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2015

IHPST THIRTEENTH BIENNIAL INTERNATIONAL CONFERENCE RIO DE


JANEIRO JULY 22-25, 2015

The theory of fermentation under the perspective of Justus von


Liebig (1803-1873) in 19th century.

Ingrid Nunes Derossi Ivoni Freitas-Reis


Universidade Federal de Juiz de Fora Universidade Federal de Juiz de Fora
Brazil Brazil
ingriderossi@gmail.com ivoni.reis@ufjf.edu.br

Abstract
The purpose of this work is approach the theory of fermentation that was written by Justus
von Liebig (1803 - 1873) in your Familiar Letters on Chemistry in 1844, which the author
is talking in the foreword, that the aim would be call the attention of the men to the
importance of chemistry, in this letters are presented numerous concepts of chemistry, like
chemistry affinity, atomic theory and his conception of which would be the phenomenon of
fermentation, that will be the focus of this work. In his nineteenth letter, the researcher
presents his point of view about the phenomenon, disagreements over the theory that
fermentation was caused by a living organism. Since century XVIII the fermentation had
been a subject of discussions involving the relationship between the chemical activities and
living activities. He was an important German scientist who contributed to the development
of chemistry, main of the organic's chemistry in century XIX, with the development of
methods to quantify and determine the composition of compounds in partnership with J. J.
Berzelius (1779-1848) and J. B. A. Dumas (1800-1884), like the identification of the
radical benzoyl, creation and highlight the importance of using concentrates of meat in the
diet.

Keywords: Justus von Liebig; Theory of Fermentation; Pasteur; 19th century.

The purpose of this work is approach the theory of fermentation that was written by
Justus von Liebig (1803 - 1873) in your Familiar Letters on Chemistry in 1844, which the
author is talking in the foreword, that the aim would be call the attention of the men to the
importance of chemistry, there are thirty six letters, in these are presented numerous
concepts of chemistry, like chemistry affinity, atomic theory and his conception of which
would be the phenomenon of fermentation, that will be the focus of this work.The
translation of the letters were followed by Liebig himself he was fluent in English. For this
work, we are going to use the fourth edition of this book of 1859, because it has all these
letters in the same volume.
Justus von Liebig was Born on May 12, 1803 in Darmstadt, a German city with
approximately one hundred and fifty thousand inhabitants today. For German, Liebig is
among the most important chemical nineteenth century, alongside Friedrich Whler (1800
1882) e Robert Wilhelm Bunsen (1811 1899). (Shenstone, 1901)

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Since he was child lived together with the productions of dyes, paints, pigments and
others products that his father Johann Georg (trader) manufactured to sell. He liked to
watch chemistry presentations of chemists of others towns which visited the fairs of
Darmstadt they were doing experiments outdoors for the population with the goal to
disseminate the science1. In one of them witnesses the reaction between silver, nitric acid
and alcohol, which generated an explosive substance that would awaken later, his interest
in the study of fulminates2 (Maar, 2006; Kurzer, 2000). Liebig determineted the
composition of fulminates of silver. (Santos, 2008)
His father Johann Georg Liebig (1775 1850) was son of a shoemaker that taught to
him sufficient chemistry to manufacture useful chemicals on a small scale and acquire a
certain fame locally during the 1820s with the lighting of his store3 using acetylene gas
prepared from heated bones. Became trader of several chemical products, like glue, varnish,
coloring, also sold tolos in the city of Darmstadt. Because of his profession developed a
atory-workshop near his house, place where Justus von Liebig has his fisrt contact with
chemistry. He was Johanns second child and son, they were nine brothers being that one
left home before he was born, one died before he had completed five years and four sisters
died in infancy. Justus just knew with his brothers Johann Georg (1811 1843), Karl (1818
1870) e uma irm Elizabeth (1820 1890). (Brock, 1997)
Johann enrolled Liebig in the Ludwig-Georgs-Gymnasium a traditional gramar school
based in classical lines by a scholar-headmaster Johann Zimmermann (1754 1829).
Liebig was eight years and entered in the school in 1811 with his older brother, others
children of his classroom were average ten years. Already in the period, Liebig didnt
accept the traditional methodologies and therefore he had por performance in the
classroom, once, he was called of sheeps head by the assistant headmaster and teased by
the rector because he said that he would like to become chemist, as can be seen in his
autobiographical notes:

With this [obvervational and empirical] bent of mind it is easy to understand that my position
at school was very deplorable; I had no ear memory, and retained nothing or very little of what
is learned through this sense. I found myself in the most uncomfortable position in which a boy
could possibly be; languages and everything that is acquired by their means, that gains praise
and honour in the school were out of my reach; and when the venerable rector of the
Gymnasium, on one occasion of his examination of my class, came to me and made a most
cutting remonstrance with me for my want of diligence, how I was the plague of my teacher
and the sorrow of myparents, and what did I think was to become of me, and when I answered
that I would be a chemist, the whole school and the good old man himself broke into an
uncontrollable fit of laughter, for no one at that time had any idea that chemistry was a thing
that could be studied. (Brock, 1997, p.6)


1
Since the eighteenth century the dissemination od science was considered fundamental part of
researcherswork see Guiton de Marveaux (17371816) in Paris and, in the nineteenth century Humphry
Davy (17781829) and Michael Faraday (1791 1867) developed several Works of dissemination of science
in the Royal Institution of Great Britain (RI).
2
The fulminates are compounds that have the anion fulminate (ONC). Due to its instability, are explosive.
(Kurzer, 2000)
3
Dont have sure about if he could iluminate all his houve or Just part of his store.

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Liebig left the gymnasium in 1817 when was fourteen years, according with his
autobiographical notes because the main focus was in linguistics and the interest and better
comprehension of him was in science and experimentation. Another possible reason, would
be the low family income.
In 1822, wishing enhance his studies, he travelled to Paris, city that was considered at
the time as the capital of science, there was very important scientists, like Joseph Gay-
Lussac (1778-1850), Pierre Simon Marquis de Laplace (1749-1827), Claude Louis
Berthollet (1748-1822) e Jean Baptiste Dumas (1800-1884), among others. Also attended
the Polytechnic School, where studied the fulminates again, which work he would take to
participate of the researches about isomerism in partner with Friedrich Whler (1800
1882).
Returning to Germany in 1824, became professor at the University of Giessen,
being designate by royal letter of Landgrave Ludwig I (1753 1848), he wanted to offer
one modern university for his subjects. After the World War II, in 1957, this university
change the name to Justus Liebig University Giessen. He became titula professor in 1825,
occupying the chair of W. L. Zimmermann (1780 1825), faculty member of the
institution. During this period, chemistry was consolidating as one practical and profitable
science, after as discipline with the creation of new training and researches institutions,
specialized journals as Annalen der Pharmacie created by Liebig in 1832 and with the e
com contribution to the formation of chemical companies such as Chemical Society,
founded in 1841 and the Societ Chimique of Paris in 1857.
There are so many works making by Liebig recognized in all the world, mainly in
the organics chemistry and agrochemical such as development methods to quantify and
determine the composition of organic compounds, in partnership with J J Berzelius (1779 -
1848) and J B A Dumas (1800 1884) in identifying the radical benzoyl. Between 1811
and 1831, improved/developed appliances for instance the called Fnf-Kugel-Apparat or
Kaliapparat the equipment of five balls used to analyze the amount of carbon in organic
compounds; identify the radical benzoyl; the creation and highlight the importance of using
extracts or concentrates of meat in the diet, especially infirm, in 1840. Remembering that in
this moment there wasnt a method to preserve fresh food and the concentrated meat kept
the minerals in their required proportions to body balance
Liebig interested in the fermentation, because it was one of the phenomena that
Berzelius was studying and showed him in 1839. This was already being studied since the
seventeenth century, by the german researcher Georg Ernst Stahl (1660 - 1734) and used by
the German industry in the manufacturing beers. Since century XVIII the fermentation had
been a subject of discussions involving the relationship between the chemical activities and
living activities. Just in 1835 e 1837, scientists, as Charles Caigniard de la Tour (1777
1859), Theodor Schwann (1810 1882), Friedrich Traugott Ktzing (1807 1892) among
others, they had found that the alcoholic fermentation generated a deposit, it was composed
by living cells and concluded that the fermentation was result of the yeast activity.
However, for Liebig the appearance of yeast was one consequence and not the cause of the
phenomenon and this is what he describes in his work. (Bensaude - Vincent; Stengers, 1992
)
According to his letter of number nineteen which the title is Oxygen is the exciting
cause of Putrefactive Transformations, all of which begin with Decay or slow Combustion

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Eremacausis, or decay, is a process of combustion at the common temperatura


Examples of Eremacausis in Bleaching; Decay of animal matter Decay or Eremacausis of
Alcohol; Acetification, Nitrification, the Eremacausis of Ammonia Making of Wines: of
Beer Bavaria Beer: cause of its superiority Aplication of the same to hasten the
Ripening of Wines, the oxygen would be the cause most energetic of all the alterations and
transformations which organic atoms undergo are. (Liebig, 1859)
Before, in the letter of number seventeen, which title is Origin of Organic Atoms;
from Carbonic Acid, Water, and Ammonia Derivation of non-azotised Vegetable
Products from Carbonic Acid and Water by Deoxidation Coupled Compounds Decay of
Organic Bodies, caused by the action of Oxygen, as seen in cut fruit Putrefaction and
Fermentation defined and described Vinous Fermentation of sugar Heat modifies
Fermentation Ferments Flavour of Wines and Spirits, according with the author, all
those processes of decomposition which began in a part of na organic substance from the
application of na external cause would spread through the whole organism, across of a
movement of the particles, for this, they should have the capacity to move freely this would
be given the presence of the water or an increase of the temperature that would result in an
increase in the ability to combine with oxygen, would be called putrefaction. The presence
of water and a suitable temperature would be indispensable conditions of the oxidising
process of decay, just as would be necessary to occur the putrefaction and the fermentation,
the dryness or a temperature below the freezing point would suspend all. (Liebig, 1859)
He defined that one putrescible substance would be that, according to the correct
conditions of temperature and humidity would be able to form news products, while non-
putrescible substances wouldnt suffer any kind of change in the same circumstances, these
would be called fermentescible and would possess the characteristic of being decomposed
when in contact with putrescent matters. This process of their decomposition will be called
fermentation. And the putrescent body by which this change is caused, would be named
ferment. (Liebig, 1859)
All putrecible substances, in the state of putrescence, would become ferments, that
is, they acquired the ability of cause one or more fermentescible substances to enter into
fermentation and the putrescent body or ferment would be present until its putrefaction was
completed.These would exert na action on organic atoms which, by themselves wouldnt
putrescible, would have a rearrangement of atoms, as if the two substances were a new
product.(Liebig, 1859)
The putrefaction and the fermentation would manifest only in the consequence of
the process of decomposition and its termination happen when were established the
equilibrium state. While the oxygen is in action, combining with any elements of one
organic substance, the original equilibrium due to attraction among the elements would be
destroyed, the substance would decompose, and in consequence of new molecular
attractions, new products would be formed and they do not suffer further changes in its
properties, a new balance would be maintained unless there were other external sources (for
instance a variation of temperature) causing disturbances. (Liebig, 1859)
The chemistry action of oxygen about the organic substances, which would consist
of an affinity or tendency of the substance to combine with this element, cease only when
he finished the capacity of the elements of the organic substance to combine with oxygen.
A perfect balance of this affinity and attraction forces, could only happen when this

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combination resulted in products that were unable to fully absorb any additional amount of
oxygen. (Liebig, 1859)
In his work, reading the letter of number twenty one, its possible to perceive that
Liebig begins to question the hypothesis of the need for a living organism to occur
fermentation and putrefaction. He began with questioning of that if the fungus or
mushroom were the cause of the destruction of the tree, or na animalcule were the cause of
the putrefaction of a dead elephant, what would be the cause of putrefaction, after death of
these organisms? What would be the cause of the putrefaction and decay of the dead
animalcule? Increasing his arguments, the author said that they also ferment and disappear
entirely, just as do the mighty tree and the gigantic animal and the final products are the
same in both cases. (Liebig, 1859)
For him would be impossible to adopt this opinion, whereas he had observed that
the presence of microscopic animals in putrescent substances were quite acidental, taht
their appearance, in most cases could be prevented by the exclusion of light, the
putrefaction and decay could go on without the least assistance from them. in thousand
cases (putrescent urine, cheese, bile or blood), no such animals were observed and that in
other cases, they appeared for the first time, in a certain stage long after fermentation has
begun. (Liebig, 1859)
Therefore, the presence of animalculae, which were often found in large numbers in
putrefying matters, couldnt in itself be considered the cause of the phenomenon, since
these animals find there to feed and to develop. Although, Liebig agree that in their
presence putrefaction would be accelerated, whatever this happen because their nutrition
presupposes the consumption of particles of the animal body for their own development
and died when their means of subsistence were exhausted, and their bodies putrefy and
decay, and, perhaps, could serve for the nourishment and development of other races of
living beings. (Liebig, 1859)
Recording that the nineteenth century was marked by the appearance of the first
theories about the evolution of living beings like the hypothesis of Jean-Baptiste Lamarck
(1744 1829) of that all those biological phenomenon are natural and the life should have
arisen from physical and chemical forces, and the first version of Charles Darwins (1809
1882) theory in 1858. (Vergara, 2008) In 1860, Louis Pasteurs (1822 1895) dissertation
about alcoholic fermentation was very important afor another theme that was focus of
debates, if the fermentation would be a chemstry process or biological. His studies about
this subject began in 1855, when he was a professor at the newly created Faculty of
Science, University of Lille and resulted in the germ theory as an attempt to explain the
process of fermentation. According to Pasteur, the fermentation only happen if there was
the presence of germs in the environment. (Gouveia-Matos, 1997)
Continuing with the Liebigs argument to defend his hypothesis that the putrefaction
would be a chemical process, which depended on the oxygen and therefore would be a
combustion. Liebig says in the decomposition of animal substances, to be extinguished
oxygen, other gases would be present, which would exert a deleterious influence and
quickly put a limit to the existence of microscopic animals. Finally, he mentions the
exemple of human excrement, which during its decay is not present animalculae, while
presenting some abundance in the same waste when in a state of putrefaction and exposed
to the atmosphere. (Liebig, 1859)

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Concluso
It was observed that Liebig's theory does not neglect the presence of
microorganisms in the process of putrefaction but argues that they were not the cause of the
phenomenon. At this point it is possible perceive the greatest controversy among Liebig
and Louis Pasteur (1822 1895) contemporary scientist who was also studying the
fermentation process, and claimed that to occur putrefaction is not necessary the presence
of oxygen, but it needs the yeast, which is a living being.
Also it is possible see as the goal of Liebig of call the attention of the men to the
importance of chemistry, it is present in the letter of number one, one of thirty six used to
defend and est presente na carta de nmero um das trinta e seis utilizadas para defender e
discuss the importance of this science, which as we remember A. G. Debus was then called
the "Queen of Sciences" and in which the scholar has dedicated his life and eventually set
up a "reference laboratory" at the time, in which all chemical specialized the world, such as
August Kekul (1829-1896), Hermann Emil Fischer (1852-1919), Charles-Adolphe Wurtz
(1817-1884), and them such as the master, formed others in their own laboratorios. So
many names that we are used to search for and respect in our chemical investigations, in
special in the organic chemistry, originated this school tha Liebig created in Giessen and
confessed he was inspired in Joseph Louis Gay-Lussac (1778-1850), that he was student of
the School of Arcueil4. (Debus, 1996)
In this letter, chemistry would be important not only when it promotes material of
interest to humanity, but also because it would present a view of the world around and
allows development of reasoning. The study of the natural sciences, as a means of
education, would be a necessity of this age, along with the all important instructions in the
fundamental principles of morality and religion, exercising the different mental faculties.
For him, the chemical thought differently and to achieve this ability, it was necessary to
combine reading and practice, as can be seen in the next excerpt:

The faculty of thinking in phenomena can only be cultivated if the mind is constantly
trained, and this was effected in my case by my endeavouring to perform, so far as my
means would allow me, all the experiments whose description I read in the books. These
means were very limited, and hence it arose that, in order to satisfy my inclinations, I
repeated such experiments as I was able to make, a countless number of times, until I
ceased to see anything new in the process, or till I knew thoroughly every aspect of the
phenomenon which presented itself. The natural consequence of this was the development
of a memory of the sense, that is to say of the sight, a clear perception of the resemblance or
differences of things or of phenomena, which afterwards stood me in good stead. (Brock,
1997, p. 10)

About fermentation, if both of them were completely correct a current point of


view their ideas suas ideias served as a basis for further study and more discoveries over
fermentation.

4
The School of Arcueil founded by Berthollet and Laplace inspired by the "Arsenal" - the name given to the
couple's home Lavoisier - received promising youngsters and financed with the help of the French
government, their studies. Gay-Lussac was perhaps one of his most brilliant "protected". (Greenberg, 2003)

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Referncias
Bensaude - Vincent, B.; Stengers, I. (1992). Histria da Qumica. Lisboa: Editora Piaget.
Brock, W. H. (1997). Justus von Liebig: The Chemical Gatekeeper. Cambridge: Cambridge
University Press.
Debus, A. G. (1996). El hombre y la Naturaleza en el Renacimiento. Mxico: Fondo de
Cultura Econmica.
Gouveia-Matos, J. A. M. (1997). Pasteur: Cincia para ajudar a vida. Revista Qumica Nova
na Escola, n6, nov, p. 20-22.
GREENBERG, A. (2003). The Art of Chemistry: Myths, Medicines, and Materials. New
York: Editora Wiley-Interscience.

Kurzer, F. (2000). Fulminic Acid in the History of Organic Chemistry. Journal of Chemical
Education, v. 77, n 07, p. 851-856.

Liebig, J. V. (1859). Familiar Letters on Chemistry, in its relations to Physology, Dietetics,


Agriculture, Commerce, and Political Economy. Munique: Bayerische Staats bibliothek
Mnchen, acervo digital.

Maar, J. H. (2006). Justus Von Liebig, 1803-1873. Parte 1: Vida, personalidade,


pensamento. Revista Quimica Nova, v. 29, n05, p. 1129-1137.

Santos, S. E. (2008). Liebig-Whler Controversy and the Concept of Isomerism. Journal of


Chemical Education, v. 85, n 09, p. 1201-1203.
Shenstone, W. A. (1901). Justus von Liebig: His life and work. California: University of
California, acervo digital.

Vergara, M. R. (2008). Ensaio sobre o termo vulgarizao cientfica no Brasil do sculo


XIX. Revista Brasileira de Histria da Cincia, v. 1, n 2, p. 137-145.

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