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Analytical chemistry in the 19th century and today

On the 125th death anniversary of Carl Remigius Fresenius (1818–1897)

Prof. Dr. Leo Gros (Hochschule Fresenius gGmbH)

The chemist Carl Remigius Fresenius died on June 11th, 1897. Among his students were Edward and Otto Mallinckrodt, sons of the founder of the company Mallinckrodt in the United States, which is still successful today. In a commemorative publication on the company’s 125th anniversary in 1992, it says: They “returned to Missouri in 1867, having received the best finest training the world had to offer. More importantly, they had also assimilated their German hosts’ painstaking devotion to quality.” Who was their host? The “famous father of chemical analysis“ [1].

Like all sciences, analytical chemistry has many fathers. What was the outstanding contribution of Fresenius, who died 125 years ago, and whose former place of work, the Chemical Laboratory Fresenius in Wiesbaden, Germany, was included in the honorary list of Historic Sites of Chemistry by the German Chemical Society in 2013?

Fig. 1 Portrait of the young C.R.F. Painting by Ludwig Knaus, Fresenius family property, on loan to the Museum Wiesbaden

This article (see note below) pays tribute to the textbooks, publications and the technical journal founded by Carl Remigius Fresenius, and goes on to explore what relevance and usefulness his work has had and still has today. In particular, there will be quotes from the young Fresenius himself (Fig. 1).

Chemistry is a language

In a lecture given at the 1842 annual meeting of German Natural Scientists and Physicians in Mainz, the 24-year-old Fresenius, assistant to Justus Liebig at the University Laboratory in Giessen, where he also earned his doctorate and habilitated (qualified as a professor), compared his young students to people learning a language:

“The language of the chemist, however, is that of experiments. Its sounds are the individual reactions; to learn them, qualitative analysis is now generally regarded as the best and shortest route ...“ [2]

That teaches young people what they need to work professionally:

“These requirements, however, are: 1) orderliness, cleanliness and skill in working; 2) keen observation, exact consideration of the circumstances of each reaction, correct calculation of the outcome of each process; 3) the ability to independently design appropriate and suitable methods for each task; and finally 4) when observing phenomena that contradict earlier phenomena, the willingness to always first look for the fault in oneself, i.e. in the absence of a condition for the phenomenon to occur.” [2]

In fact, we still speak of reaction conditions” to this day – particles react with each other, and their reactivity depends on the conditions of the environment. If the temperature is too high, they might decay; if it is too low, their speed of movement might not be sufficient for the reaction. A pH that is too low (i.e., too high hydrogen ion concentration) leads to the positive charging of certain particles and thus possibly to repulsion by other reactants. The presence of interfering substances can hinder a reaction if they react themselves rather than the desired reaction partner. For example, the purple-colored permanganate ion is reduced to the almost colorless manganese(II) only under acidic conditions; in a weakly alkaline solution, manganese dioxide, manganese(IV) is formed. If, however, the attempt is made to oxidize manganese(II) with nitric acid in the presence of interfering chloride ions, the resulting permanganate oxidizes the chloride to chlorine and is itself reduced back again; its characteristic purple color, which indicates the presence of manganese(II) in the test solution, remains absent. Students still learn that for this manganese detection method, it is essential to precipitate any interfering chloride using silver ions to separate it as poorly soluble silver chloride. What these examples from qualitative chemical analysis demonstrate applies to an even greater degree to the biochemical reactions and biotechnological processes we use today when we produce drugs or vaccines: the microorganisms do what we want them to only within narrow temperature, pH, stirring speed, as well as salt, oxygen and nutrient concentration ranges. Deviations from optimal reaction conditions lead to undesired by-products or even failure of the entire conversion.

“You can’t keep Fresenius in stock...” – the textbooks on qualitative analysis

Fig. 2 Title page of the first edition of the “Quali”, dated 1841. Archive of the Fresenius University of Applied Sciences

While studying in Bonn, 22-year-old Fresenius worked in the private laboratory of the pharmacist Dr. Clamor Marquart to deepen the understanding of chemistry he had acquired in his own garden shed laboratory and during his pharmacy apprenticeship. Fresenius's first edition of “Anleitung zur qualitativen chemischen Analyse” (Introduction to Qualitative Analysis, Fig. 2), published in 1841, written during this time and dedicated to his patron Marquart, systematically explains analytical tasks step by step. The book went through ten German editions in its first 20 years, and 16 by the time the author died. It was translated into English, French, Spanish, Italian, Russian, Dutch, Hungarian, Japanese and Chinese. From one edition to the next, it is possible to understand Fresenius’ approach: He watched his students at work in the lab, discussed issues and problems, and translated his findings into didactically better written instructions. Step by step, he added details on the analysis of water, food and many technical products. This is why his 81 pages at first eventually rose to almost 900.

“Comprehensibility of the explanations on compounds, of the analytical methods and of the overall classification scheme, all presented here for the first time in this way, are the most important features of this textbook. This sets it apart from the works of his predecessors” [3]. Professor Dr. Georg Schwedt, the author of this appreciation, republished the 4th edition of the “Quali”, the book’s nickname, as a facsimile with a detailed introduction, making it easily accessible to interested readers. [4]

When in 1845 Fresenius applied for a position at the Ducal Agricultural Institute of Nassau in Wiesbaden, he asked to buy some copies of his own book for presentation purposes. However, his publisher and bookseller replied: “You can’t keep Fresenius in stock, new editions appear too frequently.” [5]

“The hand must learn skills ...” – the textbooks on quantitative analysis

Museum Wiesbaden, Bernd Fickert

Fig. 3 The Fresenius Desiccator to dry substances in preparation for quantitative analysis, around 1880. Historical collection of the Fresenius University of Applied Sciences

In 1845, the first edition of the 518-page “Anleitung zur quantitativen chemischen Analyse” (Introduction to Quantitative Analysis) appeared. The sixth appears between 1877 and 1887, comprising two volumes and a total of 1,539 pages. Again proceeding systematically, the author gives an introduction into the working procedures. A second part is devoted to analyzing the main sample types such as water, soil, air, fertilizers, plants, minerals and other technical products. Together with the “Quali”, the “Quanti” was known as the “bible of chemical analysis” all over the world for many decades [6].

Some of the numerous apparatuses depicted in his book as woodcut illustrations were created by Fresenius himself, for example the desiccator (Fig. 3), a vessel to dry moist substances before being weighed (after all, the weight of water or any other contained solvent must remain unconsidered in gravimetric quantitative determinations). Another example is an apparatus to determine arsenic (Fig. 4), used in cases of poisoning.

Fig. 4 Apparatus to determine arsenic, e.g. in poisoning cases. C.R. Fresenius, Textbook of Quantitative Analysis, 13th Edition 1870, p. 192. Archive of the Fresenius University of Applied Sciences

Even though most of today’s expensive automated measuring instruments have replaced the old “Quanti” methods, they usually still have to be fed with samples specially prepared for this purpose. Without taking the necessary care, there is no confidence in measurement results. That considered, titration and precipitation are still good exercises in the thinking of Fresenius:

“Endowed with the most thorough knowledge, it is still impossible to determine how much salt is in a solution unless one is able to pour a liquid from one vessel into another without something splashing away or a drop running down the edge, etc. - The hand must learn the skills to perform with diligence and aptitude the operations that are necessary in quantitative analyses, and this can be acquired solely by practicing.” [7]


“This task can be fulfilled only by a periodical publication...” – the journal “Fresenius' Zeitschrift für Analytische Chemie”

“Looking after the treasure of analytical methods has hitherto been entrusted almost exclusively to textbooks ... assuming that they represent utmost perfection, they give us an exact picture of the knowledge of certain periods of time. However, they cannot also convey the knowledge of all the material that continues to accumulate between these periods. This task can be fulfilled only by a periodical publication and – when you consider how much knowledge accumulates in the meantime – only by one that is exclusively and completely devoted to the task ...” [8]

This is how, in 1861, Fresenius explained the necessity of publishing the first journal, “Fresenius' Zeitschrift für Analytische Chemie”, devoted entirely to analytical chemistry and published by him and his descendants until the beginning of this millennium.

His reasoning is still very much valid today: the progress in analytical chemistry, and thus in the knowledge to be shared by the scientific community, has accelerated and multiplied. From 1990 onwards, the papers of what was then called “Fresenius' Journal of Analytical Chemistry” appeared only in English. Since 2002, the Springer publishing house has been upholding the tradition, now merged with other European analytical journals, under the name “Analytical and Bioanalytical Chemistry” (ABC). By 2021, the 19th century annual figure of about 500 A5-sized pages had grown to 7,629 pages about twice the size. Covering 413 volumes, over 2,600 issues containing more than 103,000 papers have appeared between its foundation and December 2021.

Fig. 5 Hand-colored illustration of spectra recorded by Bunsen and Kirchhoff with their instrument. First volume of Fresenius' Zeitschrift für Analytische Chemie 1862. Archive of the Fresenius University of Applied Sciences

The first issue of Fresenius's journal featured a short paper by Bunsen and Kirchhoff containing hand-colored emission spectra (Fig. 5). The method helped the authors to discover the previously unknown elements rubidium and cesium in a lepidolite mineral and in Bad Dürkheim’s mineral water, after which they purified a salt of each of the two elements. The Bunsen-Kirchhoff Prize for Analytical Spectroscopy, named after these two scientists, is awarded every two years by the German working group for Applied Spectroscopy (DAAS) of the German Chemical Society’s Analytical Chemistry Division, the next time in 2022.

So, to this day and going forward, the journal founded by Carl Remigius Fresenius keeps serving the advancement not only of analytical chemistry, but also of chemistry and the natural sciences as a whole, as Fresenius observed at the time.

“...the importance for life...” – the social and economic benefits of chemistry

In his lecture on receiving the Venia Legendi, a permission to teach science, the then 25-year-old young scientist states:

“As chemistry grew as a science, so did its relevance for life .... In this way, chemistry has elevated pharmaceutics, mineralogy, mining and metallurgy, factories, trade and commerce. Just as chemistry now triumphs over these past successes, it will soon rejoice in having given a new impetus to the actual true source of physical prosperity, agriculture, and will soon pride itself in being a strong and lasting support for physiology and therapy.” [9]

Demonstrating that Fresenius was thinking far ahead, he gave an example of what this can mean in his 1844 essay on the legal role and tasks of a forensic court expert, having been appointed one himself.

“Among all the fields of applied chemistry, what has occupied the attention of chemists to a particular degree is determining poisons in forensic chemistry cases; this is easily explained by the importance of these issues and their significance for society ...The question arises whether it would not be more expedient to establish standard methods and lay them down in legal regulations. These methods could lead to a reliable result under all circumstances. The chemist would thus be required to conduct an investigation according to these standard methods rather than to self-chosen ones ... Just like the state watches over all other laws, it would have to take control of the laws on the standard methods established for the forensic chemist and thus arrange that they are changed if science offers the means to establish better ones ...” [10]

So as early as in 1844, Fresenius proposed the standardization of approved forensic methods that would be amended on an ongoing basis.

Entrepreneurial, pioneering, sustainable: a foundation on which to build

No commemorative day, especially not the 125th anniversary of the death of our founder Carl Remigius Fresenius, should tempt us, his “heirs”, to worship him as a hero.

But what can we learn from “Remi”, as he was called by his family, today and going forward? One reason why he must be considered a pioneer is that he focused on what he was good at, and tried to do that particularly well. He did what gave him pleasure and what he loved, and he went about this with pleasure and love. He established networks, shared and passed on knowledge and skills. He accepted new knowledge fast, but often not without performing verification experiments. When these proved successful, he would apply the knowledge and share it in his journal and books. In everything he undertook, he paid attention to what we now call sustainability, but he was also not afraid to leave behind what was no longer any good. “Being conservative is not to cling on to what was yesterday, but to live by what has always been valid ...” [11]. Applying this quote by Antoine de Rivarol to Fresenius and us today, we must convey the lasting elements of knowledge and skill, and teach science on this basis – as a tool to tackle future problems and issues professionally and successfully.

“The world is changing at breathtaking speed. We must move ahead, not try to keep up with it.” This is what the great-grandson of Carl Remigius, Wilhelm Friedrich Nils Remigius, said on his 90th birthday in 2003. Moving ahead should cover not only the science, but also its application and entrepreneurship. This is our approach to teaching at the Fresenius University of Applied Sciences.

In this sense, Ludwig Fresenius, the great-great-grandson of the “father of analytical chemistry”, is already looking forward to the 175th anniversary of the Fresenius Chemical Laboratory in 2023.

Note:

An introductory article was written for Fresenius's 200th birthday in 2018: Gros L. Scientist - Teacher - Service Provider: Carl Remigius Fresenius (1818–1897), a pioneer of analytical chemistry. q&more Eng ed. (ISSN 2702-7805) 2019 Oct 10th. Available from: https://q-more.chemeurope.com/q-more-articles/304/scientist-teacher-service-provider.html ( Forscher – Lehrer – Dienstleister: Carl Remigius Fresenius, ein Wegbereiter der Analytischen Chemie. q&more Deutsche Ausg. (ISSN 2702-7791) 25. Okt. 2019. Abrufbar unter: https://q-more.chemie.de/q-more-artikel/304/forscher-lehrer-dienstleister.html. In part, this article draws on the following catalog published on this occasion for an exhibition at the Museum Wiesbaden: Carl Remigius Fresenius, Father of the Analytical chemistry – he started with five students… Catalog for the exhibition C.R. Fresenius. Edited by the Museum Wiesbaden and the Fresenius University of Applied Sciences. Wiesbaden 2018. ISBN 978-3-89258-120-8.

________________________________________________________________________________________

Kategorie: Chemistry History | Carl Remigius Fresenius

Literature:
[1] Mallinckrodt 125th Year Anniversary. 1867-1992. Quality, Integrity, Service. Written and produced by the History Factory. Washington, D.C. ISBN 1-882771-00-1. P. 9 f
[2] Fresenius CR. Über das Thun und Treiben im chemischen Laboratorium zu Giessen, mit besonderer Berücksichtigung der Ergebnisse des letzten Jahres. In: Amtlicher Bericht über die zwanzigste Versammlung der Gesellschaft deutscher Naturforscher und Ärzte zu Mainz im September 1842. Hrsg. Gröser und Bruch. Mainz 1843:92-101. Online source of text extract (corrected): http://archive.org/stream/amtlicherbericht20gese/amtlicherbericht20gese_djvu.txt. Accessed 2021 Apr 07
[3] Schwedt G. Carl Remigius Fresenius und seine analytischen Lehrbücher: Ein Beitrag zur Lehrbuchcharakteristik in der analytischen Chemie. Fresenius Z Anal Chem 1983;315:395-40
[4] Carl Remigius Fresenius. Anleitung zur Qualitativen Chemischen Analyse. Von Georg Schwedt. Berlin, Heidelberg: Springer Spektrum; 1. Aufl. 2021. V, 358 Seiten, brosch. ISBN 978-3-662-63371-7. ISBN 978-3-662-63372-4 (eBook). DOI: 10.1007/978-3-662-63372-4
[5] Fresenius W. Zur Erinnerung an Remigius Fresenius: Erinnerungen aus meines Vaters jungen Jahren. Private print not dated. P. 10. Archive of the Fresenius University of Applied Sciences
[6] Perez-Bustamente JA. Karl Remigius Fresenius (1818-1897): Rationalization and systematization of chemical analysis. Química Analítica 1997;16:139-141
[7] Fresenius CR. Anleitung zur Quantitativen Chemischen Analyse. 6th edition 1875, volume 1, p 4
[8] Announcement of the first edition of “Fresenius‘ Zeitschrift für Analytische Chemie” 1861. Quoted after Fresenius H: Zur Erinnerung an R. Fresenius. Fresenius Z Anal Chem 36:XI ff
[9] Manuscript of C.R. Fresenius for his habilitation lecture at the University of Giessen on 27.02.1844. Archive of the Fresenius University of Applied Sciences. Fresenius had been awarded the Venia Legendi without formal proceedings six months earlier; however, he insisted on giving the lecture and disputation, like all other candidates do.
[10] Fresenius R. Ueber die Stellung des Chemikers bei gerichtlich-chemischen Untersuchungen und über die Anforderungen, welche von Seiten des Richters an ihn gemacht werden können. Annalen Der Chemie Und Pharmacie 1844; 49th edition:275–286
[11] https://www.aphorismen.de/suche?text=hängen+gestern+war&autor_quelle=Rivarol. Accessed 2021 Apr 29

Date of publication: 11-Jun-2022

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