Analytical Chemistry in the USA - Analytical Chemistry (ACS

REPORT

Analytical Chemistry in the USA in the first Quarter of This Century

I

n 1894 Wilhelm Ostwald (i) wrote, "Analytical chemistry, or the art of recognizing different substances and determining their constituents, takes a prominent position among the applications of the science, since the questions it enables to answer arise wherever chemical processes are employed for scientific or technical purposes. Its supreme importance has caused it to be assiduously cultivated from a very early period in the history of chemistry, and its records comprise a large part of the quantitative work which is spread over the whole domain of the science." Ostwald's statement is a well-deserved recognition of the role that analytical chemistry has played in the historical development of chemistry as a science. In essence, still valid today is the timehonored definition, "Qualitative (chemical) analysis deals with the detection and identification of the constituents of a sample, quantitative chemical analysis with the determination of their amounts." What has changed are the additions of many techniques which are applied to modern qualitative and quantitative analysis, combined with the increasing demands made by other scientific disciplines, including medicine, and by society (environmental, etc.). Early this century, quantitative analysis was mainly confined to solution (wet)

chemistry. On the occasion of the 1976 centenary celebration of the American Chemical Society, it is fitting to consider the contributions made by American nonanalytical chemists to our scientific discipline. Contributions by American nonanalytical chemists At the end of the 19th century and the beginning of the present one, the development of analytical chemistry as a science must be attributed to nonanalytical chemists, both in Europe and in this country. Szabadvary (2) concentrated mainly on contributions by European chemists, and so did I in a very brief historical review (3). Looking over early American chemical journals, mainly between 1900 and 1910,1 was pleasantly surprised to find many fundamental contributions to analytical chemistry. Before discussing these, tribute must be paid to the nonchemist Josiah Willard Gibbs. Exactly one century ago in an obscure journal (4) he published his classical papers, "Thermodynamic Principles Determining Equilibria." Since then the phase rule has played an important part in separations, while many modern papers dealing with equilibria in aqueous and nonaqueous media deal extensively with the concept of the chemical potential, which was introduced by Gibbs. I have selected

Analytical chemistry has been changed by the addition of many techniques that are applied to modern qualitative and quantitative analysis

0003-2700/94/0366-241 A/$04.50/0 © 1994 American Chemical Society

I. M. Kolthoff University of Minnesota

Analytical Chemistry, Vol. 66, No. 4, February 15, 1994 241 A

REPORT

only a few examples of major contribu tions by American nonanalytical chemists to the discipline of theoretical analytical chemistry. One paper, rarely referred to in the literature, is entitled "Quantitative Appli cation of the Theory of Indicators to Volu metric Analysis", published in 1910 by A. A. Noyes (5). The contents of the pa per (Figure 1) illustrate the scope of this work. Generous references are made to many Europeans working in a similar field. To my knowledge, Noyes' paper gives the first complete interpretation of acid-base titrations using indicators for the detection of the end point. The treat ment is made somewhat overcomplicated by Noyes' use of W. Ostwald's definition of "a neutralization indicator which con sists of tautomeric substances of two dif ferent structural types possessing differ ent colors, one of which greatly predominates when the indicator exists as a slightly ionized acid or base and the other when it exists as a largely ionized salt". After considering the two different tautomeric forms in the equilibrium reac tion, Noyesfinallyused the simple mod ern relation

^

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Dissociation constants of some common indicators were given at the end of his paper. The sulfonephthaleins prepared

Wilhelm Ostwald 242 A

Jodttitdebrana was the 9{estor of American physicaC chemistry and one of the pioneers of ear[y ekctroanaCyticaC chemistry. and introduced as acid-base indicators by Lubs and Clark (6) are still of use today. According to Szabadvary (7), "The first book devoted entirely to the analytical aspects of acid-base indicators was Kolthoff s'Der Gebrauch von Farbenindikatoren' published in 1920." Kolthoff had presented evidence to show that it is not only much simpler but also more cor rect to define an acid-base indicator as a substance which in the acid form has a color and a structure different from that in the alkaline form. Mention should be made of the chemi cal determination of the atomic weight of a host of elements by Theodore W. Rich ards (1868-1928), professor of physical chemistry at Harvard University, and his school. He enriched the analytical litera ture with the development of highly pre cise and accurate methods of analysis. The late H. H. Willard did his Ph.D. thesis with Richards. I remember very well the confusion in the chemical world after the first world war. Sentiments right after the war were such that the IUPAC could not function. As a result we had two atomic weight tables, the "international" and the German. In some instances the differ ences between the two tables were undefendably large. The worst difference of one whole unit was that of the atomic weight of antimony. H. H. Willard showed that the German value was the correct one (8). In 1911-12 0. Folin and coworkers pub lished a series of papers on thetitrationof various acids in ethanol, chloroform, car

Analytical Chemistry, Vol. 66, No. 4, February 15, 1994

bon tetrachloride, and glycol-hydrocarbon mixtures. Much use has been made of Folin's titration of cation acids (ammonium ions and amino acids). The fundamental work by J. B. Conant and N. F. Hall in 1927 on titrations of weak bases in glacial acetic acid supplied a strong impetus to further theoretical studies of acid-base equilibria in this solvent Several contributions by American chemists have been made to electroanalytical chemistry. In 1864 Wolcott Gibbs (9) was the first to apply electrodeposition in a quantitative way. Later, Edgar F. Smith and his students made many contribu tions to quantitative electrodeposition of cations and anions. They introduced the mercury electrode for the determination of alkali ions as well as of halides and some other anions. The booklet by Smith (10) in 1894 greatly popularized electrogravimetry. In the preface of the second edition, he stated, "Thousands of analyses are now made annually by these meth ods " The Nestor of American physical chemistry and actually one of the pioneers of early electroanalytical chemistry, Joel H. Hildebrand, was one of Smith's stu dents. His Ph.D. thesis was published in an abbreviated form in 1907 in a paper entitled "The Determination of Anions in the Electrolytic Way" (11). He introduced the rotated silver-plated platinum anode, and he deposited alkali ions on mercury, determining them titrimetrically after

Arthur A. Noyes

treatment of the amalgam with water. An excellent review of contributions to "Electroanalysis" by Americans and by chemists from other countries is found in Z. Elektrochemie, 1908 {12). Hildebrand's paper in 1913 entitled "Some Applications of the Hydrogen Electrode in Analysis, Research and Teaching" {13) gained worldwide recognition. Due credit was given in this paper to Bôttger {14) who at the end of the last century published the first paper on electrometric (Kolthoff introduced the term "potentiometric") titrations with the hydrogen electrode. Hildebrand's type of bell-shaped hydrogen electrode is still used in many laboratories. Hildebrand carried out various types of acid-base titrations—not only titrations of uncharged mono- and diprotic acids, but also of various hydrated cation acids: A P , Be2+, Ce3*, Zr4*, Τ1Λ Nd3* and Pr3*. Analytically important also are the titra tions of sodium carbonate, borax, and aniline with hydrochloric acid, and espe cially of magnesium in the presence of calcium [precipitation of Mg(0H) 2 ] and the titration curves of boric acid in the presence of various concentrations of mannitol (the latter titrations were carried out by H. Harned). Early this century fun damental studies with the hydrogen elec trode were carried out by several Ameri can chemists. In this connection a paper by Loomis and Acree {15) in 1911 entitled "A Study of the Hydrogen Electrode, of the Calomel Electrode and of Contact Po tential" deserves mentioning. An exact study on liquid junction potentials had been published in 1909 in a paper of clas sical importance by G. N. Lewis and W. Sargent {16). In his paper, Hildebrand {13) also gave an example of a redox titra tion of ferrous iron with permanganate and in this connection referred to the ex tensive paper by Crotogino in 1900 {17). A more detailed and partly theoretical study of the potentiometric titration of ferrous salts with dichromate was made in 1913 by Forbes and Bartiett {18) who rec ommended an improved procedure for the titration of ferrous iron salts. The classical book by W. Mansfield Clark {19) in 1920 dealt with all known methods of pH determination, conductiv ity, catalytic (kinetic) methods, and in de tail with indicators and the hydrogen elec trode. His well-known series of buffer

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No. 7.

THE JOURNAL OF THB

American Chemical Society

MASSACHUSETTS INSTITUTE OF TECHNOLOGY, NO. 50]

[CONTRIBUTIONS FROM THE RESEARCH LABORATORY OF PHYSICAL CLIKMISTRY OF THE

QUANTITATIVE APPLICATION OF THE THEORY OF INDICATORS TO VOLUMETRIC ANALYSIS.

By ART H PU A. No T U Received May 4, wo.

Content·. I. GENERAL CONSIDERATIONS: I . Purpose of the Article. 2. The Chemical Nature of Indicators. Equilibrium Relations of the Tautomeric Forms. 3. Equilibrium Relations of Indicators with Reference to the End-Point of Titrations. 4. Experi ments Illustrating the Relation between the Color-Change of Indicators and the Hy drogen Ion Concentration, j . Discussion of the Indicator-Function. 6. Concen tration of the Indicator. II. TITRATION OF MONOBASIC ACIDS AND MONACIDIC BASES:

7. General Formula

tion of the Theory. 8. The Error in the Titration. 9. Error in the Titration when a Neutral Salt is Originally Present. 10. The Best Value of the Indicator Function. II. Limiting Values of the Indicator-Function. 13. Limits beyond which the Titra tion is Impracticable. III.

TITRATION OF TWO MONOBASIC ACIDS OR OF TWO MONACIDIC BASES IN TUB

PRÉSENCE OF EACH OTHER: 13. Separate Titration of the More Ionized Acid. 14. Separate Titration of the More lonired Base. 13. Titration of the Less Ionized Acid or Bate. IV. TITRATION OF DIBASIC ACIDS WITH MONACIDIC BASES:

16. General Formula-

tion of the Theory. 17. Error in the Titration of the First Hydrogen. 18. Best Value and Limiting Values of the Indicator Function for Titration of the First Hydrogen. 19. Error in the Titration of the Total Hydrogen. 20. Best Value and Limiting Values of the Indicator-Function for Titration of the Total Hydrogen. V. TITRATION OF DIACIWC BASES WITH MONOBASIC ACIDS:

21. Error in the

Titration of the First Hydroxy!. 22. Best Value and Limiting Values of the IndicatorFunction for Titration of the First Hydroxy!, a j . Titration of the Total Hydroxyl. VI. SUMMARY: 24. Summary. VII. APPENDIX: 25. Values of the lomzatkm-Conslaiits of Indicators. 26. Values of the Ionization Constants of Adds and Bases.

Figure 1 . Contents of A. A. Noyes' paper on the use of Indicators in titrations. (Reprinted from Reference 5.)

solutions gained worldwide acceptance and is still in use in most chemical and biochemical laboratories. With Clark (and Lubs) also originated a series of papers (published between 1920 and 1930 in Pub lic Health Service Reports) dealing with oxidation-reduction indicators. These were mainly of biological importance with standard potentials near 0 volt (vs. SCE). L. Michaelis had coined the terms "re dox potential" and "redox indicator". How ever, some 30 or 40 years ago when I sub mitted a paper to the /. Am. Chem. Soc.

with the word "redox" in the title and text, the referee (W. M. Clark) insisted that it should be replaced with oxidation-reduc tion, as redox could easily be confused with "red ox." Although not considered of analytical importance early in this century, the seven papers in 1909 on "The Effect of Salts on the Solubility of Other Salts" by Noyes and Bray (and other co-workers) {20) and also by Harkins {21) are still recognized as containing much informa tion of importance in studies of solution


REPORT

analytical chemistry. As a scientific curiosity it may be mentioned that the authors made use of the ion activity concept introduced in 1907 by G. N. Lewis (22). Education in analytical chemistry early this century Qualitative analysis. Although the main emphasis in this section is on education in American universities, a few words should be said about the situation in Europe. Until about World War II, European universities remained ivory towers, concerned with the education of scholars and isolated from society. On the other hand, in American universities education toward a bachelor's degree was directed to provide society with useful citizens. In Europe, analytical chemistry as a separate discipline was not taught in the departments of chemistry. There may have been one or two exceptions. The only one I know of was at the University of Leipzig, where the well-known Wilhelm Bottger, a student of Wilhelm Ostwald, held the Chair in Analytical Chemistry. Pharmacy, medicine, and law were the only professions taught in European universities. When I was a student in pharmacy, it was my good luck to become a pupil of Nicolaas Schoorl, himself a student of the famous van't Hoff, Schreinemaker and Lobry de Bruin School in Amsterdam. School taught analytical chemistry as a science, in addition to courses in pharmaceutical chemistry,

J. Willard Gibbs 244 A

Quantitative anaCysL· was being taught mainly as a technique. Most teTctSoolçs on the subject

did not even mention any theory. quantitative inorganic analysis, organic qual and quant, microchemistry, qualitative inorganic, food and drug analysis, and toxicology. European universities were too (snobbishly) aristocratic to bother about education in any field of engineering or to provide a degree in nursing, home economics, medical technology, or education. Engineering was taught in 'Technische Hochschulen" or their equivalent in different languages. It is hardly necessary to mention that analytical chemistry was part of the technological curriculum. Engineering was and is part of the many "professions" taught at American universities, and this accounts for the fact that, early this century, analytical chemistry—including technical and food analysis—was taught in many U.S. universities. In most American universities qualitative analysis was taught as part of "General Chemistry." In such a course the student became well acquainted with that part of early days physical chemistry, which plays an important role in an understanding of the scientific fundamentals of qualitative and, to a considerable extent, quantitative analysis. A classical (European) book in this field was by Bottger (23) who in 1925 in the seventh edition of this book devoted the first 170 pages to general theory. This included chemical equilibria, Arrhenius' theory of electrolytes (acids, bases, salts—with equilibrium constants), properties of precipitates, Werner theory of complexation, and even eight pages of Kossel theory. In this country the outstanding book was by Julius Stieglitz (24). This book On


its several editions) is a classic, and its contents provided a major part of a course in general chemistry. As such it was also appreciated and used in Europe, even though in those days texts in English were very rare indeed, with the great majority in German. Stieglitz quite rightly considered his treatment also as a necessary introduction to theoretical quantitative analysis. This may explain why early this century quantitative analysis was taught in most universities as a laboratory course, in which a student was familiarized with techniques of gravimetric and titrimetric analysis, not only with determinations but also with "real analysis" (complex materials) (LundelT).A brief résumé of the ("theoretical") contents of the 1912 edition of Stieglitz is still of present interest. Part I consists of 155 pages: two chapters, Theory of Ionization [Arrhenius theory, electrical conductivity, migration (Hittorf) of ions, equivalent conductance, ion mobility, nonaqueous solvents (dielectric constant effects)]; one chapter, Chemical Equilibria (dissociation constants, calculation of pH in acid-base systems, indicators); and one chapter, Heterogeneous Equilibria and Colloidal Conditions. Part II includes Ion Product, Common Ion Effect, Theory of Precipitation of Sulfides, and Theory of Oxidation-Reduction (Nernst equation). Stieglitz' book had much in common with that of Bottger, and both authors referred to each other. In the practical part of his book, Stieglitz made frequent

Joel H. Hildebrand

use of the "System of Qualitative Analysis" by A. A. Noyes and W. C. Bray (25). These classical studies published in 1906 rightfully gained an international reputation, especially since, for the first time in history, the "rare elements" were included. Important new contributions to qualitative (but also to quantitative) analysis were made by Fritz Feigl in the twenties and thirties. He summarized his contributions in a book written in German, an English translation of which was published in 1940 (26). Szabadvary (2) did not refer in his book to Feigl's classical work and books, several editions of which have appeared. A few of the topics, important for spot tests as well as quantitative analysis, dealt with by Feigl were complexation, masking of reactions, factors which affect reactivity such as complex formation, catalysis, and induction (including induced precipitation), reactive functional (mainly organic) groups, "weighting" effects on solubility, and capillary phenomena. Feigl came from Vienna to this hemisphere in 1940 as a refugee from the Hitler regime. I tried to get him an academic position in this country. Unfortunately, a professor in analytical chemistry (name withheld) informed the Department of State that Feigl was a Communist, which was not true. This was the reason Feigl could not get a permanent visa for this country. He settled with his family in Rio de Janeiro. Quantitative analysis. If we consider

Julius Stieglitz

that in many universities general chemistry as well as qualitative analysis was taught on the basis of theoretical chemistry, it is not too surprising that, with some exceptions, quantitative analysis was being taught mainly as a technique. Most textbooks on quantitative analysis did not even mention any theory (cookbooks). A notable exception is the book by Fales (27). From the Preface of the 1925 edition, I quote Perhaps the dominant feature of the text is the manner in which it presents the theory. It will be found, we believe, that this work treats the theory more comprehensively and with greater thoroughness than does any other similar textbook. The customary division of the subject into gravimetric and volumetric methods on the basis of the technique employed has been abandoned, and in its place the development of the subject is based on the fundamental principles which are involved: (1) precision, (2) weighing, (3) measurement of volume, (4) neutralization, (5) solubility product, (6) oxidation-reduction, and (7) evolution and measurement of gases. Without presenting the titles of all chapters, I mention only Chapter VII: Acidimetry, Alkalimetry, General Theory, Indicators (pH, neutralization curves are discussed in detail); Chapter K: Solubility Product Principle, Adsorption, Role and Regulation of Hydroxide Ion Concentration; Chapter X: Application of Solubility Product Principle, Gravimetric and Volumetric Determination of Chlorine, Indirect Determinations; Chapter XIV: Organic Précipitants; Chapter XV: Oxidation-Reduction, General Theory; Chapter XVI: Oxidation-Reduction Calculations (Nernst equation is discussed in detail); Chapter XX: Electrolytic Determinations, Theory; and Chapter XXIII: Introduction to Systematic Analysis, Analysis of Silicate Rock, Determination of Potassium and Sodium. Some theoretical treatment was also given in Popoffs book (28), which in 90 pages deals with theoretical fundamentals^—this section being very similar to a brief theoretical treatment of general chemistry. From the electroanalytical viewpoint, in the 1924 edition the last chapter of 20 pages entitled "Electrometric (potentiometric) Titrations" is outstanding. In addition to the text it also contained 24 instructive figures. Even

though not an American publication, the book by T. B. Smith (29) published in 1929 must be mentioned. It presented an excellent theoretical treatment of the techniques of analytical chemistry. In addition to Fales, several professors of quantitative analysis introduced in their teaching in the thirties the theoretical interpretation of the technique. Without being able to mention all these teachers by name, I list only C. W. Foulk, Ν. Η. Furman, V. Mélodie, M. G. Mellon, S. Popoff, Ε. Swift, and H. H. Willard, with all of whom I have been or am personally acquainted. Foulk, who had worked for a year in Ostwald's laboratory in Leipzig, had been quite influ ential in advocating the teaching of the theoretical aspects of quantitative analy sis. He visited Schoorl and me in Utrecht in 1924, and I have a strong hunch that he was to some extent responsible for my coming to Minnesota. One difficulty which faced many teach ers, especially in state universities and many small colleges, was the poor educa tion provided by many high schools. It was my conviction that the premed stu dents at least should get a notion of what pH is and of the role it plays in acid-base equilibria in blood. Soon after my arrival in Minnesota in 1927,1 gave two lectures to the premed class on this topic. A few days thereafter on the rear platform of a streetcar, the conductor came to me and said, "I should make you pay double fare." I asked why. "Well, you gave us a very

Stephen J. Popoff


REPORT

difficult lecture, and most of us do not know what a logarithm is." In those days in a majority of high schools, the teaching was on a very low level. A colleague at Minnesota, the outstanding colloid and biochemist R Gortner, spent a great deal of time trying to improve the situation. He told me that a candidate often was asked to teach, say, math, even though his major was English or history. "Never mind," the superintendent would say, "you are hired, you get yourself a good textbook, and you can teach math." A month after I had come to Minnesota in 1927,1 was asked to give a talk before the ACS Section at Fargo, ND. In order to get travel expenses paid, I also had to give a convocation talk which was entitled "Comparison of High School Education in USA and in Holland." With the ignorance and arrogance of a newcomer, I felt that I could generalize and said among other things, "The education provided by Schools of Education is based on the fallacious theory: It does not matter what you

Theodore W. Richards

teach, if you only know how to teach." "In Holland," I added, "there are (1927) no Departments of Education, and I hope that they never will have them." (The situation now has greatly changed in this country as

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well as in Holland.) When I returned to Minnesota, my comments on Schools of Education made at North Dakota were already known, and I got quite a lecture (and licking) from the dean of that school at Minnesota Prestige in which analytical chemistry was held. In Europe as well as in this country, analytical chemists were looked down upon by chemists in the other disciplines. Wilhelm Ostwald (2) said in the preface to his book (1894) that analytical chemists were considered as the maid servants of the other classes of chemists. Even their role in industry was only that of skilled workers. As a matter of fact, it was a source of great grief to me that my early Ph.D.s who accepted industrial positions were requested to act only as analysts. In discussing the matter with my colleague, the late F. H. McDougall, head of the Division of Physical Chemistry at the University of Minnesota, he consented in 1934 that outstanding students

could major in physical and minor in ana lytical chemistry, and that I could act as a major adviser. Of course, the candidate had to take all required courses for a ma jor in physical chemistry, and the topic of the thesis had to be approved by the phys ical chemistry division. Many readers may be surprised to learn that the well-known analytical chemists J. J. Lingane and H. A. Laitinen majored in physical chemistry. Among others who majored in physical chemistry were the late H. C. Yutzy, who became a vice-president of Eastman Kodak Co., and H. L. Sanders, who intro duced in his thesis (1937) ion-selective electrodes. On the other hand, some of my early outstanding Ph.D.s with a major in analytical and a minor in physical have attained full recognition in their later ca reers. For example, V. A. Stenger became head of the Analytical Division at Dow Chemical Co. Well known, not only in this country but worldwide, is E. B. Sandell, a very successful teacher who established

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colleagues in the above commission, but also with W. A. Noyes and Linus Pauling. They told me that physical chemistry could take care of the commissions in ana lytical which I wanted to have established. In short, under W. A. Noyes as president, the entire structure of IUPAC was reorga nized. Five sections (now divisions) were established in 1951, one of which was the analytical section. It then became possible to establish various commissions repre senting the entire field of modern analyti cal chemistry. Another illustration of the low standing of analytical chemistry is the following. As mentioned in the next section, in the first decade of this century the majority of pa pers published in the /. Am. Chem. Soc. were analytical in nature. The breakdown into the various divisions of chemistry started with Vol. 31 in 1909 with two sec tions in the Table of Contents, "General, Physical, and Inorganic" and "Organic and Biological." When I served as an asso-

an international reputation with his book "Colorimetric Analysis" and as co-author of an internationally used textbook. Fortu nately, in the forties, there was general recognition that our Ph.D.s with a major in analytical, and usually a minor in physi cal chemistry, had a thorough back ground in fundamental chemistry. Internationally, recognition of analyti cal chemistry remained at low ebb. At the risk of being too personal, I like to add that in the International Union of Pure and Applied Chemistry (IUPAC), there was only one commission on "Reactions and Reagents in Qualitative Analysis" which represented analytical chemistry. In 1949 I wrote a stiff letter to Martin F. Bogert, professor of organic chemistry at Colum bia University and then President of IUPAC, explaining the poor representa tion of analytical chemistry in IUPAC. I was asked to act as an alternate at the IUPAC Conference in 1949 in London. There, I had hot arguments, not only with

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Vol. 66, No. 4, February

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247 A

REPORT

'Nowadays anaCyticaichetmstry is no [ess important than in 1903, but the other branches have grown eiçtensiveiy. 9ί. Ά. Laitinen ciate editor of the/. Am. Chem. Soc., I objected to the fact that the Table of Con tents did not list analytical chemistry as a subdivision. This became a painful issue settled, not by adding analytical to one of the sections, but by doing away with two sections altogether. American journals publishing ana lytical papers. Although Germany since 1862 had its Ζ Anal. Chem. published by Fresenius, and the United Kingdom since 1874 The Analyst (published by the Soci ety of Analytical Chemists), it took a long

time in this country before the analytical chemists had their own journal. Going over the Table of Contents of the/. Am. Chem. Soc. between 1900 and 1910,1 was impressed with the huge number of ana lytical papers of a typical classical charac ter published in this (prestigious) journal. Many analytical papers are also found in the American Chemical Journal, Technol ogy, and Industrial and Engineering Chem istry. In 1929 the first volume of Industrial and Engineering Chemistry, Analytical Edition was published. Several of us (par-

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ticularly Foulk, Willard, Furman, Popoff, Mellon, Meloche, and Swift) objected to the fact that the title did not do justice to the role of analytical chemistry as a scien tific discipline. It was not until 1948 that the first volume of our present journal Analytical Chemistry was published as Volume 20. Further details on this journal are found in the history of our Analytical Division of the ACS. From the above it is quite evident that early this century analytical chemistry already flourished in this country. As H. A. Laitinen (private comment) stated: "It is evident that a large part of American chemistry in 1903 was analytical. Nowa days analytical chemistry is no less impor tant than in 1903, but the other branches have grown extensively." References (1) W. Ostwald, Die wissenschafllichen Grundlagen der analytischen Chemie, Engelmann, Leipzig, Germany, 1894. (2) F. Szabadvary, History ofAnalytical Chem istry, Pergamon, London, England, 1966. (3) I. M. Kolthoff, Anal. Chem., 45, 24A-37A (1973). (4) J. W. Gibbs, Trans. Conn. Acad. 3,108, 343 (1874-78). (5) A A Noyes,/. Am. Chem. Soc, 32, 815 (1910). (6) H. A Lubs and W. M. Clark,/. Wash. Acad. Set., 5, m (1915). (7) F. Szabadvary, History ofAnalytical Chem istry, ρ 365, Pergamon, London, England, 1966. (8) H. H. Willard and R. K. McAlpine,/. Am. Chem. Soc, 43,797 (1921). (9) Wolcott Gibbs, Ζ Anal. Chem., 3, 334 (1864). (10) E. F. Smith (University of Pennsylvania), Electrochemical Analysis, 1st éd., Blakiston, Philadelphia, Pa., 1894. (11) J. H. Hildebrand,/. Am. Chem. Soc, 29, 447 (1907). (12) Z. Elektrochem., 14,3-12 (1908). (13) J. H. Hildebrand,/. Am. Chem. Soc, 35, 847 (1913). (14) W. Bottger, Z. Phys. Chem., 24,353 (1897). (15) N. E. Loomis and S. F. Acree, Am. J. Chem., 46, 585-635 (1911). (16) G. N. Lewis and W. Sargent,/. Am. Chem. Soc, 31,363 (1909). (17) F. Crotogino,Z. Anorg. Chem., 24,225 (1900). (18) G. S. Forbes and E. P. Bartlett,/ Am. Chem. Soc, 35,1527 (1931). (19) W.M. Clark, The Determination ofHydrogen Ions, Williams & Wilkins, Baltimore, Md., 1920. (20) A A Noyes and W. C. Bray,/. Am. Chem. Soc, 33,1643,1650,1663 (1909); W. C. Bray,i6id.,pl673. (21) W. D. Harkins, ibid., pp 1806,1827,1836. (22) G.N. Lewis, Proc Am. Acad. Sci., 43,259 (1907); Z. Phys. Chem., 61,129 (1907). (23) W. Bottger, Qualitative Analyse undihre

(24)

(25)

(26)

(27) (28) (29)

wissenschaftliche Begriindung, 4th to 7th eds., 646 pp, Engelmann, Leipzig, Ger many, 1925. J. Stieglitz, ne Elements of Qualitative Chemical Analysis, Vol 1, Fundamental Principles, Their Application, Century, NewYork,N.Y.,1912. A. A Noyes and W. C. Bray, Technology (Quarterly), Parts I and II, 19,191-291 (1906); A. A Noyes, W. C. Bray, and Ε. Β. Spear, Part III, 21,14-126 (1908). F. Feigl, Specific and Special Reactions for Use in Qualitative Analysis, with Particu lar Reference to Spot Test Analysis, transi, by R. E. Oesper, Elsevier, New York, N.Y., 1940. H. A Fales, Inorganic Quantitative Analy sis, Preface, Columbia Univ. Press, New York, N.Y, 1925. S. Popoff, Quantitative Analysis, 342 pp, Blakiston, Philadelphia, Pa., 1924. T. B. Smith, Analytical Processes, Physico Chemical Interpretation, Arnold, London, England, 1st éd., 1929,2nd éd., 1946.

This report is dedicated to Joel H. Hildebrand, a pioneer in modern electroanalytical chemistry. It was originally presented at the Division of Analytical Chemistry, Centennial Meeting, ACS, New York, NY, in 1976 and is adapted from Analytical Chemistry 1977,49(6), 481A487A

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