CHARLES V. BANKS AND ROBERT F. SIECK Department of Chemistry, Iowa State University, Ames, Iowa 50010
The Relevance of Graduate Research in
TF ANALYTICAL CHEMISTRY IS Ά fad d i n g discipline as has recently been suggested, t h e n one might say t h a t t h e question of relevance has al ready been settled. W e do not t h i n k t h a t this is the case, however, for we are convinced t h a t the discipline of analytical chemistry finds itself not in its waning years b u t r a t h e r on the threshold of an increasingly signifi cant involvement on a broad front. T h i s involvement will be not just with chemists, but with people from m a n y disciplines who are a t t a c k i n g some of the critical problems of our time. I n a recent guest editorial, P r o fessor F r a n k Westheimer stated : " T o d a y , the cry is for rele vance, and chemistry is su premely relevant. T h e known problems t h a t face society in clude population control, cure of disease, maintenance of food sup ply, development of new m a terials, and control of pollution. I t would be somewhat of an ex aggeration to say t h a t these are chemical problems. B u t it would be a gross exaggeration to say t h a t chemistry is not required for their solution." ( J ) . W e agree with Professor West heimer and would go on to suggest t h a t analytical chemistry will be a t the forefront in this endeavor. T o tackle the problems of our time, we need problem solvers, and the disci pline of analytical chemistry is one which can develop t h a t t y p e of per 56 A ·
son. T h i s is the basis for the broad involvement of the analytical chem ist. As D r . S t u a r t P . C r a m has re cently s t a t e d : "A very broad field in scope, analytical chemistry represents a large fraction of t h e research and development effort of the chemis t r y profession because it is so relevant and so pertinent to the work of all experimental chem ists." " I n this decade, research efforts will be directed toward solving the problems at hand. . . . analytical chemistry should be at the forefront of research, solving the problems of t o d a y . " (2). T h e r e are those who recently seem to have been intent on ques tioning the relevance of analytical chemistry. Others h a v e stated quite bluntly t h a t the discipline of analytical chemistry is on the w a y out. I t would seem however, t h a t it is more common to see statements which might be p a r a p h r a s e d as fol lows: "Chemical analysis is funda m e n t a l to the needs of m a n y areas of science, engineering, medicine, and even the arts and humanities." A p p a r e n t l y much of the criticism of the discipline of analytical chem istry has been more concerned with the issue of nomenclature t h a n with t h e issue of the n a t u r e of t h e disci pline itself. W e do n o t wish to enter the debate concerning w h a t the work commonly associated with analytical chemistry should be called. I t is t h e activity of the a n a
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lytical chemist which is the impor t a n t factor, not the n a m e the ac t i v i t y goes by. I t is not difficult to find a de scription for the activity of the analytical chemist. I n fact, there seems to be a plethora of descrip tions available. L e t us look a t three descriptions which h a v e been given over the last t w e n t y years. 1. ANALYTICAL CHEMISTRY
"Analytical chemistry m a y be considered as comprising all tech niques and methods for obtaining information regarding the compo sition, identity, purity, and con stitution of samples of m a t t e r in t e r m s of kind, q u a n t i t y , and groupings of atoms and molecules, as well as the determination of those physical properties and be havior which can be correlated with these objectives." (β). 2. ANALYTICAL CHEMISTRY
"Analytical chemistry is the science of chemical characteriza tion and measurements. I t in cludes the theory, methodology, and instrumentation to carry out all aspects of its operations, such as sampling, separations, chemi cal steps, physical measurements, computations, and d a t a process ing." (4). 3. ANALYTICAL CHEMISTRY
" T o d a y t h e analytical chemist is concerned about a wide spec t r u m of measurements. H e is in volved not only in determining
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what and how much is present (composition), but also what form (structure), how it is bound (valence), where it is spatially (location), and how uniformly it is distributed (homogeneity)." (5). These descriptions should suffice to give us a feel for the kinds of ac tivity which are a part of the disci pline of analytical chemistry. It is the need for these kinds of activity in a wide spectrum of. man's en deavor which furnishes the basis for the involvement of analytical chem istry in the solution of the basic problems of our time. This involve ment is claimed not in an attempt to overly glamorize analytical chem istry, but simply in recognition of the fundamental role chemical anal ysis plays in the solution of a great number of man's problems. If the discipline of analytical chemistry is to fulfill this important role in the years to come, a strong graduate research program must bo sustained. The relevance of grad uate research in analytical chem istry stems from the fact that it is through graduate research that per sons can develop the ability and the skills necessary to solve problems. The type of person produced by graduate research in the discipline of analytical chemistry, or any other discipline, as a matter of fact, will be profoundly influenced by the whole graduate education program. The context within which the pro gram is understood, the nature of the program, and the objectives of the program will all be involved in shaping the end result. We should like to discuss the context, the na ture, and the objectives of graduate research in a bit more detail. We recognize that it is a bit pre sumptuous to attempt to deal with the subject of graduate research in analytical chemistry in a short pa per, but it is, perhaps, forgivable if one keeps in mind that the intention is to be suggestive, not inclusive. As has been indicated, we think that graduate research is a very impor tant human activity, one to be valued and encouraged. However, a clear understanding of the im portance of graduate research
should begin with an appreciation of the diversity and breadth of hu man activity of which it is a part. It is in this context that the pur poseful nature of man's activity be comes clear. Graduate research, along with the rest of man's activ ity, is to be seen as part of the un ending effort to enhance the wel fare of man, to uplift the human spirit, and to create opportunity for fulfillment and expression of the hu man self. The more specific context of grad uate research is, of course, the uni versity. Just what the university is, or ought to be, is a subject of much debate these days. The func tion of the university and the rela tionship of the graduate school to the university are being questioned by persons inside and outside the academic community. At the risk of great oversimplification of some of the complex issues involved, we want to affirm the proposition that the university is first and foremost a place for education. The univer sity must be a community where the heritage of man is examined, and where the truth of the past is sub jected to scrutiny so that new in sight may bring a higher wisdom and understanding. The best tradi tion of human values should be ex amined, questioned, and reformu lated as a basis for shaping new directions for man and for society. The uni\^ersity should be committed to an untiring effort to expand the capacities and the opportunities for all mankind. Graduate research, as part of the university community should be a partici]oant in the educational em phasis. It should not be directed only at the acquisition of new in sight and new knowledge, but also should involve the development of persons with critical skills, Such persons should learn not only the method and technique of acquiring a new knowledge, but should also gain a critical perspective of the na ture of research activity and its place in the economy of human af fairs. The educational emphasis in graduate research is fundamental to the nature and function of graduate research.
Focusing now on the nature of graduate research, some comments should be made about the "basic vs. applied research" debate. We think that this is a misleading distinction which has done more to confuse than to clarify. It has been argued by many that graduate research programs do or should do basic re search while industrial research pro grams should do applied research. While there are differences in the way in which problems are defined in some instances, we suspect that close examination of the activities of various kinds of research pro grams would reveal less difference than is implied by the basic-applied distinction. It would seem that Dr. Alvin M. Weinberg (β) was right when he ar gued that basic research and applied research form a continuum, and that to try to overemphasize one at the expense of the other weakens the whole effort. Fundamental research can set a certain tone and standard in a research group which helps workers keep abreast of develop ments in all areas of science and which helps hone the critical per spective used to evaluate ongoing work. At the same time, research on more applied problems gives a certain life and reality to research activity. Applied research often opens the way for forays into new fundamental areas. Within a re search group theprcsence of applied research activity may be helpful in maintaining realistic boundaries for the whole research effort. The complimentary interplay of basic and applied research is well il lustrated in some of the work on metal (II) -ficr-dioximes. Following the discovery of the reaction be tween dimethylglyoxime and nickel ions by the Russian chemist Tschugaeff in 1905, chemists were pri marily interested in the application of this reaction to the gravimetric determination of nickel. In time, however, it was realized that if the reasons for the selectivity of this reaction could be found, it might be possible to design new reagents for the determination of other metals or to devise other procedures utilizing dimethylglyoxime.
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I t was soon learned t h a t the selectivity of the reaction was due to the unusually low aqueous solubility of the chelates of nickel, palladium, and p l a t i n u m as compared to the chelates of other metals. One of the first things necessary, of course, was t h e determination of the n a t u r e of the complex. Chemical studies, reinforced by magnetic susceptibility studies, indicated a square p l a n a r complex with two ligands per m e t a l ion, coordinated through the two-ligand nitrogen atoms. Another feature appeared to be very strong hydrogen bonding as evidenced by the lack of reaction of the hydroxyl protons with reagents such as acetic anhydride, phenyl isocyanate, dimethyl sulfate, and methyl magnesium iodide. Solution studies revealed t h a t the p r i m a r y reason for the greater solubility of the chelates with such metals as copper was the much greater tendency of these metals to coordinate additional ligands, including solvent molecules. As more powerful physical tools became available it was possible to obtain better spectra of the solid complexes and their solutions. These studies, fundamental in n a ture, led to the development of practical methods for the spectrophotometric determination of v a r i ous metals using vzc-dioximes as chromogenic reagents. I n addition,
Tabfe I:
Table II:
Analytical Applications of the v/c-Dioximes Extraction Methods
Metal Nickel
Palladium
Rhenium
References to Procedures B u t t s et al., 1950 (11); Gillis et al., 1.954 (12) CHC1 3 Hooker, B a n k s , 4-Methvliiioxime 1955 (IS) 4-Isopropyl- CHCls Hooker, B a n k s , moxime 1955 (18) 4-Isopropyl- Xylene McDowell et al., nioxime 1959 (14) CHC1 3 Nielsch, 1954 (IB) Dimcthylglyoxime CHC1 3 Hooker, B a n k s , 4-Methyl1955 (18); B a n k s , nipxime Smith, 1959 (16) 4-Isopropyl- CHC1 3 Hooker, B a n k s , moxime 1955 (18) CHC1 3 K a s s n e r et al., 1961 4-Methvlnioxime (17) Reagent(s) Heptoxime
spectral studies provided insight into the n a t u r e of the solid chelates and their solutions which suggested further fundamental studies. E v e n t u a l l y , X - r a y crystal struct u r e determinations revealed the n a ture of t h e solid complexes and confirmed the structures predicted on the basis of chemical evidence. Several differences in crystal pack-
Analytical Applications of the v/c-Dioximes Gravimetric Methods
Metal Nickel, macro
Reagent(s) Heptoxime 4-Methylmoxime 4-Isopropylnioxime
Nickel, micro
Heptoxime
Palladium
Nioxime 4-Methylnioxime 4-Isopropylnioxime
References to Procedures Voter, B a n k s , 1949 (7) B a n k s , Hooker, 1956 (8) B a n k s , Hooker, 1956 (8) Ferguson et al., 1951 (9) Voter et al., 1948 (10) B a n k s , Hooker, 1956 (8) B a n k s , Hooker, 1956 (8)
Solvent CHCls
ing became apparent. These differences h a v e led to a better understanding of t h e origin of the variation in the solubilities of the various metal (II)-vi'c-dioximes in noninteracting solvents. T o test the theories regarding the n a t u r e of the solubility differences, several new inc-dioximes and their complexes with various metals were prepared. These reagents and their complexes with metals not only p r o vided more evidence of a fundamental nature, b u t also proved to be of utility in the development of gravimetric analytical procedures. A s u m m a r y of these applications is shown in T a b l e I. Solubility studies lead to the conclusion t h a t extractions into organic media might prove worthwhile, not only by providing evidence concerning the n a t u r e of the species present in solution, b u t also, from a p r a c t i cal standpoint, b y providing suitable media for spectrophotometrie analyses. J u s t how useful such extractions proved to be is illustrated in T a b l é I I . T h e fundamental studies of the m e t a l ( I I ) -înc-dioximes h a v e not been completed. Those studies
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which h a v e been m a d e h a v e pro vided considerable information, some of which has suggested further basic work, and some of which h a s suggested practical applications. T h e research on t h e metal (II) -vicdioximes provides a graphic illus t r a t i o n of t h e inseparability of fun d a m e n t a l a n d applied research a n d illustrates t h e fact t h a t work in one area frequently leads t o , or suggests work in t h e other. This kind of research environ ment affords t h e g r a d u a t e student the opportunity t o develop a broad perspective and creative judgment in t h e definition a n d execution of research. T h e student should h a v e the opportunity to p a r t i c i p a t e in the whole research cycle, definition of the problem, gathering of evidence, and t h e evaluation of t h e evidence. Such participation is very necessary to a program of g r a d u a t e research if the individual is t o gain t h e ca pacity to define and solve problems. Some of t h e objectives of grad uate research should now begin to come into view. F i r s t of all, there are some general objectives which should be kept in mind. A very im p o r t a n t objective of graduate r e search is t h e cultivation a n d pro mulgation of t h e scientific method of inquiry. As h a s been noted above, t h e dedication to reasoned argument in t h e definition of prob lems and in t h e evaluation of evi dence and t h e insistence upon fol lowing t h e dictates of evidence a r e at t h e h e a r t of graduate research. T h e nurturing of this approach in the affairs of m e n is a great con tribution to m a n k i n d . I n addition, graduate research should continue to participate in the development of the reservoir of new knowledge a n d ability from which technology flourishes. T h e suc cesses of technology a r e no excuse for t h e excesses and abuses of which we a r e now so aware, b u t t h e ex cesses should not blind us to t h e great benefits m a n h a s accrued from technology. Continued, develop m e n t of the reservoir of new knowl edge and ability is i m p o r t a n t to man. D r . Lee A. DuBridge (18) sug gests t h a t t h e discovery of new knowledge is i m p o r t a n t t o t h e h u m a n spirit. W c agree with this a n d feel t h a t discovery of knowledge
and abilities which enlarge t h e ca pacities and opportunities of m a n are essential to t h e development of a vision by m a n . A vision of hope, not just bounded by what m a y now be possible, is very i m p o r t a n t t o t h e h u m a n spirit. I n as much as grad uate research enlarges this vision, it is an i m p o r t a n t p a r t of m a n ' s total activity. G r a d u a t e research should play a role in t h e development a n d unfold ing of wisdom a n d understanding about m a n a n d about n a t u r e . T h e basic h u m a n quest of m a n t o under stand himself and t h e world about him h a s been ' affirmed through t h e ages. G r a d u a t e research partici pates in this quest in t w o ways. First, t h e knowledge acquired in graduate research can contribute to man's Understanding and second, the research experience can help stimulate t h e researcher t o cre atively a n d enthusiastically apply himself to t h e achievement of wis dom and understanding. T h e development of an individual who is not only competent techni cally, b u t who h a s a broad perspec tive from which he can relate his work to the rest of science is a prime objective of graduate research. E s pecially in t h e discipline of analyti cal chemistry, training of t h e stu dent in t h e basic rudiments a n d giving a cursory exposure to original research is n o t enough. I t is our understanding t h a t industry and t h e society are asking for and in great need of problem solvers. I t is through t h e development of critical skills t h a t a person gains perspec tive concerning his work. If grad u a t e education is doing its job, t h e graduate student should be able t o evaluate t h e evidence uncovered in his work, t h e direction of t h e work, and t h e ramifications of t h e work from a broad perspective which a c counts for m a n y concerns, some of which m a y not be technical. I n testimony before t h e H o u s e Science Subcommittee, D r . Phillip Handler, President of t h e N a t i o n a l A c a d e m y of Sciences, suggested (19) t h a t we introduce a t r u n c a t e d form of graduate education for a large fraction of our present P h . D . candidates emphasizing course work and eliminating independent r e search for all b u t those intending to be lifelong scholars.
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Others have m a d e similar sugges tions a n d some universities a r e a l r e a d y offering a nonthesis masters degree which seems in some w a y s to follow t h e requirements outlined for the t r u n c a t e d P h . D . degree. We cannot speak for all disci plines, b u t in t h e discipline of ana lytical chemistry it seems to us t h a t the movement away from t h e r e quirement for original research would be a step in t h e wrong direc tion. As we h a v e tried to argue, we t h i n k t h a t one learns t o solve prob lems in t h e laboratory and through t h e experience associated with original research. As long as this experience continues to furnish stu dents with t h e opportunity t o d e velop problem solving skills, there will be a demand for analytical chemists with advanced degrees and the relevance of graduate research in analytical chemistry will be o b vious to all. References (1) F . H . Westheimer, Ο hem. Eng. News 48 (24),3 (1970). (2) S. P . Cram, Res./Develop. 21 (7), 16 (1970). (3) P . J. Elving, ANAL.
C H H M . 22, 962
•(1950). (4) H . A. Laitinen, ANAL. C H E M . 38, 673
(1966), (5) W. W. Meinke, ANAL. C H E M . 42 (7),
31Α (1970). (6) A. M . Weinberg, Science 167, 141 (1970). (7) R. C. Voter and C. V. Banks, ANAL'. C H E M . 21, 1320 (1949).
(8) C. -V. Banks
and D . T. Hooker,
ΑΝΑΤ.. C H E M . 28, 79 (1956).
(9) R. C. Ferguson, It. C. Voter, and C. V. Banks, Microkim. Acta 1, 11 (1951). (10) R. C. Voter, C. V. Banks, and H . Diehl, ANAL. C H H M . 20, 652 (1948).
(11) P . G. Butts, A. R. Gahler, and M . G. Mellon, Sewage hid: Wastes 22, 1558 (1950). (12) J. Gillis, J. Hoste, and Y. vanMoffaert, Chim. Anal. 36, 43 (1954). (13) D . T. Hooker and C. V. Banks, U.S. Atomic Energy Commission R e port ISC-597, 1955. (14) B . L. McDowell, A. S. Meyer, R. E . Feathers, and J. C. White, ANAL. C H E M . 31, 931 (1950).
(15) W. Nielsch, Z. Anal. Chem. 142, 30 (1954). (16) C. V. Banks and R. V. Smith, Anal. Chim. Acta 21, 4 (1959). (.17) J. L. Kassner. S. Ting, and E . L. Grove, Talanta. 7, 269 (1961). (18)'L. A. DuBridge, Science 164, 1137 (1969). (19) P . Handler, Chem. Eng. News 48 (31), 10 (1970). This paper was t h e Fisher Award Ad dress presented b y Charles V. Banks at the 160th National Meeting, ACS, Sept. 14, 1970, Chicago, 111. Work referred to was performed in t h e Ames Laboratory of t h e U. S. Atomic Energy Commission. Contribution N o . 2885. Circle No. 60 on Readers' Service Card
