摘要:

Proceedings of the Society for Analytical Chemistry Analytical Division Chemical Society CONTENTS Annual General Meetings . . The President and Society for Analytical Chemistry Gold Medallist . . . . . . Reports of Meetings . . .. Annual Report of the Councils Summaries of Papers “Plasma Excitation in Spectro- chemical Analysis” . . . . “Multi-residue Detection Sys- tems” . . .. .. “Polymer Characterisation by Chromatographic Means” . . Notice . .. .. .. 71 72 73 75 a9 92 93 97 Forthcoming Meetings Bock Cover Proc. SOC. Analyt. Chem. Vol. 10 No. 4 Pages 71-98 April 1973 PAYCAL April 1973 PROCEEDINGS THE SOCIETY FOR ANALYTICAL CHEMISTRY OF ANALYTICAL DIVISION CHEMICAL SOCIETY Hon. Secretary W. H. C. Shaw Officers of The Society for Analytical Chemistry and the Analytical Division of The Chemical Society President G.W. C. Milner J. K. Foreman Hon. Treasurer Hon. Assistant Secretaries D. I. Coomber O.B.E.; D. W. Wilson Secretary Miss P. E. Hutchinson 9/10 SAVILE ROW LONDON WIX IAF Telephone 01-734 9864 Editor J. B. A t t r i l l Assistant Editor P. C. Weston Proceedings i s published by The Society for Analytical Chemistry. Members’ subscriptions must be sent t o The Chemical Society. Non-members can be supplied with Proceedings only as part of a combined subscription with The Analyst and Analytical Abstracts. Single coples can be obtained direct from The Chemical Society Publications Sales Office Blackhorse Road Letchworth Herts. SG6 I HN (NOT through Trade Agents) price 30p post free. Remittances MUST accompany orders. 0 The Society for Analytical Chemistry Now Available ANALYTICAL SCIENCES MONOGRAPH No. I H ig h- Precision Tit ri met ry by C. Woodward and H. N. Redman lmperial Chemical Industries Limited (Agricultural Division) BRIEF CONTENTS Introduction Visual Titrations with sections on Apparatus Standard Substances and their preparation Instrumental Methods with sections on Photometric Titrations Electrometric Titrations References t o the literature of high-precision titrimetry. and assay and Standard Solutions. and Miscellaneous Techniques. Pp. viii+63 Price €250 Obtainable from Society for Analytical Chemistry Book Department 9/10 Savile Row London WIX IAF I Members may buy personal copies at the special price of f200

ISSN:0037-9697    

DOI:10.1039/SA97310FX014

出版商:RSC    

年代:1973

数据来源: RSC

摘要:

SOCIETY FOR ANALYTICAL CHEMISTRY AXALYTICAL DIVISION CHEMICAL SOCIETY Forthcoming Meetings-contilzued from back cover May-continued Friday 25th GLASGOW SCOTTISH REGION and ATOMIC SPECTROSCOPY and RADIOCHEMICAL METHODS “Traces and Tracers-the Limits of Analysis,” by J. I f . A. Leniham. “Toxicological Applications of Activation Analysis,” by H. Smith. “Analysis of Some Clinical Samples by Seutron ilctivation,” by B. W. East. “The R6le of Lead in Clinical Medicine,” by A. Goldberg. “Atomic Absorption Techniques in Clinical Biochemistry,” by G. Fell. “Studies on Lead in Blood,” by A. M. Smith. “Some Applications of Ion Selective Electrodes in Clinical Analysis,” by G. P. Department of Chemistry Thomas Graham Building University of Strathclyde GROUPS on “Metals in Clinical Analysis.” Bound.Cathedral Street Glasgow ; 9.45 a.m. SOCIETY FOR AXALYTICAL CHEMISTRY ASALYTICAL DIVISIOP; CHEMICAL SOCIETY Forthcoming Meetings May Tuesday 1st JIIDLAXDS REGIOS lointly uzth the Loughborough University of Technology LOUGH- Cheniical Society. BOROUGH “Thermal Analysis-How and Why,” by J P. Redfern. Edn ard Herbert Building The Pniversity of Technology Loughborough Leics 4.15 p.m. V’ednesday 2nd SXC’=1D meeting on “Standardisation of JIethods and Materials ” LOKDOX Wednesday 2nd STOKE-OS- TRENT Friday 4th LOXDOX Thursday 10th XLCOXBURY Tuesday 15th LOXDOS Thursday 24th SITTING- BOURSE “The Philosophy of Standards; the \Vork of the Analytical Standards Sub- “The Preparation of Certified Reference Materials for the Xctallurgical Indus- “The Preparation of Standard Chemical Substances,” by J .E. Connett “Reference Materials for Pharmaceutical Xnalysis,” by C . A. Johnson. Scientific Societies Lecture Theatre 23 Savile Row London W . 1 ; 2.30 p.m. PARTICLE SIZE ANALYSIS GROCP. Visit to The British Ceramic Research Xssociation. The British Ceramic Research Xssociation Queens Road Penkhull Stoke-on-Trent ; 10.45 a.m. Electroanalytical Group on “The Current Status of Some Electroanalytical “Coulometry” by J . Janata. “X.C. Polography,” by R. D. Jee. “On-line Polarography,” by P. 0. Kane. “Assessment of Performance of Ion Selective Electrodes,” by R. J . Simpson. “Stripping Voltammetry,” by I. Fraser. Senior Common Room Chelsea College Manresa Road London S.W.3; 6.30 p.m. EAST A % x ~ ~ ~ . ~ REGIOS arid AUTOMATIC METHODS GROUP on “The Place of Sophisticated Techniques in Consultancy Research M’ork.” “L.K.B.Reaction Rate Analyser and Calculator Output through Westrex “Use of Gas Chromatography - Mass Spectrometry for R and D Analytical Huntingdon Research Centre hlconbury Hunts. ; 11.15 a.m. SAC/XD jointly with the Industrial Division (South East Region) of the CS 011 Speakers to include C. \Vhalley l?~ J. Woodman S. G. Perry A. H. .\ndrews Scientific Societies Lecture Theatre 23 Savile Row London W.1,; 10.00 a.m. Biological Methods Group Summer Meeting. Visit t o Shell Research Laboratories Analytical Chemistry Division and Bio- logical Evaluation Division Woodstock -4gricultural Research Centre Sitting- bourne Kent; 2.15 p.m. [coiztinued hzside back couw Committee,” by E. Bishop. tries,” by P. D. Ridsdale. Techniques.” Some experiences a t HRC,” by -4. E . Street. Work,” by T. A . Gough. “The Value of Analytical Chemistry in Industry.” and H. J . Cluley. Printed by W Heffer &Sons Ltd Cambridge England

ISSN:0037-9697    

DOI:10.1039/SA97310BX016

出版商:RSC    

年代:1973

数据来源: RSC

摘要:

April 1973 Vol. 10 No. 4 PROCEEDINGS OF THE SOCIETY FOR ANALYTICAL CHEMISTRY ANALYTICAL DIVISION CHEMICAL SOCIETY Annual General Meeting of the Analytical Division of the Chemical Society THE first .Annual General Meeting of the Analytical Division of the Chemical Society was held at 2.25 p.m. on Friday March 16th 1973 in the Scientific Societies Lecture Theatre 23 Savile Ron. London W.1 The Chair was occupied by the President A h . C. Whalley B.Sc. F.R.I.C. The 71 -4 Statement of the Division’s income and expenditure had been circulated. 72 THE PRESIDENT ASD GOLD MEDALLIST [Proc. SOC. A n a l y t . Cheiia. Report of the Council for the year ending March 1973 (see pp. 75 to 88) was presented by the Honorary Secretary and adopted. The Scrutineers Nrs. R. 11. Jordan and l l r . P.C. \Yeston reported that the following had been elected officers for the coming year- President-G. ly. C. IIilner D.Sc. F.R.I.C. 1I.Inst.P. Past Preszdemk serving on the Counczl-;l. G. Jones -1. A. Smales T. S. ll'est and C. Vice-P~esidents-R. Belcher F. C. Shenton and C. E. Iyaterhouse. Honoiwy Treasurer-J. K. Foreman. Hoizora~y Secretaq-iT. H. C. Shaw. Hmiovary Assistant Secretaries-D. I. Coomber (Programmes Secretary) and D. IT. Iyilson. Other Jlembers of Cowicil-The Scrutineers further reported that 578 valid ballot papers had been received and that votes had been cast in the election of Ordinary Members of Council as follows-P. G. iy. Cobb 426; J. B. Damon 310; iY. T. Elwell 431; J. A. Hunter 240; G. F. Kirkbright 338; G. E. Penketh 327; R. Sawyer 405 J. 11. Skinner 356; and G.Svehla 203. The President declared the following to have been elected Ordinary Members of Council for the ensuing two years-P. G. W. Cobb \T'. T. Elwell G. F. Kirkbright G. E. Penketh R. Sawyer and J. 11. Skinner. H. E. Brookes J. F Herringshaw A. G. Hill R. Sinar A. Totvnshend and J. iyliitehead having been elected members of the Council in 1972 will by the Rules of the Division remain members of the Council for 1973. A. J. Amos (Chaziwza~z of the Centeiiniy Comutittee) D. Betteridge (Chazvnzaiz of the Programmes Committee) H. J. Cluley (Chazrniaii of The -1nalyst ddbzsovy Boavd mid Erecittzl L' Committee) D . C. Garratt (Chairmnz of the =1 izalvtical Methods Committee) -1. C. Bushnell (Chairman of the Sortla Tl-est Region) LV. Dunnet (Chairiizan of the Scottish Region) J. D. R. Thomas (Chairman of the TVesteriz Regton) S. Greenfield (Chazman of the Midlands Regzoiz) and J. S. Leahy (Chazrnznn oftlze East Anglia Regioiz) will be ex-ofJiczo members of the Council for 1973. Jlr. Whalley then introduced the incoming President Dr. Milner ~ h o would take office a t the Annual General Meeting of the Chemical Society in Swansea on Xarch 28th. -4fter the business outlined above had been completed the meeting was opened to visitors and the retiring President of the SA4C/.1nalytical Division delivered his Presidential Address (which will be published in a subsequent issue of Proceedzizgs). \T'halley.

ISSN:0037-9697    

DOI:10.1039/SA973100071b

出版商:RSC    

年代:1973

数据来源: RSC

摘要:

72 THE PRESIDENT ASD GOLD MEDALLIST [PYOC. SOC. Analyt. Cheaa. The President and Society for Analytical Chemistry Gold Medallist As announced in the January issue of Proceediiigs (p. I) Council on the recommendation of its Honours Committee has decided to award the seventh Society for AAnalytical Chemistry Gold Medal to GEORGE TYILLIASI COLIX SIILSER who was also elected President a t the Annual General Meeting held on March 16th. George llilner was educated a t Doncaster Grammar School from 1929 to 1936 and entered Sheffield University in 1936 to study science. He took part in sports and represented both School and University a t rugby football. After graduating with First Class Honours in 1939 at the outbreak of war he joined the staff of the Bragg Laboratory a t the Saval Ordnance Inspection Laboratory in Sheffield and during this period of his career he worked with Mr.E. J. Vaughan on the application of absorptiometric and polarographic techniques to the analysis of metals and alloys. In 1946 Milner accepted the post of Lecturer in Chemistry at the University of Hull but returned to the Bragg Laboratory in 1948 to work on analytical problems arising from the Atomic Energy project. In 1961 he moved to the -4nalytical Chemistry Group of the The Seventh Society for Analytical Chemistry Gold Medallist G. W. C. MILNER D.Sc. F.R.I.C. M.1nst.P. April 19731 REPORTS OF MEETINGS 73 Chemistry Division at A.E.R.E. Harwell. When the Analytical Sciences Division was formed at Harwell Milner was appointed Group Leader of the Actinide Analysis Group and he has now held this position for the past 10 years.He has published many papers on a wide range of analytical topics and was awarded the degree of D.Sc. by Sheffield University in 1969 for his contributions to analytical chemistry. He is the author of a book entitled “Principles and Applications of Polarogrsphy and Other Related Techniques,” and co-author of “Coulometry in Analytical Chemistry.” He is a member of the Editorial Board of the Journal of Electroannlyticnl Chemistry. For the past 6 years he has been deeply involved in the financial affairs of the Society for Analytical Chemistry as its Honorary Treasurer and he has played a leading rBle in the negotiations with the Chemical Society that resulted in the trial period of Amalgamation that began in January 1972. He has served on the Finance Board of the Chemical Society since the beginning of the trial Amalgamation. He acted as the Secretary of the Polarographic Discussion Panel set up by the Society in the early 1950s and eventually became Chairman of the Special Techniques Group for 1959-60. He has served on the Council of the Society for the periods 195841,1964-66 and 1967-73. For relaxation away from work walking and gardening are particular interests.

ISSN:0037-9697    

DOI:10.1039/SA9731000072

出版商:RSC    

年代:1973

数据来源: RSC

摘要:

April 19731 REPORTS OF MEETINGS 73 Reports of Meetings NORTH WEST REGION A JOINT Jleeting of the Region with the Manchester and District Section of the CS was held at 6 p.m. on Wednesday March 7th 1973 at the John Dalton Faculty of Technology The Polytechnic Manchester. The Chair was taken by Mr. P. R. Falkner of the ManChester and District Section of the CS. A lecture on “High Performance Liquid Chromatography” was given by Mr. C. F. Simpson. -1 JOINT Meeting of the Region with the Liverpool and District Section of the CS was held a t 7 p.m. on Thursday March 29th 1973 in the Department of Chemistry and Biology The Polytechnic Liverpool. The Chair was taken by the Chairman of the North \Yest Region Jlr. ,4. C. Bushnell. A lecture on “The Chemist a t Sea” was given by Professor J. P. Riley.SCOTTISH REGION -\ SPECIAL Meeting of the Region was held a t 4 p.m. on Monday March 26th 1973 in the Thomas Graham Building University of Strathclyde Cathedral Street Glasgow. The Chair was taken by the Chairman of the Region Mr. W. Dunnet. A lecture on “The Understanding and Development of Flame Spectroscopy” was given by Professor C. Th. J. Alkemade. WESTERN REGION hs Ordinary Meeting of the Region was held at 6.30 p.m. on Friday March 9th 1973 at the George Hotel Chepstow. The Chair was taken by the Chairman of the Region Dr. J. D. R. Thomas. A discussion on “Instrument Breakdown and Running Repairs” was introduced by 0. G. Tucknott. WESTERN REGION AND ATOMIC SPECTROSCOPY GROUP -1 JOINT Meeting of the Western Region and the Atomic Spectroscopy Group was held a t 12.15 p.m.on Friday March 23rd 1973 a t the School of Chemistry The University Bristol. The Chair a t the morning session was taken by the Vice-chairman of the Atomic Spectroscopy Group 3lr. D. Smith and at the afternoon session by the Chairman of the \Vestern Region Dr. J. D. R. Thomas. The subject of the meeting was “Separation Techniques in Atomic Spectroscopy” and the following papers were presented and discussed “Co-precipitation as a Separation Tech- nique in X.R.F. Spectrometry,” by G. Himsworth ; “Determination of Trace Elements in 74 REPORTS OF MEETINGS FProc. SOC. Apzalyt. Chem Food and Drugs Using Separation and Concentration Techniques,” by R. D. Cunningham ; “Combined Electrolytic Extraction and Atomic Absorption for the Determination of Metals,” by J. B. Dawson; “Volatilisation Techniques in Atomic Absorption Spectroscopy,” by I .Cochrane ; “Analytical Applications of Gas Chromatography of Metal Chelates,” by R. S. Rarratt. MIDLANDS REGIOS X NEETIKG of the Region was held at 6.30 p.m. on Friday March 2nd 1973 in the Haworth Building The University Birmingham. The Chair was taken by the Chairman of the Region 3Ir. S. Greenfield. Owing to Dr. Pfibil’s delayed arrival in this country an impromptu meeting was held and the following short papers were presented “A Brief Description of the Coupling of an H.F. Plasma Torch and a Direct Reading Spectrograph,” by S. Greenfield; “Candolumin- escence,” bj? -4. Townshend; “Molecular Emission from Cavities,” by S. Bogdanski. .As Ordinary Meeting of the Region was held at 6.30 p.m. on Tuesday March 6th 1973 in the Haworth Building The University Birmingham.The Chair was taken by the Chairman of the Region Xr. S. Greenfield -A NEETIKG of the Region was held a t 4 p.m. on Tuesday March 13th 1973 a t the University of Technology Loughborough. The Chair was taken by the Vice-chairman of the Region Dr. D. Thorburn Burns. A lecture on “Recent Research in the Analytical Laboratory of the J. Heyrovsky Insti- tute” was given by R. Pfibil. -4s Ordinary Meeting of the Region was held a t 6.30 p.m. on Tuesday March 20th 1973 at the Boots Company Pennyfoot Street Nottingham. The Chair was taken by the Chair- man of the Region Mr. s. Greenfield. A lecture on “The Future of the Analytical Chemist” was given by A. G. Jones. A lecture on “Enzymatic IIethods of Analysis” was given by A. Townshend. NORTH EAST REGION .A JOINT Meeting of the North East Region with the Modern Jlethods of Analysis Group of the Sheffield Metallurgical and Engineering Association was held a t 2 p.m.on \Vednesday Xarch 14th 1973 in the Conference Room B.I.S.R.A. Hoyle Street Sheffield. The Chair for the first half of the meeting was taken by the Chairman of the Modern Methods of A4nalysis Group of the Slieffield Metallurgical and Engineering Association Dr. J. Richardson and for the second half by the Chairman of the North East Region Mr. J. \I’hitehead The subject of the meeting was “Recent Trends in Analysis” and the following papers were presented and discussed “Non-flame hlethods of Atomisation in Atomic Absorption Spectroscopy with Particular Reference to the Analysis of Alloys,” by J. B. Headridge; “Determination of lletal Traces by Catalytic Analysis Based on Landolt Reactions,” by G.Svehla; “Thermometric and Enthalpimetric Nethods in Analytical Chemistry,” by L. S. Bark “Sacred Cow or White Elephant?” by R. A. Chalmers. E.GT AKGLIA REGION AND SPECIAL TECHSIQL‘ES GROCP -\ JOIST Meeting of the East Xnglia Region and the Special Techniques Group was held a t 2.30 p m. on Tuesday March 13th 1973 a t the Lecture Theatre Ipswich Civic College Rope \Talk Ips\vich. The Chair was taken by the Chairman of the East -4nglia Region Mr. J. S. Leahy. The subject of the meeting was “Chemiluminescence” and the following papers were presented and discussed “Candoluminescence-A New Technique of Flame Spectroscopic -lnalysis,” by A. Townshend; “The Use of Cliemiluniinescent Reactions in Gas Analysis,” by C.Narain and J. Glover. IIICROCHERIICAL METHODS GROUP THE eighty-fifth London Discussion Meeting of the Group was held a t 6.30 p.m. on Wednesday 3Iarch 7th 1973 a t the Royal School of Mines South Kensington London S.W.7. The Chair was taken by the Chairman of the Group Dr. D. A. Pantony. A discussion on “Non-aqueous Titrations” was introduced by D. C. M. Squirrell. This meeting was postponed from February 28th because of the rail dispute. -4pri1 19731 AKWJAL REPORT O F THE COUNCILS 75 BIOLOGICAL METHODS GROUP AN Ordinary Meeting of the Group was held a t 2.30 p.m. on Thursday March Sth 1973 at the Pharmaceutical Society of Great Britain 17 Bloomsbury Square London W.C.1. The Chair was taken by the Chairman of the Group Dr. L. Singleton. A lecture on “The Rationale of Control of Sterile Areas” was given by I. Martin. PARTICLE SIZE ANALYSIS GROUP As Ordinary Meeting of the Group was held a t 2.30 p.m. on Wednesday March 7th 1973 in the Polymer/Chemical Engineering Building University of Technology Loughborough. The Chair was taken by the Chairman of the Group Dr. M. J. Groves. The subject of the meeting was “On-line Methods of Particle Size Analysis” and the following papers were presented and discussed “Quality Measurements for Powdered Solids and \’iscous Fluids,” by >I. S. Beck K. T. Lee and N. G. Stanley-Wood; “Particle Size Distribution in Real Time,” by B. H. Watrasiewicz ; “On-stream Analysis Lsing Automatic Particle Counters,” by R. J. Akers.

ISSN:0037-9697    

DOI:10.1039/SA9731000073

出版商:RSC    

年代:1973

数据来源: RSC

摘要:

April 19731 AKWJAL REPORT O F THE COUNCILS 75 Annual Report of the Councils March 1973 THE full significance of passing events may sometimes not be apparent to those who take part in them and it is only when such events have become part of the fabric of history that their true effect can be understood. There could however have been few members of the Society for Analytical Chemistry (SAC) who as 1971 drew to a close were not aware that the SAC was approaching a momentous turning-point in its history. On January lst 1972 the day that marked the formal beginning of the three-year trial period of amalgamation with the Chemical Society (CS) the SAC became also the Analytical Division (AD) of the “new” and enlarged CS. The long period of negotiation that preceded this event left the Council in no doubt that many problems and difficulties lay ahead in fulfilling a dual rale but this was coupled with the determination that the SAC would do all that lay within its power to make amalgamation work effectively.4 s part of the amalgamation agreement the SAC remained responsible for financing the activities of the AD until the end of 1374 by which time a decision on final amalgamation or withdrawal under agreed terms will have been taken. For discussion of these and other matters primarily of concern to the SAC the Council met regularly during 1972 and these meetings were followed by meetings of the AD Council at which representatives of the CS were welcomed. It was anticipated that the opportunity for Fellows of the CS to join two Divisions as part of the basic CS annual subscription would lead to a large influx into the AD of CS members whose interests lay within the field of analytical chemistry but who had not previously sought membership of the SAC.Indeed by the end of the year AD membership had reached a figure nearly three times that of the SAC membership. In addition many CS members irrespective of their Divisional affiliation signified their wish for membership of the SACIAD Subject Groups. Thus the SAC found itself early in 1972 with considerable financial and administrative problems not the least of which was effective communication with the large number of new members. Council had decided that each member of the AD should receive without extra charge a copy of Proceedings and this action has done much to give the AD a coherence not readily attainable in any other way.Nevertheless there remained difficulty in establishing contact with Group members particularly those who were not members of the AD since it proved financially impossible to continue the practice of posting notices of Group meetings to each Group member individually. It was therefore decided that all information on Group meetings would be included in a Bulletin to be circulated at suitable intervals with Proceedings and sent direct to Group members outside the Division. The first of these Bulletins appeared in September 1972. 76 AKXUAL REPORT OF THE COVNCILS _PVOC. SOC. Analyt. Chem. After considering the administration of all Subject Groups attached to the Divisions the CS Council agreed that a membership charge of 50p per Group would be necessary from the beginning of 1973.Bearing in mind that membership of Groups had always been open to SAC members without additional charge the SAC/AD obtained agreement to the proposal that any AD member subscribing ,Q towards the cost of supplying Proceedings would be entitled to free membership of the AD Groups in which he was interested. A special financial concession was made to SAC members and different arrangements were made for membership of the Joint Pharmaceutical Analysis Group. Throughout the year nominated representatives of the SACjAD have served on the CS Council and its various Boards and Committees as follows- Council .. .. .. .. . . . . The President Professor R. Belcher Mr. 11‘. H. C. Shaw Professor R. Belcher Mr. \V. H. C. Shaw Interdivisional Committee * . . . . . The President Executive Committee .. .. . . . . The President Publications Services Board . . . . . . Dr. A. A. Smales External Relations Board . . . . . . . . 11r. D. If‘. Wilson Finance Board . . . . . . * . . . Dr. G. \Y. C. JIilner Industrial Division Council . . . . . . Dr. A. C. Docherty Continuing Education Committee . . Dr. A. A. Smales News Publications Committee . . . . . . Xrs. D. Butterworth Membership Committee . . . I * . . Mr. A . G. Jones Primary Journals Committee . . . . . . Dr. H. J. Cluley Kational Conference Committee . . . . . . Dr. D. Betteridge Library Committee . . .. .. .. . . Dr. R. C. Chirnside UKCIS Board . . . . .. .. . . Xr. A. G. Jones Accommodation Committee . . . . . . The President Dr. D. I. Coomber Dr. G. F. Kirkbright Dr. D. I. Rees The Scientific programme of the SAC/AD and its Groups and Regions again covered many fields of interest to analytical chemists and a full list of conferences and meetings held during the year is appended to this Report.The first symposium to be held by the SACjAD after the formal start of amalgamation took place at the University of Glasgow in March. It was organised in honour of Cecil L. Wilson Professor of Analytical Chemistry in the Queen’s University of Belfast in recognition of his long andvariedservices to the teaching and practice of analytical chemistry and also in celebration of his 60th birthday. It had been intended to hold the Symposium at the Queen’s University but the political disturbances in Belfast led to a change of venue to Glasgow where a traditional Celtic welcome awaited Professor Wilson’s many friends who came to pay tribute publicly and in private to a distinguished analytical chemist.The Symposium included a two-day scientific programme an exhibition of laboratory equipment and a full social programme. The Organising and Local Committees are to be congratulated on arranging a most successful symposium which was later fully reported in Proceedi figs. The scientific programme associated with the first Annual General Meeting of the enlarged Chemical Society which took place in Manchester during April centred on the ten Symposia organised by the six Divisions of CS and by the Interdivisional Committee. The Symposium arranged by the SAC/Analytical Division on “Recent Trends in Analytical Chemistry” included the First Theophilus Redwood Lecture “Fads and Fashions in Chemistry in General and Analytical Chemistry in Particular,” which was given by Professor S.Siggia of the University of Massachusetts U.S.A. There followed in the day and a half allocated to the Analytical Symposium seven lectures given by speakers of international repute on various topics of current analytical importance. The holding for the first time during the period of a cs Annual Meeting of sessions devoted entirely to analytical chemistry provided a welcome April 1973 ANNUAL REPORT OF THE COUNCILS 77 opportunity for chemists from other disciplines to learn something of present developments in the analytical field and their relationship to progress in other spheres of chemistry. A t a time when the political and economic affairs of many European nations are being harmonised it is fitting that the first European conference on analytical chemistry Euro- analysis I should have taken place during 1972.Held a t the University of Heidelberg the conference was organised jointly by the Analytical Division of the German Chemical Society the Section for Analytical Chemistry of the Royal Dutch Chemical Society and by the Society for Analytical Chemistry. Subsequent to the setting up of the joint organising committee the Federation of European Chemical Societies came into being and it was then agreed that Euroanalysis I should be the first of a series of Conferences planned to be held under the sponsorship of the Federation a t three-yearly intervals in various centres. These develop- ments represent a logical extension of the highly successful joint meetings of the SAC with the Royal Dutch Chemical Society held in 1968 and 1970.The Conference was attended by about 450 delegates from more than 20 nations including 46 delegates from the U.K. which was well represented in the plenary lectures and discussion papers. Although there were some language difficulties the conference proved a successful one which will be followed by Euroanalysis I1 to be held in Budapest during 1975. Plans for the celebration of the SAC Centenary in 1974 progressed well during the year; the Centenary Committee and the Alternative Programmes Committee both met several times to discuss general organisation and social events and to select a symbol for use in connection with the Centenary. Copies of the first circular were ready for distribution a t Euroanalysis I and were later sent to all U.K.members of CS with Chemistry in Britain. The Programmes Committee entrusted with responsibility for the scientific programme of invited papers had by the end of the year agreed upon the general format of the programme and some details of the scientific sessions. Early in 1972 the SAC received approval for the setting up of the Analytical Chemistry Trust Fund of which the Elected Members of Council are Trustees. The Council of the SAC subsequently authorised the transfer of the SAC long-term investments to the Trust. Only part of the investment income from this source is included in the statement of the SAC’s annual income. The significant reduction in the number of outside subscribers purchasing the SAC’s journals for 1972 is attributed partly to the need to increase subscription rates at the beginning of the year but also to computer problems referred to later in this Report.The Honorary Public Relations Officer has continued the policy of improving and streng- thening the publicity afforded to Society and Divisional activities ; posters for Society meetings and major meetings organised by Groups and Regions are now distributed to representatives in industrial organisations as well as to those in academic establishments. A display stand for Society publications and other material has been obtained and was put into use during the year a t conferences and other meetings. The history and current activities of the Society’s subject Groups have been featured in a series of articles in Proceedings and it is hoped that these articles will be informative for the many new members who have joined the Groups during the year.The Society has now received the scroll bearing the coat-of-arms granted by the College of Arms and a simplified version of the arms has been used as the motif for a tie available to all members. JOLRSALS- The rate of publication of papers in The Awlyst recovered from last year’s set-back; the 1972 volume contained 169 papers (and 3 “Communications”) in 1008 pages compared with 141 papers (and 2 “Communications”) in 896 pages in 1971. The number of new manuscripts offered for publication during the year was 202 compared with 215 in the previous year. Circulation ran into difficulties owing to problems in computerisation. Since January 1969 The Chemical Society has handled the SAC’s non-member subscriptions from its ware- house in Letchworth.After three years of successful operation a decision by The Chemical Society to transfer all the publications handled at Letchworth to a computerised subscription list was implemented a t the begining of 1972. It was some months before all the problems involved had shown themselves and by the autumn the difficulties of operating the corn- 78 ANXAL REPORT OF THE COUSCIL~ [Proc. SOC. Aqzalyt. Clzem. puterised system had become so great that it had to be abandoned (at least temporarily) and the former “manual” system re-introduced for 1973. Members’ records and journals requirements were also put on to a computer a t the same time although this is a different computer from that used for non-members’ subscriptions.The problems that arose from this operation were not recognised until late in the year but it is intended that membership records will continue to be computerised. This will entail every member giving scrupulous attention to detail when he or she completes the membership form each year for otherwise the computer will be wrongly instructed as to the members’ require- ments. The failure of the non-member subscriptions’ computer system (SOzrEKs) has led to such confusion that it was impossible to say whether there had been a real fall in demand by subscribers or whether some renewals had simply not “got through.” For the circulation to members however the story was different; for the first time in the Society’s history members were able to decide whether they would subscribe to The Aizalyst.It is pleasing to report that a t the time the December issue was distributed 1501 members were receiving it compared with 2013 a t the end of 1971 when all members received it as a right. There has been a fall in non- members’ subscriptions from 4969 copies in 1971 to 4649 in 1972. When copies sent to libraries and institutions in exchange for the journals of other organisations are taken into account the audited total distribution was 6277 against 7151 in 1951. The Proceedings reached a record total of 304 pages in 1972 (280 in 1971) and its distribu- tion also rose (from 5649 to 8938) by virtue of it being distributed free of charge to all members of the Analytical Division. The nominal charge of k1 to members was imposed for the 1973 volume in an effort to recover some of the extra expense that had during 1972 been borne entirely by the SAC out of the income received from the sale of its other journals; it is expected that this may adversely affect the circulation in 1973.Features during the year in addition to the usual accounts of Conferences and Ordinary Meetings and summaries of the papers presented a t them have included the series of articles referred to earlier on the SACIAD’s twelve Groups. There have been no staff changes during the year. The Sub-committee on Books and Other Publications has been active; the second volume of Selected Annual Reviews (delayed by problems associated with the present universal difficulty in finding authors with time to spare to write Review Papers of any kind) will have appeared by the time this report is in print.The first of a series of Monographs (“High- precision Titrimetry,” by C. LVoodward and H. N. Redman) was published in February 1973 and the second volume of Annual Reports on Analytical Atomic Spectroscopy is in hand for publication in Spring 1973 the first volume having been published in July 1972. The Pro- ceedings of the Second Conference on Particle Size Analysis was published in book form during the year. Analytical Abstracts has had a very successful year with the production of 9854 abstracts (on 1296 pages) compared with 9186 abstracts on (1204 pages) in 1971. This increased produc- tion has resulted in the important achievement of reducing the time gap between the publica- tion of an original paper and of its abstract to only 7 months. With our present means of production this is the minimum attainable.These successes are due to our having maintained continuity of staff and to the fact that the Author section of our six-monthly Indexes is now being prepared outside the office by hIrs. Alison Hardwick a former editorial assistant. There have been two changes in the constitution of the Editorial Committee-the resignation of Dr. B. Fleet who has been succeeded by Dr. S. J. Lyle and the loss of Dr. Sorman Evers through his death in October 1972. Dr. Evers was the first Editor of Aizalytical Abstracts and after his retirement in 1963 he retained an active interest in its production. He was responsible for the subject indexes until 1970 and then became one of our regular abstractors. The audited figure for the monthly circulation in 1972 was 6128 compared with 6589 in 197 1.ANALYTICAL METHODS COhIMITTEE- The year has seen some changes in the membership of the Analytical Methods Committee and in its approach to contemporary problems. For the first time guide lines for the com- position of the Committee in relation to the areas of experience of the members have been laid down and the Committee has been reconstituted within this framework. In an attempt April 19731 ANSUAL REPORT OF THE COUNCILS 70 to ensure prompt consideration by the Committee of analytical problems engendered by legislation both national and international or of new developments in analysis two small Sub-committees have been set up. The function of these Sub-Committees is to collect and collate information in their spheres of interest and to make their recommendation to the Committee a t the earliest opportunity.Revision of “Reference Substances for Use in Organic Micro-analysis” was completed during the year and the revised specifications were published in the September issue of The Analyst. This revision of specifications last issued in 1962 was carried out by a joint panel of the Analytical Standards Sub-committee and the Microchemical Methods Group. The report containing the specifications has been submitted to the International Union of Pure and Applied Chemistry and to the International Standards Organisation for consideration as possible international standards. Compilation and editing of the second edition of “Official Standardised and Recom- mended Methods of Analysis” is now almost complete and publication in the first half of 1973 is expected.The Committee is very grateful to Dr. N. W. Hanson for undertaking the task of producing this book after Nr. S. C. Jolly had been obliged to withdraw from participating owing to other important commitments. Full details of the Committee’s work will be published in the separate Annual Report of the Analytical Methods Committee. In 1972 Council unanimously endorsed the recommendation of the Honours Committee that Gold Medals of the Society be awarded to Dr. A. A. Smales Head of the -4nalytical Sciences Division and to Dr. G. 14‘. C. Milner Group Leader in the Analytical Sciences Division of the Atomic Energy Research Establishment Harwell in recognition of their outstanding contributions to the furtherance of analytical chemistry. I t is a most fitting tribute to the world-wide renown of the work carried out in the analytical laboratories a t Harwell that this is the first occasion that a dual award has been made and that the recipients are both members of the same establishment.The Society is proud to welcome Dr. Smales and Dr. Milner as Gold Medallists. There are many aspects of the Society’s work that Council cannot deal with directly and tlie responsibility for guidance on policy for carrying out detailed planning and for the implementation of decisions that must perforce be delegated to the various Committees of Council whose Chairmen during the year were as follows- Abstracts Editorial Committee . . . . . . hlr. A. G. Jones Aizalyst Advisory Board and Executive Committee Dr. H. J. Cluley Analytical Methods Committee . . . . . Dr.D. C. Garratt Centenary Committee . . . . . . . . Dr. A. J. Amos Finance Committee . . . . . . . . . Hon. Treasurer Group Liaison and Policy Committee . . . h1r. D. \V. \Vilson Honours Committee . . . ,. . . . . The President Programmes Committee . * . . . . . Dr. D. Betteridge Publications Policy Committee . . . . . . Dr. A. A. Sniales In addition to those who serve on these Committees there are many who devote much of their time and effort to Society activities by organising Group and Regional meetings repre- senting the Society as the Analytical Division on the Council Boards and Committees of the Chemical Society maintaining liaison with outside bodies and in a diversity of other ways. To them all and to the permanent staff for their continued support Council expresses its thanks.Membership of the Society for Analytical Chemistry at December 31st 1972 totalled2170 a decrease of 61 since December 31st 1971 when the SAC membership list was closed as part of the amalgamation agreement with tlie Chemical Society. The enlarged membership of the SAC/.halytical Division consequent upon amalgamation is reflected in the marked increase 80 ASNUAL REPORT OF THE COUNCILS [Proc. SOC. A9talyt. Chem. in membership of the Divisional Regions and Groups that had been attained by the end of the year- Regions- North West Region . . .. . . . . Scottish Region .. * . .. .. Western Region I . . * 4 .. Midlands Region . .. .. .. North East Region . .. . . . . East Anglia Region . . .. . . . . Atomic Spectroscopy Group . . . . . . Automatic Methods Group . . . . .. Biological Methods Group .. .. .. Education and Training Group . . . . Electroanalytical Group . . . . . . Microchemical Methods Group . . . . Particle Size Analysis Group . . .. Radiochemical Methods Group . . * . Special Techniques Group . . . . . . Thermal Methods Group . . . . .. GYOU~S- Chromatography and Electrophoresis Group Joint Pharmaceutical Analysis Group . . .. I .. . . . . . . . . .. .. . . . . .. . . I . * . . . . . .. 1971 1972 226 827 101 301 150 610 273 657 205 688 136 644 7 50 1979 796 2394 362 1265 837 2934 108 1255 245 1176 753 1262 275 978 305 950 774 1513 295 838 465 1341 A t the end of the year membership of the Analytical Division totalled 6169. LOSG ~VEMBERSHIP- The congratulations of good wishes of the Council are extended to bIr. A. T. S. Babb Dr. D. C. Garratt Dr.C. W. Herd and Dr. G. V. James who have each completed 40 years of membership. DEATHS- The Council records with regret the deaths of the following members- R. G. Baskett J. S. Merry E. 31. Chatt E. A. Rayner B. A. Ellis C. J. Regan N. Evers T. E. JVallis F. IT;. Hares Chronological List of SAC/Analytical Division Region and Group Meetings 1972 January 12th London SAC/-Analytical Division jointly with the Chiltern and Middlesex Section of the Chemical Society. 13th Stoke-on-Trent Midlands Region Elwell Award 1972. “Photoelectron Spectrometry,” by D. Betteridge. “The Determination of Traces of Nickel by Gas - Liquid Chromatography,” by R. S. Earratt. “An Automated Method for the Determination of Urinary Aminolaevulinic Acid,” by Miss J. R. Cooke. “Infrared Study of Hair Lacquer Residues,” by Miss J .S. Crockett. “Assay Methods for Three Leucocyte Hydrolases Involved in Sphingolipid Metabolism,” by D. R. Tunley. 13th London Joint Pharmaceutical Analysis Group Annual General Meeting. “The European Pharmacopoeia,” by H. S. Grainger. April 19731 ANKUAL REPORT OF THE COUNCILS 15th Salford North \Yest Region Annual General Meeting. 19th hliddlesbrough North East Region Annual General Meeting. 19th London Microchemical Methods Group. “The Analyst’s View of Pollution,” by G. Nickless. “The Scientific Examination of Questioned Documents,” b y Professor C. L. Wilson. Discussion on “Meat Analogues,” introduced by T. T. Gorsuch 81 21st Cardiff ?Vestern Region Annual General RIeeting. 21st Glasgow Scottish Region jointly with the Glasgow and West of Scotland Section of the Chemical Society.27th Birmingham Midlands Region. “Fibre Examination Techniques for Identification and Characterisation Purposes,” by J. E. Ford. “Water for Industry-Production and Quality Control,” by T. D. Rees. “Analytical Aspects of Auger Spectroscopy,” by Jf. Thompson February 2nd London SAC/Analytical Division on “Nuclear RIagnetic Resonance and Electron Magnetic Resonance in Analytical Chemistry.” “Nuclear Magnetic Resonance and its Applications t o Structural and Quantitative Analysis,” by “Purity Control by S.M.R.,” by I. J. Lawrenson. “Electron Magnetic Resonance as a n Analytical Tool,” by B. D. Flockhart. 31. E. A. Cudby. Pnd London Radiochemical Methods Group. Discussion on “The Implications of New Regulations Governing the Transport of Radioactive Materials,” introduced by E.J . Wilson. 8th Sheffield Korth East Region and Microchemical Methods Group jointly with the Jlodern Methods of Analysis Group of the Sheffield Metallurgical and Engineering Association on “The Determination of Fluorine.” “Why Fluorine Analysis ? ” by T. R. Farnworth. “Recommending a Standard Method for Fluorine-The Work of the SAC Sub-C,ommittee for Fluorine “Fluorine and the Organic Elemental Microanalyst,” by B. T. Saunderson. “The Determination of Fluorine in Non-metallic Materials by Direct Electron Excitation,” by “Toxic Properties of Inorganic Fluorine Compounds,” by R. Y. Eagers. (r2nalytical Xethods Committee),” by R. J . Hall. bl. Corbett. 8th London Special Techniques Group. “Analysis of Solid State Materials by hlossbauer Spectroscopy,” by T.C. Gibb. “Suclear Quadrupole Resonance Spectroscopy in Chemistry,” by J . A. S. Smith. “E.S.R. as a Probe for the Structure and Reactivity of Free Radicals,” by B. C. Gilbert. 1311 Edinburgh Scottish Region jointly with the Edinburgh and South East Scotland Section of the Chemical Society and the Edinburgh University Geological Society. “Source Excitation Energy Dispersive Analysis in the Southern Uplands,” by I\‘. E. Stephens and “Integrated Mineral Exploration in Scotland,” by 11 J . Gallagher. ”Rase Metal Prospecting in Scotland Theory and Method,” by n1. J . Russell. P. Bowden 16th Bristol Western Region and Education and Training Group. Discussion on “Imaginative Novel Practical Work,” introduced by G. Sickless J. Rlendham V. J. Jennings and J . D. R. Thomas. 17th Birmingham Midlands Region.“Inorganic Analysis by Gas Chromatography,” b y W. I. Stephen. 82 ANKUAL REPORT OF THE COCXILS [Proc. Soc. Analyt. Chem. 17th London Radiochemical Methods Group. “The Philosophy of the Pharmaceutical Control of Short-lived Radionuclide Preparations,” by “The Production of Short-lived Radioactive Substances for Medical Research,” by D. J . Silvester. “The Use of Isotopically Labelled Compounds in Drug Substance and Formulated Product Stability J . C. Charlton. Studies,” by H. E. Hudson and M. F. Jones. 18th London Chromatography and Electrophoresis Group. Discussion on “Accuracy and Precision in Quantitative Chromatography,” introduced by G. W. 22nd and 23rd Ormskirk Thermal Analysis Group on “Kinetic Data from Thermal Analysis.” “Some Observations on the Shapes of TG Curves and the Kinetic Parameters Derived from These “Interpretation of Data from Programmed Thermogravimetry,” by J .R. MacCallum. “Attempts t o Measure Kinetics of Reactions in the Ncighbourhood of Hot Wires,” by K. A. W. Hill. “Some Problems Encountered in Obtaining Kinetic Data from Thermoanalytical Measurements,” “Kinetic Studies Using Thermal Volatilisation .4nalysis,” by I. C. McNeill. “Kinetics of Polymerisation,” by K. E. J . Barrett. “Kinetics of Decomposition of Inorganic Solids,” by hl. C. Ball. Goodman. Curves,” by M. A. Hughes. by M. D. Judd. March lst Hoddesdon East Anglia Region on “Aspects of Quality Control During Manufacturing.” “Quality Control in the Pharmaceutical Industry,” by F. R. Soer. “Quality Control of Wines and Spirits,” by L. A. Warwicker.“Quality Control in the Food Industry,” b y P. Lindley. lst Stevenage Particle Size Analysis Group. “Ideas on the Exact Determination of Size and Shape,” by H. Sutton. “The Effect of Particle Size on Tensile Strength,” by I). C.-H. Cheng. 3rd Bath Society Annual General Meeting. 8th London Microchemical Methods Group. “Photoluminescence in Analysis and Research,’ by C. A. Parker. Discussion on “Is There a Need for Impurity Standards in Organic ;\nalysis?” introduced by G. A. Vaughan. 8th York Sorth East Region on “Present Trends in Analytical Research.” “.%nalytical Chemistry at the University of Strathclyde-Some Problems in Tracc Inorganic Analysis,” “Some Current Kesearch in Chemistry at Birmingham University,” by A . Tomnshend. “A Review of Some Recent Studies in Analytical Chemistry a t Loughborough University of Techno- by J .RI. Ottaway. logy,” by D. Thorburn Burns. 9th London Joint Pharmaceutical Analysis Group. Discussion on “Sew Drug Applications How Much and How F a r ? ” introduced by S. Hall and F. G. Farrell. 16th Nottingham Midlands Region on “Carbon in Effluents.” 21st London Special Techniques Group. 23rd and 24th Glasgow SAC Symposium 1972 on “Recent Advances in General Analytical Chemistry. ” 24t11 Chepstow \Yestern Region. April Sth London SAC/Analytical Division on “Exploration Geochemistry.” Two papers by H. -4. C. RIontgomery and T. D. Rees and J . R. Gordon. “Son-linear Light Scattering and New Kinds of Spectroscopy,” by Professor D. A Long. Discussion on “Safety in the Chemical Laboratory,” introduced by P. Holroyd. “Economics of Mineral Exploration,” by P.C. D. Cazalet. “Chemical Analysis for Exploration Geochemistry,” by h l . Thompson “llarine Geochemistry of RIanganese and Manganese Sodules,” by S. E. Calvcrt. April 19731 ANNUAL REPORT OF THE COUNCILS 83 10th to 14th Manchester CS Annual Meeting; SAC/Analytical Division Symposium on “Recent Trends in Analytical Chemistry.” First Theophilus Redwood Lecture “Fads and Fashions in Chemistry in General and Analytical “Metabolic Studies with Radioisotopically-labelled Drugs,” by D. T’. Parke. “The Contribution of the Analytical Chemist t o Progress in the Chemical Industry,” by C. Whalley. “Useful Steric Effects in Inorganic Chemistrv.” bv Professor H. 31. !i. H. Irving. Chemistry in Particular,” by Professor S. Siggia. “Thermal Analysis in PerspecGve,” by R.C.’$Iacgenzie. “Collaborative Analysis and the Standardisation of Analytical Llethods,” by H. Egan. “Data Handling in Gas Chromatography,’’ by D. R. Deans. “run Sensors of High Specificity,” by Professor W. Simon. - 12th Keele Atomic Spectroscopy Group on “Atomic Spectroscopy in Ceramic Analysis.” 17th to 21st London Thermal Analysis Group Third Thermal Analysis School. Speakers A. D. Ambrose R. Julietti P. D. Salt G. Oliver and J. H. Rigby. “Introduction to Thermal Analysis,” by J . P. Redfern. “Theoretical Basis for Thermal Analysis,” by D. Dollimore. “Thermodynamic Properties of Polymers,” by R. C. Roberts. “Kinetic Parameters from Thermal Analysis Data,” by K. E . J. Barrett. “Applications to Fats and Waxes and in the Petroleum Industry,” by I. C. \Yylie. “Thermal Degradation of Polvmers.” bv Professor D.A. Smith. “.-\pplicationgto Plastics Rubbers ’Fibies Paints Adhesives and Composites,” b y 4. R. Westwood. “Evolved Gas Analysis,” by J 1%’. Youren. “Applications to Pharmaceuticals Agricultural Chemicals and Foodstuffs,” by R. E . Waller. 17th Glasgow Scottish Region jointly with the Glasgow and \Vest of Scotland Section of the Chemical Society. 20th Newcastle upon Tyne North East Region and Chromatography and Electrophoresis Group jointly with the Liquid Chromatography Sub-Group of the Gas Chromatography Discussion Group of the Institute of Petroleum on “High Performance Liquid Chromato- graphy in Columns.” “Modern Methods of Functional Group Analysis,” by Professor S. Siggia. “Instrumentation for High Efficiency Liquid Chromatography,” by T.1Vilkins. “Use of Polarographic Detectors in Liquid Chromatography,’’ by R. J . Maggs (read by Mrs. D. “Some Applications of Organic Chemical Analysis by High Pressure Liquid Chromatography,” by Simpson) S. A. Parris. 26th Bristol Western Region and Particle Size Analysis Group on “Local Interests in Powder C,haracterisation.” “Particle Sampling in a Chimney PlLme Visibility Study,” by R . T. Jarman “Surface Area and Particle Size Measurements on Alumina,” by IV. T. Hughes. “The Effect of Pigment Particle Size on Printing Ink Properties,” by D. Carr. “The Determination of Particle Size Distributions for Kaolin and Othcr Minerals,” by L. F. Gate. 27th London Automatic Methods and Education and Training Groups. Discussion on “Analytical Chemistry-the Seed for Interdisciplinary Training,” introduced by G.E. Penketh and J. K. Foreman. ZSth London Electroanalytical Group. Discussion on “Trends in Electroanalysis,” introduced by P. 0. Kane A. E. Bottom R. D. Jee R. Briggs and D. Band. May 4th Harwell Radiochemical Methods Group Visit. loth London Microchemical Methods Group. 11 t h Iyeybridge Biological Methods Group. Discussion on “The Handling of Unstable Samples,” introduced by I. Dunstan and \V. G. Duncombe. Introductory talk by I. Davidson followed b y a tour of the Biological Products and Standards Department of the Central Veterinary Laboratory Ministry of Agriculture Fisheries and Food. lBth Loughborough JIidlands Region jointly with the Lougliborougli Universitj- of Techno- logy Chemical Society. “The Plasma Torch-What is i t ? IVhat will it do?” bv S.Greenfield and. P. B. Smith. 84 AKSUAL REPORT OF THE COUNCILS [Pvoc. Sac. Annlyt. Chent. 17th and lSth Swansea SAC/Analytical Division on “Research Topics in Analytical Chemis- tr57.” “Candoluminescence-4 Potential Flame Technique for Trace Inorganic rlnalysis,” by S. Bogdanski. “The ‘Sensitised’ Catechol Violet Reaction and its Utilisation in the Spectrophotometric Determination “The Determination of Tin in Steels by Solvent Extraction Followed by Atomic-absorption Spectro- “Amalgam Reduction of Titanium(IV),” by G. A. East. “Thermometric and Enthalpimetric Determination of Soma Xitrogen-containing Bases and Some “Simultaneous Spectrofluorimetric Determination of Tetracaine and Procaine or Benzocaine,” by “Studies Concerning Metal Chelates of 1-Hydroxyanthraquinone,” by Mrs.31. Jackson and &I. A. “Thermal Studies and Gas Chromatography of Some Metal Beta-diketonates,” b y J. Warren and “The Trace Determination of Peroxides in Hydrocarbons,” by I. J. Thomson and G. C. Bell. “The Determination of Free and Total Fluoride in Milk,” by J . A. W. Dalziel and A. V. Dangi. “Trace Metals in Soils by Ultramicro Atomic Spectrometry,” by A. Oborne and Professor T. S. \Vest. “Jlicrowave Excited Detectors for Gas Chromatography,” b y R. 11. Dagnall and P. Whitehead. “Some Consequences of the ‘Auto’ Degradation of Polystyrene-based Exchangers,” by G. M. Armitage “hIutual Interferences Between the Atomic-absorption Determination of Calcium and Some Other “Spectrophotometric Study of the Acid - Base Equilibria in Aqueous Solutions of the 1,4-BellZO- “Developments in Photoelectron Spectroscopy,” by S.K. Hasanuddin. of Tin in Steel,” by A. Ashton A. G. Fogg and D. Thornburn Bwns. photometry,” by A. Sowerbutts and J . B. Headridge. Physiologically Active Alkaloids,” by L. S. Bark and J. K. Grime. A. C. hlehta. Leonard. A. G. Smeeth. S. J . Lyle and 5:. C. Nair. Elements,’’ by A. Harrison and J. RI. Ottaway. diazepines,” by I. Davidson and W. F. Smyth. 25th London Biological Methods Group. “Statutory Requirements for Toxicological Examination and Control of Plastics,” by D. SV. Plester. “Practical Problems in Examination and Control of Plastics for Pharmaceutical Use,” by J . E. Pentelow. 26th Norwich East Anglia Region on “Safety and Legal -4spects of Food Additives.” “Determination of Traces of Toxic Metals in Foodstuffs by Atomic-absorption Spectroscopy,” by “Analytical Aspects of Food Additives and Packaging,” by I.E. Burrows. “Packaging Legislation-Some Analytical Requirements,” by X. W. Robertson. G. Xelson and D. L. Smith. June 2nd London Electroanalytical Group. Sth London Joint Pharmaecutical Analysis Group. 22nd and 23rd Stirling Pu’orth \Vest Scottish and North East Regions 3licrochemical Methods Atomic Spectroscopy Chromatography and Electrophoresis and Radiochemical Methods Groups on “Selectivity in Trace Analysis.” “Developments and Trends in Analytical Research and Instrumentation,” by J . B. Flato. Original papers. Discussion on “Detection Limits,” introduced by G. F. Kirlrbright and D. A Pantony. Plenary Lecture “Selectivity in Trace Element Analysis,” by A. A. Smales. “Automatic Hollow-cathode Analysis for Tracc Elements in High Temperature Alloys,” by K.Thornton. “The Determination of Small Amounts of .Aluminium in Steel by Atomic-absorption Spectroscopy,” “The Use of Separation Procedures for Atomic-absorption Spectroscopy in Clinical Chemistry,” by “Some Factors Governing Limits of Detection in Separation Systems,” by R. K. Goodall. “2-Xlkyl-substituted Quinolinols as Solvent Extraction Agents,” by F. R. Haba G. H. Kazi and “i\uto-oxidation of Stilbenes,” by P. Spahr and E. 1’. Truter. “Selectivity in the Application of Activation Techniques Based on the Measurement of Prompt “The Mass-spectrometric Determination of Small Amounts of Gases Particularly in Coated Particle “The Analysis of Impurities in Inorganic Natrices by Flameless Atomic-absorption Spectrophoto- “Combined Electrolysis and Atomic Absorption for the Extraction and Determination of Metals in Plenary Lecture “Selectivity in Trace Analysis the Detection and Estimation of Compounds,” by “Some Sources of Contamination in Trace Analysis,” by R.0. Scott and .4. M. Ure. by R. H. Jenkins. H. T. Delves. D. A. Pantony. Radiation Emitted During Charged-particle Irradiation,” by T. B. Pierce. Fuels,” by J . W. lIcPlillan B. L. Taylor and G. J . Weldrick. metry,” by C. W. Fuller. Biological Materials,” by T. F. Hartley and D. J . Ellis. H. Egan. April 19731 ANNUAL REPORT OF THE COUSCILS 85 “Practical Improvements in the Selectivity of Neutron-activation Analysis,” by R. F. Coleman “Problems in the Determination of Oxvnen in Steel bv Reducing Fusion.” bv G. D. Hall. “Programmed Elution Thin-layer Chiokatography a’s a Techlique in’ t h e Selective Analysis of Phenols ” hv 1 .M. Philn. ~ _I ~~ - -~~~ r. ~ ~ ~ . ~ ~ ~ . . “Trace Analysis of GC - MS,” by E. Clayton. “Pitfalls in the Measurement of Drug Availability,” by J. P. Glynn. “A New Gas Chromatography Detector Tunable to a Wide Range of Elements,” by \V. R. &Lean D. L. Stanton and G. E. Penketh. “Spark Source Mass Spectrometry,” by K. B. LVrigley. “Some Applications of Heteropoly Acids for Amplification Procedures in Atomic-absorption Spectro- “Trace Metal Analysis in the Sub-nanogram Range Using Anodic Stripping Voltammetry,” by 27th Salford North West Region Automatic Methods and Electroanalytical Groups on “The Use of Enzymes in Analysis.” “Water-insoluble Enzymes,” by Professor S. A. Barker.“Enzyme Electrodes,” by B. Fleet. “Trace Analysis by Enzyme Inhibition and Activation,” by A. Townshend. scopy,” by H. N. Johnson G. F. Kirkbright and Professor T. S. West. I. Fraser. August 28th to September Ist Heidelberg SAC/Analytical Division jointly with the Analytical Chemistry Division of the German Chemical Society and the Section for Analytical Chemistry of the Royal Dutch Chemical Society. Euroanalysis I. September 5th ru’ottingham Midlands Region on “Liquid Chromatography.” “High Performance Liquid - Solid Adsorption Chromatography.” by R. Amos. “High Efficiency Liquid Chromatography and its Applications in the Pharmaceutical Industry,’’ by F. Bailey. 12th Keele Joint Pharmaceutical Analysis Group on “The Training of the Analyst \\’hat Do We Need and What are We Getting?” “Seeds of Larger Industrial Units,” by C.Daglish. “Needs of Smaller Industrial Units,” by D. 0. Singleton. “Needs of Official Laboratories and Institutions,” by G. F. Phillips. “Undergraduate Training,” by C. G. Butler. “Postgraduate Training,” by SV. D. Williams. 13th and 14th Salford Particle Size Analysis Group on “Techniques for Particle Charac- terisation.” “iincillary Techniques,” by H. J. Scullion. “Size Limiting Gauges,” by P. R. Kiff. “Projected Area Measurement and blicroscopic Techniques,” by 31. I. Barnett. “Hydrodynamic Techniques,” by R. G. Blezard. “Volume Measurement,” by T. Allen. “Surface Area Measurement,” by P;. R. Thompson. “Presentation of Data and Statistical Analysis of Results,” by C. R . G. Treasure. 13th to lEth Canterbury Microchemical Methods Chromatography and Electrophoresis Automatic Methods Radiochemical Methods and Electroanalytical Groups on “Chemical Analysis and the Environment.” Pleizavy Lectuve by H.Egan “ilnalvsis for Airborne Contaminants to Assess Effects on Health.” bv B. T. Comniins “Meth-ods of Analysis for Traffic Pollutants,” by H. N. 31. Stewart. “Radiochemical Analysis for Pollution Control a t the Laboratory of the Government Chemist,” by “Sea 1Yater Analysis with Special Reference to Pollution,” by J P. Riley. “Sampling and Analysis of River Water,” by D. C. Hinge. “Analysis of Toxic Species in Water,” by XI. J . Stiff. “Analytical Problems Associated with Marine Radioactive Waste Disposal,” by J . W. R . Dutton. “Measurement and Control of Toxic Hazards in the Industrial Environment,” by S. J . Silk.“Analytical Techniques for the Determination of Contaminants in Factory Atmospheres,” by R. LYood. “Analysis for Residues of Pesticides and their Degradation Products in the Environment,” by I<. I. D. I. Cooniber. Rpvnnn - . . . . - .. . “The Determination of Lead in the Environment-A Multi-technique Approach,” by J S. Hislop A. Parker and M. W. S. Webb. 86 ANKUAL REPORT OF THE COUNCILS [Proc. SOC. Analyt. Chem. 15th Hull North East Region on “Alcohol-Its Determination.” “The Determination of Alcohol for Revenue Purposes,” by R. J . Meslep. “The Determination of Alcohol in Pharmaceutical Preparations,” by D. A. Elvidge “The Determination of Alcohol in Blood and Urine,” by A. S. Curry. 20th Hereford Western and Midlands Regions. “Recent Developments in X-ray Fluorescence Analysis,” by P.W~ Hurley. %th Cardiff Western Region. “Enzymes in Analysis,” by G. G. Guilbault 28th Salford North West Region and Thermal Methods Group on “Organic Applications of Thermal Analysis.” “The Thermal Degradation of Cellulose in Nitrogen,” by D. Dollimore and B. Holt. “Thermometric Titrimetry,” by L. S. Bark October 2nd London Electroanalytical Group. “Polymer Membrane Ion Selective Electrodes,” by G. Baum 3rd Glasgow Scottish Region. “Selectrode-the Universal Ion Selective Electrode,” by Professor J. RiiiiEka. 4th London SAC/Analytical Division on “Ion Selective Electrodes.” “Selectrode-the Universal Ion Selective Electrode,” by Professor J. RBiiEka. “Selectivity and Sensitivity of Ion Selective Electrodes,” by J U. R . Thomas. “Measurement Techniques for Ion-selective Electrodes,” by hI.J . 1). Brand. 5th Cambridge East Anglia Region Annual General Meeting. “Forensic Analysis in the Equine Field,” by M. S. LIoss. 5th Preston Korth West Region. “Environmental Conservation An Analyst’s S‘iew,” by G. B. Crump. j t h London Electroanalytical Group on “Current Research Topics in Electroanalytical Chemistry. ’ ’ “Some Studies Using Sulphide Ion Selective Electrodes,” by A. Patham. “Application of Cathode Kay Polarography to Analysis of Body Fluids,” by E. d’Essien. “Electrochemical Detectors for High Pressure Liquid Chromatography,” by C. J . Little. “Partial Anodic Oxidation of Aliphatic Hydrocarbons in Aprotic Solvents,” by D. Clark. “A Study of the Factors Influencing Response Times of Ion Selective Electrodes,” by T. H. Ryan Bth Bristol Western Region.loth Richmond Sorth East Region. 1 Ith Cambridge Atomic Spectroscopy Group on “Atom Rescrvoirs.” “Selectrode-The Universal Ion Selective Electrode,” by Professor J. RhiiEka. “Consumer Protection,” by 11. Kellner “Flames and Alternatives to Flames,” by L. de Galan. “Chemistry of Metals and Free Radicals in Flames,” by E. 31. Rulewicz. “Determination of Non-metal Atoms i n the Vacuum U.Tr.,” by D. Husain. 12th London Joint Pharmaceutical Analysis Group. Discussion on “High Pressure Chromatography,” introduced by $1. Pinnegar F. Bailey and I<. Wilkins. 18th Liverpool North West Region jointly with the Liverpool Branch of the Pharmaceutical Society of Great Britain. “Tablet Manufacture,” by A. W. Xewberry. April 19731 ASSUAL REPORT OF THE COUXCILS 87 19th London Biological Nethods Group on “Non-prescription Antibiotics in Animal Food- stuffs Their h’ature and Analysis.” “Flavomycin,” by G.Nesemann. ”Virginiamycin,” by B. Boon. “Zinc Bacitracin,” by B. Grynne. 19th Burton-on-Trent Midlands Region. “Analytical Problems in the Brewing Industry,” by G. A. Howard. 20th Glasgow Scottish Region and Education Training Group. Discussion on “Training of Food Analysts,” introduced b y R . 11. Johnson J. Thomson and D. R . 0 s borne. November lst London SAC/Analytical Division jointly with the Pesticides Group of the Society of Chemical Industry on “llulti-residue Detection Systems.” “Introduction,” by M. Sharratt. “hlercury and Organochlorine Residue Analysis of Fish and Aquatic hIammals,” by A. V. Holden. “Determination of Residues Arising from Fumigation Practice,” by S.G. B. Heuser. “Organophosphorus and Carbamate Detection Systems,” by J . H. A. Ruzicka. “The Isolation and Identification of Toxic Mammalian Metabolites of Phosphorothionate Pesticides,” “An Approach t o the Detection of Pesticides Poisoning in LVildlife,” by P. J. Bunyan. “One of the Problem Families-The PCBs,” by R. Edwards. by A. F. Machin. 3rd Glasgow Scottish Region Annual General Meeting. “Industry and Forensic Science,” by J. K. RIcLellan. 8th Durham City North East Region. Discussion on “Precision and Accuracy in Chemical Analysis,” introduced by R. -4. Chalmers and .%. A. Greenfield. loth Swansea Western Region. 14th Birmingham Midlands Region Annual General RIeeting. 15th Eastham Xorth West Region jointly with the Carlett Park Chemical and Physical Society.17th London Automatic Methods Group Annual General Meeting and Electroanalytical Group Annual General Meeting. “Analytical Aspects of Photoelectron Spectroscopy,” By D. Betteridge. “Forensic Science,” by P . G. W. Cobb. “Myths and Legends in Analytical Chemistry,” Professor R. Belcher. “Enhancement of Chemical Measurement Techniques Using On-line Digital Computers,” by Professor S. P. Perone. 21st London Special Techniques Group Annual General Meeting followed by a meeting on “Plasma Excitation in Spectrochemical Analysis.” “The H.F. Plasma Torch,” by S. Greenfield P. B. Smith and H . McD. McGeachin. “The JIicrowave Plasma Torch,” by R. hI. Dagnall and B. L. Sharp. “The Plasma Jet,” by E. A. du Bois and R . hiarriott. 22nd London Chromatography and Electrophoresis Group Annual General Meeting followed by a meeting on “Polymer Characterisation by Chromatographic Means.” “Isomerisation Problems in the Analysis of Some Polyester Resins,” by D.F. G. Pusey and W. A. “The Application of Gel Permeation and Affinity Liquid Chromatography to the Analysis of Poly- “Decomposition Products of Xylon,” by G. C. East C. J . Lupton and E. V. Truter. Ledger. butadienes,” by R. J . J. Simkins and E. J . Gallacher. 22nd London Particle Size Analysis Group Annual General Meeting followed by a meeting on “Applications of Particle Size Analysis to Pharmacy.” “The Methods of Inspecting Intravenous Fluids for Particulate Contamination,” by &I. J . Groves “Particle Size Analysis of Pharmaceutical Aerosols,” by J H. Bell. “The Influence of Particle Size on the Formulation of Hard Gclatiri Capsules,” by J .11. Newton. 88 AXNUAL REPORT OF T H E COUXCILS [Proc. SOC. Analyt. Chem. 22nd Loughborough Midlands Region. “Enhancement of Chemical Measurement Techniques Using On-line Digital Computers,” by Professor 23rd London Thermal Methods Group Annual General Meeting followed by a meeting on “Inorganic Applications of Thermal Analysis.” S. P. Perone. “Thermal Decompositions in Inorganic Compounds,” by D. \V. A. Sharp. “The Thermal Decomposition of Manganese Oxy-salts and Manganese Oxide Transformations ” by “Thermoanalytical Studies of Pyrotechnic Mixtures,” by F. S. Scanes. “The Thermal Decomposition of Some Double Carbonates,” by R. M. McIntosh and J. H. Sharp. “Appplication of Thermal Analysis to N.T.C. Thermistors,” by E. D. Macklen.“Thermal Analysis of Serpentine Asbestos and Related Minerals,” by L. F. Monkman. K. H. Tonge. 27th London Microchemical Methods Group Annual General Meeting Radiochemical Methods Group Annual General Meeting and Education and Training Group Annual General Meeting followed by a Cheese and Wine Party. 29th Cardiff Joint Pharmaceutical Analysis Group. Open Forum on “Questions and Answers in pharmaceutical Analysis.” Panel members C. A. Johnson L. E. Coles L. M. htherden ill. Ogden and J. Chissell. December lst London Atomic Spectroscopy Group Annual General Meeting. “The Past Ten Years,” reviewed by the four past Chairmen of the Group W. T. ElweI1 J . B. Damson W. J . Price and W R. Nall. 5th Teesside North East Region on “The Analysis of Gaseous Effluents.” “It’s in the Air,” by B.T. Leadbeater. “Field llethods for the Determination of Airborne Toxic Contaminants,” by E. C. Hunt. “Sampling and Analysis of Airborne Contaminants to Assess the Effect on Health,” by B. T. Commins. Gth London SAC/Analytical Division. 7th Glasgow Scottish Region jointly with the Glasgow and FYest of Scotland Section of the CS and the Andersonian Chemical Society. “Analytical Applications of Molecular Complexes,” by A. Townshend. “Atomic Spectroscopy for Pollution Control,” by Professor T. S. West. 7th London Biological Methods Group Annual General Meeting. Discussion on “Biological Standards,” introduced by D. R. Bangham. Sth Cardiff Western Region jointly with the South East Wales Section of the CS. “Some Views on the Cost Effectiveness of Analytical Research,” by C. Whalley. 12th Birmingham Midlands Region and Special Techniques Group. “Ion-beam Thin-foil Spectroscopy,” by I. Martinson. 13th Risley North West Region. A short illustrated talk on the broad principles and applications of activation analysis was given by G. R. Gilmore. 13th London Microchemical Methods Group Debate. “This House Considers that the Microchemical Methods Groups has Outlived its Usefulness.” For the motion Professor R. Belcher and D. A. Pantony and against the motion Professor T. S. West and D. W. Wilson. C . WHALLEY President W. H. C. SHAW Honorary Secretary

ISSN:0037-9697    

DOI:10.1039/SA9731000075

出版商:RSC    

年代:1973

数据来源: RSC

摘要:

April 19732 PLAS3IA EXCITATION I N SPECTROCHEAIICAL ANALYSIS 89 Plasma Excitation in Spectrochemical Analysis The following are summaries of the three papers presented a t a meeting following the Annual General Xeeting of the Special Techniques Group held on Kovember Blst 1972 and reported in the January issue of Proceedings (p. 3). The H.F. Plasma Torch BY S. GKEESFIELD P. B. SMITH AND H. MCD. RICGEACHIN (Albright altd Wzlson Ltd. Oldbury CYarley Wovcestershire) THE electrodeless inductively coupled torch used daily for the analysis of a wide variety of samples for over 4 years was described. After a discussion of the concepts of equilibrium and temperatures of different kinds it was concluded that a source in or near local thermo- dynamic equilibrium had advantages over a non-equilibrium source both for the elimination of matrix effects by a high kinetic temperature and for the reduction of fluctuations in the emission from the source.Matrix effects were classified into those which have little effect on the plasma conditions and those such as the introduction of elements of low ionisation potential which can produce a dramatic change in the plasma parameters such as the electron density. The source described has a sufficiently high kinetic temperature to be free from the first type of effects. The result of the second type of effects is consistent with a rise in temperature as well as a rise in electron density; this result is in sharp contrast to the effect on a d.c. arc where a fall in temperature is well established. Spectral interference was classified into three instances where the unwanted radiations were respectively the continuum irrelevant atomic lines and band spectra.The interference from the first two classes increases with temperature whereas some band spectra e.g. the Swan bands of C, can be eliminated with a high temperature. The C K bands can be sup- pressed by using oxygen as the coolant gas but this in turn gives rise to bands in the ultra- violet region. The choice of appropriate conditions therefore depends on the wavelength of interest. Limits of detection are complex functions of operating conditions such as the input power the gas flows the part of the tail flame observed and the nebulising system. In everyday use with standard conditions solutions of 1 p.p.m. (and occasionally 0-01 p.p.m.) to 1000 p.p.m. are analysed with coefficients of variation of typically 1 to 3 per cent.Ex- perience shows that when it seems worthwhile to do so the lower limits can be improved significantly by adjustment of the plasma parameters. By a suitable choice of conditions the background can usually be reduced to a level such that exposures of over 1 hour are usable. The source can be left running unattended for an indefinite time and is therefore ideally suitable for use with an automatic sampler. The Microwave Plasma Torch BY R. 11. DAGNALL AND €3. L. SHARP (Chemistvy Departrnewt Iiizpcrial College of Scie?ice and Technolog>' .Loizdoiz S. W.7) ~IICROW'AVE plasmas operating a t 2450 NHz with input powers of between 15 and 200 W have recently been the subject of considerable study with regard to their potential as excitation sources for analytical spectrometry.The purpose of this paper was to consider the basic plasma mechanisms and to relate these to operating paramztcrs and analytical performance. Plasma stability depends on the establishment of dynamic equilibrium between ionisation of the argon carrier gas and free electron loss by diffusion and recombination processes. The parameters that primarily influence this equilibrium are the magnitude and frequency of the field and the gas pressure. Ionisation in any electrical plasma depends on the field having sufficient magnitude to raise a given fraction of the electrons above the ionisation potential within a period equivalent to the free electron lifetime. Given that this condition is fulfilled the efficiency of the process is determined by the ratio of the collision frequency to the field frequency.Elastic collisions between electrons and atoms interrupt out of phase motion of the electrons and therefore promote efficient coupling of the field to the plasma. However such collisions damp the electron energy and therefore an optimum breakdown pressure can be found at which the two processes are in the most favourable balance. For example it 90 PLAShIA EXCITATION 13 SPECTROCHEXICAL ANALYSIS [P?‘Oc. sot. A?%n&. Chenz. has been determined that in argon a t 992 MHz the optimum breakdown pressure is 1 torr. Measurements of the temperature and electron density made on argon plasmas a t atmos- pheric pressure yield electron temperatures of about 5600 OK neutral gas kinetic temperatures of about 1000 OK and electron densities of about 6.9 x 10l5 ~ m - ~ .The source is not therefore in complete local thermodynamic equilibrium (LTE) but application of the Griem criteria shows that partial LTE exists in the sense that the excited argon states are populated primarily by electron collisions. Ground-state population is controlled jointly by radiation and collision processes and therefore approaches a coronal equilibrium. The large difference between the kinetic gas and electron temperatures strongly influences the analytical application of this type of plasma. The low gas temperature means that considerably less energy is available for the vaporisation of materials than would be available in LTE sources with similar temperatures. Furthermore the presence of excess of molecular species especially those known for their quenching properties e.g.N, CO and H, will depress electron energies by inelastic collisions and hence decrease the rate of ionisation to the level a t which the plasma is quenched. Sampling is therefore of critical importance and in general samples must be presented in sub-microgram amounts and in the vapour phase. Provided that this is accomplished efficient excitation of spectra enables high-sensitivity determinations to be made on a wide range of molecular and atomic species. Typical applications to date include- Trace determination of elements following atomisation from a heated platinum loop.1 Typical detection limits obtained were cadmium 2.0 x 10-13 g; arsenic 4.2 x 10-11 g; beryllium 1.2 x 10-lo g; and iodine 1-2 x g. Interference studies for cadmium on a range of matrices including phosphate silicate aluminium sodium and vana- dium showed that only vanadium interfered.Specific determination of compounds eluted from a gas - liquid chromatographic column.2 Detection limits of 2 x 10-16 g s-l for carbon 10-l1 g s-1 for phosphorus and 2 x g s-l for chlorine were reported and the technique was applied to the determination of phosphorus residues from pesticides.3 Determination of the ratio of hetero-atom to carbon in species eluted from a gas - liquid chromatographic column by simultaneous monitoring of two appropriate spectral lines.4 Qualitative identification of volatile species e g . arsenic mercury and selenium vaporised from rock samples heated in an induction furnace (Department of Geo- chemistry Imperial College private communication 1971).Monitoring of volatile halides evolved during the course of a metallurgical conversion reaction (Department of Metallurgy Imperial College private communication 1972). It was therefore concluded that provided the sampling problem could be overcome microwave plasmas are a versatile and relatively cheap excitation source for use in analytical emission spectrometry. REFERENCES 1 . 2 3. 4. Aldous K. M, Dagnall R. M. Sharp B. L. and West T. S. Analytica Chirn. .4cta 1971 54 233 McCormack A. J. Tang S. C. and Cooke \V. D. Analyt. Cheiw. 1966 37 1470. Bache C. A. and Lisk D. J. Ibad. 1965 37 1477. Dagnall R. M. West T. S. and Whitehead P. Ibzd. 1972 44 2076. The Plasma Jet BY D. R. MARRIOTT (BISRA-The Corporate Laboratories of the British Steel Covporation Hoyle Street She@eld) A PLASMA can be simply defined as an inert gas that has been “compressed” and excited to a high energy state and consists of conducting ions rather than atoms or molecules.The energy available within such a plasma makes it eminently suitable as a spectrographic source. In a d.c. plasma jet an inert gas is forced into a helical path between two annular elec- trodes. The “compression” of the plasma is therefore achieved by the geometry of the hardware as well as the thermal and electromagnetic “pinch” effects present in all forms of plasma generation. Once generated the plasma is maintained by the passage of a low voltage direct current typically between 20 and 40 A. April 19731 PLASMA EXCITATIOS I N SPECTROCHEMICAL AK;ALYSIS 91 Early designs involving the two-electrode approach1 were found to be subject to plasma instability.Owen2 in 1962 incorporated a third point electrode located a t the tip of the plasma flame. By providing a point source of electrons against which the plasma could stabilise improvements in analytical precision were achieved. Design developments of a plasma jet suitable for use as a spectrographic source were outlined culminating in a design for a plasma jet developed for the analysis of steel powders (Fig. 1). In the operation of such a plasma jet the optimisation of operating parameters for specific applications is necessary. T Fig. 1. D.c. plasma jet A> anode; B nyloninsulator; C cathode E sample support gas flow; F sample feed gas flow; T tangential gas flow; and 0 optical path t o spectrograph The use of d.c.plasma emission for the analysis of solid particulate matter was found to be feasible. The main difficulties encountered have been concerned with the particle size distribution of the sample. Ideally a sample comprising particles of uniform size will give a stable measurable signal when fed into a plasma by gas entrainment. In practice mono-size distributions are rarely encountered. It has been found that a practical alternative is to conduct soine degree of particle size selection and to analyse such a metered sample by using an internal standard and a ratio signal-integration technique. In this way it has been found possible to determine the carbon manganese sulphur and silicon contents of steel powders. The development of a d.c. plasma emission analytical method has been part of a broader project designed to develop a total analytical system for the rapid analysis of molten steel.By coupling the plasma analysis with a device for the atomisation of liquid steel and a powder transport system it has been found possible to reduce the analysis time of steelmaking products from G to 12 minutes to approximately 30 s. The d.c. plasma jet has been shown therefore to be an emission source capable of analysing not only liquids but also solids. In comparison with other plasma sources the plasma jet is less versatile as a laboratory tool than the radio-frequency generated plasma. I t is however considerably less costly to install and it is particularly useful in industrial applications in view of its simplicity of operation robustness and ease of servicing. REFERESCES 1. 2. Nargoshes M. and Scribner B. F. Specfrochinz. Acla 1959 138. O w n L. E. AppZ. Specfmsc. 1861 16 150.

ISSN:0037-9697    

DOI:10.1039/SA9731000089

出版商:RSC    

年代:1973

数据来源: RSC

摘要:

92 MULTI-RESIDUE DETECTIOS SYSTEXS [Proc. SOC. A nnlyf. Clzeaz. Multi-residue Detection Systems The following is a summary of one of the papers presented a t a Joint Meeting of the SAC/Analytical Division and the Pesticides Group of the Society of Chemical Industry held on Kovember lst 1972 and reported in the Sovember 1972 issue of Proceedings (p. 231). Summaries of four other papers presented at this meeting mere published in the February 1973 issue of Proceedings (pp. 31-37). Four of the papers presented will be published in full in the June issue of Pesticide Science. Some Procedures for Isolating Toxic Metabolites of Phosphorothionate Pesticides from Animal Tissues and Fluids BY A. F. ?rIACHIN New Haw Weybridge Surrey) (Biochemistry Depavtnzent M’inistvy of Agricultawe Fisheries and Food Central Vetevinavy Laboratovy MODERN spectroscopic methods have made the technical difficulties of identifying metabolites formed in vivo mainly those of isolating the substantially pure compounds from biological materials.The purification and identification of three metabolites of diazinon (two hydroxy- diazinons and a dehydrodiazinon) have been described in detail elsewhere b3 and their possible toxicological importance has been ~onsidered.~ In this paper the chromatographic pro- cedures used in these separations together with some more recent improvements are discussed. The methods which include thin-layer gas column and high-pressure liquid chromatography should be generally applicable to metabolites of phosphorothionate pesticides. Thin-layer chromatography is useful both for recognising toxic metabolites by their inhibition of esterases and for isolating them.The procedure of Mendoza \4’ales McLeod and McKinley5 is particularly valuable for recognition as it is simple sensitive and largely unaffected by co-extractives; it also allows easy differentiation between direct and indirect inhibitors of cholinesterase. A second detection system described by Braithwaite,6 provides information about the phosphoryl moiety phosphorothiolates and phosphorothionates but not phosphates are detected on acidified silica-gel layers by spraying with 2,6-dichloro-p- benzoquinone-4-chloroimine. Thiolates give yellow and thionates orange - red spots when treated in this way.’ The method is mainly useful in the later stages of purification because it is less sensitive and more affected by co-extractives than the enzyme-inhibition procedure.Preparatively thin-layer chromatography has been most used for separating the two hydroxy derivatives of diazinon from urine. A chloroform extract of the urine is concentrated and streaked on to layers of fluorescent silica. After development with acetone - hexane (1 + 4) the bands of interest are eluted and each is separately chromatographed. The process is repeated usually three or four times until the products are judged by gas chromatography to be about 90 per cent. pure and a final separation is then carried out on specially purified silica (Jlachery Nagel & Co. silica gel N-HR/UV254) with ethyl acetate - hexane (2 + 3) as solvent. Gas chromatography is used extensively for detecting metabolites that contain phos- phorus determining residues and monitoring the progress of purification.A thermionic detector is generally used its high and selective sensitivity probably make it more suitable than the specific but less sensitive flame-photometric detector. Only once during this work has a compound been wrongly thought to contain phosphorus but several metabolites might not have been noticed originally if the detector had been less sensitive. Gas chromatography is convenient for isolating metabolites in microgram amounts for mass spectrometry for which purpose an instrument designed especially for the collection of labile compoundsB is used. It is not satisfactory for purifying the much larger amounts needed for nuclear magnetic resonance measurements however owing to the difficulty of collecting large fractions quantitatively.Column chromatography was originally used to purify the two hydroxydia~inons,l-~ but is now used only to isolate dehydrodiazinon from fat,3 by an extension of Wood’s clean-up procedure.9 Column chromatography is tedious but so far has been the only way to separate dehydrodiazinon from the much larger amounts of diazinon and fat which accompany it. April 19733 POLYMER CHARACTERISATION BY CHROMATOGRAPHIC MEAXS 93 High-pressure liquid chromatography is now being used for some of the isolations. Simple equipment including a pump built at this laborator~7,~O is used with a commercial ultraviolet detector. The work is a t an early stage but the two hydroxydiazinons have been successfully separated from chloroform extracts of urine (details have been given else- where4).The main difficulty a t present is to combine sufficiently high efficiency and capacity in the same column. There seem to be possibilities of achieving the combination with some of the micro-particulate adsorbents which are now available however and it seem likely that high-pressure liquid chromatography will become extremely useful for separations of this kind. REFERENCES 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. Machin A. F. Quick RI. P. Rogers H. and Anderson P. H.,Bull. Enviroz. Coiitam. Toricol. Machin A. F. Quick &I. P. Rogers H. and Janes N. F. Ibid. 1972 7 270. Janes N. F. Machin A. F. Quick 31. P. Rogers H. Mundy D. E. and Cross A. J . J . Agric. Fd JIachin A. F. Pestic. Sci. 1973 in the press. Mendoza C. E. Wales P. J. McLend H. -4, and McKinley W. P. .4mzZyst 1968 93 34. Braithwaite D. P. Nature Lond. 1963 200 1011. Stenersen J. J . Chronzat. 1971 54 77. Machin A. F. and Morris C. R. Analyst 1972 97 289. Wood X F. Ibid. 1969 94 399. Machin A. F. Morris C. R. and Quick 31. P. J . Chromat.. 1972 72 388. 1971 6 26. Chera. 1973 21 121.

ISSN:0037-9697    

DOI:10.1039/SA9731000092

出版商:RSC    

年代:1973

数据来源: RSC

摘要:

April 19733 POLYMER CHARACTERISATION BY CHROMATOGRAPHIC MEAXS 93 Polymer Characterisation by Chromatographic Means The following is a summary of one of the papers presented a t a Meeting following the Annual General Meeting of the Chromatography and Electrophoresis Group held on November 22nd 1972 and reported in the January 1973 issue of Proceedirgs (p. 3). Decomposition of Nylons in the Solid State BY G. C. EAST S. K. KAKAR C. J. LUPTOK* AKD E. V. TRGTER (Textile Chemistry Laboratory The University Leeds L S 2 9 J T ) EXPOSURE of nylons to high temperature or to y-rays causes them to become brown and to decompose ; this paper is concerned with the chemistry of the early stages of decomposition. Degradation of nylon 6 and nylon 66 in the solid state yields very many non-volatile products.The more common products have been identified and pathways for their formation have been deduced. These pathways indicate that several other classes of compounds should be formed and the experimental evidence suggests that they are present. The experimental methods were the same for both types of nylon. THER31.4L DECOMPOSITIOK- Samples of thoroughly cleaned nylon fibre were heated for various times nylon 6 at 160 "C and nylon 66 a t 180 "C. One series was heated in a free supply of air and a second series was heated in a stream of nitrogen; only the former series became brown. Free carboxyl groups were determined by titration in benzyl alcohol a t 180 "C. Amino groups were determined by dissolution of the sample in hot phenol - methanol (7 + 3) and titration of the cold solution against aqueous hydrochloric acid.The results showed that for treatments for a given period the concentrations of both free carboxyl groups and free amino groups fell as the temperature was raised. For example for nylon 6 the concentration of free carboxyl groups fell from 74 to 38 mequiv kg-1 after 9 hours a t 200 "C in nitrogen; con- currently the concentration of free amino groups fell from 44 to 25 mequiv kg-l. A small proportion of the fall in concentration of the end groups can be attributed to further polymerisation. For example the relative viscosity of a 1 per cent. solution of nylon 66 (in 90 per cent. formic acid which was 2 N with respect to potassium chloride) in- creased from 1.46 to 1-50 for a sample that had been heated for 12 hours at 180 "C in nitrogen. * Science Research Council Scholar.94 POLYMER CHARACTERISATION BY CHROMATOGRAPHIC MEANS [Proc. Soc. Aftalyt. Chem. These values correspond approximately to an increase in relative molecular mass from 14 000 to 14500 and would consume end-groups to the extent of 2-5 mequiv kg-I. A larger pro- portion but not the whole of the remainder can be attributed to the formation of carbon dioxide and ammonia. Samples of degraded nylon were treated for 24 hours in a Soxhlet apparatus with various solvents including water aqueous pyridine ethanol methanol benzene - acetone and ether. In 110 instance could extractable material be detected showing that the non-volatile fragments must still be linked to the solid. Samples were then liydrolysed in 5 N hydrochloric acid at 110 'C for 24 hours in the absence of oxygen and the products were fractionated in two ways firstly by steam distillations from acidic and then from basic solution to yield volatile acids (fraction IA) volatile bases (fraction IR) and a non-volatile residue ; and secondly by chroma- tography on a cation-exchange resin (Amberlite CG lZO) to yield a fraction containing acidic and neutral compounds (fraction IIA) and a second fraction (11B) containing basic compounds.The brown products are bases which are non-volatile in steam. Y-IRRADIATIOK Samples of cleaned nylon were sealed in ampoules either in vacuo or in air and irradiated (cobalt-60) at the rate of 2 Mrad h-l for 250 hours (we thank Dr. J. H. Kcighlcy and G. Gather- all for these samples). Subsequently the samples were liydrolysed and fractionated as indicated above.-~S.~LYSIS- Each fraction was examined very intensively by thin-layer chromatography using stand- ard techniques. Confirmation of identity was obtained by gas - liquid chromatography or by ion-exchange resin chromatography as appropriate. All treatments led to the formation of several classes of compounds from both nylons and each class was represented by several liomologues. In addition there were indications of se\wal other classes of compounds that have not yet been satisfactorily identified. It seems likely however that hydroxy-acids and hydroxy-amines aldehydic acids and aldehydic aniines are formed in the presence of oxygen and that unsaturated acids and unsaturated amines are formed in the absence of oxygen. DISCCSSION- Firstly thermal dissociation of the various bonds in tlie polymer will occur in proportion to the \ d u e of exp(-E/RT) uhere E is the appropriate bond energy; the products are radicals.Secondly because the temperature at which decomposition has been allowed to proceed is well below the melting- point of the polymer molecular motion in the solid is severely restricted. Consequently radicals will be able to react with only their immediate neighbours. Table I1 shows the encrgies of bonds analogous to those in nylon together with their probabilities of fission at 180 "C relative to the probability of fission of the N-CH boud. I t suggests that all the products must be derived from fission of thc IiitrogeIi-metliylene carhon (N-CH,) bond; the next weakest bond the carhonyl-methylene carbon (CH,-CO) bond is more than 20 000 times less likely to rupture.Table I1 does not include data for cvtr). type of hond encountered in nylon; in particular the CH,-CO hond is undoubtedly niorc stablc than the unlisted hydrogen-carhoxyl oxygen (COO-H) bond. Severtheless tlie probabilities show that random fission of the bonds in nylon1 is very unlikely. The consequences of this postulate will be explored for tlie thermal decomposition of nylon 66 in the absence of oxgyen. The results are summariscd in Table I. Two general principles underlie tlie following arguments. The primary reaction is dissociation into radicals- -CO(CH,),CONH(CH,J,- + -CO(CII,),CONH* - *CH,(CH,),NH - nylon 66 unit arriido radical alkyl radical The radicals may become stablc entities by transfer of hydrogen from one radical to the (1) Hydrogen transfer from the alkyl radical to the amido radical leads to other by re-arrangement by re-combination or by a combination of these three processes.CHAH -CO(CH,)&ONH + CH2=CH(CH,),NH- or - ' - (CH,),-N- cyclic iminc arnide allrenamine Cyclic imines are formed only if the alkyl chain is of a suitable length. April 19731 POLYMER CHARACTERISATION BY CHROMATOGRAPHIC MEAXS TABLE I PRODUCTS FROM THE DEGRADATION OF YYLO?JS Nylon 6 Nylon 66 A I A 7 Thermal Irradiation Compound -v- Thcrmal Irradiation - Air Monoacids jvoin Fraction IA- Formic acid . . .. ++ Acctic acid . . . . ++ Propionic acid . . . . + Uutyric acid . . . . + Valcric acid . . . . +++ Caproic acid . . . . 0 Oxalic acid . . . . ++ Malvnic acid . . . . + + Succinic acicl . . .. T T Glutaric acicl . . . . ++ Adipic acid .. .. +++ Methylamine . . .. + Ethylaminc . . .. + Propylamine . . . . 4- -I- Butylamine . . . . +++ Pcntylaminc . . . . +++ Hesylaminc . . . . 0 Pyrrolidinc . . . . -+ Piperidine . . . . Methylpiperidine . . 0 Hexamethylenciminc 0 Hexamethylenediaminc 0 Glycine . . . . .. 6- Alaninc . . . . ++ Diacids front Fraction I I A - I Amines .froin Fraction IB- - c-Aminocaproic acid . . + + A,mnir~o-acids fvom Fvaction IIB- - y-Aminobutyric acid . . + + 8-Aminovalcric acid . . + + c-Aminocaproic acid . . + + + Aspartic acid . . .. + Glutamic acid . . . . + a-Arninoadipic acid . . + 1,Z-DiaminoethaIie . . 0 1,3-Diaminopropane . . 0 1,4-Diaminobutane . . 0 1,S-nianiinopentane . . 0 1.6-Diaminohesane . . 0 Diamines from Fraction IIB- Vacuum ++ ++ + + ++ +++ ++ + i+ + -1- +++ I ++ + -t -i- + +++ +++ ++ ++ + ++ + + + + + + +++ + + + + +++ - - T Air -I- + ++ + -1- + +++ 0 ++ ++ ++ -t + +++ + + -1- + + -I- + +++ 0 ++ 0 0 + 0 0 - + + -I- ++ +++ + + - 0 0 0 0 0 - Nitrogen - +I+ + - 1 - + -++ 0 0 n 0 -I- + + 4- + + .I ~ -'- -1- ~ . + - T + + +++ 0 + + + + 1 0 0 0 + 0 '+ +++ +++ Air - + -L -I- -t t + f++ + + + + -1- ++ I- + + + +++ 0 0 ++ + 0 +++ 0 -.- T t + ++ +++ + ++ ++ + + + 0 + +++ t Vacuum I-+ ++ + +++ 0 T - ... 0 0 0 .L I + ++ ++ ++ ++ I++ +-+ ++ 1 1 - - - -I # 0 T + -+ -+ +++ 0 0 0 ++ ++ i t +++ f (2) Hydrogen transfer from the amido radical to the alkyl radical leads to -CO(CH&CHZCONX + CH,(CH,),NH- imido diradical alkylamiiie The imido diradical re-arranges to the isocyanate -CO(CH,),CH,NCO. If hydrogen transfer does not take place- (3) re-combination leads to no apparent change; 95 (4) the amido radical rearranges to the hydroisocyanate radical -CO(CH,)JHC*O which combines with its neighbouring alkyl radical -CO(CH,),NHCO(CH,),NH-.The net effect is that the positions of the NH and CO groups have been interchanged. To account for the formation of homologues it is necessary to postulate that at 180 "C the methylene carbon radical-carbon (CH,-CH,*) bond of an alkyl radical is very unstable. I t is known that the presence of an odd electron in a molecule has a weakening effect on the '36 POLYMER CHARACTERISATION BY CHROMATOGRAPHIC RlEnNS [PYOC. S O C . YZd-yt. Chem. neighbouring bonds. The alkyl radical loses a methylene unit and yields a shorter alkyl radical which can in turn lose one carbon atom. The methylene units are presumably evolved as ethylene which is known to be one of the volatile degradation products of nylon.After hydrolysis of the degraded nylon 66 the following groups of homologues are to be expected- from process (1)-cyclic imines and alkenamines ; from process (2)-alkylamines ; from process (3)-alkyl diamines; from process (4)-w-amino-acids. Of these products only the alkenamines have not yet been satisfactorily identified but there is strong evidence for their occurrence. The postulates do not explain how the observed monocarboxylic acids are formed. Hence some other bond in the polymer must also break. If despite the improbability of the idea indicated in Table 11 fission of the CH,-CO bond is invoked then one of the consequences of allowing the primary radicals to become stable entities by mechanisms analogous to those described is that dicarboxylic acids should be formed.In fact there was no evidence for the presence of any dicarboxylic acid except adipic acid. Hence monocarboxylic acids must be derived by fission of a bond not listed in Table 11. One such bond is the CH,COO-H bond; its rupture leads via subsequent decarboxylation to the formation of monocarboxylic acids but not to dicarboxylic acids. That the CH,-COOK bond is relatively weak is supported by the observation that nylon undergoes some decarboxy- tion at 160 0C.3 TABLE I1 PROBABILITIES AT 180 "c OF THE FISSION O F VARIOUS BONDS RELATIVE TO THAT OF THE NH-CH BOND Bond Relative Bond energyjkcal probability CH,-NH CII,-CH CII,-co 62 1 .o 71 4.6 x 10-5 80 2.1 x 10-9 OCI-NH- 83 7.4 x lo-" N-H 84 2.5 x 10-11 C-H 98 3.5 x lo-'* c=o 173 3.5 x 10-84 The relative importance of the four processes listed above can be deduced from the approxi- mate yields of the various classes of product.They were monocarboxylic acids 240; amines 100; diamines 15; and amino acids 6 mg per 100 g of nylon 66. Clearly processes (1) and ( Z ) the hydrogen-transfer processes are important; process (3) is less important and process (4) is a minor one. Precisely the same postulate will explain the course of the thermal decomposition of nylon 66 in air. Dccomposition follows the same pathways as before except that the alkyl radicals react with oxygen to yield dicarboxylic acids which have been identified and hydroxy- and aldehydic acids and hydroxy- and aldehydic amines which appear to be present although they have not yet been satisfactorily identified.If the imido diradical were to re-arrange to the cyclic compound More important than any of these is the decarboxylation process. There is no satisfactory explanation for the formation of amino diacids. H the formation of a-aminoadipic acid in the absence of oxygen would be expected. Table I shows that the formation of amino diacids from nylon 66 requires oxygen so this route is acceptable only if the terminal unit undergoes reaction at both ends. The same postulates and the same schemes of reaction suffice to explain how the observed products except the amino diacids are derived from the thermal treatment of nylon 6 in air. SOCIETY FOR ANALYTICAL CHEMISTRY AXALYTICAL DIVISION CHEMICAL SOCIETY For irradiative decomposition the concept of bond fission a t random seems reasonable.Kevertheless the analyses reveal that the products differ very little from those observed for thermal decomposition. It seems therefore that the net effect of irradiation is not consistent with random bond fission. Most of the observed products for both nylons are readily derived from the earlier postulates and schemes The formation of diamines and dicarboxylic acids from nylon 6 i r t vacm shows that under these conditions the interchange reaction process (4) is more important than for thermal decomposition. The effect of oxygen in the irradiation experiments is minimal; its most important effect is to generate dicarboxylic acids from nylon 66. REFERENCES 1. 2. 3. Derminot J. Belin C. and Leclercq B. Bull. Inst. Text. Fvance 1968 22 899. Strauss S. and Wall L. A, J . Res. Nafn. Bur. Stand. 19.58 60 39; 1959 63A 269. Edel G. and Etienne H. Bull. I m t . Text. Fvance 1969 23 343.

ISSN:0037-9697    

DOI:10.1039/SA9731000093

出版商:RSC    

年代:1973

数据来源: RSC

摘要:

SOCIETY FOR ANALYTICAL CHEMISTRY AXALYTICAL DIVISION CHEMICAL SOCIETY Notice IYTERKXTIONAL SYMPOSIUII ON LIQUID SCINTILLATION COUNTING THE following social programme has been organised as entertainment for delegates and their wives attending the liquid scintillation counting symposium to be held a t the Hotel Metropole Brighton. M o n d a y September 3 d - introduce the delegates. Tuesday September 4th- to Firle House has been arranged. 15th Century and is famous for its paintings. at the Brighton Aquarium and includes a display of dolphins. Wednesday September 5th- A full day visit to Goodwood House has been arranged for the Ladies including Lunch in the State Room. The Symposium Dinner will be held in the Winter Garden of the Hotel Metropole. The registration fees are subject to 10 per cent Value -Added Tax and it has therefore been necessary t o increase the fees originally announced in the February issue of Proceediitgs (pp. 46-45) to A11 for registrations before June 30th Ale-50 for registrations after June 30th and i3.30 for guests. Anybody wishing to receive further details and registration forms is asked to contact Miss P. E. Hutchinson Society for hnalytical Chemistry 9/10 Savile Row London W1X 1AF. Early application is advised as places are restricted on the visits. SEPTEMBER 3RD TO GTH 1973 BRIGHTOX There will be a reception in the evening a t the Hotel RIetropole in order to welcome and The Ladies are invited to visit the Brighton Flower Festival while in the afternoon a visit This house has been the home of the Gage family since the In the evening a reception has been arranged

ISSN:0037-9697    

DOI:10.1039/SA9731000097

出版商:RSC    

年代:1973

数据来源: RSC