The Development of Chromatography THE
TEARS 1971-72 represent three important anniversaries related to the various chromatographic techniques: the 100-year anniversary of the birth of Tswett, the inventor of adsorption chromatography ; the 30-year anniversary of the development of partition chromatography; and the 20-year anniversary of the first paper on gas-liquid partition chromatography. The purpose of this report is, 011 the occasion of the Seventh International Symposium on the Advances in Chromatography, to note
LESLIE S. ETTRE Encyclopedia of Industrial Chemical Analysis John Wiley & Sons, Inc., 605 Third Ave., New York, N.Y. 10016
the importance of these anniversaries and summarize the results of the pioneers that led to the techniques used today. The development of chromatographic techniques alone would assure a permanent place for the pioneers-11. S. Tswett, A. J. P. Martin, R . L. AI. Synge, and A. T. ,James-in the history of chemistry. However, their merit is more than t h a t ; they not only described new techniques but also properly interpreted them, summarized the theoretical basis of the techniques, and showed the possibilities of practical
applications. Thus, their work is an example of how scientific work should be carried out. Twsett, Martin, Synge, and James represent the starting points in a line of distinguished scientists, all of n.hom contributed greatly to the advancement of chromatography. It is impossible t o deal in this report with their activities; also, we cannot deal here with the development of ion exchange, thinlayer, and gas adsorption chromatographic techniques, each of which probably would merit a report in itself. Holyever. it should be em-
REPORT FOR ANALYTICAL CHEMISTS
On the occasion of the Seventh International Symposium on Advances in Chromatography, this Report deals with the importance of the work of Tswett and the circumstances which led to the development of liquid-liquid and gas-liquid partition chromatography
phasized that the pioneers only represent the start, and without the achievements of many known and unknown chemists and scientist,, we would not be where we are today. Adsorption Chromatography: The Life and Work of Tswett
For almost every invention, one can find persons who worked earlier and more or less carried out similar investigations but who are still not considered as the inventors of given techniques, processes, or machinery. Usually, the person recognized as the real inventor not only utilized or
described a phenomenon but also could interpret it and apply it knowingly for some purpose. The situation is not different in chromatography. Tswett certainly had his forerunners who described separation obtained by selective retardation on a column containing a solid substance. The most important person in this field was David Talbot D a y (1859-1925), who was connected with the US.Geological Survey for 28 years and served as the director of its Division of ?\Tinera1 Resources for 21 years. H e demonstrated in 1897 that when
ANALYTICAL - "_
crude oil fractions are pressed through pulverized Fuller's earth, a certain fractionation takes place and, in the forthcoming years, investigated this phenomenon in detail. H e reported on his results in 1900 a t the First International Petroleum Congress in Paris and then three years later a t the 43rd meeting of the U S . Geological Society in Kashington, D.C. (For details on the activities of D a y and his collaborators and their publications, see ref. 1 and 2 . ) It should be noted, however, that, although D a y recognized the analytical potential
CHEMISTRY, VOL. 43, NO. 14, DECEMBER 1971
._
21 A
&
Dcies S/P give you more for your money thari anyone, anyplace?
Here’s our plan for selling you half as many lab recorders. Some things, you want to look at on an X-Y basis. That calls for a recorder. Other things, you want to look at on an X-time basis. That calls for another recorder. Two jobs. Two recorders. It seems so logical. But then, a lot of things seem logical to most recorder-makers: like using separate sheets of paper for every record. Like letting the pen handle the X axis while the bar handles the Y axis. To them, logical. To you, inconvenient. Because every time you switch from one experiment to another, you have to put in another piece of chart paper. And wonder if it’s aligned. And always worry about what part of the X-Y response is response and how much is inertia. And every time you switch from X-Y to X-time you have to switch record e rs.
How L&N can help. What we’ve done is come up with an illogical-from a traditional standpointlab recorder: The Speedomax XL 683 series. The Speedomax XL 683 is two very good recorders. A very good X-Y recorder and-at the flick of a switch-a very good X-t
7
recorder. We sell it as one very good recorder. Which is why we’ll sei1 half as many. One of the things that makes it very good is a roll of paper 100 recording frames long, instead of 100 sheets of chart paper. One roll of 100 pushbuttonaligned recording frames. Instead of 100 alignment problems. Another thing that makes it very good is the way it records. The pen (lowinertia) moves. The paper (low-inertia) moves. The bar ( hi g h - i ne rt i a) does n ’t . That’s why we can spec XL-recorder response in terms of balance time, not slewing speed. And they can’t. All told, just about the best flat-bed recorder you can get. We only wish we could sell twice as many of them.
Don’t let our good reputation fool you. You probably have us filed under “Bridges and Pots” or under “Industrial Recorders.” These aren’t the only places we belong. Not anymore. Because now we’re prepared to lay claim to a larger share of your wherecan - I -get - he1p f i Ie-a section called, perhaps, the “measurement people.” We’re ready now, with equipment for R&D, Q.C., and standards labs. For liquid analysis. For electrical measurements, Temperature measurements And, of course, recording, indicating and controlling. In the lab and out. Mail the quick-service card and we’ll get started.
One of a series in which we go looking for trouble. And business.
i
b
@Automated Business Systems
Count the curve Feed Numatron an analog signal from a thermocouple, RTD, strain gauge-any voltage- or current-output sensor. It gives you digits back. Five significant digits. With lab-like performance (six month zero stability, k 5 . 0 pV; typical full range conformance, 0.1C); and process-environment ruggedness.
Circle K 1 1 on our quick-service card
Circle K 1 2 on our quick-service card
Signal pollution clean-up
pH Lab-in-a-lid
Two new d - c amplifiers featuring exceptional rejection of AC common mode and normal mode signals. Can be used as null detectors, directreading indicators, or low-level isolating or deviation amplifiers in applications involving signals from 0.1 microvolt to 100 volts.
Take L&N’s new portable pH/selective ion lab wherever the ions are: lab, plant or field -weather or not. Rugged, gasketed, convenient; it gives lab performance in severe environments time after time after time.
Other things Circle No. Fast flat-bed recorder K15 One or two-pen Speedomax XL 680 Series flat-bed recorders balance to full-scale change in less than 0.5 second. Accurate to + 0 . 2 5 % of span.
Upstanding versatility XL 600 Series low-profile lab recorders offer one- or two-channel recording on a 9 % ” vertical strip chart; fixed millivolt or thermocouple ranges; AZAR (adjustable zero, adjustable range) spans from 100 pV to 100 V, with optional r+ 1000°/~ calibrated zero suppression. Single, dual, or ten-speed chart drive. Tilting chart table; easy chart tearoff many other convenience features.
Record, file, find, fast Infotrak’s a new idea in recordkeep1ng , And record -f i nd i ng . Lets you record periodic, cyclic, or transient measurements on individual 5” x 8” K e y s o r e cards-so ygu can file them, and find them, fast. Span and zero adjustments. Pushbutton speed selection. Compact (6” x 6”) case. Ail solid state.
*
Circle K 7 0 on our quick-service card.
Circle K 1 4 on our quick-service card.
Circle K 1 3 on our quick-service card.
Service card missing? Write us direct
Gentlemen Send me information on the items I’ve circled K10 K11
K12 K13
K14 K15
K16
K17
K18 K19
0 Please have your representative call
K16
Lab pH and ion-selective meters Four easy-on-the-eyes meters with excellent stability, each keyed to your level of need: low-cost General Purpose to super-competent Digitai.
K17
Portable resistance1 conductance bridge For take-it-where-the-action-is measurements of solutions ranging from ultra-pure water to strong acids, bases or salts. Accurate. Sensitive. Battery or line operation.
K18
Speedomax H Recorders
K19
Record any variable (or up to 123, in multi-point multi-bank mode) on 6 ’ h ” strip chart Or use 3” radius round-chart model
Name Title Company Street city LN 12
Small-Case Controllers Electromax Ill controllers, with analog or digital indication, accept virtually any sensor input, provide full range of control actions.
State ~___
ZIP abcdefghiiklmlo
_.
Report for Analytical Chemists
of the process icvestigated, he and his co-workers interpreted incorrectly the physicochemical basis of the separation, calling it a capillary diffusion process. This is mainly the reason why today, Tswett and not D a y is recognized as the inventor of adsorption chromatography. llichael S. Tswett's life and activities are fairly well documented (3-6) although some of the statements in these summaries are contradictory. His life was a fascinating one, and a typical example of the troubled life encountered later by so many other European scientists mho, due t o the events beyond their control, had to settle a t places far from their homes or find refuge after losing everything. His scientific work shows the activity of one of the clearest and most conclusive minds. Michael S. Tswett was born on M a y 14, 1872, in ,4sti, Piemonte, Italy, as the son of Simeon Tswett, a Russian subject, and his wife Maria Dorosza, an Italian. H e grew up in Switzerland, studied there, and graduated with a P h D ; in 1896, he moved t o Russia and, in ,January 1901, after spending a few years in minor jobs, he found a permanent position a t the University of Warsaw (Poland was then part of Russia). H e successively served as assistant, associate, and full professor a t the University, the School of Veterinary Medicine, and the Institute of Technology of Warsaw until Korld War I interrupted his life. I n 1915, he left Warsaw with the Institute of Technology which was evacuated to Nishi Novgorod (today: Gorkiy) before the advancing German troops. I n 1917 he became ill and spent some time in the Caucasus recuperating, then accepted the chair of botany a t the Vniversity of *Jurjeff. [This was then the name of the city; its German name is Dorpat. After World War I, this area became Estonia, and the city's name was changed from the Russian Jurjeff to the Estonian name Tartu. When, in 1940, Estonia again became part of Russia (the Soviet Union), the Estonian name was kept.] I n the fall of 1918, the University was evacuated to Voronezh before the advancing German troops; he first decided to stay but, a t the
last minute, followed the University group. His illness a t t h a t time was already advanced, and he died in Voronezh on June 26, 1919, probably of heart disease. H e was buried in the cemetery around a monastery which (and this is the last intervention of history in Tsmett's life) was destroyed in World War I1 during the fighting with the German troops, and thus, his grave cannot be located anymore. I n practically his whole working life, Tswett dealt with investigations related to chlorophyll. Toward the end of the 19th century, many scientists showed interest in the pigments occurring in the leaves of plants, but there was no real way to separate them from each other and to check their identity in different plants. Since these substances are very labile, one could not be sure whether material obtained through chemical manipulation really corresponded to the form existing in the living plant. Tswett's approach was different ; he was looking for a physical method which would permit the separation of these pigments from each other and from closely related compounds that others felt to represent the same substances. For he was convinced that chlorophyll, as isolated by other researchers, was not a single substance. I n his work, he systematically checked a large number of solvents capable of extracting the pigments from vegetable matter, and more than 100 solid substances capable of selective retardation of the individual pigments through adsorption, and he also deducted a number of important rules for the adsorption phenomenon. His first paper in which his preliminary work was summarized was presented on March 21, 1903, before the Biological Section of the Warsaw Society of Yatural Sciences and published in Russian in the proceedings of the Society (7) ; it is also available in English translation ( 4 ) . The title of the paper is "On a Kew Category of Adsorption Phenomena and Their Application to Biochemical Analysis," and in it, he, in essence, describes chromatography without yet naming it as such. Three years later, in his
KEITHLEY'S NEW CURRENT AMPLIFIER MAKES SMALL CURRENTS INTO GIANTS
...faster than anything Whether used in mass spectroscopy, f a s t s e m i c o n d u c t o r p r o d u c t i o n tests, photomultiplier outputs, or whatever, t h e Model 427 Current Amplifier opens n e w d i m e n s i o n s i n low l e v e l c u r r e n t m e a s u r e m e n t s . It c a n p e r f o r m o p t i murnly for dynamic range or response t i m e , according t o user's wishes. I t features sensitivity t o 10-14ampere, switchselected rise t i m e s t o 15 microsecond a n d over 80 d B dynamic range. Built-in zero suppression a n d overload protection a d d t o operating convenience.
. . . . . , , . , 1 0 1 4 to 1 0 3 A RISE T I M E . . . . . . 15 p S to 0.3 sec. RANGE
DYNAMIC R A N G E , 40 to 80 dB STABILITY.
. . . . , . 500 p V / " C
. . .10-3to IO-~OA PRICE. . . . . . . . . .$795 U.S.A. SUPPRESSION
SEND FOR TECHNICAL LITERATURE TODAY
m
KEITHLEY I N S T R U M E N T S U S A 28775 AURORA ROAD CLEVELAND. OHIO 44139 EUROPE 14 AVENUE VlLLARDlN 1009 PULLY SUISSE
CIRCLE 76
ON
READER SERVICE CARD
ANALYTICAL CHEMISTRY, VOL. 43, NO. 14, DECEMBER 1971
25A
do you want in atomic absorDtion? Simultaneous analyses of two metals? And compensation for matrix interferences? To zip through hundreds of routine analyses ? The Jarrell-Ash Dial-Atom II is just the thing for rigorous, routine, day-in dayout use. It's as big in performance as it is easy on
your budget. Note all these traditionally "expensive" features you'll find on the low-cost Dial-Atom 1 1 : Direct concentration readout. Fast dial-an-element wave1e ngt h selector. Bu i It in hollow cathode lamp warmup. Scale expansion t o 1OX. Flame emission capability.
.
Multi-element analyses without lamp warm-up ? The hollow cathode lamp turret on the Jarrell-Ash Atomsorb holds up to six lamps on warm-up. To switch lamps, just rotate the turret. No waiting. Switching oxidants and lighting the burner, moreover, are just a matter of turning a control and pushing a button. More pluses: Direct concentration readout. Two switch-selectable gratings. Corrosion-resistant laminar flow burner. Scale expansion to 1OX. Flame emission capability.
--
You'll find analytical capabilities like that only with the Jarrell-Ash Model 800. Its u n i q u e d u a l - c h a n n e l double-beamdesign makes it the most advanced instrument of its kind. Consider, too, its other h i g h performance features: Digital readout. Signal integration. Scale expansion to 25X. Flame emission.
CIRCLE 4 8 ON READER SERVICE CARD
26A
ANALYTICAL CHEMISTRY, VOL. 43, NO. 14, DECEMBER 1971
Equal efficiency in flame emission and atomic absorption ? That calls for the JarrellAsh Model 500. Its exceptional versatility and superb
optics will especially please the researcher. Reasons why: a high resolution monochromator. Selection of eight wavelength scanning speeds. Interchangeable gratings. Unobstructed burner area. For a product bulletin on e a c h Jarrell-Ash a t o m i c a b s o r p t i o n i ns t r u m e n t , circle the number given below on the readers' service card.
A two remarkable papers entitled “Physico-Chemical Studies of Chlorophyll. T h e Adsorptions” (14), and “Adsorption Analysis and the Chromatographic Method. Application in the Chemistry of Chlorophyll” (9) published in the journal of the German Botanical Society, he very clearly defined the technique. It is worthwhile to quote from his first paper (8a) : “When a petroleum ether solution is filtered through a column of an adsorbent (I use mainly calcium carbonate which is tamped firmly into a narrow glass t u b e ) , then the pigments are resolved, according to the adsorption sequence, from top to bottom, into various colored zones, since the more strongly adsorbed pigments displace the more weakly adsorbed ones, and force them farther downward. This separation becomes practically complete when, after the pigment solution has flowed through, a stream of pure solvent is passed through the adsorbing column. Like light rays in the spectrum, the different components of a pigment mixture, obeying a law, are resolved on the calcium carbonate column and then can be qualitatively and quantitatively determined. I call such a preparation a chromatogram and the corresponding method the chromatographic method.”
It is generally assumed that the word “chromatography” has its origin in the Greek words chroma (color), and graphe (writing). However, already Tswett ( 8 b ) emphasized that:
“It is self-evident that the adsorption phenomena described are not restricted to the chlorophyll pigments, and one must assume t h a t all kinds of colored and colorless chemical compounds are subject to the same laws.” Actually, one may question whether Tswett really meant (‘color writing” when coining the name chromatography ( 1 0 ) . The interesting fact is t h a t the surname of
Tswett, in Russian, is identical with the Russian word for color ( 4BET) and, as expressed by Purnell ( l l ) , “It would be nice to think t h a t Tswett, whose name, in Russian, means color, took advantage of the opportunity to indulge his sense of humour.” I n his later papers, Tswett developed even further his technique -the separation of substances by retardation through selective adsorption. Tswett did not invent adsorption; this had been described well before him and also explained from the theoretical point of view (e.g., in the books of W. Ostwald from 1891-95). Also, scientists before him had separated plant pigments by selective solution. Tswett’s merits are in the generalization of the technique as a n analytical method and in the detailed investigations of the role of various adsorbents and solvents. As pointed out by Zechmeister ( 1 ) , “Tswett’s achievement is superior to Day’s in two respects. First, he recognized and correctly interpreted chromatographic processes; and second, he devised a useful laboratory method t h a t includes as an important feature the development of chromatograms by pure solvents. The distances between the individual zones are thus increased and complete resolutions advised within minutes.” Although Tswett published his most important papers in German journals (German was then the general language of chemistry), his work and the importance of the chromatographic technique were probably not understood immediately. It is interesting to note t h a t Palmer ( l e ) rein 1922 in the US., ported on a number of chromatographic experiments, giving credit to Tswett, but his work went largely unnoticed. Only 25 years after the publication of Tswett’s two basic papers was his work taken out of oblivion by Kuhn e t al. (IS, 14) who applied it successfully to the separation of carotene and egg yolk xanthophyll into their isomeric compounds. From there on, the development of adsorption chromatography was straightforward. ANALYTICAL CHEMISTRY, VC
NEW
JOURNAL
X-RAY SPECTRO METRY First Issue January 1972 Although an estimated 8000 X-ray instruments are currently employed in almost every field of science, specific up-to-the-minute information on X-ray spectrometry has not been readily accessible. In the past, papers relating to this ever-expanding technique were scattered over a vast number of journals published throughout the world. But now the very latest information on the theory, development and application of X-ray spectrometry is available under one cover in X-RAY SPECTROMETRY. Published quarterly, this international journal embraces the use of sources based on electrons, X-ray photons etc, and covers both wavelength and energy dispersion systems, data handling methods, and the application of the X-ray technique to structural analysis. Editor- in-c hief Ron Jenkins, 27 Salem Road, Westport, Connecticut, U.S.A. Regional Editors United Kingdom: Dr G Hendry, University of Birmingham, England France: R Tertian, Centre de Recherches d’Aubervilliers, 93 Aubervilliers. Netherlands: Drs J L de Vries, N V Philips, T.Q. lllp Eindhoven, Netherlands. Scandinavia: Dr L Backerud, lnstitutet for Metallforskning, Drottning Kristinasvag 48, Stockholm, Sweden. South Africa: Dr A Strasheim, National Physical Laboratory, Pretoria, South Africa. Canada: Prof B M Gunn, Department of Geology, University of Montreal, Montreal 101. Editorial Advisory Board Prof H Chessin; J F Croke; P W Hurley; G L Kerrigan; Prof K Fujimori; Prof F Rinaldi; M A Kemper; D F Sermin; H Ebel.
Annual Subscription
$25.00
(Four issues per volume, I vat. per year)
Send for FREE copy of first Issue
Heyden It Son Ltd, Spectrum House, Alderton Cres, London NW4 3XX, England CIRCLE 5 2 ON READER SERVICE CARD
43, NO. 14, DECEMBER 1971
27A
Report for Analytical Chemists Partition Chromatography
DEWAR.GET OI'K CONTROL. Air Products offers cryogenic refrigerators priced to your temperature needs.
You choose and pay for a Cryo-Tip@ refrigerator on the basis of the temoerature range. The AC-1 ranges 'from 300°K down to 68°K; the AC-2 and AC-2L down to 1 6 ° K ; the AC-3L to 3.6"K; and the LT-3 to 2°K. You don't have to buy a wider temperature range than you need. You don't get involved with specialty dewars and complex electrical controls, either. You simply meter the flow at the control panel and it stays within 0.1"K for either the economical cylinder gas Cryo-Tip refrigerators or the LT-3 Liquid Helium Transfer System. Each Cryo-Tip refrigerator can be
CIRCLE 3
28A
ON
fitted with a variety of vacuum shrouds for all applications. They're part of the complete line of accessories that adapt the Cryo-Tip system to low-temperature studies like these: IR, UV, Visible, Nuclear, M o s s bauer and Raman Spectroscopy. magnet studies like EPR, N M R , ESR. field ion microscopy, X-ray diffraction, lasers. Call A1 Koury at (2151 395-8355 for information, or write to Advanced Products Dept., Air Products and Chemicals, Inc., P.O. Box 538, Allentown, Pa.
READER SERVICE CARD
ANALYTICAL CHEMISTRY, VOL. 43, NO. 14, DECEMBER 1971
~
It is rare in the history of science that somebody can claim a number of major inventions. One of those men is A. J. P. Martin. Thirty years ago, together with Synge, he invented partition chromatography and demonstrated its use with a liquid carrier ( 1 5 ) . Three years later, together with Consden and Gordon, he described paper chromatography as a simple variant of liquid partition chromatography ( 1 6 ) . Then, 20 years ago, in cooperation with James, he showed the validity of their prediction in the first paper on partition chromatography that a gas could be used as well as the carrier instead of a liquid ( 1 7 ) . K i t h this publication, the unparalleled growth of gas-liquid partition chromatography began. Today, one could not even imagine chemistry and biochemistry without partition chromatography, and its importance is best demonstrated by the fact that Martin and Synge received the 1952 Sobel prize in chemistry for their work. thus joining the few scientists who have received the Sobel prize for a development in analytical chemistry. The history of the development of the three techniques is fascinating and is described in detail by Martin (18) and James ( 1 9 ) . As Martin explained, he early became interested in distillation columns. I n 1931, when Winterstein (who, two years earlier with Kuhn and Lederer, brought back adsorption chromatography from oblivion) demonstrated a t Cambridge Vniversity the separation of carotene on a chalk column, Martin realized that the processes involved in the separation are similar in both techniques. This early thinking resulted later in the expression of the efficiency of chromatographic columns by using terms established in distillation theory (HETP, number of theoretical plates). A t Cambridge University, when working on the separation of carotenes, Martin developed a very complicated countercurrent extraction apparatus and continued to utilize this technique for the separation of amino acids in wool when, in 1938, he moved to the Wool Industries' Research Association where Synge became his collaborator.
Report for Analytical Chemists
However, the whole system was extremely complicated and difficult to operate, and therefore, he tried to develop some other technique which would do the job. As described by bIartin (18):
“In 1940, it occurred to me that the crux of the problem was that we were trying to b o r k two liquids in opposite directions simultaneously . . . Then I suddenly realized that it rvas not necessary to moye both the liquids; if I just moved one of them, the required conditions were fulfilled. I was able to devise a suitable apparatus the very next day, and a modification of this eventually became the partition chromatograph with which we are now familiar.” I n their early work, chloroform containing a small amount of alcohol was used as the mobile phase, water as the stationary phase, and silica gel as the support; they could separate the monoamino monocarboxylic acids, and, according to Martin, “One foot of tubing in this apparatus could do substantially better separations than all the machinery n.e had constructed until then.” I n their paper, Martin and Synge ( 1 5 ) emphasized that, by the selection of suitable mobile phase-stationary phase combinations, the technique can be used for many other separations. and they predicted t h a t : “The mobile phase need not be a liquid but may be a vapour. We show below that the efficiency of contact between the phases (theoretical plates per unit length of column) is far greater in the chromatogram than in ordinary distillation or extraction columns. Very refined separation of volatile substances should therefore be possible in a column in which permanent gas is made to flow over gel impregnated with a nonvolatile solvent in which the substances to be separated approximately obey Raoult’s law.” I t is interesting to note that, although this prediction clearly and unequivocally predicted the possibility of gas-liquid partition chromatography, nobody picked it up,
and it took 10 years until Martin, then wit,h A. T. James, proved its great potential.
a new way to record nanosecond transients
Paper Chromatography
Liquid partition chromatography, as described originally by Martin and Synge, had superior separation power. However, in their original work, using water as the stationary phase and silica gel as the support, they were unable to separate the dicarboxylic and basic amino acids. They realized that the problem lay in the adsorptive power of silica gel and thus, were looking for some other support. As Martin explained, he had seen a “paper chromatogram” of dyes before and thus their first choice was paper. First, they used circles of papers in a Petri dish containing water; a drop of the amino acid solution was placed in the center of the paper, and water-saturated butanol was fed to the center of the paper; when i t reached the edge, the paper was dried and sprayed with ninhydrin, a substance found by Gordon to give proper color reaction with the amino acids, enabling the detection of their spots. Later, they used paper strips in boxes, in an atmosphere saturated with water, and the edge of the paper was dipped into the solvent (the moving phase). They also learned to run the paper in two dimensions. This is how paper chromatography, which revolutionized biochemical analysis, was born ( 1 6 ) . Gas-Liquid Partition Chromatography
As mentioned earlier, Martin and Synge predicted, in their original paper, the possibility of using a gas as the moving phase in partition chromatography. However, nobody thought to test experimentally this prediction a t that time although gas adsorption chromatography underwent an important development in the 1940’s. (See, e.g., the works of G. Hesse, E. Cremer, S. Claesson. E. Glueckauf, and C. S. G. Phillips; for a listing of their papers, see Bibliography, ref. 20). I n 1948, Martin moved to the National Institute for Xedical Research, where -4. T. James, who had previously been working with Synge. joined him. They were engaged in research work which did
WD 2000
waveform digitizer* For years now, transient, random, or slowly varying signals have been recorded by photographing a CRT trace, then laboriously measuring the picture to obtain data for analysis. This is a slow, tedious process. It isn’t too accurate. And it isn’t computer-compatible. The new WD-2000 Waveform Digitizer gets you out of this messy picture-taking business! This unique precision instrument captures and digitally records a single waveform by sampling the signal amplitude twenty times over the duration of the measurement. The amplitude of each sample is converted into an &bit digital number and stored in a memory. The waveform is instantly displayed on the instrument’s built-in CRT screen, while a direct digital output transfers the sampled waveform to computer, typewriter, magnetic tape, or other digital input devices for permanent storage or analysis. With its input risetime of 1.2 ns. the WD-2000 Waveform Digitizer can record any phenomenon occurring over several nanoseconds to twenty milliseconds, making it particularly well-suited for recording waveforms in such diverse applications as shock testing, kinetic chemistry, plasma research, radar signal analysis, s e m i c o n d u c t o r testing, electronic design, pattern recognition studies, and seismic and acoustical research. For complete details and application data . . .
*SEND
FOR NEW 24-PAGE BROCHURE,
LRS LeCROY RESEARCH SYSTEMS CORP. 126 North Route 303 West Nyack, N. Y. 10994 Phone: 9141358-7900
Innovators in Instrumentation CIRCLE 81
O N READER SERVICE CARD
ANALYTICAL CHEMISTRY, VOL. 43, NO. 14, DECEMBER 1971
29A
Report fur Analytical Chemists
An important announcement from...
COW-MAC GOW-MAC’S designers have significantly improved the standard thermal conductivity GC, 69-500.
All major features of the 69-500 have been retained with these major new features: Proportional temperature control for the detector Steel case Single unit design for reduced set-up time. GOW-MAC’S Model 69-550 is highly individual and impossible to compare.
The detector is the same as that used on many higher priced G.C.s. High sensitivity is assured. Detector oven features provide high versatility. The low price is important to y o u . . . because you can use a low-cost, dependable 69-550 for routine lab work and save your research G C for the use for which you bought it. Hundreds of users around the world are finding the exciting new G.C.s from GOW-MAC the answer to many problems arising in both laboratory and plant. For example: A simple G C is more easily operated, providing more efficient use of p e r s o n n e l . A n e c o n o m i c a l G C permits more money to be allocated for necessary but costly instrumentation. In various analyses which are repetitive, an inexpensive GOW-MAC gas chromatograph is the ideal instrument for both control laboratory and plant.
You owe it to yourself to learn more about this concept of highly utilitarian, specific instrumentation. Send for more data and prices. More and more analytical chemists bring G O W - M A C G C s into their labs. . , for good reason. I
................................
iI I
I I I I I
,
I I I 1 I
GOW-MAC Instrument Co., 100 Kings Road Madison, N.J. 0 7 9 4 0
1
I I I I
I
rn Telephone 2 0 1 / 3 7 7 . 3 4 5 0
Please send brochure on 69-550
I
Name
I I I I I
Address Company City
State
Zip-
L-__--__---------_------_--------J CIRCLE 47 ON READER SERVICE CARD
30A
ANALYTICAL CHEMISTRY, VOL. 43, NO. 14, D E C E M B E R 1971
I I
I
not result in any success, and Dr. James became so discouraged that Martin suggested that they switch to a project that surely must workto test the prediction of the possibility of gas-liquid partition chromatography. A request to try to develop a more advanced method for fatty acid analysis came as a good model for the investigations. Their work succeeded fairly rapidly, and soon the new technique was born; their paper was submitted for publication on June 5, 1951, and published in the first part of 1952 in Biochemical Journal ( 1 7 ) . I n their original work, James and lllartin added the sample by a pipet a t the front of the column and determined the eluted fractions by titration, and it was fairly difficult to record the “chromatogram.” I n the same year, D . H. Desty of British Petroleum, K. H. R a y of I.C.I., and R. P. IT7. Scott of Benzole Producers -4ssn. contacted Martin about the separation of hydrocarbony and then the possibility of using a thermal conductivity detector (applied at that time by Claesson) in gas adsorption chromatography was raised. I n the next three years, the applicability of the new technique to a \Tide variety of problems was sholvn, and in 1955, the first commercial instrument appeared on the market. The rest is history which those of us who “joined the club” in its early period will never forget. Sometime ago I read about life in the Spanish ports in the years after Columbus’ return from the S e w World, lvhere every ship brought something n e r , interesting. and exciting in treasures, people, and tales about new discoveries. We ivho have participated in the development of gas-liquid partition chromatography since its beginning, probably felt similarly ; every new issue of the journals, every meeting we have attended has brought something new and interesting that everybody wanted to try out in his own laboratory the next day. It is o proper to quote D r . Lipsky ~ l i finished one of his lectures (21) by paying tribute to D r . Martin: “He has twice made outstanding contributions to this field-in his discovery of partition chromatog-
Report for Analytical Chemists
raphy and in his pione,ering work on gas chromatograph y. H e has thus altered, for the better, the lives of many of us. TWe, his scientific colleagues, thaiik him for allowing us to share with him this wonderful adventure.” Interaction of ChromatographieTech niques
It is interesting to note that, until fairly recently, some art1ificial classification harriers have 1.ieen dividing the various types ci f chromatography, and scientists rarely deserted their own fields, IMartin being a rare expection. A few years ago, however, these artiificial barriers started to corrode. Scientists who, during the genesis of gas chro..2LL matography became i d e nLu: cu. Jw .W IUI it, started to be active in the other branches of chromatography. As a result of this healthy development, chromatography is treated today more and more by a unifying approach. This happening is a natural one, and the proper way development of a complex method is carried out. It starts in different channels which, for some time, look like separate techniques with nothing in common. But, sooner or later, it becomes clear t h a t these channels are not parallel but approach each other and, a t a given time, converge.
L
From this point on, they are developed together, benefiting from each other’s achievements. Today, chromatography is the most widely used analytical technique, and there is practically no laboratory in the world where i t is not practiced. It permits results which otherwise would be impossible. Present-day chemists who, in less than 30 min, can separate a complex multicomponent mixture and establish its concentration often do not realize that, until fairly recently, the solution of this problem would probaby have required weeks of hard work. All of us who are active in this field should therefore appreciate the genius of the pioneers of this technique.
(6) X. Sakodynsky, Chromatographia, 3, 9 2 4 (1970). (7) M. S. Tswett, PTOC. Warsaw Sac. Nat. 56. Biol. Sect.. 14. minute No.6 (1903). , ~ (8) M. Tswett, Be?’. Deut. Bot. Ges., 24, 313-26 (1%) ; the two quothtions are from n 322 and 323~ ~~~~~~. (9) M. Tswett, Ber. Deut. Bot. Ges., 24, 384-93 (1906). (10) 1,. S. Ettre, Chromatographia, 3, 9 5 4 (1970). (11) H. Purnell, Gas Chromatography, P 1. Wilcy 8- Sons, New York, N.Y., 1962. (12) L. S. Palmer, “Camtinoids and Related Pigments,” Chemical Catalog Co., NPWYork. N.Y.. 1922. ~
.~~
(16) R. Consden,, A. H. Gordon, and A
References
(1) L. Zechmeister, “Historical Introduction,” in “Chromatographv.” E. Heftmann, Ed., 2nd ed., pp 3-10, Reinhold, Xew York, N.Y., 1967. (2) V. Heines, Chem. Tech., 1, 280-5 (1971). (3) C. DhkrP, Condollea (Geneva), 10, 23-73 (1943). (4) G Hessp and H . Weil, Michael Tswett’.T F m t Paper on Chronatogmphy, M. Woelm, Eschwege, Germany, 1954.
1 Prktihe 6f Yilev & Sans, Xew
Leslie S. Ettre is ezecutive editor of the 18-volume “Encyclopedia of Industrial Chemical Analysis,” published by John Wiley & Sons, Inc. Mr. Ettre graduated in 1945 from the Faculty of Chemical Engineering o f the Institute of Technology, Budapest, Hungary. He became interested in chromatography in 1957 while employed at LURGI-Companies in Frankfurt am Main, Germany. From 1958 to 1968, he was working in gas chromatography at Perkin-Elmer Corp., serving in the last years as chief applications chemist. He has over 70 publications, mostly in the field of gas chromatography, is author of the book, “Open Tubular Columns in Gas Chromatography,” and editor o f the books, “The Practice of Gas Chromatography,” (with A. Zlat-
~
T
D X“”d...
“!&J
. . “0“ OD
9“
llnlll
(17) A. T. James and A. J. P. Martin, Biochem. J., 50, 67%90 (1952). (18) A. J. P. Martin, “Historical Backaround,” in Gas Chromatopmohy in Biology and Medicine,’: R.Porter, Ed., PP 2-10, J. & A . Churchill Ltd., London, Endand, 1969. (19) A. T.$mes, “The Development of an Idea, in “Gas Chromatography.” H . J. Noebels, N. Urenner. and R. F. Wall, Eds., pp 247-54, Academic Press, 1961. (20) R. L. Pecsok, Ed., “Principles and Practice of Gas Chromatoeraphy,” Wiley & Sons, New York, N.Y., 1959, pp 154-6. (21) S. R. Lipsky, “Gas Chramataaraphy; The Anatomy of a Scientific Revolution,” in “Gas Chromatography in Uiology and Medicine,” R. Porter, Ed., pp 11-16, J. & A. Churchill Ltd., London, Endand, 1969.
kis) and “Ancillary Techniques of Gas Chromatography” (with W . H. McFadden). He is a member of the editorial advisory board of the Journal of Chromatographic Science, one of the regional editors of Chromatographia, and serves as chairman of the Subcommittee on Nomenclature of ASTM Committee E-19 on Chromatography. Mr, Ettre is a member o f ACS, ISA, the New York Academy o f Sciences, the British Society for Analytical Chemistry and Gas Chromatography Discussion Group, and a fellow of the American Institute of Chemists. Lesl ie Ettre has cooperated 7uith Albert Zlatkis in the organization o f ,,-”,;“*“7r I u G L v I I u L the InL-! ucf” y~rbpy” o;”L u ^^ Advances in Chromatography since t heir beginning. I__^
ANALYTICAL CHEMISTRY, VOL. 113. NO. 14, DECEMBER 1971
31 A
~
