Intern. Zs. f. Gesch. u. Ethik tier Naturwiss., Techn. u. IVied., 4 (1996): 19-30 0036-6978/96/010019-12 $ 1.50 + 0.20 �9 1996 Birkhtiuser Verlag, Basel

Chemical Kinetics as Part of Physical Chemistry in the XIXth Century and at the Beginning of the XXth Century: Analysis of the Origin and Development of Phenomenological Kinetics

Viktor A. Kritsman

Abstract

Dieser Artikel beruht auf meinem Vortrag fiber ,,Origin and Development of the Phenomenological Kinetics as an Important Pm't of Physical Chemistry: 19th-20th Centuries" auf dem XIXth Interna- tional Congress of History of Science (Zaragoza, Spain), 1993. In dieser Abhandlung wurden die Entstehang und Entwicklung der phgnomenologischen chemischen Kinetik vom 19. his zum Beginn des 20. Jahrhunderts aufgund der von mir frtiher entwickelten Methode der Erforschung des geschichtlichen Prozesses der Chemie analysiert. Die historische Analyse wurde mit den verschie- denen Reaktionsmodellen verkniipft, die den wichtigsten kinetischen Theorien als Grundlage gedient hatten. Es wurde auch eine neue Definition der ph~nomenologischen chemischen Kinetik vorge- schlagen. Sie wird als Lehre vonder Reaktionsgeschwindigkeit betrachtet und durch die Verwendung physikalischer Modelle der ldnetischen Gastheorie interpretiert.

At the beginning of the 1850s, the description of chemical reactions by means of formulae had clearly demonstrated the importance of the time factor for studying reactions. At this time chemists finally acknowledged the necessity of studying reaction rates. The development of chemical statics and dynamics in the 1850s- 1870s also stimulated the emergence of phenomenological chemical kinetics as an important part of physical chemistry in the 1880s I. The doctrine of reaction velocity and its interpretation on the basis of the kinetic theory of gases is called phenomenological chemical kinetics. In this doctrine, rates of reactions were studied and calculated mainly theoretically ("formally").

A hundred years later, chemical kinetics had become the theory that deter- mined to a large extent the nature and the trends of research in physical chemistry. Its concepts, laws, models and methods are widely applied now in various branches of science and technology which deal with the transformation of matter and energy by means of chemical reactions 2. This increased importance of chemical kinetics has attracted the attention of many researchers to the problems of its history and methodology from the t880s until now 3.

NTM N.S. 4(1996) 19

F O R S C H U N G - R E S E A R C H Viktor A. Kritsman

Although historical studies have provided much information on factual details, several important matters concerning the development of chemical kinet- ics have not yet been investigated, among them:

- the concept of time in chemistry before the emergence ofphenomenoIogi- cal chemical kinetics in the 1880s;

- the existence of different models (physical, chemical, mathematical) ap- plied to the explanation of the process of chemical reaction; their origins and interaction;

- the transition from the model of "simple" reaction to the model of the reacting system, and the reasons why phenomenological kinetics was replaced by new theories in the 20th century.

In our analysis of the origin and development of phenomenological kinetics, we have used the principles of historical analysis and periodisation of chemical kinetics described above 4. My historical analysis of the origin and development of chemical kinetics is principally about the emergence of the system approach. Special attention is paid to different types of reaction models (see Fig. 1). On the basis of this approach, I identify four periods in the history of chemical kinetics (see Fig. 2). The first three are connected with the origin and development of phenomenological chemical kinetics. In short, the stages of this process can be formulated as follows.

Period I: Prehistory of chemical kinetics (up to the 1850s)

During the scientific revolution of the XVIIth century, chemists developed a view of a reaction as simple combination, dissolution and recombination of particles. These transformations were taken to be instantaneous. In the XVIIIth century this concept of the chemical reaction was implicitly formulated in various tables of chemical affinity, which summarized the results of the comparative studies of chemical processes by Antoine Lavoisier, Torbem Bergman and others. At the turn of the XIXth century, these tables of affinity were replaced by the analysis of states of equilibrium, which were understood as the result of a balance of the forces of affinity of direct and reverse reactions in chemical processes on an almost mechanical analogy (see Claude Louis Berthollet chemical statics (1800- 1803) 5 .

Some investigations at the end of this period had showed, however, that mechanical models of forces of affinity could not account for the pecularities of chemical transformations. For this purpose, several specific chemical models (signs, formulae) were developed.

20

Chemical Kinetics as Part of Physical Chemistry F O R S C H U N G - R E S E A R C H

r

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3 o

O1

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r

m

3 o n~

U"

Fig. 1 1. 2.

3.

4.

5.

6.

7.

8 .

9.

10.

II.

12.

13.

XVIII C. XlX C. XX C. ~

13.

Mechanical "force" models of reactions (R. Descartes, I. Newton, a.o. - Up to middle XVIJI c.). Analogy of mechanical and chemical processes (K. Wenzel, C. Berthollet, a.o. - Second half of the XVIII/beginning of the XIX cc.). Improving the static model of chemical equilibrium (J.L. Gay-Lussac, M. Chevreal, G. Rose

- Up to 1850s). Transition from the static to the dynamic model of chemical transformation (L. Wilhelmy, M. Berthelot, C. Guldberg- 1850s-1870s). Studying the reaction rates, based on the model of the kinetic theory of gases (Collision of spheres, J.H. Van't Hoff, S. Arrhenius, W. Ostwald a.o. - 1880s-1890s). Further development of the theory of collisions (W.G. McLewis, C. Hinshelwood, I. Christi- arisen a.o. - 1910s-1930s). Formation and development of the transition state based on the physico-chemical model of the transition state-"activated complex" and used for the "kinetic description of different reactions (M. Polanyi, M. Evans, H. Eyring, K. Laidler, C. Hinshelwood, N.N. Semenov a.o. - 1930s-1990s). Compiling and studying the Tables of affinity (E. Geoffroy, I. Newton, T. Bergman, A. Lavoisier a.o. - 1700s-1770s). The use of symbols to describe transformation mechanisms (A. Lavoisier, W. Higgins, E. Fulham, N. Clemant a.o. - 1770s-1810s). The use of formula models to describe the mechanisms of complex reactions (H. Davy, J. Liebig a .o . - 1820s-1850s). Early attempts at finding the interrelation between the rates and mechanisms of reactions (A. Kekule, O. Laurent, A. Vernon Harcourt, W. Esson, N. Menshutkin a .o . - 1850s-1870s). Systematically combined physical and chemical models for the kinetic description of different reactions (W. Ostwald, R. Ltither, N.A. Shilov a.o. - 1890s-1900s). Study of simple and complex reactions (including chain reactions), the base of a new physico-chemical model (M. Bodenstein, W. Nernst, C. Hinshelwood, N.N. Semenov a.o. - 1910s-1930s).

NTM N.S. 4(1996) 21

F O R S C H U N G - R .E .SEARCH Viktor A. Kritsman

<

5-

3 t 'D

o

" a

- ~

Q . .

~

XVII C.-XVlII C. XlX C. XX C.

Fig.2. Formation and development of chemical kinetics (periodization) 1. Period I. Prehistory of chemical kinetics - up to 1850s. 2. Stage 1. Doctrine of "affinity" as the basis for studying reactions. Beginning of the concept

of time in chemistry: XVIII-be~nning of the XIXth century. 3. Stage 2. Creating the prerequisities of chemical kinetics: 1800s-1840s. 4. Period II. Emergence of basic concepts of chemical kinetics (1850s-1870s). 5. Period IlL The development of phenomenological chemical kinetics (1880s--1900s). 6. Stage 1. Elaborating the kinetic classification of simple reactions regarded as stages of

complex transformations: 1880s-1900s. 7. Stage 2. Studying the regularities of complex reactions: 1890s-1900s. 8. Period IV. Transformation of chemical kinetics into a science of the interrelation between the

rates and mechanisms of reactions: 1910s-1990s. 9. Stage 1. Investigations of the interrelation between the rates and the mechanisms of simple

and complex reactions: 1910s-middle 1930s. 10. Stage 2. Development of chemical kinetics as a science of the interrelation between the rates

and the mechanisms of the reactions: late 1930s-1990s.

Period II: Emergence of basic concepts of phenomenological chemical kinetics (1850s-1870s):

The understanding of chemical structure in the XIXth century (theory of chemical constitution before 1860) was closely connected with the development of the

concept of the temporal cont inui ty of chemical reactions (Nicola C16ment,

Charles Desormes, Alexander Wi l l iamson a.o.) 6 (see Fig.3). Thus the time factor came into consideration, leading later, mainly in XXth century, to the investiga-

tions of the rate and mechanisms of reactions and relations between them.

22

Chemical Kinetics as Part of Physical Chemistry F O R S C I ' t U N G - R E S E A R C H

t ' )

B .

3 I O i e'~ 1 ~ i m_

t

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7'0 8'0 9'0 XlX 10 ~ 20 3'0 4'0

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3 O

O

/ i I

11 i

_ _- - _- - - _- _- _ _ __ _ _ _ _ _

••4o 5.

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Fig. 3. Main trends in the use of time to characterize the reactions: XVIII c.-1850s 1. First concepts of a multi-stage reaction. W. Higgins, 1789; E. Fulham, 1794. 2. Elaborating the first mechanisms of multi-stage catalytic reactions. 1790s- 1850s. D. Clement,

Ch. Desormes, H. Davy, W. Higgins, J. Liebig, A. Williamson. 3. Acceleration - indicator of reaction rate, 1840s. 4. Time - a function of the multi-stage nature of a process, 1850s, J. Liebig. 5. Separation of chemical dynamics from statics. 1850s, A. Williamson. 6. Application of mechanical analogies to estimate chemical affinity. 1770s, C. Wenzel. 7. Time - the major indicator of dynamics. 1850s, A. Williamson.

An important point was reached with the development o f the concept o f the limit of reversible reactions. This concept was widely discussed in the 1850s- 1870s (Williamson, Ludwig Wilhelmy, Marcelin Berthelot, Cato Guldberg, Peter Waage a.o.) (see Fig.4). 7 Around this time, the idea o f reaction rate as a mathe- matical function of concentration was being developed.

Historians often say that Wilhelmy's study of the rate of the reaction of the catalytic inversion o f sucrose (1850) was ignored by contemporary chemists. 8 True, there were relatively few citations o f his paper, but there are still good grounds for believing that it was read and that it influenced the subsequent development o f this theory and contributed to the transition f rom static to dynamic models of Chemical equilibrium.

In 1861-1863 the Russian chemist Dmitriy Mendelee v stated in his influential textbook on organic chemistry that without the study of reaction rates one could not understand chemical processes (especially complex reactions of organic compounds) 9.

vrrr~i N.s. 4(1996) 23

FORSCHUNG - RESEARCH Viktor A. Kritsman

2. Z B E

3 ~

~- 1 20, 30, 40, ~60 7,'}/// 80,

Fig. 4. Formation of concepts of the conditions of chemical equilibrium reactions: 1800s-1870s 1. "Chemical statics", 1801-1803, C. Berthollet. 2. Experimental study of equilibrium reactions of the exchange of salts. 1840s-1850s, R.

Bunsen, H. Debus, J. Malaguti, M. Margerittes, D. Gladstone. 3. Formation of the concept of dynamic equilibrium and the derivation of the principal postulate

of chemical kinetics. 1870s, J.H. Van't Hoff, C. Guldberg, P. Waage. 4. Electrochemical theories of atTmity. 1810s-1830s, J. Berzelius, H. Davy, M. Faraday. 5. Analogy between physical and chemical processes, 1850s-1870s, R. Clausius, A. Sainte-

Claire Deville, L. Pfaundler, A. Horstman, D.I. Mendeleev. 6. Formulation of the law of mass action, based on mechanical models of reversible reactions.

1860s-1870s, M. Berthelot, L. Pean de Sainte Gilles, C. Guldberg, P. Waage, J.H. Van't Hoff.

A new understanding of the mechanisms of chemical reactions was achieved in the middle of the XIXth century with the development of the concept of intermediate atonlic group, which is produced in the course of a reaction and, depending on the conditions of the process, can be transformed in different ways, resulting in different final products (A. Laurent, A. Kekule). This model, which had developed from the earlier ideas of J. Dumas, Ch. Gerhard and others, found a more exact formulation in the XXth century in the theory of transition state or the theory of absolute reaction rates.

A combination of physical, chemical and mathematical models was used in a series of investigations of chemical dynamics, in particular in the study of the complexity of chemical reactions in the 1860s by Berthelot and Leon Pean de Saint-Gilles, Guldberg and Waage, August G. Vernon Harcourt and William Esson (see Fig. 5). 10

24

Chemical Kinetics as Part of Physical Chemistry F O R S C H U N G - R E S E A R C H

1. ~ 3 . 112" II 4.

3

- 5. 6. 3 o

;3"- ,,<

t 'b

3 o t,-,

1860 1865: 1870 1875 1880

\

Fig. 5. Origin of the fundamentals of chemical dynamics: 1850s-1870s. 1. Modelling the "elementary act" reactions allowing the redistribution of atoms during the

formation of a new atomic associate in the reaction. 1850s, R. Bunsen, H. Roscoe, A. Laurent, A. Kekule.

2. Principles of the theories of chemical structure and of intermediate compounds formed during reactions. 1850s-1870s, A. Kekule, A.M. Butlerov, V.V. Markovnikov.

3. Mechanisms of complex reactions, based on formula models. 1850s-1870s, J. Liebig, A. Williamson, M. Berthelot.

4. Principles of chemical affinity and the kinetic concepts in the study of the structural-kinetic regularities. First s tage- late 1870s, N.A. Menshutkin.

5. Verification of the major chemical notions in studies of reactions. 1850s-1860s. A. Kekule, S. Cannizzaro a.o.

6. The study of the main kinetic regularities of complex reactions. 1860s, A. Vernon Harcourt, W. Esson.

7. Consideration of kinetic characteristics in identifying the individual elements of a kinetic system. 1850s, L. Wilhelmy.

8. Distinction between the regions of chemical statics and dynamics. 1850s, A. Williamson. 9. Establishment of the main principles of chemical kinetics. 1880s Van't Hoff, S. Arrhenius. 10. Showing the dynamic aspect of chemical statics when analyzing formula models. 1850s,

A. Williamson.

Especially important for understanding the reaction system and its kinetic description were a series of publications by the chemist Vernon Harcourt and the mathematician and chemist Esson in 1866-1867.

NTM N.S. 4(1996) 25

F O R S C H U N G - R E S E A R C H Viktor A. Kritsman

Period IH: The development of phenomenological chemical kinetics as part of physical chemistry (1880s-1900s):

The chief founders of phenomenological chemical kinetics, in the 1880s, Jacobus Henricus Van't Hoff and Svante Arrhenius, chose as the fundamental subject of study the idealized simple element of reaction - normal chemical transformation (Van't Hoff, 1884). II The kinetic equation of this transformation was strongly connected with the law of working masses and the molecularity of reaction was also taken into account.

Both Van't Hoff and Arrhenius clearly understood the complex nature of real chemical reactions. They chose the simplest normal chemical transformation as an idealization of the element of reaction, for which a simple physical model could be applied.

The Russian chemist Nikolay Alexandrovich Menshutkin introduced the idea of correlations between the structure of the reagents and the rate of reaction (structural-kinetic regularities) in a series of articles (1877-1906). Finally, these developments formed a basis for semi-empirical methods of calculating the constants of reaction rates - the so-called correlation analysis in chemistry, especially in organic chemistry.

Studies of these structural-kinetic regularities contributed to the emergence of chemical kinetics in the XX century as the science of interrelations between the rates and mechanisms of reactions la

Chemical historiography traditionally attributes to Arrhenius (1889) 13 the first use of the concept of activation energy (E) in the resulting equation of the temperature dependence of the constant of rates of reaction (k) 14 - nowadays known as the Arrhenius kinetical equation : k = Ae -E/RT (1)

This interpretation is, however, inaccurate. S. Arrhenius only outlined the way to the notion of activation energy and showed the possibility of deriving the equation later named after him. He used in his original equation (1889) not the activation energy, but the thermal effect of reaction (q): k = Ae -qmr (2). Later, especially during the development of collision theory in the 1910s-1930s, applications of this equation suggested the replacement ofq by E, leading to this well-known formula for constants of reaction rate k as a function of temperature (T) (see formula 1). This formula gained wide recognition in the 1930s-1990s and was applied to many kinetic problems in various fields of science and technology (Cyril Hinshelwood, Emir A. Moelwyne-Hudges and others) 15.

The formation of phenomenological chemical kinetics was connected with the wide use of very simple physical models, especially in the 1880s-1890s (see Fig. 6). The applicability of these models was not proved but postulated: a clear example of this is Van't Hoff's main kinetic principle and natural kinetic classifications of reactions.

During the second stage of the third period (ca. 1890-ca. 1900), chemists began to study complex reactions (successive, parallel, autocatalytic, etc.). At this

26

Chemical Kinetics as Part of Physical Chemistry F O R S C H U N G - R E S E A R C H

F; u

3 0 t-~

" 0

o m~

3 0 Q..

18'80

.

2 ] 7

1. 6 ~ 9. "I/"/

Fig. 6. Main trends in the formation of phenomenological chemical kinetics: 1800s-1900s. 1. Kinetic interpretation of molecularity. 1850s-1880s, L. Wilhelmy, C. Guldberg, A.G. Vernon

Harcotu-t, J.H. Van't Hoff. 2. The notion of reaction rate constant. 1850s-1880s, L. Wilhelmy, M. Berthelot, C. Guldberg,

P. Waage, A. Vernon Harcourt, J.H. Van't I-loft. 3. Regularities in the rates of "normal chemical transformation", J.H. Van't Hoff, 1880s. 4. Kinetic classification of complex reactions. 1880s-1900s, W. Ostwald, A. Konovalov, R.

Li.ither. 5. Derivation of the principial kinetic laws. 1880s, J.H. Van't Hoff. 6. Deviation from the course of a "normal chemical transformation". 1880s-1890s, J.H. Van't

Hoff, S. Arhenius, W. Ostwald. 7. Establishing the nature of the temperature dependence of reaction rate constant. 1880s, S.

Arrhenius. 8. Investigation of the structural-kinetic relationships. 1870s-1900s, A. Menshutkin, G. Karrara,

A. Lengfeld, A. Brusov. 9. Investigation of the influence of the nature of an "indifferent" solvent on the reaction rates.

1890s-1910s, N.A. Menshutkin, V. Meyer, G. Carrara. 10. Study of the mechanisms of complex reactioas. 1890s- 1900s, J.H. Van't Hoff, C. Engler, A.N.

Bach. 11. Research into the temperature dependence of reaction rate constants. 1880s, J.H. 'Can't Hoff,

M. Konrad. 12. Interpretation of this dependence, based on the concept of "active molecules": S. Arrhenius,

1884-1889. 13. First ideas about "activation energy". 1850s-1900s, L. Wilhelmy, L. Pfaundler, C. Guldberg,

W. Ostwald, C. Engter. 14. Kinetic theories of the XXth century.

NTM N.S. 4i1996) 27

FORSCHUNG - RESEARCH V i k t o r A. K r i t s m a n

time, chemical formula models began to be widely used for calculating the kinetic characteristics of reactions with their rates and mechanisms being taken into account (for example, the works of Arrhenius, Wilh. Ostwald, C. Engler etc.).

C o n c l u s i o n s

- My historical analysis of the origin and development of phenomenological chemical kinetics (and general chemical kinetics) is based on the history of the system approach. Special attention is paid to different types of reaction models.

- The formation of phenomenological chemical kinetics as the science of reaction rates and their interpretation by means of very simple physical models of the kinetic gas theory thus showed that chemists were unable to make a deep study of the reaction systems within the framework of this kinetic theory.

- The limits of phenomenological chemical kinetics became clear by the 1900s, when chemists understood that the further study of the processes of reaction required more complex physical and chemical models.

- However, the main theory ofphenomenological chemical kinetics has not died out. It is possible to show some continuity between the old theory of J. H. Van't Hoff and S. Arrhenius (1880s) and modem kinetic theories of the elementary act of reactions (collision theory and theory of absolute reaction rate) and more complicated reactions (including chain reactions).

Acknowledgments

I am grateful to the staff of the Deutsches Museum (especially to Prof. Dr. Wolf P. Fehlhammer and Prof. Dr. Otto P. Kr~tz) and the Institute of the History of Natural Science of the Ludwig Maximilian University of Munich (Prof. Dr. Menso Folkerts and Prof. Dr. Bri~tte Hoppe) for their constant interest in and support of this research work. I am also indebted to Dr. Alexey Kozhevnikov and Dr. Dmitry B ayuk (Institute of the History of Natural Science and Technology of the Russian Academy of Sciences, Moscow) and Dr. Richard Lorch (Institute of the History of Natural Science of the Ludwig-Maximilian University of Munich) for their comments on the manuscript draft of paper, Prof. Dr. Paul Haake (Westleyan University, Middletown, USA) and Dr. R. Lorch (University of Munich) for correcting my English.

28

Chemical Kinetics as Part of Physical Chemistry FORSCHUNG - RESEARCH

Annotations

This article has been written on the basis of my lecture "Origin and Development of the Phenomenological Kinetics as an Important Part of Physical Chemist~: 19th -20th Cen- tures" at the XIXth International Congress of History of Science (Zaragoza, Spain, August 1993). The main principles of my scientific-historical analysis of the development of the ideas about chemical processes are the results of the investigation in the history of physical chemistry in the 1960s-1990s. These results were developed in my later researches: See notes 2-4. The first description of chemical kinetics I found in the book: Muir M. M. Patisson, A Treatise on the Principles of Chemistry, Cambridge, 1884; for the earliest history of the development of studies of reactions see the article: Kritsman, Viktor A., "Liebe", "Hag" und andere Ursachen chemischer Reaktionen, Chemie in unsererZeit, 1994, H. 5, S. 259-266. Kritsman, V. A., Razvitie kinetiki organicheskikh reakcij (Development of the kinetic of organic reactions), Nauka, Moscow 1970 (Russian). Kritsman, V. A., Strukturno-kineticheskie zakonomernosti. Istoricheskij otsherk (Structural- kinetic regularities. Historical essay), Nauka, Moscow 1974 (Russian). Kritsman, V. A., Khimicheskaya kinetika (Chemical kinetics), Vseobtshaya istoriya khimii, Istoriya uchen(ya o khimicheskom protsesse (Universal Histo~. of Chemistry, The Histol~y of Doctrine of a Chemical Process), Nauka, Moscow 1981, pp. 268-350, 390-402 (Russian). Kritsman, V. A., Formirovanie osnov khimicheskoy kinetiki (Formation of the fundamentals of chemical kinetics), D. Sc. (Dr. II) Dissertation, Institut istorii estestvoznaniya i tekhniki AN SSSR (Institute of the History of the Natural Sciences and Technology, Academy of Sciences of the USSR), Moscow 1989 (Russian). Emanuel, N. M., Zaikov, G. E., Kritsman, V.A, Cepnye reaktsii, lstoricheskiy aspekt (Chain reactions. An historial aspect), Nauka, Moscow t989 (Russian). Kritsman, V. A., A new approach to the historico-scientific analysis of the formation of the fundamentals of chemical kinetics, Institut istorii estestvoznaniya i tekhniki AN SSSR, Moscow, 1990. Kritsman, V. A., The influence of the ideas of chemical thermodynamics on the formation of chemical kinetics in the XIX century, Histo O, and Philosophy. Facts, Trends, Debates, Singapour-New Jersey-London, 1991, p. 480-491. Viktor A. Kritsman, Zur Geschichte der chemischen Kinetik. Die Entwicldung der neueren Anschauungen, Dtsch. Museums Wiss. Jahrbuch, 1999/93, S. 211-229. Kritsman,V. A., "Liebe", "Hal3" und andere Ursachen chemischer Reaktionen, Chemie in tmserer Zeit, 1994, H. 5,259-266. For a list of the most important of these questions in: Emanuel, Zaikov, Kritsman, see note 2, pp. 63-67; Kritsman, A new approach .... see note 2. p. 15; Kritsman, Formirovanie osnov..khimicheskoy kinetiki., see Note 2, pp. 244-252; Kritsman, Vseobtshaya istoriya khimii, pp. 390--402; Kritsman, Chemie in ,mserer Zeit, see note 1. This periodization and other main results were developed in my Dr. Sc. Dissertation (1989), see reference 2. C. L. Berthollet, Essai de statique chimiques, "~ 1-2, Paris, 1803. See Kritsman, Chemie in unsererZeit, note I, 2. See Kritsman, Vseobtshava istoriya khimii..., note 2 and Kritsman, V. A.: Kurzer Abriss tier Begrtindung der klassischen chemischen Kinetik, In: Abhandlungen der 2. Intern. Konfer. Geschichte der Chemie und chemischen Technologie, Budapest, 1996, im Druck. L. Wilhelmy, Ueber das Gesetz, nach welchem die Einwirkung der S~iuren aufden Rohrzucker stattfindet, Poggendorffs Annalen der Physik und der Chemie, 81 (1850), 413-428, 499-526; See also: Ostwald, W., Die Inversion des Rohrzuckers, Journalfiir praktische Chemie. 29 (1884), S. 385-386; Rodnyi, N. l., Solov'ev, Yu. I., Wilhelm Ostwald, Leipzig 1975 (Ubers. a. d. Russischen). D. I. Mendeleev, Organicheskaya khimiya (Organic chemistry), St. Petersburg, 1861 ; 2th. ed. Ibid, 1863 (Russian); See Kritsman, V.A., D. I. Mendeleev o khimicheskom processe (D. I.

NTM N.S. 4(1996) 29

F O R S C H U N G - RESEARCH Viktor A. Kritsman

Mendeleev about chemical process), Khimiya v shkole (Chemistry in the school), (1984), N3, pp. 16-19 (Russian).

l0 See Kritsman, V. A., Vseobtshaya istoriya khimii .... note 2 and Partington, J. R., A History of Chemistry. Macmillan and Co, London 1964, pp. 583-595.

It Van 't Hoff, J. H., Etudes de dynamique chimique, Amsterdam, Frederik MiJller et Co., 1884; See: Van't Hoff, J. H., lzbrannye trudy po khimii (Selected works for the chemistry), Nauka, Moscow 1984 (Russian).

t2 Menshutkin, N. A., Issledovanie obrazovaniya uksusnykh efirov pervichnykh spirtov (Inves- tigation of forming of the acetous ethers of the primaries alkohols), Zhurnal russkogo fisiko-khimicheskogo obtshestva (Journal of the Russian chemical-physical socie~) 9 (1877), pp. 326-342 (Russian); See also: Kritsman, V.A., Osnovnye napravleniya nauchnoy dey- atel'nosti N. A. Menshutkina (Base directions of N. A. Menshutkins scientific activity), Voprosy istorii estestvoznanixa i tekhniki (The problems of a history of natural sciences and technology), N26 (1969), pp. 53-57 (Russian), and Kritsman, V. A., Razvitie kinetiki organi- cheskikh reakcij, note 2.

~3 Arrhenius, S., Uber die Reaktionsgeschwindigkeit bei der Inversion von Rohrzucker durch S~iuren, Zeitschrift derphysikalischen Chemie, 4 (1889), pp. 226-248.

14 See : Ihde, A. I., The development of modern chemistry, Harper and Row, New York, Evanston, London 1964, p. 410.

15 See Kritsman, Deutsches Museum, Wissenschafiliches Jahrbuch, note 2 and Kritsman, X/X International Congress of History of Science, 22-29, August 1993, Zaragoza (Spain) 1993, Book of Abstracts, Zaragoza 1993, P. 3-7, P. 9.17 see note 1. See also Laidler, K. M.: The world of Physical Chemistry, Oxford, New York, Toronto 1993. Kritsman, V. A., Zaikov, G. E.: Chemical kinetics and chain reactions. Historical aspects, Nova Science Publishers, Inc., New York 1995.

Author ' s address:

Dr. sc. Dr. V ik to r A. K r i t s m a n

D e u t s c h e s M u s e u m

M u s e u m s i n s e l I

D - 8 0 5 3 8 Mt inchen

30