Samuel Parsons Mulliken: Pioneer in Organic Qualitative Analysis

Samuel Parsons Mulliken: Pioneer in Organic Qualitative Analysis

16 Bull. Hist. Chem. 24 (1999) SAMUEL PARSONS MULLIKEN: PIONEER IN ORGANIC QUALITATIVE ANALYSIS vd . Ad, Unvrt f Mhtt, Ahrt Introduction fr brprt h Shl n 88, S rd fr t r n ll pthr hp. Wth th hlp Mt htr jr n th dd fr th 0 f n f th frt Whlrht Sntf nd hlr thrh th 0 rbr th rn lttv hp (6, h ntrd MI n th fll f 88. S nl lbrtr— fndl, thr. lnt frnd nd fll brprt ntv, Arthr Whtvr th rlltn, "rn l" rvd nd A , l ntrd MI tht fll. ntn t rv n prp, t ntbl th d Mlln, rvd Whlrht hlrhp vlpnt f rtl thnn nd ll nl ll. nd tdd htr. A ntr, nd Stt rn lttv nl n t Mlln prfrd hl xprnt tthr t th rn htr lrl n Arn n bth thr fl h, t t th d f vntn, bn n th lt nntnth ntr b r. thr prnt (4. Sl rn Mlln t th Mhtt Inttt f hnl (MI (, 2. Mlln pnt t f h Graduate School rr rrhn, thn, nd rtn b bt rn l t MI. h ppr dtl th pnrn Aftr rdtn n htr fr MI n 88, S rl f rfr Mlln n th dvlpnt f tht htr t th Unvrt f Cnnnt fr n tt rn lttv nl nd prnt r n Atnt n Chtr. , tthr th rltd pt f h d lf. An rlr pbl fll MI rdt Arthr A. (86, At tn n E UCEUS, th ffl pbltn f th . Gll (86, nd rdr . llrd (8, thn trv rthtrn Stn f th Arn Chl S ld t Grn t pr rdt td. Althh h t, lthh thn n th dvlpnt f rn rnll ntndd t r n Adlf vn r lb l, nl dvtd t Mlln prnl lf n Mnh, S vntll nrlld t th Unvrt f nd prfnl rr (. pz t r ndr th drtn f hnn Wln. Mlln rvd h r. n htr n Early Life in Newburyport, Massachusetts th r f 80 nd rtrnd t Ar (, 8. S pnt th ntr f 80 ndtn phl Sam Mulliken was born in the family home t 46 h hl rrh t MI. In prn 8 h btnd Strt n brprt n br , 864. rl ptn ll n Chtr t th nl tblhd ntrt n htr r fr rdn "Cnvrtn Clr Unvrt n Wrtr, Mhtt (. r n Chtr" b n Mrl, th b tht bth n th 82 d r h rd t rn Mr h fthr, M Mlln, nd h n, brt (h Cll At n Chtr, thn rtrnd t Clr tr bl rz, 66, rd (4, . Aftr rdtn t r bth Intrtr n Orn Chtr nd Bull. Hist. Chem. 24 (1999) 17 Acting Head of the Chemistry Department from 1892- .....comprises practice in the methods of ultimate 94. While at Clark he conducted and directed research analysis, exercises in the preparation of a variety of typical organic substances, and a series of experi- on the electrolysis of organic compounds (10). Subse- ments illustrating the characteristic reactions of the quently, he worked for a year as a Research Assistant in different classes of substances and their identifica- Oliver Wolcott Gibbs' private laboratory in Newport, tion and separation (emphasis added by author). Rhode Island. In the Fall of 1895 Sam accepted an ap- The "series of experiments" highlighted the descriptive pointment as Instructor in the Chemistry Department at chemistry of the organic functional groups and the "iden- MIT (11, 12). While at MIT he was promoted to Assis- tification and separation" illustrated a practical use of tant Professor in 1905, Associate Professor in 1913, and this knowledge. Thus the emphasis on descriptive chem- Professor in 1926 (13). istry and practical use initiated in the inorganic qual course was applied to the organic laboratory course. The Massachusetts Institute of Technology - The 1896-97 MIT Annual Report states (20): Early Years and Arthur A. Noyes the special course of laboratory experiments on the detection and separation of the various classes of Arthur A. Noyes had been in the MIT chemistry depart- organic compounds, inaugurated last year ... has been ment for five years when Mulliken returned as a faculty considerably extended and improved by the publica- member in 1895. Noyes, though initially trained as an tion of textbook to accompany it. So far as is known, organic chemist, soon embraced physical chemistry a course of this kind is not as yet presented by any while simultaneously developing a life-long interest in other institution. The success which has attended its inorganic qualitative analysis. As early as 1892 Noyes introduction here, is, therefore, worthy of special published a set of notes for the inorganic qual class at notice. MIT (14). He wrote these because the available texts were either too brief or too encyclopedic for the under- Organic qualitative analysis as a part of the graduate laboratory (15). In the preface to the third edi- chemistry curriculum was born tion of the notes, written in 1897, he stated (16): The exact date on which these changes came into effect ....qualitative analysis is a satisfactory method of is difficult to determine because the inclusion of events teaching a part of descriptive chemistry chiefly be- cause it unites into a connected in official catalogs and reports often follows their ac- whole a great variety of isolated tual implementation. However, facts, and because it makes evident the facts that the accompanying to the student a practical use of the textbook was published in 1896 information presented to him. (21), and that the 1896-7 annual In further pursuance of this dual report contains a discussion of the "descriptive chemistry" and "prac- altered course suggest that the tical use" approach, Noyes and the change was made in the fall of newly appointed Sam Mulliken set 1896. The fact that a description out at once to revamp the organic of the revised laboratory program laboratory (17). As a result of their first appeared in the 1897-8 cata- work, the descriptions of the or- log is explained by the early pub- ganic laboratory changed, reflect- lication date of the catalog. It is ing the shift in pedagogical philoso- reasonable to conclude that phy. In the 1896-97 MIT catalog Mulliken and Noyes began their the organic laboratory is described collaboration on organic qual as as including (18): soon as Mulliken arrived in the fall of 1895, if not before. the methods of ultimate analysis, followed by exercises in the prepa- ration of a variety of typical or- The First Textbook ganic substances and in original research. brtr Éxprnt n th In the following year the catalog Cl tn nd Idntf tn f Orn Sbtn, pub- read (19): Samuel P. Mulliken, MIT 8 ll. t. Ch. 24 ( lhd n 86 b nd Mlln (2, th frt any organic compound may be accurately iden- tt trtnt f rn lttv nl d tified in much less time than by determining its com- nd fr th d lbrtr. In th prf t t position by combustion, etc. thrd dtn t ttd tht th (22: In 04, ftr ht r f pntnl dtld lb .....supplement to the ordinary course of instruction rtr r, Mlln pblhd A Mthd fr th Idn in preparation work (and).... although the primary tftn f r Orn Cpnd l I (28). purpose of the experiments ... is to illustrate the char- h vl ntn dtld drptn f thd acteristic reactions of organic compounds, their ana- lytical significance is a feature of no slight impor- tance .... h drptv nd prtl pt f th r r dtntvl dffrnt fr th l rtn rn ntht thd f th t. tbl, Ir n ndd th txt, ttn tht b drv n "t t nt rt, t r hnll ... tht n pnn tn f th nd" nd d nt. ntd th nd Mlln txt n th lttr t r nd td tht t "ll b f rv" (23). h Mlln frt, brf fr nt n f trt pnnn th nxt 26 r, n hh h tlnd th nl nd dntftn f pr rn pnd. ntrt n rn pnd dntf tn vntll trnd h ntr prfnl tv t trd th ffrt. dvlpd nd tht r n ndrrdt nd rdt rn lttv nl h th tdnt rd n pplbl lbrtr thn nd h ltd h rtn nd pn tvt t th rn lttv nl vl h rrhn nd bt t pblh. h Mlln Sh fr th Idntftn f r Orn Cpnd A. A. Noyes fr th tt dntftn f rn pnd In th lt 80 Mlln rrh ffrt hftd ntnn rbn nd hdrn r rbn, hdrn, pltl t h rn l r. nfrn pr nd xn. It l nld drptn f bt 2,00 nttn nd pbltn nldd ppr n th d pr rn pnd pd f th lnt. ttn f thl lhl ln (24, nd n xtr h thd bd lrl n hl rtn, l (2 nd th dttn f th ntr rp (26. Aftr thh tt fr phl prprt r nldd. bt 00 h ppr t hv bndnd pblhn Sbnt Mlln "Mthd" vl flld: prt jrnl rtl n nl nd l rtn, l I (2 n 0 dl th rl dtff ptn ntd t pblh th prt f jr r l II (0 n 6 ntn drptn f rn n tt rn lttv nl. pnd ntnn ntrn nd l IV (31) n In brr f 0, t tn f th rtht 22 pltn f rn pnd ntnn rn Stn f th Arn Chl St, Mlln lnt thr thn rbn, hdrn, xn, nd n tlnd h rn lttv nl h n n trn.

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