摘要:

Proceedinas - - - - - ~ ~of the Analytical Division ofThe Chemical Society21 9221222222228235239239240240240242244CONTENTSEdward Jorden M D (1569-1632):Early Contributions to SolutionAnalysisSilver MedalSociety for Analytical ChemistrySummaries of Papers'High-performance LiquidChromatography''The Interface Between Industryand Akademia-How do youIntroduce Specialised AnalyticalTechniques to Students?''Applications of Chromatography inthe Textiles Field'ObituaryMidlands Region SecretaryIUPAC ReportAnalytical Division DistinguishedP u bl i cat i o ns ReceivedConferences and MeetingsAnalytical Division DiaryService AwardVolume 16 No 8 Pages 21 9-244 August 197PADSDZ 16(8) 219-244(1979)ISSN 0306-1 396PROCEEDINGSAugust 1979OF THEANALYTICAL DIVISION OF THE CHEMICAL SOCIETYOfficers of the Analytical Divisionof The Chemical SocietyPresidentR. BelcherHon.SecretaryP. G. W. CobbSecretaryMiss P. E. HutchinsonHon. Treasurer Hon. Assistant SecretariesJ. K. Foreman D. I. Coomber, O.B.E.; D. C. M. Squirrel1Hon. Pub ficity and Pubfic Relations OfficerDr. A. Townshend, Department of Chemistry,University of Birmingham, Birmingham, B15 2TTEditor, ProceedingsP. C. WestonProceedings is published by The Chemical Society.Editorial: The Director of Publications, The Chemical Society, Burlington House, London, W1 V OBN.Telephone 01 -734 9864. Telex 268001.Subscriptions (non-members): The Chemical Society, Distribution Centre, Blackhorse Road,Letchworth, Herts., SG6 IHN.Non-members can only be supplied with Proceedings as part of a combined subscription with The Analysfand Analytical Abstracts.@ The Chemical Society 1979~~~~~ANALYTICAL SCIENCES MONOGRAPH No.4Electrothermal Atomization forAtomic Absorption Spectrometryby C. W. FullerAt the present time the two most successful alternatives t o the flame appear to bethe electrothermal atomizer and the inductively-coupled plasma. In this book anattempt has been made t o provide the author's views on the historical develop-ment, commercial design features, theory, practical considerations, analyticalparameters of the elements, and areas of application of the first of these t w otechniques, electrothermal atomization.The chapter headings are as follows: History; Theoretical Aspects of theAtomization Process; General Experimental Conditions; Analytical Conditionsfor the Determination of the Elements by Atomic Absorption Spectrometry;Applications (Oil and Oil Products; Metals; Rocks, Minerals and Soils; Waters;Plants; Food and Drugs; Biological Fluids; Biological Tissues; Air Particulates;Refractory Oxides and Related Materials; Other Analytical Applications;Theoretical).Clothbound 135pp 83" x 5" 0 85186 777 4 f6.75 ($13.50)CS Members f5.50THE CHEMICAL SOCIETYDistribution Centre, Blackhorse Road, Letchworth,Herts., SG6 1 HN, Englan

ISSN:0306-1396    

DOI:10.1039/AD97916FX026

出版商:RSC    

年代:1979

数据来源: RSC

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August, 1979 CONFERENCES AND MEETINGS 243Analytical Division Diary, continuedSeptember, coiztinuedPlenary lecture : “Pollution of Lough Neagh,a Multi-disciplinary Approach,” by Pro-fessor R. B. Wood.“The Different Forms of Phosphorus inFreshwater,” by R. J. Stevens.“Reduction of Nutrient Input to LoughNeagh by Phosphorus Removal at SewageTreatment Works,” by A. V. Gray.“River Lagan Water Quality-Objectivesand Options,” by J. E. Eveson.“The Determination of Polynuclear Aro-matic Hydrocarbons in Water,” by N. T.Crosby.“The Potential of Algal Culture in WasteWater Treatment,” by M. K. Garrett.“Dye Removal from Water Using AbsorptionTechniques,” by G. McKay and M. S.Otterburn.Friday, 28th-Plenary lecture : “Spectrochemical Analysis ofEnvironmental Pollutants in AgriculturalMaterials,” by A.M. Ure.“The Release of TCDD A t Seveso,” by A. J.Howard.“Organochlorine Pesticide Pollution inNorthern Ireland,” by D. B. Harper,“Organometallic Compounds in Relation toPollution,” by Professor G. Glockling.The Queen’s University, BelfastAnalytical Divisional DiarySEPTEMBER “Practical Problems Encountered in Micro-Monday and Tuesday, 10th and llth,9.15 a.m.: GlasgowThermal Methods Group jointly with the Poly-mer Degradation Discussion Group affili-ated to the Macromolecular Group of theCS on “The Use of Thermal Methods in theStudy of Polymer Degradation.”“Some General Considerations,” by ProfessorN. Grassie.“The Use of Thermal Methods to StudyOxidation,” by N. C.Billingham.“Applications of Thermal MechanicalMethods,” by Professor J. K. Gillham.“,4pplication of Thermal Methods to theStudy of Polyimides,” by W. W. Wright.“Applications of Pyrolysis - GLC in the Studyof Polymer Degradation,” by R. Lehrle.University of Glasgow.Wednesday, 12th, 2 p.m.: SwanseaWestern Region and Electroanalytical Group on“Ion Selective Electrodes-What Do TheyOffer the Analyst?”Speakers to include J. D. R. Thomas.University College of Swansea, SingletonPark, Swansea.Monday to Friday, 17th to 21st: LondonRadiochemical Methods Group : Workshop inLiquid Scintillation Counting.Queen Elizabeth College, London.scopic and Image Analysis ParticleMeasurement, ” by T. J. Buggs.“Analytical Examples of Pattern Recogni-tion,” by D.Betteridge.“Computational Practice in Pattern Recogni-tion,” by L. Kryger.The University, Lancaster.Wednesday, 19th, 7 p.m.: Port SunlightNorth West Region on “Analytical A\spects ofSpeaker: J. Waters.Unilever Ltd., Hulme Hall, Port Sunlight.Biodegradability.’’Wednesday to Friday, 26th to 28th: BelfastInterdivisional meeting in conjunction withthe Microchemical Methods Group and theElectroanalytical Group on “Inorganic andOrganic Pollutants in the Troposphere andNatural Waters.”Wednesday, 26th-Plenary lecture : “Physicochemical Processesof Pollutants in the Atmosphere,” b>-Professor K. H. Becker.“The Photochemical Production of Ozone inthe Lower Troposphere over NorthernIreland,” by W. D. McGrath.“Oxidative Control of Pollutants,” by D.C.Ayres.“Recycling Carbon Dioxide from FossiIFuels,” by B. R. Eggins.“The Analysis of Metals in AtmosphericParticulates,” by H. J. Duncan and C.Tuesday to Thursday, 18th to 20th:LancasterCS Autumn Meeting : Analytical Division McDonald.Symposium on “New Numerical Methods, “The Analysis of Asbestos in AmbientOptimisation and Pattern Recognition.” Atmospheres,” by P. G. Byrne.Wednesday, 19th-“Criteria for Rejection of Data (StatisticalMethology for the Criteria of ReliabilityApplied to the Results of Chemical Analy-sis),” by Mrs I. Calus.“Correlation of Data,” by B. A. Moore.“The Optimisation of Response in AnalyticalChemical Procedures,” by W. H. Swann.Thursday, 20th-“Applications of Fourier Methods,” by D. C.Champeney .“Modelling and Application of PatternRecognition Systems,” by J . Kittler.Thursday, 27th-Plenary lecture : “Current Activities andFuture Priorities in Air and Water Pollu-tion Research,” by W. S. Clough.“Water Quality Surveillance in a Highly Re-used River,” by D. C. Hinge.“Inorganic and Radioactive Pollutants of theClyde Sea Area,” by A. B. MacKenzie.“The Fate of Soil a t Sea,” by A. J. O’Sullivan.“Estuarine Pollution with Particular Refer-ence to Belfast Lough and the Tidal RiverLagan,” by J . A. Wilson.[continued inside back coverPrinted by Heffers Printers Ltd Cambridge Englan

ISSN:0306-1396    

DOI:10.1039/AD97916BX028

出版商:RSC    

年代:1979

数据来源: RSC

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Vol. 16 No. 8 August 1979 of the Analytical Division of the Chemical Society Edward Jorden MD (1569-1632): Early Contributions to Solution Analysis Modern chemical analysis has developed from metallurgical assays and from the study of mineral waters (Fig. l).1-4 Edward Jorden is of interest in that he made significant contribu- tions to the latter field and was a direct link with the continental analytical and iatrochemical traditions5 via his friendship with Adreas Libavius.DISCOVRSE O F NATVRALL BATHES AND MINERALL WATERS. Wherein firit the originall ofFountaines in general1 is dcclarcd. Then thenatureanddiffcrenccs of Minerals,with ex- amples ofparticular Bathcs from mofi of thcm. Ncxt the gcncration of Mincralrin the carch, from whence both thcatluall hcatc of Bathcs, and lhcir vcriucs arc proucd to proccedc.dyo 61 rbAt ncant, M~ntrak WAtrrr Arc 10 6e cxamiffed rrd dijoarrrd. And lailly, of thc naturcand vfes ofBathcs, bur cfpcci- ally ofoor Bathcs ar B i l k in Sommrr/r@re. ‘By EDJORDEN P.mTbyjcle. L O N D O I V : Printed by T H o M A s H A R P E R, Fig. 1. E. Jorden (1631). I 631 Continental renaissance developments in solution analysis, culminating in the work of Fallopius, became available in English in the Hill-Baker translation of Gesner’s “Treasure of Euronymus” in 157@; these included the redis- covery of the gall test for iron.The next English reference to the gall test was in 1626 by Edmund Deane in his report “Spadacrene Anglica”’ on the waters of Knaresborough (Harrowgate). A far more comprehensive and carefully referenced work, but omitting the gall test, was Jorden’s “Discourse of Katurall Bathes and Mineral Waters,” 1631,8 further editions of which appeared in 1632, 1633, 1669 and 1673.9 Jorden’s procedure for the identification of salts was based primarily on distillation and re- crystallisation of the residue prior to examina- tion of crystal form.If one did not wish to wait for the salts to crystallise “There is another way by precipitation .. . .” (Fig. 2). This description is an early, and may well be the first, example of the use of an acid - base indi- cator.2P911 The red dye may have been cochineal or kermes, although Brazil wood can- not be ruled out as it was also a common dye for scarlet in the seventeenth The analytical aspects of Jorden’s text were quickly accepted and frequently referred to by others,l2P and although his views on the origin of hot springs were refuted in detai1l4,l5 they were, at the time of writing, a coherent account of enlightened late-Renaissance views on the subject.5 Bibliographic material on Jorden is based on the records of Thomas GuidottgJs and on the “Roll of the Royal College of Physcians,”17 which cites Guidott as does Woods’ “*Athenae 0xon”ls; these are summarised in the “Diction- ary of National Biography.”19 Jorden was born in 1569 a t High Halden, in Kent, and was the younger son of a gentleman of good family.He studied at Oxford, probably a t Hart Hall, travelled on the continent, meeting Libavius, and obtained an MD a t Padua (G 1591), where he became familiar with the work of Fallopius and earlier contributors to the development of methods for the examination of mineral waters who were connected with that University.Upon returning to England he first became a Licentiate (November 7th, 1595) and then a Fellow (December 22nd, 1597) of the Royal College of Physicians, London. Jorden ac- quired the confidence of King James I and was employed to investigate a supposed case of demoniacal possession, which he attributed to hysteria.20 He moved to Bath and prior to his 219220 EDWARD JORDEN Proc.Analyt. There is an other way by precipitation, whereby thofe mineral1 fiibflanccs are flricken downe from their concrete iuyces which held them, by addition offornc oppofitc fibfiance. And this is of two forts : either Salts, as Tartar, Soape, Ahes, Kelps, Vrint, &c.Or fowre iuyccs, as Vinegar, Ly. mons, Oylc of Vitrioll, Sulphur, &c. I n which 1 bauc obkrucd that the Salts arc propcr to blcw colours, and the other to red: for example, take a piece of Scarlet cloath, and wet it in Oyk of Tartar (the firon cfl of ghat kindc) and it prefintly becomes blew: d, it a- gainc in Oyle of Vitriol, and it becomes red againe.Fig. 2. E. Jorden (1631), page 76, lines 11-22. Div. CJzem. Soc. death in 1632 was a popular and respected physician in that town. Jorden was interested in the manufacture of alum and claimed to have improved the process, although he lost money in this activity.l6 He married a daughter of Mr. Jordan, a Wiltshire farmer, whom he met whilst sheltering from a storm on Salisbury plain.Assessment of Jorden’s chemical merit has varied with time. Payne stateslg “The know- ledge of chemistry displayed in his discourse on baths is not remarkable, even for the age in which he lived,” which is at variance with Jorden’s near contemporaries’ views12J3 and the fact that Libavius, in his most important work “Alchemia,”2l listed Jorden first among a group of friends which included Tycho Brahe.11 Recent s t u d i e ~ ~ - ~ confirm Jorden’s innovative contributions to solution analysis via the use of crystal form and an acid - base indicator; in this latter respect he clearly pre-dates Boyle.This is not to detract from Boyle’s achievements in this area, which added greatly to the range of indicators and to the generality of the terms acid and base.22-24 References Rath, G., Sudhoff’s Archiv., 1957, 41, 1.Debus, A. G., Chymia, 1958, 8, 41. 1. 2. 3. Debus, A. G., “The English Paracelsians,” Oldbourne, London, 1965. 4. Debus, A. G., “The Chemical Philosophy,” Volumes I and XI, Science History Publica- tions, New York, 1977. Debus, A. G., in Schneer, C. J., Editor, “To- ward a History of Geology,” M.I.T.Press, Cambridge, Mass., 1969. Gesner, G., “The Newe Jewel1 of Health,” corrected and published by George Baker, H. Denham, London, 1576. (This is avail- able in facsimile, No. 381 in English Experience, Theatrum Orbis Terrarum B.V., Amsterdam, as are refs. 7 and 8.) 5. 6. 7. Deane, E., “Spadacrene 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. Anglica; or, the English Spaw-fontaine of Knaresborow,” (M.Flesher) for J . Grismand, London, 1626 [No. 651, English Experience (1974), also reprinted with introduction by J. Rutherford, Wright, Rristol, 19221. Jorden, E., “Discourse of Natural1 Bathes and Mineral1 Waters,” T. Harper, London, 1631 [No. 393, English Experience (1971)I. The Second Edition, 1632, was “in many points enlarged” and all subsequent editions are based on it.The 1669 edition was edited by Thomas Guidott and included some particulars of the author’s life and a portrait (normally missing from copies,l9 including all the copies in the UK and Ireland located via Wing, D., “Short-Title Catalogue 1641-1700” for Index Society by Columbia University Press, New York, 1945 and those in the Wellcome Historical Medical Library and in Dawson Rare Books, Catalogue 268, 1978).Debus, A. G., Ambix, 1962, 10, 29. Rancke-Madsen, E., in Bishop, E., Editor, “Indicators,” Pergamon Press, Oxford, 1973. That is a treatise of the nature and vertues of Tunbridge Water,” for R. Boulter, London, 1671. Johnson, T., “ThermaeBathonicae . . . . ,”Lon- don, 1634. French, J., “The York-shire Spaw, or a Treat- ise on Four Famous Medicinal Wells, -,” for E.Dod and N. Ekins, London, 1652; reprinted Halifax, 1760. Wittie, K., “Scarborough Spaw, or a Discrip- tion of the Nature and Vertices of the Spaw a t Scarborough in Yorkshire,” London, 1660. Guidott, T., “A Discourse of Bathe and the Hot Waters There-with an Account of the Lives, and Character of the Physicians of Bathe,” for H. Brome, London, 1676.(Latin Edition 1691.) Munk, W., “The Roll of the Royal College of Physicians of London,” Volume I, 1518- 1700, Longman, Green, Longman and Roberts, London, 1859. Rowzee. L., “The Queen’s Wells.August, 1979 SAC SILVER MEDAL 221 18. Wood, A. W., “Athenae Oxonienses,” New Edition by P. Bliss, F. C. and J. Rivington, London, 1815 (reprinted B. Franklin, New York, 1967). Payne, J. F., in Lee, S., Editor, “Dictionary of National Biography,” Volume 30, Smith, Elder & Co Ltd., London, 1892 [available in compact (micrographic) edition, Oxford University Press, 19751. Jorden, E., “A Brief Discourse of a Disease Called Suffocation of the Mother -,” J . Windet, London, 1603. 19. 20. 21. Libavius, A., “Alchemia. Operg. . . . allatura,” E x . I. Saurius, imp. P. Kopffij, Francofurti, 1597. SzabadvAry, F., Periodica Polytechnica (Buda- pest), 1975,18, 339 (lecture delivered a t the Centenary Celebrations of the Society for Analytical Chemistry, 1974). Thorburn Burns, D., and MacDaeid, D. A., Orbital, 1978 (2), p. 14. Thorburn Burns, D., “Proceedings of Euro- analysis 111,” Applied Science, London, in the press. D. THORBURN BURNS 22. 23. 24.

ISSN:0306-1396    

DOI:10.1039/AD9791600219

出版商:RSC    

年代:1979

数据来源: RSC

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August, 1979 SAC SILVER MEDAL 221 Society for Analytical Chemistry Silver Medal As announced in the June issue of Proceedings (p. 188), the seventh Society for Analytical Chemistry Silver Medal has been awarded to Dr. D. Midgley. Derek Midgley was born in April, 1944, a t Chadderton in Lancashire. He moved to Glasgow in 1955, where he was educated a t the High School and later at the University. After graduating in 1966 with a BSc with first class honours in Chemistry, he stayed on a t Glasgow in the Physical Chemistry Department to study for a PhD.In the course of his work on the thermodynamics of complexing in electrolyte solutions, he developed interests in two themes, the use of ion-selective electrodes and the theory of potentiometric titrations, which persist to the present time.In 1970 Dr. Midgley joined the Central Electricity Generating Board to work in the Analytical Chemistry Section a t the Central Electricity Research Laboratories in Leather- head. His work there has been concerned mainly with the application of ion-selective electrodes to the analysis of highly pure waters, such as are found in the steam-water circuits of modern power stations.The concentration of the analyte in these waters is invariably below 1 mg 1-1 and is frequently less than 10 pg 1-1. To date, ammonia, carbon dioxide, sodium, chloride and copper ion-selective electrodes have been investigated for this purpose. Through working with these low concentrations he has become interested in the non-Nernstian re- sponses of ion-selective electrodes at low con- centrations of analyte and the problems of defining the limit of detection. In parallel with the above work, Dr.Midgley has collaborated with Dr. C. McCallum on the use of computers to treat potentiometric titra- tion data so as to yield linear titration plots. Acid - base titrations of various degrees of complexity have been studied. More recently, Dr.Midgley has been involved in the chemistry of the chlorination of cooling waters. A Fellow of the Chemical Society since 1966, Midgley has been a member of both the Analyti- cal and Faraday Divisions since 1972. He has been a member of the Society for Electrochem- istry (now the Electrochemistry Group of the Faraday Division) from 1968 onwards. In 1976 he became a Member of the Royal Institute of Chemistry. Dr. Midgley has presented or published some three dozen research papers and is the co- author (with Dr. K. Torrance) of a book entitled222 HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY Proc. Analyt. Div. Chenz. SOC. “Potentiometric Water Analysis,” which analysis. In 1979 he joined the Editorial describes the use of ion-selective electrodes in Advisory Board of Talaiztn.

ISSN:0306-1396    

DOI:10.1039/AD9791600221

出版商:RSC    

年代:1979

数据来源: RSC

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222 HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY Proc. Analyt. Div. Chenz. SOC. High-performance Liquid Chromatography The following is a summary of one of the papers presented at the Annual General Meeting of the Analytical Division held on March 16th, 1979, at Brighton. Injection Techniques in Liquid Chromatography C. F. Simpson School of Molecular Sciences, University of Sussex, Falmer, Sussex, BN9 1RH The technique of liquid chromatography has been greatly developed over the past ten years, both in our understanding of the processes involved in the various separation procedures and in the instrumentation currently commercially available.If one was to ask what have been the most significant advances in columns used, the answer would undoubtedly be the use of small particles of 5-10 pm in size, of narrow particle size distribution, our understanding of how these materials should be packed reproducibly to give high-efficiency columns and the recognition of the infinite column diameter effect proposed by Knox and Parcher.1 On the instrumentation side, the pumping system has received considerable attention and pumps currently available are satisfactory, if expensive.Detectors, however, are still a problem ; the ultrayiolet detector has now been considerably refined, although the detector cell volume is still far too large for high-efficiency separations2 With instrumentation, probably the most neglected and most important feature of the liquid chromatographs lies with the sample introduction ~ y s t e m . ~ All other things being equal, bad sample application can com- pletely negate the use of a high-efficiency column. This paper considers the requirements for sample introduction and the equipment available at present.Requirements for Sample Introduction There are two cases to consider, analytical technique and preparative-scale technique. Analytical Technique variance of the elution curve obtained on the recorder chart o& is given by Let us first consider the various contributions to elution band broadening.The over-all 02ytot = &col + &nj + 4 e o n n + 4 d e t &tot = &Ol and the minimum attainable variance occurs when i.e., external contributions to band broadening are negligible compared with the intrinsic broadening obtained within the column.If we consider each of these terms we see that aid,, will always give a contribution to band broadening because of the finite volume of the detector cell; this can be minimised by making the detector cell volume as small as possible. For example, reducing the cell volume from 25 to 1 pl increases N from 2 380 to 15 400 and decreases o2ydet from 28.7 to 11.3 pL4 The quantity u",,,,, is the variance associated with the connection between the column out- let and the detector cell inlet.Table I5 illustrates the effect of various differing radii column- detector connectors. Clearly a marked reduction in column efficiency is obtained on increasing the bore of the connecting tube, illustrating that the minimum length of connecting tube is best and preferably the minimum bore.Indeed, it is preferable to connect the column outlet directly to the detector cell in order to minimise this e f f e ~ t . ~ I t must be pointed out, however, that dispersion does not occur so dramatically in connecting tubes of very narrow bore, less than 0.25 mm, andAugust, 1979 HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY 223 TABLE I EFFECT OF DIFFERING RADII COLUMN-DETECTOR CONNECTORS Detector cell volume 8.0 p1; connection tube length 228 mm.Connecting tube borelmm N $"COnIl/W 0.25 3 195 11.22 0.50 2 100 44.88 1 .oo 1 200 179.5 0.25* 4 125 74.6 * 1 520 mm. indeed appreciable lengths can be tolerated except when using very high-efficiency columns. For example, a 1 520 mm length of 0.25 mm bore tube gave a column efficiency of 4 125 plates.This apparent increase in N is due to the longer residence time within the tube giving a fallacious column efficiency. Thus, of the extra column effects that lead to band broadening we now require to consider the sample introduction method. A comparison of the column efficiencies and k' values for three solutes, syringe-injected under stopped-flow and flowing conditions (these injections were not made on-column5 but into the mobile-phase stream) showed that under dynamic conditions better column efficiencies are obtained, although the k' values remain constant.A comparison of the effect of sample volume using appropriately diluted samples but with the same sample load5 showed that for fast moving (low k') peaks sample volume has a profound effect on column efficiency, although this decrease in efficiency diminishes as k' increases. A comparison of four different methods of sample introduction,6 vix., (a), syringe-injected into the top of a PTFE plug, ( b ) , syringe-injected through a PTFE plug on to stainless-steel mesh, ( c ) , sample .valve-capillary through a PTFE plug on to stainless-steel mesh and ( d ) , sample valve-split stream-capillary through a PTFE plug on to stainless-steel mesh, showed that syringe injection on to the stainless-steel mesh, ( b ) , produced the highest column efficien- cies with the split-flow system (d) giving slightly lower results. The loop injector produced distinctly inferior results.Finally, Fig. 1 shows an exaggerated example of the effect of dead volume at the column head. It will be seen that disastrous results are obtained compared with an on-column injection.This effect is most important with sample introduction methods employing syringe injection into a flowing mobile phase stream and for sample valve injection of the sample; it also highlights a point about commercial columns, the ends of which are terminated with a stainless-steel sinter that is permanently pressed into position.This structure makes it impossible to inspect the column head from time to time in order to ascertain whether the packing has bedded down with use, a problem that can occur with even the best packed of columns. From the above it is clear that the highest column efficiencies are obtained by syringe injection and preferably into the chromatographic bed.' This arises for two reasons, a better injection profile is obtained by injecting into the packing and back-diffusion is negated, and the mobile phase is flowing across the entire cross-section of the chromatographic bed, thus producing more favourable stream lines into which the sample is placed.The sample is then transported down through the column away from the wall, preserving the infinite diameter effect .8 3 9 However, syringe injection into the column packing has serious disadvantages in spite of the good results that can be obtained. There is a marked tendency for the syringe needle to block with the microparticulate packing; this effect can be minimised by injecting under stopped- flow conditions with no apparent loss in column efficiency, but for accurate retention volume measurements this technique is precluded because of the finite time for pressure to build up using constant-flow pumps.Much more important, however, is the problem that the bed is disturbed, indeed over a limited number of injections a hole is formed at the column head, which can give rise to distorted peaks or doublets.l* After packing the column, the top 2-4mm of packing are removed with a suitably modified reamer, a disc of 8 p m stainless-steel mesh is placed on top of the packing and the vacant space filled with 3040 pm ballotini beads; if required a PTFE frit can be inserted above the beads in order to prevent Fortunately, a simple solution exists to circumvent this problem.224 HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY Proc.Analyt. Div. Chem. SOC. their loss on laying the column down. Injection is performed by introducing the syringe needle until it just touches the stainless-steel frit and the sample is injected. The presence of the ballotini beads minimises diffusion of the sample and at the same time promotes a suitable flow stream-line at the column head. This technique is probably the best method of sample introduction.It does, however, depend upon the type of injector used. These are available in two forms, septum and non- septum types. A well constructed septum injector should possess two attributes, a needle guide to ensure that the sample is placed on the axis of the column, and a suitable support to hold the septum firmly in position. In addition, the guide holes for the syringe needle should be just big enough to permit the needle used to pass.This construction ensures that the minimum area of septum is exposed to the moving phase and, more importantly, that the needle penetrates the same hole, thus minimising breakdown of the septum. An additional advantage of topping a column with ballotini arises when a septum disinte- grates; if the debris is allowed to accumulate on the column head, apparent column efficiency deteriorates as a result of an adsorptive layer being produced.I t is simple to remove this debris with the ballotini present; no disturbance of the packing occurs and all that remains is to top up with fresh ballotini in order to return to the original column performance. Fig. 2 gives details of two types of injector that are suitable for syringe injection, a single- septum and a double-septum type, which are suitable for column inlet pressures of 100-150 and 200-250 bar, respectively.The principal disadvantage with these designs is that the septa are continually pressurised with moving phase, which can shorten their life. Another form includes a slide valve below the septum to prevent this occurrence.J MobilGhase inlet Fig. 1. Effect of column head dead volume. Fig. 2. Syringe septum injectors. In order to remove the problem of a septum, but still retain the ability to use syringe injec- tion, septumless injectors have been constructed, and while these do the job for which they are intended, unfortunately the designs available only permit injection into the mobile-phase flow, which can give rise to additional problems. The three designs available are shown in the next Figure, Fig.3 (a)-(c), and are available from Hewlett-Packard, Packard-Becker and Siemens, respectively. These systems permit sample application under high-pressure conditions and they perform this task satisfactorily. Their principal disadvantage lies in not injecting the sample at the optimum position indicated above (also see below). An alternative method of removing the problem of septa while still retaining sample applica- tion to the optimum position is the use of the stopped-flow technique.In this method, an injector with a needle guide similar to that shown in Fig. 2 is used, but without an entry port for the needle; to make an injection, the mobile-phase flow is switched off or diverted (prefer- ably the latter), a short time allowed for the pressure within the column to fall, and the sealing cap removed.The sample is injected with a syringe in the optimum position, the cap replaced and the mobile-phase flow restarted. Because of the low diffusion rates in liquids (about lo6August, 1979 HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY 225 Valve U Colu 4 Sealing screw I niet Syringe installation Inlet 1 Seals Inject position 1 Sliding valve Column 1 Syringe installation Inject position 1 Inlet Sealing + Load position Inject position Fig.3. ( a ) , Septumless injector, Hewlett-Packard ; ( b ) , septumless injector, Packard-Becker ; (c), septumless injector, Siemens.times slower than in gases) a minimum dispersion of the sample is experienced, provided that it is injected slowly; a fast injection will create turbulence with attendant mixing. The major disadvantage of this technique rests in the finite time taken for the mobile-phase flow to re- stabilise, and hence accurate retention volume data cannot be obtained. In all instances of syringe injection, problems can be experienced in attaining the desired reproducibility of sample size, either because of syringe malfunction or lack of technique, and clearly one would wish to inject samples using relatively untrained personnel.Sample valve injection provides a method of ensuring sample size reproducibility, and several valves are available on the market. All of the sample valves that are available operate by substantially the same means; the226 HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY PYOC.Analyt. Div. Chem. SOC. volume to be injected is either stored in the valve rotor itself (up to 5 pl) or in an external loop system, the volume of which can be as great as is desired. Note that injection volumes using the external loop type will include the volume incorporated in the rotor.A fairly recent innovation in the design of sample valves, which allows a variable volume of sample to be admitted into the loop, was first developed by Waters Associates with the U6K injector. Subsequently, Micromeritics and, in particular, Rheodyne have introduced similar valves. On loading the valve, the sample occupies a portion of the loop available and on switching to inject the sample the flow passes in the reverse direction, thus ensuring minimum dilution of the sample. Note, however, that the dilution obtained is also a function of the bore of the sample loop; narrow bore loops are to be preferred.The internal or external volume (or variable volume) is loaded with the sample and the valve switched, which causes a momentary interruption in mobile-phase flow ; it then passes through the sample loop, sweeping the sample on to the column head.Providing the column is well packed right up to the sealing sinter, thus presenting no dead volumes at the column head, and providing the delivery tube from the valve is resting on the sinter, an adequate injection will occur and i t will be entirely reproducible (with fixed volume loops).But the sample will not be applied in such a way as to preserve the infinite column diameter effect be- cause the presence of a column inlet sinter will diffuse the sample over a substantial area of the packing, as indicated above (Fig. 4). In addition, the total mobile-phase flow passes into the column via the delivery tube so that the desirable flow streamlines will not be present at the column head.It is interesting to note the velocity with which the mobile-phase (and sample) pass through the delivery tube. At 2 m min-l the linear mobile phase velocity through a 0.005-in tube is 263 cm s-l, through a 0.010 in, 65.8 cm s-1 and through a 0.02 in, 16.45 cms-l. These flow velocities are sufficiently fast to bore a hole in the column head if only a simple mesh is used.Thus, the mode of the operation of a sample valve is relatively simple. Herein lies the problem. Fig. 5 illustrates this effect. Mobile phase and sample 1 Sinter or gauze f Fig. 4. Effect of point injec- tionon t o asinter, usinga septum- less injector or valve injector. Fig. 5 . Effect of point injection on t o a sinter plotted against time. Clearly, the requirement for optimum, reproducible sample injection is a combination of syringe injection with sample loop capability, and indeed Webber and McKerrel16 have indi- cated that a point injection by-pass system is efficacious. Unfortunately, in their construction they used a 1 mm i.d.type injection tube, which would lead to sample dilution and hence reduce the apparent column efficiency.Kirkland et al.ll have confirmed these findings and demon- strated a marked improvement in peak symmetry. A diagram of the split-stream system used by the author is shown in Fig. 6. This is essentially the same as Webber and McKerrell’s construction, except that the injection needle is 0.006 in (0.125 mm) i d . and a by-pass ball valve is incorporated.This system permits investigation of the additional parameter of rate of sample injection. By prior calibration, using the micrometer needle valve, the ratio of mobile-phase flow passingAugust, 19Y 9 HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY 227 through the injection needle to the over-all column flow can be determined so that varying sample injection rates for differing sample sizes and flow-rates can be investigated.Some typical results are given in Table 11. TABLE I1 EFFECT ox COLUMN EFFICIENCY OF VARYING SAMPLE INJECTION RATE Column efficiencies, N Flow-rate/ml min-l Sample size/pl Sample loop Syringe Split stream 2 1 2 460 4 232 7 200 (0.5 s ) 5 2 842 4 538 3 416 (0.5 s) 5 832 (1.5 s) 6 050 (3.0 s) 10 3 120 4 404 3 642 (0.5 s) 6 806 (1.5 s) 5 800 (3.0 s) The results indicate that, depending on the sample size, the rate of injection has a substantial effect on column efficiency but that the split-stream method gives superior column efficiency except when large sample volumes (5 and lOp1) are injected in 0.5 s. Slower injections provide a great improvement in column efficiency.Full details of the results of this investiga- tion into the rate of sample injection will be published elsewhere.Preparative-scale Sample Injection In this technique the object is to introduce the sample as an even layer at the column head. Point injection is not a requirement and, in fact, it would be deleterious to column performance as a result of overloading the adsorbent. Overloading is used in preparative work, but if it is spread over the entire cross-section it is not as deleterious to column performance as is point- source overloading, which gives rise to considerable tailing with its attendant problems of cross- contamination be tween fractions collect ed.Injection by syringe Syringe injection can be used to transfer sample to the column head, usually under stopped- flow conditions, and if necessary replicate injections can be made to achieve the required sample load.In this way an even distribution of sample across the column cross-section can be obtained, particularly if the sample is injected into a layer of ballotini beads. Syringe injection under dynamic conditions is not easy to perform, partly because of the back-pressure on the plunger of the syringe but principally because of the bad sample distribu- tion at the column head.The latter problem can be alleviated by injecting the sample into the head of a fairly deep layer of 0.5-mm ballotini (about 10 mm for a 0.5-in column). The sample will be distributed fairly evenly over the head of the packing, thus minimising the point- injection overloading problem. This technique can also be successfully used when using sample valves for sample introduction. Sample valve introduction Undoubtedly this is the most convenient method of injecting samples into preparative columns, but it is necessary to employ special sample distributing heads in order to ensure even sample application.The simple technique of injecting the sample at the head of a layer of ballotini as outlined above is satisfactory but not the optimum; Wehrli12J3 has produced a distributing head that will allow sample application under both syringe and sample valve methods.Fig. 7 shows a diagram of the design features, which include distribution baffles and glass spheres to ensure even distribution of the sample. Split-stream sample introduction de Jong et aLf4 have compared in detail three different modes of preparative-scale sample introduction, including a split-stream injector, and demonstrated that a reduction in peak228 Proc. Analyt.Div. Chem. SOC. asymmetry was observed with this last method. However, the results obtained indicated that other factors can contribute to loss in efficient preparative-scale chromatography, and probably the column-end terminator needs careful investigation in order to optimise the design for efficient removal of the eluting sample.THE INTERFACE BETWEEN INDUSTRY AND AKADEMIA m-, N:edle valve Injection valve -11 Sinter 0.005” Needle Ballotini Mesh &- \, i l l valve By-pass line Sinter or Gauze Distribution baffles Glass spheres (bal lot in i ) Fig. 6. Split-stream injection giving control of rate Fig. 7. Wehlri preparative injection head. of sample introduction. References 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. Knox, J. H., and Parcher, J. F., Analyt. Chem., 1969, 41, 1599. ,Maggs, K. J ., in “Practical High Performance Liquid Chromatography,” Heyden, London, 1977, Bristow, P. A . , and Knox, J . H., Chromatographia, 1978, 10, 279. Scott, R. P. W., and Kucera, P., J . Chromat., in the press. Simpson, C. F., in “Practical High Performance Liquid Chromatography,” Heyden, London, 1977, Webber, T. J. N., and McKerrell, E. H., J . Chromat., 1976, 243, 122. Majors, R. E., Analyt. Chem., 1972, 44, 1722. Kirkland, J . J., J . Chromat. Sci., 1969, 7, 7. Kirkland, J. J., J . Chromat. Sci., 1971, 9, 206. Karger, B. L., Conroe, K., and Engelhardt, H., J . Chromat. Sci., 1970, 8, 242. Kirkland, J . J., Yau, W. W., Stoklosa, H. J., and Delks, C. H., J . Chromat. Sci., 1977, 15, 303. Wehrli, A., in Huber, J. F. K., Editor, “Instrumentation for High Performance Liquid Chromato- Wehrli, A., 2. Analyt. Chem., 1975, 277, 289. de Jong, A. W. J., Poppe, H., and Kraak, J- C., J . Chromat., 1978, 148, 127. Appendix 1. Chapter 13. graphy,” Volume 13, Chapter 6, Elsevier, Amsterdam, 1978.

ISSN:0306-1396    

DOI:10.1039/AD9791600222

出版商:RSC    

年代:1979

数据来源: RSC

摘要:

228 THE INTERFACE BETWEEN INDUSTRY AND AKADEMIA Proc. Analyt. Div. Chew. SOC. The Interface Between Industry and Akademia-How do You Introduce Specialised Analytical Techniques to Students? The following are summaries of four of the papers presented at a joint meeting of the Education and Training and Specialised Techniques Groups held on November Sth, 1978, at the North East London Polytechnic. Analytical Techniques Currently Used in Industry-Which Techniques are Insufficiently Taught? G.A. Newman Analytical Department, Research Division, Kodak Ltd, Headstone Drive, Harrow, Middlesex How does one generalise on which techniques are insufficiently taught ? Some universities and polytechnics have strong schools of analytical chemistry but most do not, so there will be aAugust, 1979 THE INTERFACE BETWEEN INDUSTRY AND AKADEMIA 229 great disparity in the emphasis placed on analytical work.Where the word university is used in this paper, this also implies polytechnics. Most academics have to cope with an ever- increasing syllabus because of the advances in our knowledge, and the rapid developments in analytical knowledge must surely rival those of the other branches of chemistry? How all this knowledge is imparted by those universities which run “classical” degree courses is not known.Other establishments operate the modular type of undergraduate courses so that, given a choice, the student may opt not to undertake any analytical work! The industry is composed of small, medium and large companies employing from none to hundreds of analysts.Some firms carry out research work and they often have close links with universities, while others only carry out work directly to support production and may only be involved in routine quality control. Laboratories operate in different ways ; some use graduates to operate complete ranges of techniques, while others expect the individual to specialise.In addition, some industries have specified needs that cannot be covered adequately by academic courses. Another fundamental question to ask is “Should fully trained analysts come from the uni- versities or should industry train the individual extensively?” I think that the answer lies between these two situations. Analysts should be fully conversant with the range of tech- niques, but be trained by industry for the specific area of work relevant to their particular industry and in great depth for the topic they select.Perhaps vacation employment of under- graduates should be better organised as vacation training ? Now let us look at the difficulty of generalising for industry. Techniques Used in Industry I represent what is, by British standards, a moderately large industrial organisation with a sizeable research division.We need a comprehensive range of techniques and instruments to aid the solution of our problems and hopefully this is typical of industry. Let us consider what these techniques are and indicate some about which new graduates are unsure. It is surprising what a range of techniques and instrumentation is required to support a research and manufacturing organisation (Table I).Analytical Techniques Generally Not Well Taught Chromatography and spectroscopy are among the best methods although comprehensive coverage is often difficult because there are rapid advances taking place. Although emission spectrography is widely used in industry, perhaps it is considered to have been superseded by atomic-absorption analysis, which is not correct.The differences between emission and atomic-absorption methods should be made apparent and an appreciation is important of the various sources for emission spectrography. X-ray fluorescence spectrometry is not covered thoroughly, particularly matrix effects, but X-ray diffraction is often well described. Trans- mission and scanning electron microscopy techniques are well-known but the importance of the addition of energy-dispersive X-ray analysis may not be apparent. Because of advances in instrumentation these old-established methods are still important, e g ., pulsed polarography for trace metal analysis (p.p.b. level), cyclic voltammetry, electrochemical detectors (for HPLC) and ion-selective electrodes.TABLE I Electroanalytical techniques are singled out. ANALYTICAL TECHNIQUES USED IN INDUSTRY Chromatography Spectroscopy Atomic and physical Other techniques TLC Vibrational (infrared, Elemental, C, H, N, etc. *Electrochemistry GLC Raman) *Emission *Thermal HPLC Electronic (ultraviolet, AA *Environmental (Other specific methods, visible) *X-ray *Classical chemical e.g., GPC for polymers.) Mass spectrometry Particle size NMR Electron microscopy * Techniques insufficiently taught.Thermal methods of analysis have never been appreciated by academics but they find great Is it because there is no general theoretical basis, or because applica- application in industry.230 R o c . Analyt. Div. Chem. SOC. tions are often in specific areas, e.g., polymers? Examples of techniques often used are differential thermal analysis, thennogravimetry, differential scanning calorimetry, thermo- mechanical analysis, dynamic mechanical analysis and flammability testing.Effluent and environmental aspects of analysis are not well covered, perhaps because we live in an age of specialisation and undergraduate degree courses specific to this topic are available. Analysts should be aware of the methods and techniques available.Classical chemical analysis, separation techniques and wet-chemical methods (e.g., oxidation and ashing) appear unfashionable today, and attempts are made to solve most analytical problems by instrumental means. Some aspects of this classical approach, such as samples and sampling (Table 11), are fundamental to analysis. A newly qualified graduate should know where to find such information.THE INTERFACE BETWEEN INDUSTRY AND AKADEMIA TABLE I1 SAMPLING OF LOTS ACCORDING TO SIZE OF BATCH A batch is composed of a number of lots. Number of lots Proportion to be sampled, O,; Minimum number 2-20 20 2 21-60 10 4 61-200 7 6 201-500 5 15 501-1 000 4 25 > 1 000 3 40 To add to the complexity, academics must manage to maintain a current awareness of advances in techniques (Table 111) and to disseminate such knowledge.TABLE m CURRENT AWARENESS Surface characterisation techniques Advances in established techniques Pyrolysis GC F.D. Mass spectrometry Ion chromatography (HPLC) Electronic and mechanical Role of microprocessors and computers Automation With automation, a young graduate starting life with a small firm should be aware of the benefits, improvements and advantages of some forms of automation.There are various forms of automation from automatic sampling to total control of instrument, process and results. In particular, the revolution that is occurring with the increasing use of micro- processors should be made apparent. Why Are These Techniques Insufficiently Taught? The short answer to that question is that there is not enough time, but the underlying reasons for this need to be considered.Open the “Situations vacant” pages of any scientific journal and there are a high proportion of vacancies for analysts, yet at the seats of higher education analytical chemistry is treated as the poor relation of other branches of chemistry! Analysis encompasses a knowledge of inorganic, organic and physical chemistry, yet is not considered to be of equal importance.Is it considered to be a means to an end, i.e., a branch of science that plays a secondary or supportive role to the others? Analytical chemistry should be an integral part of every undergraduate course, not an optional extra. Every new graduate will either use analytical methods, or need to come into contact with others who do so, in the course of his work. Enhance the importance of analysis and some of the problems can be overcome. There are not enough schools of analytical chemistry in the universities, particularly for postgraduate work.Why not?A ugust, 1979 23 1 I have always sup- ported the comment of Professor H.A. Laitinenl that the modern analyst should be “jack of all trades and master of one.” We would hope that a new graduate would have background knowledge of a variety of techniques and hope to train him extensively within a specified field. Perhaps with a person attaining a higher degree it would be necessary to place the training emphasis the other way round.The person should be capable of making the right decisions on how to solve problems in analytical science. With many new graduates there is not a basic knowledge of analysis, let alone energy and enthusiasm for the subject. This is partly a prob- lem of the present generation but must originate to some extent from a lack of exposure to analysis. For interest and enthusiasm we believe greatly in visual aids, such as colour slides and slide - tape presentations. This approach fulfils two objectives: it enables more informa- tion to be conveyed in a shorter time, e.g., block diagrams of instruments; and it brings com- plex instruments into the lecture room and stimulates interest by showing applications in industry, after theoretical aspects have been covered. I am sure that industry would be prepared to co-operate in providing applications suitable for visual aids.In increasing the throughput of knowledge the university syllabus would be covered more efficiently, although a handout of the lecture notes would be essential. A large amount of information, broadly based, can be disseminated in a short time on a relatively complex topic.Coping with an increasing curriculum and stimulating the interest of students can be achieved by increasing the use of visual aids and training programmes and the use of more enlightened practical work. L. A. Haddock2 comments on the relationship between a firm’s research laboratory and its works laboratory, and if you substitute “research” with “academic” and “works” with “industry,” the statement is still true.He states that “It is more necessary for frequent meetings between the two groups to occur in order to inject vitality into the technical thinking of the works group and reality into the thinking of research people.” References THE INTERFACE BETWEEN INDUSTRY AND AKADEMIA What are we trying to achieve and what should the end product be? Closer liaison between academics and industry is essential.1. 2. Laitinen, H. A., Analyt. Chem., 1972, 44, 889. Haddock, L. A., “Analysis in the Chemical Industry,” Pergamon Press, Oxford, 1968. Teaching the Principles of Surface Analysis 0. Betteridge Chemistry Department, University College of Swansea, Swansea, SA2 8PP The teacher faces a number of constraints and challenges; the subject matter must be interest- ing, relevant and related to that discussed by colleagues, it must be possible to present the material in a limited time and the student must have the time and facilities to read around the subject.If it is accepted that the discussion of methods is concentrated upon electron spectroscopy, then one or two lectures will suffice as an introduction to an important growth point of analytical chem- istry and provide for cross-fertilisation with other courses on spectroscopy and surface chem- istry.From this view point the teaching of surface analysis has many attractions. The lecture(s) might be along the following lines. Definition of Analytical Problem The precise definition of a surface is not easy, but it is helped by analogy and demonstration.First consider a lawn. What is the analysis of a lawn? Is it the ratio of weeds to grass, the ratio of bricks to subsoil or the elemental analysis of a representative plug? In the last instance the significance of the grass and daisies will be lost in the analysis of the “representa- tive” bulk. Secondly, consider a mirror. By breathing upon it, a thin layer of water, adsorbed carbon dioxide and the remnants of the Colgate ring of confidence will have destroyed the optical characteristics that make a mirror what it is.Again it is easy to note that the mirror consists of layers of material in which the surface and the backing film of silver are232 Proc. Analyt. Div. Chem. SOC. crucial to its performance, yet a chemical analysis of the bulk yields little in the way of useful information about the performance of the mirror.In further examples, discussed below, it will be seen that the physical characteristics of many things are affected crucially by the chemical composition of the outmost atomic layers (2-20 A or 0.2-2 nm). THE INTERFACE BETWEEN INDUSTRY AND AKADEMIA Definition of the Techniques The two branches of electron spectroscopy relevant to the problem are X-ray photoelectron spectroscopy (XPS or ESCA) and Auger spectroscopy (AES) .1-4 [Ultraviolet photoelectron spectroscopy (UPS) is more difficult to embrace in a short account because it deals with the complex valence region.] It is probable that these techniques have been discussed in a basic spectroscopy course.If they have not, the basic idea of irradiating the sample with X-rays or electrons and measuring the energy distributions of photoelectrons or secondary electrons is fairly easy to convey.The energy relationships and discussion of inner atomic levels comple- ments the basic chemistry course and also the discussion of X-ray fluorescence (XRF) in the analytical course. Reference can be made to the escape depth of electrons being much less than that for X-rays, which explains why the surface sensitivity of XPS and AES is much greater than that of XRF.Both XPS and AES serve to identify all of the elements on the surface except hydrogen and XPS may also reveal the oxidation state of an element. Examples of Applications The wear of a Zub~icant.~ “Molyslip,” which is basically molybdenum(1V) sulphide, was placed between two steel plates, which were then rubbed together until the lubricant broke down.There are easily discernible changes in the Mo 3d peaks as Mo(1V) is oxidised to Mo(V1) and in the S 2p peak as S(-11) goes to S(0) and S(V1). Before this study the existence of elemental sulphur as a breakdown product was not suspected. By means of ion etching combined with XPS, Hercules established a concentration profile for a tooth that had been regularly brushed with toothpaste containing tin(I1) fluoride.One of the surprising results is the extent to which fluoride diffuses into the tooth, leaving a surface layer of tin oxide. This example brings out the quantitative side of XPS. PoZZution rnonitorilzg with copper Copper plates were exposed to the atmosphere.At first copper sulphide is formed, but this is oxidised. This study brings out the significance of chemical reactions on the surface. The surfaces of embrittled and de-embrittled steels were examined, after fracture, by AES. The elements carbon, chromium, iron, nickel, oxygen and phosphorus are easily identifiable. A depth profile was established by ion etching coupled with AES scanning.It is shown that in the de-embrittled steel phosphorus has concentrated within 1.5 nm of the fracture. The potential for scanning AES, owing to the ease of focusing an electron beam, can be mentioned. In these examples it is assumed that ion etching is a reasonable procedure for depth pro- filing. However the possibility of causing damage to the sample or in bringing about ion- induced reactions has to be borne in Because the subject of surface analysis is such a growth area it is difficult to recommend good texts for undergraduates. This may be a temporary difficulty as several books are coming into print.There are useful conference pr~ceedingsl-~ which contain a number of easily followed examples of applications of electron spectroscopy to surface analysis, and a stocktaking account of the analytical aspects contains references to a number of pioneer- ing papers.* The XPS spectrum was run at frequent intervals.Effect of $uoride toothpa~te.~?~ The results are also compared with those for XRF. Fracture of Further reading. References 1. 2. Shirley, D. X., Editor, “Electron Spectroscopy,” North Holland, Amsterdam, 1972.Caudano, R., and Verbist, J ., Editors, “Electron Spectroscopy-Progress in Research and Applica- (Also published in Volume 5 of J . Electron Spectrosc. Relat. tions,” Elsevier, Amsterdam, 1974. Phen .) 3. 4. 5 . West, A. R., Editor, “Molecular Spectroscopy,” Heyden, London, 1977. Betteridge, D., Analyst, 1974, 99, 994. Atkinson, I. B., and Swift, P., Wear, 1974, 29, 129.August, 1979 THE INTERFACE BETWEEN INDUSTRY AND AKADEMIA 233 6.7. 8. 9. Hercules, D. M., in Caudano, R., and Verbist, J . , Editors, “Electron Spectroscopy-Progress in Hercules, D. M., Physica Scripta, 1977, 16, 169. Murata, K., Ikeda, S., Utsunomiya, T., and Yasui, A., Talanta, 1976, 23, 529. Palmberg, P. W., in Shirley, D. A,, Editor, “Electron Spectroscopy,” North Holland, Amsterdam, Research and Applications,” Elsevier, Amsterdam, 1974, p.81 1 . 1972. Electronics in the Service of Analytical Chemistry J. P. Leppard Wolfson Bioanalytical Centre, University of Surrey, Guildford, Suvvey, G U2 5XH The views now expressed are derived from running, with the help of enthusiastic teaching allies, a number of intensive courses in electronics appreciation related to instrument function, both vacation courses for professional chemists and biochemists and a service course for under- graduates.There is certainly a need for such courses, but with certain provisos. In the first place, the pace of practical work will tend to be limited to that of the weakest students. It is therefore helpful to have a class that is fairly uniform in ability or background, or both.Coupled with the fact that some people have no interest in, or talent for, electronics, it is preferable that participation in the course be voluntary, and that applicants be sorted out, if not selected, by an assessment such as an elementary word-association questionnaire. The course should not be examined, and indeed in the case of undergraduates can appropriately be given in the post-examination teaching gap at the end of an academic session, thereby not adding to syllabus congestion. Secondly, a high content of practical work seems to be of the utmost importance in being conducive to a successful course, and we generally aim at devoting about half of the course to practical work, with the students in matched pairs.The third important consideration is the scope intended for the course, which aims merely at familiarisation. We make it clear to participants that we do not seek to make them into electronic engineers in the space of a week, and that electrical rather than electronic knowledge is the cornerstone. The teaching programme is in fact restricted to topics relevant to under- standing the workings of analytical instruments and modules that are in general use for analysis in chemical laboratories, notably recorders and detector assemblies. The aim of the courses is to enable participants to select equipment appropriate to their needs after an enlightened appraisal of relevant specifications, to trace, and even in some circumstances to rectify, faults in their equipment with the aid of the relevant manual and to undertake straightforward constructional projects designed to make their instruments more versatile or more appropriate to their needs.This restriction to electronics relevant to instruments simplifies the choice of material to be taught, and helps ensure that the participants will not be overburdened. Timetable hours of lectures devoted to the following topics.instruction. even attempted.) tion to the potential divider, the potentiometer and Wheatstone’s bridge. is introduced, followed by means of rectification and the elements of d.c. power supplies. A typical undergraduate timetable might consist of 12 hours of practical work with some 14 Basic electricity (3 hours). This topic consists of essential revision, comparable with A-level (It is futile to expect any recommended pre-reading to have been grasped or The emphasis is on circuit diagrams and Ohm’s Law, showing their applica- The nature of a.c.Origins of signals in instruments (18 hours). AmPliJication and junction devices (1;- hours). Recorders and integrators (13 hours). A perspectives lecture. Mainly concerned with applications rather This lecture can be used to illustrate applications Only to this Mainly concerned with impedance matching and than mechanisms.(within the circuitry of this equipment) of circuit elements previously described. extent can data handling feature in a one-week course. feedback. Types of circuit and coupling (1 hour). Clocks and oscillators (1 hour). Relays, microswitches and filters are introduced.234 and their cures.amplifier circuit diagram. THE INTERFACE BETWEEN INDUSTRY AND AKADEMIA Proc. Analyt. Div. Chem. SOC. This topic includes sources of noise Includes tracing hypothetical faults with the aid of an Szgnal-to-noise ratio and adventitious signals (1 hour). Some common types of fault (1 hour). Digitisation and logic (1 hour).Instruments with the back o f (2 hours). Demonstrations, to show that the insides of instru- ments are not sacrosanct or awesome. Films would be useful but we have not so far found any satisfactory ones. We usually recommend a good inexpensive book1 for extra-curricular reading. The practical sessions consist of various exercises giving experience in the use of measuring instruments, especially the multimeter and oscilloscope, specification checking, fault tracing and the construction of a simple light detector and amplifier.Other topics for inclusion will no doubt come to mind, and the proportions of the timetable allocated to the different lectures could be varied, but it would be a mistake, in this type of course, to try to talk about the theory of electronics without relating it to the needs of the practising chemist (as we have done by confining ourselves to the context of instrument electronics).Similarly, there is no substitute for actually soldering circuits together and measuring the voltages in them, and to this end there must be plenty of practical work included. Further, insofar as each successive course requires improvement and up-dating, it is important to seek candid comments from the students in retrospect.Provided that these conditions are fulfilled, and that there is avoidance of over-earnestness, to which specialist electronics lecturers may be prone, a successful teaching programme can be achieved, to the gratification of all concerned. Reference 1. Young, S., “Electronics in the Life Sciences,” Macmillan, London, 1973.The Handling of Analytical Chemical Data P. G. Barker University of Durham Science Laboratories, South Road, Durham, DH1 3LE There is a rapidly expanding spectrum of analytical techniques (particularly instrumental) enabling the scientist to collect data. This commodity, once acquired, usually involves the scientist in some form of mental effort in order to convert it into information that is more meaningful, both to himself and to those who may wish to use it.Transforming the raw data in various ways frequently eases its assimilation. Bagrit, in his book “The Age of Automation” suggests that one of the basic driving forces for technological advancement is the human need to supplement those faculties which, for one reason or another, are incapable of meeting the demands placed upon them.Thus, advancement in analytical science and instrumen tation can be thought of as being an extension of the observational capacity of human beings, while computers, in their many varied forms, represent an extension of man’s cerebral capacity, that is, his ability to store and process information. There are some interesting implications associated with the combination of analytical science, the practical aspects of computer science and certain elements of human science.With cautious mixing, and in the correct proportions, it is possible to produce a new species called a “data scientist.” This rather rare species is one who has a wide knowledge of physical science, particularly analytical techniques, is well versed in the skills and techniques of com- puter science, in particular those aspects relevant to data collection and data handling, and has a deep understanding of human science.The latter, of course, provides the ethical basis for what he does and guides him in the development of standards and a professional attitude towards the work he is likely to undertake.On the analytical front he should understand a wide variety of analytical methods (conventional, instrumental and automated) and be capable of designing new techniques and instrumentation to support these methods. This may involve How should this new species be educated?August, 1979 APPLICATIONS OF CHROMATOGRAPHY IN TEXTILES FIELD 235 the utilisation of microcomputers, minicomputers, mainframes or super-computers. It may even involve the use of local, national or international computer communications support net- works.Naturally, the act of joining together a set of basic components to build a more com- plex analytical system (typical of that which one might find in an automated laboratory) will require not only an understanding of interfacing standards (e.g., IEEE 488, Camac, Carrick, etc.) and techniques but also a capability with respect to the design of his own interfaces where necessary.In summary, the data scientist should be capable of utilising the currently avail- able computer hardware technology to supplement and ease every aspect of his work. As the data that the data scientist collects will need to be stored and then subsequently accessed at some future date, some part of his training should involve his acquiring an under- standing of the methods of design of data base systems.If necessary, he should be capable of constructing a data base to contain experimental data either by using some commercially available packages or else via the utilisation of more primitive resources.He should be aware of the existence of the accepted nationallinternational data centres (the Mass Spectrometry Data Centre, the Crystallographic Data Centre, etc.) that are responsible for the handling of large collections of standard reference data and, if necessary, be able to supply information t o or retrieve information from such centres. Because his experimental data will need to be processed and transformed in various ways, the data scientist should be familiar with the wide variety of tools available to aid him in this task, ranging from the slide rule to the analogue computer to array processors, etc.The selec- tion of a tool appropriate for the job in hand is a consideration that should not be overlooked. However, mere familiarity with processing resources that are available is insufficient as there is a vast range of computer programs now available to perform all sorts of data handling opera- tions. An awareness of the range of products available and an ability to select processing software relevant to the particular application under consideration is vital if he is to do his job correctly and efficiently.Over the last two years there has been an explosive growth in new techniques of analysis and data handling. Not only do students find it difficult to stay informed but educators them- selves are frequently unable to find the necessary time to learn about the new techniques by browsing through books or journals. Methods that are more efficient and less time-consuming are required. Can computer technology play a useful role in the education of future data scientists, and the re-education of those who educate them? The answer, of course, is yes. Techniques such as Computer Augmented Instruction (CAI) and Computer Based Training (CBT), and other related instructional systems, are now well-established tools within the USA, both within the industrial sector and within schools and colleges. Some small steps have been taken towards introducing this type of teaching in schools and universities within the UK (e.g., the “Computers in the Curriculum’’ project) but the major strides have been made by industry. The PLATO system (from Control Data Corporation) originally developed at the University of Illinois, the ASET system (from Sperry Univac) and the Interactive Instructional system (from IBM) are typical of the type of instructional packages that are now available; undoubtedly, the PLATO system is the most spectacular. The interested reader will find examples of its use in the appropriate chemical literature.

ISSN:0306-1396    

DOI:10.1039/AD9791600228

出版商:RSC    

年代:1979

数据来源: RSC

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August, 1979 APPLICATIONS OF CHROMATOGRAPHY IN TEXTILES FIELD 235 Applications of Chromatography in the Textiles Field The following are summaries of three of the papers presented at a meeting of the North East Region and the Chromatography and Electrophoresis Group held on March 21st, 1979, at The University, Leeds. Identification of the Internal Lipids of the Wool Fibre by Thin-layer Chromatography H.E. Crabtree, P. Nicholls and E. V. Truter Textile Chemistry Laboratory, The University, Leeds, LS2 9 J T Irrespective of the detergent and the technique used for scouring greasy wool, removal of the grease is apparently never complete. When the proportion of residual lipid on the wool is236 APPLICATIONS OF CHROMATOGRAPHY IN TEXTILES FIELD Proc. Analyt. Div.Chern. SOC. determined gravimetrically by extracting it with an organic solvent, low results (about 0.3%) are obtained with dry wool and non-polar solvents, and high results (about 1.2%) are obtained with conditioned wool and polar solvents. The conventional explanation is that the lipid is protected by a barrier of soap, generated during the scouring process, which is hardly soluble in dry, non-polar solvents but which is soluble or dispersable in polar and wet solvents. Examination of the residues obtained with various solvents by means of thin-layer chroma- tography showed that the additional lipid extracted by polar solvents is rich in cholesterol, which should easily be washed off the fibre, and rich in fatty acids even when a synthetic detergent has been used for scouring the wool.Both the solubility effects and the variations in composition would readily be explained if it could be demonstrated that the fibre contained an internal lipid that was rich in cholesterol and fatty acids. Accordingly, the surface lipid was removed from dry, raw wool with 2-methylpropan-2-01, a solvent that penetrates into the dry fibre extremely slowly, and the internal lipid was subsequently extracted from the condi- tioned fibre with benzene - methanol azeotropic solvent.Thin-layer chromatography of the internal lipid on silica gel with various eluting agents, such as ether - light petroleum (4 + 1) and benzene - ethyl acetate (17 + 3), both with and without 1% acetic acid, showed that it contained ten components. One, component 5, was far more abundant than all of the others; a second, component 4, was present in reasonable abund- ance, and the other eight were minor components.The transient colours formed on the adsorbent with sulphuric acid indicated that components 1, 5, 6, 7, 8, 9 and 10 contained steroids. By spraying chromatograms with iron(II1) hydroxamate reagent and with molyb- date reagent, it was found that components 1,2, 6, 7 and 8 were esters and that components 6, 7, 8 and the material at the origin contained phosphorus.After small amounts of the indi- vidual components had been isolated by preparative thin-layer chromatography, the two most abundant components were identified as cholesterol and a mixture of fatty acids; their propor- tions in the internal lipid, determined by the mass - area method, were about 72 and l2%, respectively.The proportion of cholesterol varied inversely with its opportunity for under- going autoxidation; there was less in the tip segment of the fibre than in the root segment, and less in fine fibres than in coarse fibres. The products of its autoxidation were the two minor components 9 and 10, which were the isomeric 7cc- and 7~-hydroxycholesterols.Components 6 , 7 , 8 and the material at the origin were found to be related by two-dimensional chromatography, using the same solvent for both elutions. Component 6 decomposed to give the other three substances, and component 8 decomposed to give the component at the origin. The precise constitution of these phospholipids has not yet been determined.After the hydrolysis of components 1 and 2 the alcoholic moieties were found to be choles- terol and glycerol, respectively. Their acidic fractions, together with the free acids, were methylated and examined by use of gas - liquid chromatography. All three samples contained many acids but at very low concentrations; the main components were docosadienoic acid (80%) in component 2, hexadecanoic, octadecanoic and octadecenoic acids in component 1, and the last three acids in component 4.Chromatography of the methyl esters of the free acids (component 4) on silica gel impregnated with silver ions indicated the absence of dienoic acids, and none could be detected by gas - liquid chromatography. The glyceride is almost ex- clusively composed of one compound, the docosadienoate.The presence of glycerides, to- gether with the fact that these and the free acids are almost wholly composed of the same three acids that are typical of fats, indicates that the internal lipid and the external lipid are separate entities. Polyacrylamide Gel Electrophoresis in the Presence of Sodium Dodecylsulphate in Wool Protein Purification and Relative Molecular Mass Determination B.Ahmadi and P. T. Speakman Department of Textile Industries, The University, Leeds, LS2 9 JT Reduced wool was disrupted mechanically in distilled water. fied by centrifugation and chromatographed on Sepharose CL-4B. The resulting solution was clari- The protein in the mostAugust, 1979 APPLICATIONS OF CHROMATOGRAPHY I N TEXTILES FIELD 237 concentrated retarded fraction, plasmolysis protein, might contain protein chains aggregated together specifically, as they were in the wool fibre, or randomly aggregated together.Plas- molysis protein was therefore treated with a buffer solution containing 1 yo 2-mercaptoethanol, in order to break cystine residue disulphide cross-links b2tween protein chains, and with concentrated urea and 1% sodium dodecylsulphate, to break hydrogen bonds between the chains.This treatment allowed individual protein chains to migrate independently during electrophoresis on polyacrylamide gels. The movement of a protein during electrophoresis depends on its relative molecular mass, its shape and its charge. During the treatment with 2-mercaptoethanol, urea and sodium dodecylsulphate, molecules of this last reagent are adsorbed on to protein molecules in the ratio of 1.4 g of sodium dodecylsulphate to 1 g of protein.This appears to be true for nearly all protein molecules, irrespective of their amino acid composition. Consequently, all proteins dissolved in neutral buffers containing sodium dodecylsulphate acquire a negative charge due to the adsorbed sodium dodecylsulphate molecules.The charge due to acidic and basic pro- tein side chains is negligible compared with the charge due to adsorbed sodium dodecylsulphate molecules, and therefore the total charge on a protein is proportional to its length (relative molecular mass). Further, the many negative charges along protein molecules apparently cause them all to assume a similar, extended conformation in solution.As a result of these effects the different distances travelled by different proteins during electrophoresis under the same conditions depend only on their relative molecular masses. The distance that a protein has travelled is found by dyeing the protein on the gel after electrophoresis. If a number of proteins are treated with 2-mercaptoethanol, urea and sodium dodecylsulphate, and are subjected to electrophoresis in parallel under the same conditions, a graph of log relative molecular mass plotted against distance travelled is a straight line.Clearly, the relative molecular mass of a protein can be determined in this type of experiment if protein chains of known relative molecular mass are used to obtain a calibration line.The accuracy of the method is claimed to be better than 1Oy0.l The relative molecular masses of the protein chains in plasmolysis protein determined in this way were 44 000 and 58 000, con- sistent with the relative molecular masses determined in the ultracentrifuge. There was also a smaller amount of a third protein with a relative molecular mass of 105000, apparently a dimer consisting of one 44k molecule and one 58k molecule linked by a non-reducible cross- link.2 Separate slices containing the 44k and 58k pro- teins were cut from many gels.The slices containing each protein were combined and set in more polyacrylamide gel, from which the protein was run by electrophoresis into a small volume of buffer s ~ l u t i o n . ~ The purified proteins were then used to obtain graphs relating the amounts of each protein in bands in acrylamide gels to the intensity of staining of the bands by Coomassie Brilliant blue, measured with an integrating Joyce - Loebl densitometer.These graphs were used to determine the relative amounts of 44k and 58k protein in plasmolysis protein . We suspected from the results of experiments with another wool protein that before treat- ment with 2-mercaptoethanol, urea and sodium dodecylsulphate the plasmolysis protein solution might consist of protein molecules composed of four protein chains held together in a specific arrangement by hydrogen bonds and cystine disulphide cross-links. In order to test this possibility, plasmolysis protein was treated with a cross-linking agent, dimethylsuber- imidate The technique also has a preparative use.CH,OC( =NH) (CH,),C( =NH)OCH, before being exposed to 2-mercaptoethanol, urea and sodium dodecylsulphate. The methyl- imidate groups in the dimethylsuberimidate molecule can react with the side chain amine groups of two lysine residues, and if the lysine residues are in two of the protein chains of the specific aggregate, then the two chains will be cross-linked together with a non-reducible cross- link.Obviously, cross-linking is more likely to occur between chains within a four-chain pro- tein molecule rather than between chains in two different four-chain molecules. Hydrolysis of the methylimidate groups by water competes with their reaction with amine side chains. High pH values favour the cross-linking reaction rather than the hydrolysis, but too high a pH may dissociate plasmolysis protein into its component chains before they are cross-linked to-238 APPLICATIONS OF CHROMATOGRAPHY IN TEXTILES FIELD Proc. Analyt.Div. Chem. Soc. gether. If one imidate group in a dimethylsuberimidate molecule is hydrolysed and the other reacts with a lysine residue amine group, then that amine group is blocked from taking part in a crosslink.Some lysine residue amine groups may take part in the formation of intra-chain cross-links and thus be prevented from taking part in an inter-chain link. Also, the number of lysine residue amino groups in appropriate positions to form cross-links between chains may be limited. For these reasons cross-linking might be incomplete , and after cross-linking a solu- tion of a four-chain protein would be expected to contain molecules in which none of the chains, two chains, three chains, or all four chains, are cross-linked t ~ g e t h e r .~ When cross- linked plasmolysis protein was treated with 2-mercaptoethanol, urea and sodium dodecylsul- phate, and examined by polyacrylamide gel electrophoresis, the gels showed five protein bands: the two monomers, relative molecular masses 44k and 58k; the dimer, 105k; the trimer, 150k; and the tetramer, 204k.The subsequent pentamer and hexamer bands were faint. This result showed that plasmolysis protein consisted of four chains, probably two 44k and two 58k chains2 The same techniques have been used to show that another wool protein, merokeratin A,, prepared by limited trypsin digestion of reduced wool or reduced plasmolysis protein, also has four chain^.^ References 1.2. Weber, K., and Osborn, M., in Neurath, H., and Hill, R. L., Editors, “The Proteins,” Volume 1, Third Edition, Academic Press, New York and London, 1975, pp. 179-223. Ahmadi, B., Boston, N. M., Dobb, M. G., and Speakman, P.T., “Proceedings of the International Conference on Fibrous Proteins, Massey University, 1979,” Academic Press, New York and London, in the press. 3. 4. 5. Ahmadi, B., Analyt. Biochem., 1979, in the press. Peters, K., and Richards, F. M., Ann. Rev. Biochem., 1977, 46, 523. Ahmadi, B., and Speakman, P. T., F E B S Lett., 1978, 94, 365. Analysis of Fatty Amides by Thin-layer Chromatography D.L. Connell and P. R. A. Spahr S. Jean Purdy and E. V. Truter Sandoz Ltd., Calverley Lane, Horsforth, Leeds Textile Chemistry Laboratory, The University, Leeds, L S 2 9 JT Amides, amines and quaternary ammonium compounds containing one or two long alkyl chains find many applications in the textile industry, particularly as cationic surface-active agents, fabric softening agents and anti-static agents.The normal synthetic route is by thermal dehydration of the ammonium salt of a fatty acid to the amide, then, at a higher temperature, to the nitrile and thence, by hydrogenation, to amines and substituted amines, which on treat- ment with a methylating agent yield the quaternary ammonium salt. The relative reactivities of the individual centres in the first step of the synthetic process have been elucidated for an unsymmetrical compound containing three reactive centres, namely, hydroxyethylethylenediamine, by analysis of the products of its reaction with less than three equivalents of stearic acid.Thin-layer chromatography of the product on silica gel with benzene - methanol and toluene - methanol in various proportions ranging from 6 + 1 to 12 + 1 revealed the presence of at least eleven components, of which five were present only in trace amounts.Those components containing primary amino groups were identified by spraying chromatograms with ninhydrin reagent. To determine which components still con- tained reactive centres, the product was examined by the technique of acetylation on the adsorbent in two dimensions.The same agent was used for both elutions, and the sample was treated with acetic anhydride after the first elution. Second- ary amino groups could not be converted into their acetyl derivatives by treating them with acetic anhydride on the adsorbent, whereas primary amino groups were readily acetylatable. This finding was confirmed by tests with N-octadecyl propylenediamine.It was also found The results revealed unexpected differences in the reactivities of the amino groups.August, 1979 OBITUARY 239 that, after the acetylation step, the amount of residual acetic acid on the adsorbent was suffi- cient to cause a marked lowering of the R, values of compounds containing basic groups. Com- pounds containing secondary amino groups were retarded to a greater extent than those con- taining primary amino groups; amides were unaffected.This effect was useful in helping to identify those compounds which contained primary or secondary amino groups, but it could present difficulties in interpretation because compounds that are not changed by the reaction do not necessarily lie on the diagonal of the chromatogram. Individual components of the product were recognised by their reactions on the adsorbent, and after the individual components had been isolated by a combination of fractional crystal- lisation and preparative thin-layer chromatography their identities were confirmed by ele- mental analysis, infrared spectroscopy and mass spectrometry. The main components of the mixture are the diamide ester, the diamide, the secondary amide ester, the secondary amide and the tertiary amide. There was no clear indication of the presence of the iminazoline, which was one of the expected products. In separate experiments, however, equimolar amounts of stearic acid and hydroxyethyl ethylenediamine reacted at 160 "C to give a high yield of the iminazoline. The relative amounts of the various components of the mixture indicated that the order of reactivities of the individual centres is NH> NH,> OH, but for acetylation on the adsorbent the order of these groups is reversed.

ISSN:0306-1396    

DOI:10.1039/AD9791600235

出版商:RSC    

年代:1979

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August, 1979 OBITUARY 239 Obituary Mr. Stanley Dixon Stanley Dixon was born in Gainsborough, Lincolnshire, in 1895 and was educated a t Gainsborough Grammar School and then Sheffield University, where he obtained an MSc in 1917. His working career started as an assistant to the Public Analyst of the Cities of Sheffield and York, and after a short spell of service in the Royal Navy he became chief assistant to the Public Analyst of Derby County.In 1920 he passed the Branch E examination of the Institute of Chemistry (now MChemA4) and became a Fellow in the following year. In 1929 Stanley Dixon became Public analyst and Official Agricultural Analyst to the City of Cardiff and was appointed in the same capacity to the County Borough of Swansea in 1943. These posts he held for the remainder of his working life, retiring in 1961 after many years of faithful service.He always took a keen and active interest in his professional societies and was a Member of Council of the S-4C on several occasions; he was also Chairman of the Local (Western) Section from 1958-1960. Mr. Dixon was very fortunate in having a very happy family life, having married Phyllis, the third daughter of John White, a former County ,Analyst to the County of Derby. He was justly proud of his two sons, the elder being Professor of Bacteriology a t the University of Alberta and the other Director of Mathematical Studies a t Churchill College, Cambridge.However, Stanley Dixon will be remembered by his colleagues as a meticulous analyst and an ambassador for the profession of Public Analysts.He was a jovial and likeable person who, to my certain knowledge, did not have an enemy in the world. It was a privilege and a pleasure to have worked for him and to have known and enjoyed the company of his family and friends. He leaves a widow, two sons, two daughters-in-law and two grandchildren, who, like many others, miss him very much. He passed away fairly suddenly on April 3rd, 1979, after a full and active life, in his 85th year. L. E. COLES Midlands Region Secretary Since the report of the Midlands Region Dr. R. S. Barratt as Honorary Secretary. Mr. Annual General Meeting was published (March Brookes’ address is 35 Dunster Road, West issue, p. 89), Mr. H. E. Brookes has replaced Bridgford, Nottingham, NG2 6JE.

ISSN:0306-1396    

DOI:10.1039/AD9791600239

出版商:RSC    

年代:1979

数据来源: RSC

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240 IUPAC REPORT Proc. Analyt. Div. Chern. SOC. Publications Received Laboratory Experiments in College Chem- Trace Element Analysis of Geological istry. Fourth Edition. Materials. G. Brooks King, William E. Caldwell and Max R. D. Reeves and R. R. Brooks. Chemical B. Williams. Pp. xiv + 334. New York, Analysis, Volume 51. I’p. x + 421. New Cincinnati, Toronto, London and Melbourne : York, Chichester, Brisbane and Toronto : John Van Nostrand.1979. Price k5.95 softback. Wiley. 1978. Price f119.50. Molecular Spectra and Molecular Structure. IV. Constants of Diatomic Buffers for pH and Metal Ion Control. Molecules. New York, Cincinnati, Atlanta, Dallas, San 176’ London: Chapman and lg7’ (first K. P. Huber and G. Herzberg. Pp. xvi + 716. D* ‘errin and Boyd Dempsey* ’P* viii f Francisco, London, Toronto and Melbourne published in hardback 1974).Price L4qg5* Van Nostrand Reinhold. 1979. Price L20.65. Photometric and Fluorometric Methods of Report on the Seventeenth Period of Work- Analysis. Metals. ing December 1974 to November 1977. Foster Dee Snell. Pp. xxiv + 2167. New Bureau of Analysed Samples. Report No. 476. York, Chichester, Brisbane and Toronto : John Pp.27. Newby, Middlesbrough, Cleveland : Wiley. 1978. Price f198; $195. Bureau of Analysed Samples Ltd. 1979. Gratis. Parts 1 and 2.August, 1979 PUBLICATIONS RECEIVED 241 Vogel’s Textbook of Quantitative Inorganic Analysis including Elementary Instru- mental Analysis. Fourth Edition. Revised by J. Bassett, R. C. Denney, G. H. Jeffery and J. Mendham. Pp. xxxii + 925.London and New York: Longman. Price k14. 1978. Chemical Kinetics and Transport. Peter C. Jordan. Pp. xvi + 368. New York and London: Plenum Press. 1979. Price k13.54. Spectrochemical Analysis by Atomic Absorption. W. J. Price. Pp. xii + 392. London, Phila- delphia and Rheine: Heyden. 1979. Price $28.50; L14.25; DM65.50. The Chemical Analysis of Bismuth. Sup- plements 20-22 of The Bulletin of the Bismuth Institute.Roland S. Young. Pp. 12. Brussels: The Bismuth Institute. 1978/9. Price Gratis. Quantitative Organic Analysis via Func- tional Groups. Fourth Edition. Sidney Siggia and J. Gordon Hanna. xii + 883. New York, Chichester, Brisbane and Toronto: John Wiley. 1979. Price ,532; $60.75. Asbestos. Volume 1. Properties, Applica- tions and Hazards.Edited by L. Michaels and S. S. Chissick. Pp. xiv + 553. Chichester, New York, Brisbane and Toronto: John Wiley. 1979, Price L25. Chemical Analysis by Microwave Rota- tional Spectroscopy. Ravi Varma and Lawrence W. Hrubesh. Chemical Analysis, Volume 52. Pp. xii + 206. New York, Chichester, Brisbane and Toronto : John Wiley. 1979. Price ,515; $28.50. Densitometry in Thin Layer Chromato- graphy.Practice and Applications. Edited by Joseph C. Touchstone and Joseph Sherma. Pp. xvi + 747. New York, Chiches- ter, Brisbane and Toronto: John Wiley. 1979. Price L21; $39.55. Metal /3-Diketonates and Allied Derivatives. R. C. Mehrotra, R. Bohra and D. P. Gaur. Pp. viii + 382. London, New York and San Francisco : Academic Press. 1978. Price $20.50. Stability Constants of Metal-Ion Com- plexes.Part B. Organic Ligands. Compiled by Douglas D. Perrin for the Inter- national Union of Pure and Applied Chemistry Analytical Chemistry Division Commission on Equilibrium Data. I UPA C Chemical Data Series-No. 22. Pp. viii + 1263. Oxford, New York, Toronto, Sydney, Paris and Frank- furt: Pergamon Press. 1979. Price $150. Ionisation Constants of Organic Acids in Aqueous Solution.Prepared for publication by E. P. Serjeant and I3oyd Dempsey for the International Union of Pure and Applied Chemistry -4nalytical Chem- istry Division Commission on Equilibrium Data. IUPAC Chemical Data Sevies-No. 23. Pp. xii + 989. Oxford, New York, Toronto, Sydney, Paris and Frankfurt : Pergamon Press. 1979. Price $125. Proceedings of the 5th European Sym- posium on Polymer Spectroscopy (ESOPS 5 ) in Cologne, September 1978.Edited by D. 0. Hummel. Pp. xii + 332. Weinheim and New York: Verlag Chemie. 1979. Price DM88 (softback). Handbook of Aerosol Technology. Second Edition. Paul A. Sanders. Pp. xii + 526. New York, Cincinnati, Atlanta, Dallas, San Francisco, London, Toronto and Melbourne : Van Nostrand Reinhold. 1979. Price L20.65. Trace Metals in the Environment. Volume 5. Indium : An Appraisal of Environmental Exposure. Ivan C. Smith, Bonnie L. Carson and Fritz Hoffmeister. Pp. xxii + 552. Ann *4rbor, Mich. : Ann Arbor. Distributed by John Wiley, Chichester. 1978. Price i15.20. Chemistry of Wastewater Technology. Edited by Alan J. Rubin. Pp. xii + 498. Ann Arbor, Mich. : Ann Arbor. Distributed by John Wiley, Chichester. 1978. Price ,518.90. Porous Silica its Properties and Use as Support in Column Liquid Chromato- K. K. Unger. Journal of Chromatography Library, Volume 16. Pp. xii + 336. Amster- dam, Oxford and New York: Elsevier. 1979. Price Dfl120. graphy.

ISSN:0306-1396    

DOI:10.1039/AD979160240c

出版商:RSC    

年代:1979

数据来源: RSC

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242 CONFERENCES AND MEETIKGS PYOC. AnaZyt. Div. Chew. SOC. Conferences and Meetings Trace Organics in Environmental Samples September 5-6, 1979, Guildford For analysts who have to deal with “natural” organic matrices, a pioneer symposium which may not have come to your attention is to be held at the University of Surrey. Part- attendance could foster debate on analytical problems with crops, foods, soils and water.Contact Dr. E. Reid, Tel. 0483-71281. BA 79 Septembev 3-7, 1979, Edinbuvgh The 141st meeting of the British Association for the Advancement of Science will take place a t Heriot-Watt University. The Chemistry sec- tion is Section B and i t starts on September 4. The discussion in the morning of Thursday September 6 is entitled “The Scientist as Industrial Designer’’ and it will be led by Dr.C. W. Suckling FRS of Imperial Chemical Industries Limited. His theme will be the controversial issue of the extent to which the education of scientists helps them perceive the relevance of pure science and problems in open systems outside the laboratory. Further details of the meeting as a whole are obtainable from Miss J. J. Dring, British Association for the Advancement of Science, 23 Savilc: Row, London W1X 1AB.Third ICP Workshop and Symposium September 11-13, 1979, London Scientific Conference Services are organising the next Inductively Coupled Plasma Spectroscopy Workshop and Symposium. This annual event, the third one to be held, will take place at Chelsea College. The format of this year’s workshop has been extended to include an opportunity for workers in the field to give short presentations on their own results and experiences in the use of ICP’s in analytical situations.This increased scope is reflected in the inclusion of the word symposium in the title of the meeting. The format of the Workshop part of the meet- ing will be similar to those held previously a t which several acknowledged experts in the field gave introductory talks on the principles, practice and applications of inductively coupled plasma spectroscopy.At the third meeting, however, participants will have the opportunity to examine and operate several plasma systems from different manufacturers, who will be present a t the meeting to demonstrate their equipment. There will, therefore, be a unique opportunity to compare the hardware available from the different manufacturers during the course of the workshop, a very valuable exercise for anyone contemplating the purchase of a system.The organisers will be pleased t o hear from anyone who would like to present a paper at the meeting. For further information please write to Scientific Conference Services Limited, 14 Trading Estate Road, London, NWlO 7LU. 1980 Pittsburgh Conference illarch 10-14, 1980, Atlantic City, New Jersey, “SL4 The Board of Directors of the Pittsburgh Con- ference on -4nalytical Chemistry and Applied Spectroscopy have decided that the 1980 con- ference will be held a t Atlantic City.For the past 12 years the conference has been held in Cleveland, Ohio, having left Pittsburgh because of a hotel strike.A number of symposia have already been organised but papers can be submitted on all aspects of analytical chemistry and applied spectroscopy. Authors wishing to submit a paper should provide a 300-word abstract in triplicate bearing the title of the paper, the name(s) of the author(s), the organisation(s) in whose laboratories the work was done and their address(es), the name of the author who will present the paper underlined and a signature and date in verification of the fact that the material in the paper has not been published or presented previously. Abstracts should be sent to n’Irs.Linda Briggs, Program Secretary, 437 Donals Road, Pittsburgh, Pa. 15235, USA. CS/RIC Annual Chemical Congress April 9-11, 1980, Durhaw The 1980 ,Annual Congress will be held a t the University of Durham.The Analytical Sym- posium will be entitled “Modern Techniques for Surface Characterisation’’ and will include lectures by J . M. Thomas, E. D. Hondros, D. G. Xmour, D. W. Palmer, V. Leroy, R. Holm, P. Echlin and R. Berneron. Persons wishing to present an oral paper or a poster a t the meeting should submit a title and briefAugust, 1979 CONFERENCES AND MEETINGS 243 synopsis (not more than 100 words) by October For further information on the meeting con- 1, 1979, to: Dr.John F. Gibson, The Chemical Society, Burlington House, London W 1V OBN. tact Dr. Gibson at the above address. Fifth SAC Conference July 20-26, 1980, Lancaster Scientific Programme The scientific programme of the 1980 SAC Con- ference will cover all aspects of analytical chemistry and will consist of plenary lectures, contributed papers, workshops and specialist sessions involving the Subject Groups of the Division.The plenary lectures will be “Ana- lytical Instrumentation for the 1980s” (Pro- fessor H. V. Malmstadt), “Plasma Spectroscopy Comes of Age” (Mr. S. Greenfield), “Moral Ageing of Analytical Methods” (Professor G.E. Baiulescu) and “Assessing the Analytical Quality of the Clinical Laboratory” (Professor T. P. Whitehead). The Conference will mainly consist of the presentation of about 200 contri- buted papers arranged into sessions such as Bio- chemical Analysis, Education and Training in Analytical Chemistry, Historical Aspects, Particle Size Analysis, Pollution and Environ- mental Control, Production Control, Clinical -4nalysis, Geological Analysis, Microchemistry, Pharmaceutical Analysis, Problems Arising from the EEC and Other Regulations and Surface Analysis, and sessions accommodating various techniques, e.g., Atomic Spectroscopy, Bio- logical Methods, Molecular Spectroscopy, Separation Techniques, Thermal Methods, Automation (including the use of minicom- puters and microprocessors), Electroanalysis, Radiochemical Methods and Special Techniques.A large number of titles of papers have already been submitted, but further contributions are invited. Titles and abstracts in a form suitable for publication (up to 200 words) must be sub- mitted before November 30th, 1979, to the Scientific Secretary] Professor L.S. Bark, c/o Analytical Division, The Chemical Society, Burlington House, London, W 1V OBN. In addition to the above lecture programme, some of the specialist Subject Groups of the Division have undertaken to arrange sessions of topical interest as follows: a poster session on various aspects of teaching and training ; special sessions and discussion periods concern- ing the broader aspects of atomic spectroscopy and automatic methods, including applications of microprocessors ; a lecture and discussion on “Some Analytical and Philosophical Aspects of Environmental Control in the Pharmaceutical Industry” ; and discussion periods on aspects of chromatographic and electroanalytical methods. More details about these and other aspects of the Conference are given in the second circular] copies of which can be obtained from the Secretary of the Analytical Division at the address given above.

ISSN:0306-1396    

DOI:10.1039/AD9791600242

出版商:RSC    

年代:1979

数据来源: RSC