesopotamia, some of which contain the components of soap manufacture (44).
Whether these ingredients were purposely added together or rather just
combined as a coincidence is still debatable.
There is no evidence that the alkaline substances used by the Mesopo-
tamians for the production of soap were causticized (22). The preparation of a
soap of pure salts of fatty acids would imply a caustification of the alkali by
quicklime (CaO) (45). This means that lye (NaOH) or caustic potash (KOH)
would be produced by treating the soda/potash with quicklime as follows:
Caustic soda (i.e. lye) and caustic potash are used nowadays for the production
of soap (3,8). The advantage of this caustification is that insoluble CaCO3 is
formed and the alkali metal (Na+ or K+) hydroxide remains free in solution.
Rather, the Mesopotamian soap produced from alkali carbonates would have
resembled that manufactured in some parts of the world today, known as cold or
semiboiled soap (22). In either such case, the hydrolysis of the triglyceride
would be ineffective, resulting in a mixture of soap and partially hydrolyzed
products that would produce a liquid mixture.
Nor is there any evidence of how (or if) the alkali was extracted from the
plants, although the Babylonians were familiar with alkali plants for the
extraction of essential oils (35). It has been hypothesized that some more recent
operations to extract the alkali may resemble those used by the Mesopotamians,
which include the slow combustion or incineration of the dried plants, then a
washing or leaching of the ash followed by drying until a salt cake forms on the
sides of the vessel. The crude product would then be calcined to remove the
water and destroy any organic substances remaining. However, this detailed
process for the manufacture of soda or potash was most likely beyond the
common laborer and was reserved for the use of royalty and the priesthood (22).
For the more common household chores the ash was probably stirred in the
water and the solution was then filtered before use to remove insoluble
impurities. This method of containing the ash in a cloth bag which was then
immersed in the wash water was utilized until the 19 th century CE, when soap
became cheap enough to displace the alkali plant ash (22).
Soap in Egypt
Egyptians, especially those of the priest caste, also placed great emphasis on
personal cleanliness, with frequent washing of the hands and fingers both before
and after eating (28). However, despite the frequent ritual ablutions and
washings of the ancient Egyptian priests there is little evidence that soap was
known to them, unless a mixture of natron and clay or steatite (soapstone) was
used, both of which the Egyptians were well-acquainted with (31,46). There
existed some unknown means of removing grease from clothing, which has been
suggested to be either natron or fuller’s earth (47). The Eber’s papyrus (1550
BCE) contains a number of recipes in which alkaline substances are boiled
together with oils and fats (48). While it is probable that soaps and plasters were
obtained from these processes, they were never specifically mentioned (28). In a
similar manner, the Berlin medical papyrus (Brugsch Papyrus) (1350 – 1200
Soap, too, is very useful for this purpose, an invention of the Gauls for
giving a reddish tint to the hair. This substance is prepared from tallow
and ashes, the best ashes for the purpose being those of the beech and
yoke-elm: there are two kinds of it, the hard soap and the liquid, both of
Figure 6. top: Roman Baths in Bath, England [Photochromic color print 1890-
1900, Library of Congress Prints and Photographs Online Catalog] bottom:
Bronze Strigil, Roman Period (30 BCE – 395 CE) or later [Courtesy of Los
Angeles County Museum of Art]
Soap is made from cooking beef, goat, or wether fat, mixed in with lye
and quicklime. The best soap is judged to be Germanic, because it is
However, it has been reported that Galen did not write this and the source is
rather a pseudo-Gallenic medieval handbook that has unfortunately propagated
through the literature (18,59,60). It has been proposed that the German soap may
have been soft soap made from the ashes of land plants (containing potash),
while the soap of Gaul was a hard soap made from the ashes of sea-shore plants
(containing soda) (54). Additional references to soap by Greek writers include
the alchemist Zosimos of Panopolis (250 CE), who mentions both soap
(σαπώνιον) and soap-making (σαπωναρικής τέχνης) in his writings (54,61), and
Aretaeus of Cappadocia, a prominent Greek physician of the 2 nd century CE,
who included the medical use of soap in his writings (54).
Alternatives to true soap were also utilized for cleansing purposes. Putrid
urine was collected on Roman street corners and from public urinals as a source
of ammonia for use in various chemical processes, especially the washing of
cloth (18). The Roman fuller, or cloth-launderer (Latin fullo), would wash the
cloth by trodding upon it in a tub of putrid urine to clean it. The effectiveness of
using putrid urine results from the high content of ammonium carbonate
((NH4)2CO3) present, which reacts with fats and oils to produce a light
saponification (22). This business of collecting putrid urine for washing was
taxed by the government of Emperor Vespasian (69 – 79 CE), and this tax,
urinae vectigal commentus est, continued for a period of two centuries (18). On
account of the disagreeable smell, fullones (plural) in Rome were obliged to
reside in less-populated areas such as the suburbs (18).
The Papyrus Graecus Holmiensis, or Stockholm Papyrus as it is also
known, is a codex from 300 CE containing recipes for the manufacture of dyes
and colors, and includes soap in one of its preparations (42,62,63):
It should be noted that the Phoenician dye described here was not the same as
the more famous mollusk-derived Tyrian purple. There are also numerous
mentions in the Papyrus of using soap weed, which was most likely soapwort
(Saponaria officinalis), in the cleansing of textiles (62,63):
Conclusion
The earliest written records of soap-making date to 2200 BCE in
Mesopotamia (40,43). However, because saponification can occur by the simple
combination of fat and plant-ash, it is highly likely that soap was made, whether
intentionally or not, before this time. The slightly complicated process of
rendering the fats and oils and combining it with alkali could not have been
developed spontaneously. There must have been a series of steps or procedures
that slowly evolved, where each step resulted in a process useful enough to be
adopted in its own right. One proposed sequence of development is that people
used sand or ashes to remove the grease from skin. If they rinsed the ashes off
with water, the water and their skin would become slippery, which was because
of the dissolved alkali salts. This water would clean better because the dissolved
alkali reacts with the grease, converting it into soap. The more grease that was
dissolved in the solution, the better it cleans because more soap is formed. At
some point the ashes were discarded and the solution from leached ashes or
concentrated alkali salts were used (15).
In the Mesopotamian period, soap was primarily made from oil and plant
ash. The Mesopotamians used it mainly for medical purposes, but also for
cleansing. The Egyptians did not identify soap as such, but it is possible that
they were familiar with it, through the combination of alkali and animal fat
(48,49). There is evidence of soap residue being found in ancient Egyptian
artifacts, but it cannot be definitively concluded that this was not the result of
slow degradation of the original material (50,51). The Greco-Roman world was
familiar with soap and soapmaking, using it for medical, textile, and
beautification purposes, but not for personal hygiene. There is also archeological
evidence that soap was used in various Roman painting techniques (64-67). It is
also quite probable that soap production was occurring in other parts of the
world and other civilizations during this time, but no evidence has yet been
found to confirm it (25,54).
Soap production in antiquity was most likely a small craft industry,
especially in the Mesopotamian and Egyptian periods, where locally available
materials were used in its formation. However, the large expanse of the Roman
empire allowed for the movement of materials and processes, one of which was
soap that was imported from the Gauls (24). It is possible that there was some
Acknowledgements
The authors would like to thank Zvi Koren for his input on the etymology
of soap, and Ganesh Bala for helpful discussions about the history of soap and
its relationship to that of oils and perfumes. Thanks are also given to Trent
Anderson, fellow member of the Rasmussen research group, for his feedback on
this manuscript.
References
1. IUPAC Compendium of Chemical Technology Gold Book; International
Union of Pure and Applied Chemistry; Version 2.3.3, 2014.
2. Smulders, E.; Rybinski, W.; Nordskog, A. Laundry Detergents, 1.
Ullmann’s Encyclopedia of Industrial Chemistry, Vol. 20; Wiley-VCH,
2011; pp 355-391.
3. Preston, W. C. The Modern Soap Industry, Part I. J. Chem. Educ. 1925, 2,
1035-1044.
4. Snell, F. D. Soap and Glycerol. J. Chem. Educ. 1942, 19, 172-180.
5. Twitchell, E. The Separation of Solid and Liquid Fatty Acids. J. Am. Chem.
Soc. 1895, 17, 289-295.
6. Gunstone, F. D. Fatty Acid and Lipid Chemistry; Aspen Publishers:
Gaithersburg, MD, 1999; pp 61-86.
7. Scrimgeour, C. M.; Harwood, J. L. Fatty Acid and Lipid Structure. The
Lipid Handbook; Gunstone, F. D., Harwood, J. L., Dijkstra, A. J., Eds.;
CRC Press: Boca Raton, 2007; pp 1-16.
8. Preston, W. C. The Modern Soap Industry, Part II. J. Chem. Educ. 1925, 2,
1130-1139.
9. Gunstone, F. D.; Harwood, J. L. Occurance and Characterization of Oils
and Fats. The Lipid Handbook; Gunstone, F. D., Harwood, J. L., Dijkstra,
A. J., Eds.; CRC Press: Boca Raton, 2007; pp 37-141.