摘要:

Proceedings of the Society for Proc. SOC. Analyt. Chem. Vol. 7 No. 5 Pages 77-88 Analytical Chemistry CONTENTS Reports of Meetings . . .. 77 “Application of Microchemical Techniques in Pet rochem ical and Allied Industries” .. 80 “Selective Electrode Systems”. . 83 Obituary .. .. .. .. 86 Membership Changes . . . . 87 Publications Received . . . . 87 Notices .. .. .. .. 88 Forthcoming Meetings Back cover May 1970 Vol. 7 No. 5 May 1976 PROCEED I N GS THE SOCIETY FOR ANALYTICAL CHEMISTRY OF President of the Society T. S. West Hon. Secretary of the Society W. H. C. Shaw Hon. Treasurer of the Society G. W. C. Milner Hon. Assistant Secretary of the Society D. 1. Coomber Secretary Miss P. E. Hutchinson 9/10 SAVILE ROW LONDON W I X IAF Telephone 01-734 6205 Editor J. B. Attrill Assistant Editor Miss C. M. Richards Telephone 01-734 3419 Proceedings is published by The Society for Analytical Chemistry and distributed t o all members of the Society and t o subscribers with The Analyst; subscriptions cannot be accepted for Proceedings alone. Single copies may be obtained direct from the Society’s Distribution Agents The Chemical Society Publications Sales Office Blackhorse Road Letchworth Herts. (NOT through Trade Agents) price 0 The Society for Analytical Chemistry 5s. post free. Remittances MUST accompany orders. THE SOCIETY FOR ANALYTICAL CHEMISTRY Radiochemical Methods Group welcomes visitors to an Exhibition of Radiochemical Instruments at the Borough Polytechnic Borough Road London S.E.1 on Thursday July 9th 1970 10 a.m. to 6 p.m. Further details can be obtained from Mr. M. A. Crook Borough Polytechnic London S.E. 1

ISSN:0037-9697    

DOI:10.1039/SA97007FX017

出版商:RSC    

年代:1970

数据来源: RSC

摘要:

THE SOCIETY FOR ANALYTICAL CHEMISTRY Forthcoming Meetings- corrtinued “Some Problems in the Determination of Trace Amounts of Platinum in “The Determination of Trace Amounts of Sulphur Compounds in Gases,” by University of St. Andrews St. Andrews. Glass,” by C. VV. Fuller. G. M. S. Duff. July Thursday 2nd and Friday 3rd CARDIFF WESTON SECTION and MICROCHEMICAL METHODS GROUP on “Trace Analysis “The Determination of Trace Amounts of Bismuth and Oxygen in Ferrous “Analytical Control in an Integrated Steelworks,” by P. Gale. “Trace Analysis Using Spark-source Mass Spectrometry ” by D. Nicholas. “Photopolarographic Absorption Spectroscopy-A Possible New Technique “Aspects of Pre-concentration and Separation Techniques,” by G. Xckless. “Determination of Trace Elements in Sea Water,” by J. P.Riley. “Pyridylazonaphthols and Phenols as Analytical Reagents,” by D. Betteridge. “Catalytic Methods of Trace Inorganic Analysis,” by A. Townshend. “Time-biased Periodic D.E.P.,” by E. Bishop and T. J. N. Webber. “Principles of Selective Ion-sensitive Membrane Electrodes,” by J. D. R. “Calcium Ion Sensitive Electrodes,” by G. J. Moody. University of Wales Institute of Science and Technology (UWIST) King with Emphasis on Inorganic Aspects” Alloys,” by J. B. Headridge E. D. Rawsthorne and J. Richardson. for Analysis and Structural Determination,” by D. R. Crow. Thomas. Edward VII Avenue Cardiff. THE SOCIETY FOL ANALYTICAL CHEMISTRY Forthcoming Meetings May Thursday 28th LONDON Friday 29th to Monday June 1st LLANDUDNO Saturday 30th COLEFORD June Tuesday 2nd LONDON Thursday 25th and Friday 26th ST.ANUREWS ELECTROANALYTICAL and AUTOMATIC METHODS GROUPS on “On-line Electro- “The Rapid Determination of Mercury in Urine by Automatic Anodic “Newer Designs of Electrocheniical Sensors,” by A. A. Diggens. “Plant Application Problems with Electrochemical Sensors,” by G. V. R. The Leicester Lounge 44 Glasshouse Street London IT. 1 ; 6.30 p.rn. XORYH OF ENGLAND SECTION Summer Meeting. “ Josiah Wedgewood and His Contribution to the Potting Industry,” by Imperial Hotel Llandudno. ~I‘ESTERN SECTION Summer Meeting on “History and Topography of the Forest of Dean. Lecturer and guide Revd. Canon R. J. Mansfield. Including a visit to the Forest of Dean. Angel Hotel Coleford ; 12.30 p.m. chemical Sensors.” Stripping Voltammetry,” by P. 0 . Kane. Mattock. iY. A. Billington.JOINT PHARMACEUTICAL ANALYSIS GROUP Discussion Meeting on “Good Manufacturing Practice,” introduced by L. Levi B 4. “order J. Lightbown E. Lax and 0. Wallen. British Medical Association House Tavistock Square London W.C. 1 ; 2.30 p.m. SCOTTISH and NORTH EAST SECTIONS ATOMIC SPECTROSCOPY and RADIO- CHEMICAL METHODS GROUPS on “Trace Analysis.” Plenary lecture by T. S. West. “The Practical Application of the High Frequency Plasma Torch to “The Determination of Trace Metals in Biological Material by Atomic “Trace Element Analysis in Natural Waters,” by J P. Riley. “Chemical Interferences in the Determination of Transition Elements by Atomic-absorption Spectrophotometry Indirect Determination of Traces of Titanium and Aluminium,” by D. T. Coker and J . M. Ottaway. “Mechanically Separated Laminar Flames,” by A.M. Ure. “Some Enzymatic Methods of Trace Analysis,” by A. Townshend. “Determination of Traces of Metals by Catalytic Analysis Based on Landolt “Determination of Anions by Catalytic Methods,” by J. M. Ottaway and “The Determination of Trace Elements in Antique Silver by Nuclear “Some Recent Applications of y-photon Activation,” by J . S. Hislop and “The R61e of the Computer in Trace Neutron-activation Analysis,” by J. W. “Some Applications of Radiochemical Group Separations in Neutron- “The Study of Engine Wear by Neutron-activation Analysis,” by R. Oliver. Spectroscopy,” by P. B. Smith and S. Greenfield. Spectroscopy,” by J . B. Dawson. Reactions,” by G. Svehla. C. Tuladhar. Techniques,” by R. Wellurn and J. E. Whitley. D. R. Williams. McMillan and J. W. Haynes. activation Analysis,” by G. C. Goode and A. R. Wilson. [Continued inside back covey Printed by W Heffer & Sons Ltd Cambridge England

ISSN:0037-9697    

DOI:10.1039/SA97007BX019

出版商:RSC    

年代:1970

数据来源: RSC

摘要:

May 1970 Vol. 7 No. 5 Reports of Meetings ORDINARY MEETING AN Ordinary Meeting of the Society was held on Thursday and Friday May 7th and 8th 1970 in the Department of Chemistry The University Birmingham. The Meeting was devoted to short papers on “Research Topics in ilnalytical Chemistry Some Current Work in Universities and Colleges.” On Thursday the Chair was taken by the President of the Society Professor T. S. West and the following papers were presented and discussed “A Kon-flame Method for the -4tomic- absorption Spectrophotometric Determination of Cadmium in Solutions Almalgams and Alloys,” by D. R. Smith and J. B. Headridge; “The Determination of Low Levels of Tungsten in Alloy Steels,” by D. R. Marriott A. G. Fogg and D. Thorburn Burns; “A Study of Several Chromium Polyphosphate Glasses,” by F.Snape ; “The Potentiometric Determination of Organic Hydroxyl Employing Enhancement Techniques,” by R. L. Parry- Jones and E. J. Greenhow; “Metal - Metallochromic Indicator Complexes as pH Indicators,” by R. A. Chalmers and F. I. Miller; “Polarographic Studies of Substituted 2-Thiobarbituric hcids,” by LV. F. Smyth G. Svehla and P. Zuman. On Friday the Chair was taken by the Chairman of the Midlands Section Mr. W. M. Lewis and the following papers were presented and discussed “The Atomic-spectroscopic Deter- mination of Ruthenium,” by 15’. B. Rowston J. M. Ottaway and Mrs. M. Stulik; “The Spectro- phosphorimetric Determination of Zinc with 2(2’-hydroxyphenyl)benzoxazole,” by P. R. U’ood and L. S. Bark; “Computer Calculation of Flame Compositions and Free Atom Fractions in Analytically Useful Flames,” by R.M. Dagnall and M. R. G. Taylor; “The Hydrolysis of Cyanogen Chloride,” by P. L. Bailey; “Determination of the Reactivity of Lysine in Proteins,” by M. S. Otterburn and R. S. Asquith; “The Determination of Iodine after Twenty-four Fold Amplification,” by J. ’111. Hamya and A. Townshend. XORTH OF ENGLAND SECTION A JOIKT Meeting of the Section with the North Lancashire Section of the Royal Institute of Chemistry was held at 7.30 p.m. on Friday April 17th 1970 in the Harris Technical College Preston. The Chair was taken by the Chairman of the North of England Section Mr. R. Sinar. A lecture on “The Analysis of Plastics-Why and How?” was given by ,4. G. Jones. 77 78 REPORTS OF MEETINGS [Proc. SOC. Analyt. Chem. WESTERN SECTION A DISCUSSION Meeting of the Section was held at 6.30 p.m.on Friday April 17th 1970 at the George Hotel Chepstow. The Chair was taken by the Chairman of the Section Dr. T. G. Morris. A discussion on “Analytical Problems of the Public Analyst” was introduced by L. E. Coles . MIDLANDS SECTION THE fifteenth Annual General Meeting of the Section was held at 6 p.m. on Wednesday March l l t h 1970 in the Haworth Lecture Theatre Chemistry Department The University Birmingham 15. The Chair was taken by the Chairman of the Section Mr. W. M. Lewis. The following Office Bearers were elected for the forthcoming year Chairman-Mr. W. M. Lewis. Vice-Chairman-Mr. P. G. W. Cobb. Honorary Secretary-Mr. S. Greenfield Research Department Albriglit & Wilson Ltd. P.O. Box No. 3 Oldbury Warley Worcs. Honorary Treasurer-Dr.A. Townshend. Members of Committee-Mr. B. E. Balfour Mr. H. E. Brookes Mr. R. T. Clark Mr. R. Cox Dr. V. J. Jennings Mr. D. M. Peake Dr. D. Thorburn Burns and Mr. W. B. Yeoman. Mr. H. Pugh and Mr. E. J. Stinton were appointed as Honorary Auditors. The Annual General Meeting was followed at 6.30 p.m. by an Ordinary Meeting of the Section at which a lecture on “Catalytic Methods of Analysis” was given by A. Townshend. A JOINT Meeting of the Section with the Forensic Science Society was held at 6.30 p.m. on Wednesday April 15th 1970 in the Lecture Theatre Boots Pure Drug Co. Ltd. Pennyfoot Street Nottingham. The Chair was taken by the Chairman of the Midlands Section Mr. lt7. M. Lewis. The following paper was presented and discussed “Recent Advances in Toxicological Analysis,” by A.S. Curry. A JOINT Meeting of the Section with the Mid-Anglia Section of the Royal Institute of Chemistry was held at 6.45 p.m. on Wednesday April 22nd 1970 at the Luton College of Technology Luton. The following paper was presented and discussed “Automatic Analysis-An Industrial View-point,” by P. G. Jeffery. The Chair was taken by the Chairman of the Midlands Section Mr. W. M. Lewis. NORTH EAST SECTION A JOINT Meeting of the Section with the Teesside Section of the Royal Institute of Chemistry was held a t 8 p.m. on Tuesday April 21st 1970 in the Teesside Polytechnic Borough Road Middlesbrough. The Chair was taken by the Chairman of the Teesside Section of the Royal Institute of Chemistry Dr. P. Smith. A lecture on “Automation of Gas Chromatographs” was given by D.R. Deans. CHROMATOGRAPHY AND ELECTROPHORESIS GROUP AN Ordinary Meeting of the Group was held at 2.30 p.m. on Thursday April 23rd 1970 at the Portsmouth Polytechnic Burnaby Road Portsmouth. The Chair was taken by Mr. J. D. R. Thomas. The subject of the meeting was “Comparison of Chromatographic Techniques” and the following papers were presented and discussed “Choice of Optimum Chromatographic Technique,” by S. G. Perry; “The Chromatography of Urinary Phenolic Acids,” by P. Smith; “A Comparison of Thin-layer Chromatography and Gas - Liquid Chromatography as Applied to the Examination of Volatile Oils,” by A. XI. Humphrey. May 19701 REPORTS OF MEETINGS 79 BIOLOGICAL METHODS GROUP AN Ordinary Meeting of the Group was held at 10.15 a.m. on Thursday April 16th 1970 at the Royal College of Physicians 11 St.Andrews Place Regents Park London N.W.l. The Chair was taken by the Chairman of the Group Dr. I. D. Fleming. The meeting took the form of a Symposium on “Pharmacological Screening of New Drugs 111” and the following papers were presented and discussed “Anti-Parkinson Drugs,” by R. Stephens; “P-Blocking Drugs,” by A. M. Barrett; “Appetite Suppressants,” by A. B. Wilson; “Hypoglycaemic Agents,” by G. A. Stewart; “Anti-tumour Agents,” by T. A. Connors; “Chemotherapy of Intestinal Nematodes,” by J. E. D. Keeling. AUTOMATIC METHODS GROUP A DEMONSTRATION Meeting of the Group was held at 10.30 a m . on Thursday April 9th 1970 at the Middlesex Hospital Medical School Cleveland Street London W.l. The Chair was taken by the Chairman of the Group Mr. D. C. M. Squirrell.The following introductory paper was presented and discussed “The R81e of the Instru- ment Manufacturer in the Development and Exploitation of Inventions,” by G. C. Collins. The following apparatus was demonstrated “A Simple Rectified Radiofrequency Conducti- metric Apparatus Applicable to Liquids,” by W. Sebborn ; “Multiple-column Systems In- volving the Use of Porous-layer Open Tubes for Identification and Analysis in Gas Chromato- graphy,” by D. W. Grant; “Extraction Device for Removing Bottom Layers,” by C. G. Taylor ; “A Fully Automatic Apparatus for Operating a Suspended-level Viscometer,” by B. L. Nichols N. Payne and J. V. Simons; “The Micro-ionisation Trace Gas Analyser,” by C. Sarain; “An Electrical System Used to Ignite Samples for Combustion Studies,” by D. E. Faulkner ; “A Simple Accurate Injection Gun for the Repetitive Administration of Liquids,” by D.E. Faulkner ; “An Eight-channel Table for Weighing Mice Incorporating an Automatic Counting System,” by D. E. Faulkner; “A Detector System for Use in Liquid Column Chro- matography,” by T. B. Davenport ; “A Fully Automatic Apparatus for Stripping Analysis,” by B. Fleet ; “Determination of Ammonia by an Automatic Ultraviolet Absorptionietric Method,” by W. Johnson J. M. Skinner and R. R. Sotheran; “Portable Electrochemical Analysis Unit,” by K. Steed; “Radiofrequency Titrimeter,” by R. K. Quigg K. I. Miller and G. SxTehla; “Automatic Signal Attenuator,” by D. F. C. Crawley ; “Automatic Extraction Identification and Determination of Quinizarin in Gas Oils,” by R. Sawyer P. B. Stockwell and I<.B. Tucker. THERMAL ANALYSIS GROUP THE second Thermal Analysis School was held by the Group from Monday to Friday April 6th to loth 1970 at the Cement and Concrete Association Fulmer Grange Slough Bucks. The following lectures were given Introductory Lecture by D. Dollimore ; “Theoretical Basis for Thermal Analysis,” by R. A. W. Hill; “Present Status and Future Development of the Techniques,” by J. P. Redfern; “Instruments,” introduced by R. C. Mackenzie ; “Applications to Inorganic Materials,” by J. H. Sharp ; “Applications to Metallurgical Problems,” by J. Mackowiak ; “Applications to Organic Compounds including Polymers,” by R. C. Roberts ; “Low Temperature Thermal Analysis,” by I. C. Wylie ; “Quantitative Thermal Analysis,” by F. IY. Wilburn. The school included three practical periods and evening discussions. PARTICLE SIZE ANALYSIS GROUP As Ordinary Meeting of the Group was held at 2.30 p.m. on Wednesday May Gth 1970 in th School of Pharmacy University of London 29/39 Brunswick Square London W.C.1. The Chair was taken by the Vice-chairman of the Group Mr. K. Marshall. The subject of the meeting was “Sieving” and the following papers were presented and discussed “The Effect of Particle and Aperture Shape on Sieve Analyses,” bv Professor D. C. Freshwater ; “The Alpine Air-jet Sieve,” by T. M. Jones ; “Electro-formed Micro-mesh Sieves,” by F. J. Colon; “Felvation,” by M. W. G. Burt.

ISSN:0037-9697    

DOI:10.1039/SA970070077b

出版商:RSC    

年代:1970

数据来源: RSC

摘要:

80 MICROCHEMIC4L TECHXIQUES IN PETROCHEMICAL INDUSTRIES [PrOC. SOC. Analyt. Chem. The Application of Microchemical Techniques in the Petrochemical and Allied Industries The following is a summary of one of the papers presented at a Joint Meeting of the Microchemical Methods Group with the Mid-Southern Counties Section of the Royal Institute of Chemistry held on September 19th and 20th 1969 and reported in the October 1969 issue of Proceedings (p. 182). Summaries of the other papers presented at this meeting were published in the January 1970 issue of Proceedings (p. 4). Quantitative Elemental Analysis of Small Liquid Samples (less than 1 ml) by X-ray Fluorescence BY R. W. WILLIAMS (The British Petroleum Company Ltd. BP Research Cedre Chertsey Road Sunbury-on-Thamcs Middlesex) X-RAY fluorescence spectrometry is a fairly comprehensive method of qualitative and quantitative analysis for elements.For quantitative analysis on very limited volumes of solutions a means must be found to present reproducibly a suitable specimen to the spectrometer. If the required elements are present in sufficient concentration the solution can be diluted to give the required volume for analysis in a standard sample cell. However when the elements are present as trace quantities other means must be found which will provide maximum characteristic X-radiation of reproducible intensity from each analysis element. From 10 to 15 ml of sample are normally required for quantitative elemental analysis of liquids by X-ray fluorescence when a Philips PW 1540 spectrometer is used. This paper describes a technique developed at the BP Research Centre which enables quantitative analyses to be carried out on 0.6 ml of liquid by using a simple cell insert.The cell insert has for obvious visual reasons been affectionately christened “Sputnik. ” Other methods of analysing small volumes of liquids are by spotting on to filter-paper or Mylar film but as the available intensity is decreased the determination of trace concentra- tions is sometimes impracticable. QUANTITATIVE ELEMENTAL ANALYSIS ON SMALL VOLUMES OF LIQUID THEORETICAL CONSIDERATIONS- Critical depth-The critical depth is that depth of the specimen beyond which there is I t is no additional increase in emitted characteristic radiation with increasing depth. determined by primary and secondary absorption of X-rays within the specimen.l f l l l l l l l 0 t 2 4 6 8 10 12 14 Specimen o 2-56 5-32 7.6810.2412.80 15.36 Specimen depth 1-28 votume ml. mm Fig. 1. Critical depth determination 4.5 ml of tetraethyl lead per U.K. gallon -4vgas standard; L radiation May 19701 MICROCHEMICAL TECHNIQUES I N PETROCHEMICAL INDUSTRIES 81 For trace element analysis in hydrocarbon solutions the critical depth normally exceeds 12.5 mm and with the standard cell of the Philips PW 1540 spectrometer this requires a sample volume in excess of 10 ml. This is demonstrated in Fig. 1 which shows the variation in intensity with volume of sample and corresponding depth. As the primary objective in quantitative X-ray fluorescence analysis is to relate charac- teristic intensity with concentration of emitting element then with sample depths less than the critical value the depth must be kept constant to eliminate variation in intensity with depth.Cell insert “S@t.rzik”-The following factors were considered in the design of the cell insert reproducible constant depth ; maximum irradiation area ; ease of cleaning cell and insert ; rapid introduction of sample; and elimination of air from irradiated volume. A schematic diagram of the cell insert is shown in Fig. 2. t 1 I Fig. 2. “Sputnik” cell insert (all measure- ments in cm) (a) elevation cross-section; (b) plan view The cell insert used in the analyses described in this paper was turned from a bar of aluminium but other materials can be used. In practice the insert is placed in a normal cell and the liquid sample poured on to the conical face. The liquid drains through the perimeter grooves and enters the space between the concave base and the cell window driving the displaced air up through the axial bore.Provided the cell window is kept taut a reproducible sample volume and depth is obtained. The analytical sample volume is 0.6 ml the sample depth at the centre 1.524 mm and the surface area presented to the incident beam 5-94 cm2 as for the standard cell. APPLICATIONS OF THE CELL INSERT- The following is a brief summary of some analytical applications of the cell insert at the BP Research Centre Sunbury and BP Chemicals Limited Epsom Division for the analysis of small liquid samples. Lead in @etroZs-The method covers the direct determination of lead as tetraethyl or tetramethyl lead over the concentration range 0.05 to 6-00 ml of tetraethyl or tetramethyl lead per U.K.gallon. 82 MICROCHEMICAL TECHNIQUES IN PETROCHEMICAL INDUSTRIES [Proc. Soc. Aizalyt. Chem. The net intensity of the lead La radiation is obtained directly on the sample and the leap content determined by comparison with a previously established calibration graph; the analysis time is 5 minutes per sample. TABLE I COMPARISON OF RESULTS Sample code . . .. .. . . . . A B C D E F G H J JFull 2.84 0.83 3.04 1-43 0.84 1.43 2.61 0.65 1-98 Tetraethyl lead* m1 per U*K' ga1lon\Tnsert 2.95 0.84 3-07 1.47 0.84 1-47 2-69 0.71 2-03 A comparison of analyses made using normal volumes and small volumes of sample is given in Table I. Repeatability results over 11 determinations were mean tetraethyl lead content 3.192 ml per U.K. gallon; standard deviation 0.019 ml per U.K.gallon; and repeat- ability (95 per cent. confidence limits) 0.053 ml per U.K. gallon. Rhodium in mixed light hydrocarbon solutions-The method covers the determination of rhodium in mixed light hydrocarbons over the concentration range 7 to 1000 p.p.m. of rhodium. Silver is used as an internal standard to compensate for variations in sample composition. The ratio of the net intensity of the rhodium Ka line to the silver Ka line is obtained on an aliquot of the sample to which a standard amount of silver has been added. The rhodium concentration of the sample is obtained from a previously prepared calibration graph of concentration versus the same ratio. The analysis time is 15 minutes per sample. Nickel and vanadium in crude oils and distillates-The method covers the direct determi- nation of nickel over the concentration range 3 to 100 p.p.m.and vanadium over the range 3 to 250 p.p.m. I t fully compensates for normal variations in sulphur content and hydrogen- to-carbon ratio for nickel and partially for vanadium. The ratios of the net intensities of the nickel Ka line and vanadium K a line to their adjacent background intensities is obtained directly on a portion of the sample. The nickel and vanadium content is obtained from previously prepared calibration graphs of concentra- tion versus the same ratio. The analysis time is 10 minutes per sample. 0 I- +. 2 Nickel p.p.m. Fig. 3. Nickel calibration with cell insert x nickel in SAE 10 base oil; and 0 nickel in SAE 10 containing 3 per cent of sulphur P is peak intensity and CB is corrected background intensity Calibration graphs are shown in Figs.3 and 4 and a comparison of analyses made with a full cell and with the cell insert is given in Tables I1 and 111. May 19701 SELECTIVE ELECTRODE SYSTEMS TABLE 11 COMPARISON OF RESULTS Sample No. . . . . ,. .. .. 1 2 3 4 5 * . .. 23 23 23 1.5 13 Nickel p.p.ni. { F:lrt 24 24 24 16 15 TABLE I11 COMPARISON OF RESULTS Sample No. . . .. * . .. .. 1 2 3 4 5 Full . . .. .. 1S9 193 1’76 49 49 Vanadium p.p.m. {Insert 200 207 177 51 53 6 13 13 6 38 41 7 15 1 1 7 45 47 8 20 20 8 91 94 53 9 27 26 9 63 71 Polymerisable materials-At the Epsom Division of BP Cheniicals Limited the cell insert has been used for the determination of titanium in polymerisable materials. The onset of polymerisation occurs almost immediately the sample is irradiated and with normal sampling methods utilising 10 ml or more of sample a change in count rate takes place throughout the time necessary to accumulate sufficient counts for precise analysis.The change in count rate is attributed to excess concentration of the titanium on the cell window. As the mass absorption coefficient of titanium for titanium Kw. radiation is greater than the original matrix this leads to a decrease in the measured intensity of the titanium Kw. radiation. With the cell insert 0.6 ml of sample is used and although polymerisation occurs the amount of titanium concentrate is less than with the normal volume and the degree of absorption negligible. The applications of the cell insert described in this paper dealt with organic solutions but it can be applied to any type of solution. The technique is but one of the many important applications of X-rays as an analytical tool in the petroleum industry. Increasingly more complex refinery processes the growth of the petrochemical industry and the processing of new materials are making heavy demands on the skill and ingenuity of the X-ray specialist but it is a challenge that is being met. Permission to publish this paper has been given by The British Petroleum Company Limited.

ISSN:0037-9697    

DOI:10.1039/SA9700700080

出版商:RSC    

年代:1970

数据来源: RSC

摘要:

May 19701 SELECTIVE ELECTRODE SYSTEMS Selective Electrode Systems THE following are summaries of the papers presented at the Inaugural Meeting of the Electro- analytical Group held on November 26t11 1969 and reported in the February issue of Pro- ceedings (p. 26). Recent Developments in Glass and Solid-state Electrodes BY A. I<. COVINGTON (Department of Physical Chemistry The University Newcnstle-~~poiz-T?ine NE 1 7R U ) RECENT developments in ion-selective electrodes have been variously described as “a whole new technology for chemical measurement,” a “break-through in electroanalytical chemistry akin to the discovery of lasers in optical physics,’’ a “Pandora’s box with yet undiscovered treasures,” the present state of the art being comparable with that of polarography 30 years ago.In his lecture Dr. Covington reviewed developments in solid-state heterogeneous (pre- cipitate) membrane electrodes and glass electrodes elaborating on his recent article in Chemistry in L3ritain.l He emphasised that the mechanism of operation of these electrodes including glass electrodes was still far from being understood. This did not however affect their use in a wide variety of analytical techniques and monitoring procedures provided that due account was taken of their limited selectivity in the presence of certain interfering ions. A valuable monograph on the subject had recently appeared which presented invited papers from a Symposium held in Washington in January 1969. REFERENCES 1. 2. Covington A. I<. Chem. Brit. 1969 5 388. Durst R. A. Editor “Ion Selective Electrodes,” N.B.S.Special Publication No. 314 Government Printing Office Washington D.C. 20402 1969. 84 SELECTIVE ELECTRODE SYSTEMS [Proc. SOC. Analyt. Chew. Recent Developments in Liquid Ion-exchange Resin Membrane and Related Electrodes BY B. FLEET (Chemistry Department Imperial College Imperial Institzkte Road London S. W.7) GLASS and solid membrane electrodes represent typical ion exchangers in that the electrode material is a water-insoluble solid matrix. Ion exchange can also occur between two im- miscible liquid phases and a range of ion-selective electrodes has been developed that is based on well established solvent-extraction systems. The mechanism of operation of these elec- trodes is in most cases analogous to that of the corresponding glass and solid-membrane electrodes in that it is primarily an ion-exchange process.1 The physical arrangement in most liquid membrane electrodes is that the liquid exchanger resin is supported on a thin inert membrane (either cellulose acetate or a glass frit) that separates the aqueous internal reference solution from the test solution.Since the liquid ion exchanger must be water immiscible it is generally used in the form of a solution in a high molecular-weight alcohol or ester. Typical ion exchangers that have been found to be suitable are the long-chain phosphate esters (Mn+ salts) as cation exchangers and the higher quaternary ammonium compounds as anion exchangers. The incorporation of long-chain alkyl groups on the site ion ensures solubility in the organic phase. Electrodes for some 9 or 10 cations and anions are now commercially available (Beckman Ltd.Sunley House Croydon Surrey; Corning Glass International 3 Cork Street London W.l; Orion Research Inc. whose U.K. agent is E.I.L. Ltd. Richmond Surrey) but with the inclusion of various electrodes in the development stage and allowing for the use of electrodes to measure ions other than the principal ion the number of possible applications is far greater. For example electrodes for calcium and water hardness (bivalent M+) are now widely used in applications as diverse as pollution control and clinical analysk2 Liquid membrane electrodes for Cu2+ and Pb2+ have been developed3 based on a substituted thio-acid as the active ion exchanger ; the selectivity characteristics of both electrodes however are inferior to the more recently developed mixed-crystal solid-membrane electrodes.An electrode showing a virtually non-selective response to a wide range of bi- and tervalent metal ions has also been reported.* The ion exchanger used in this application was dinonylnapthalenesulphonic acid in nujol. As an example of the use of an anion-selective liquid-membrane electrode the work of Coetzee and Freiser5 is of interest as it illustrates both the advantages and limitations of liquid- membrane electrodes. These authors used an ion-association system based on the methyl tricapryl ammonium ion. A wide range of ions can be measured after converting the exchanger into the appropriate form; however in all instances the selectivity is only moderate and is entirely dependent on the extractability of the interfering ion into the organic phase.Most commercial electrodes by careful screening of the ion exchanger are able to improve on this situation but the general statement still holds true. Of the commercially available anion electrodes the perchlorate,6 nitrate and borofluoride ones,' which are all based on substituted o-phenanthroline - metal complexes as the active exchangers fill important gaps in analytical technique as few convenient methods are available for the determination of these important anions. One of the most exciting of the recent developments in this field has been the observation that certain macrocyclic antibiotics show a high degree of specificity for monovalent cations.s Simon and c o - w o r k e r ~ ~ ~ ~ ~ J ~ have investigated a wide range of antibiotics and the most promis- ing of these has been found to be valinomycin which shows a favourable selectivity for potassium ions over sodium and ammonium.Using an electrode of this type the direct measurement of potassium-ion activity in sera is possible (B. Fleet and H. von Storp un- published work). The structurally related but simpler cyclic polyethers12 show a comparable but less favourable response. The other important breakthrough in the fabrication of these electrodes has been the introduction of immobilised-matrix liquid-membrane electrodes. Shatkay and co-workers13J4 have shown that a calcium-selective electrode membrane can be prepared by incorporating t heonyltrifluoroacet one in poly (vinyl chloride) with t ribut ylphosphate added as a secondary May 19701 SELECTIVE ELECTRODE SYSTEMS 85 plasticiser.Electrodes based on this principle and responsive to calcium and nitrate ions are now commercially available. A prototype solid-membrane potassium electrode has recently been described.15 In addition to their analytical applications these electrodes by virtue of the fact that they measure ionic activity are ideally suited for following the rates and equilibria of chemical reactions. As a typical example the rates of some fast ion combination reactions have been studied with a flow-through liquid-membrane electrode.16 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. REFERENCES Sandblom J. Eisenman G. and Walker J. L. jun. J . Phys. Chem. 1967 71 3862. Durst R. A. Editor “Ion Selective Electrodes,” N.B.S. Special Publication No. 314 Government Printing Office Washington D.C.20402 1969. - op. cit. p. 61. Harrell J. B. Jones A. D. and Choppin G. R. Analyt. Chem. 1969 41 1459. Coetzee C. J. and Freiser H. Ibid. 1969 40 1128. Hseu T. M. and Rechnitz G. A. Analyt. Lett. 1968 1 629. Carlson R. M. and Paul J . L. A m l y t . Chem. 1968 40 1292. Stefanac Z. and Simon W. Chirnia 1966 20 436. I’ioda L. A. R. Wachter H. A. Dohner R. E. and Simon W. Helv. Chim. 4cta 1967 50 1373. Stefanac Z. and Simon W. Micvochem. J. 1967 12 125. Pioda L. A. R. and Simon W. Chimia 1969,23 72. Pederson C. J. J . Amer. Chem. Soc. 1967 89 7017. Shatkay A. Analyt. Chem. 1967 39 1056. Bloch R. Shatkay A. and Saroff H. A. Biophys. J. 1967 7 865. Kedem O. Furmansliy M. Loebel E. Gordon S. and Bloch R. Israel J . Chem. 1969 7 87. Fleet B. and Rechnitz G. A. Analyt. Chern. in the press.Recent Developments in Galvanic Sensors BY J12f TENYGL* (Chemistvy Depavtment Imperial College Imperial Institute Road London S. W.7) THE possibility of using galvanic sensors for continuous analysis was illustrated by the deter- mination of oxygen. The polarographic and coulometric principle was reviewed and special attention was devoted to membrane-covered electrodes and to electrodes covered with a film of electrolyte. Polarographic measurement of oxygen in gases by the use of a mercury-pool electrodel is suitable for the determination of oxygen concentrations above 1 per cent. The reading of this type of analyser is dependent on the temperature (the temperature coefficient is about 2 per cent. per degree Celsius) and also on the flow-rate; however above a certain flow-rate this dependency reaches an almost constant limit.In the discussion a method for the continuous regeneration of the mercury-pool electrode by addition of a small amount of mercury ion to the supporting electrolyte was described. The mercury-pool electrode is continuously “plated” by a layer of freshly deposited mercury.2 A typical example of using the coulometric principle for determining oxygen was described. This consisted of an analyser with a porous silver ele~trode.~ The reading of this type of analyser depends on the flow-rate only and is independent of the temperature. In the Clark type of electrode the solid disc electrode is protected by a thin polyethylene membrane from the approach of ionic and macromolecular substances; only oxygen (and other gases) can diffuse through the membrane to the working electrode.The reading is temperature dependent (coefficient 3 to 5 per cent. per degree Celsius) and because of the low penetration of oxygen this type of electrode is suitable only for determination of the higher oxygen con- centrations.* A system in which the membrane covers both the indicating electrode and the oxygen reference electrode which is independent of the permeability of the membrane (B. Fleet and J. Tenygl unpublished work) was also described together with the enzyme electrode for the determination of glu~ose.~ The Hersch type of electrode covered with a thin layer of electrolyte can work in a polaro- graphic mode (diffusion controlled) or in a coulometric mode (flow-rate controlled) The rate of diffusion of oxygen through a thin layer of electrolyte is very high and this type of electrode is useful for determining low concentrations of oxygen.6 * Present address J.Heyrovskg Institut of Polarography Prague Czechoslovakia. 86 OBITUARY [Proc. SOC. Analyt. Chem. There are many possibilities for indirect measurement of oxygen one of which is its deter- mination in liquids by stripping the oxygen by means of a stream of an inert gas. A typical example of the indirect measurement is pneumatic p~larography.~ The sample is electrolysed by a constant current and the concentration of oxygen in the oxygen - hydrogen gas mixture produced by electrolysis is measured with the oxygen analyser. REFERENCES 1. 2. 3. 4. 5. 6. 7. NovAk J. V. A. Colln. Czech. Chem. Commuiz. 1956 21 662. Tenygl J. Thesis Czechoslovak Academy of Sciences 1961 ; Czechoslovak Patent No. 106,185. Keidel F. A4. Ind. Engng Chem. 1960 52 490. Mancy K. H. Ocun D. A. and Reilley C. N. J . Electvoa~ialyt. Checn. 1962 4 65. Updike S. J. and Hicks G. P. Nature 1967 214 956. Hersch P. Instrum. Pract. 1957 11 817 and 937. Tenygl J. Colln. Czech. Chem. Cornmun. 1968 33 4141.

ISSN:0037-9697    

DOI:10.1039/SA9700700083

出版商:RSC    

年代:1970

数据来源: RSC

摘要:

86 OBITUARY [Proc. SOC. Analyt. Chem. Obituary GEORGE WILLIAM FERGUSON the December meeting of the Essential Oils Sub-Comniit tee of the Analytical Methods Committee we all thought our chairman Dr. George William Ferguson looked far from well but none of us realised that he was so ill. He collapsed on King’s Cross Station on his way home and was taken to the Royal Free Hospital where he died on Saturday December 13th aged 63 without regaining consciousness. George William Ferguson was an only child and was born at Wallasey Cheshire on May 7th 1906. He was educated at the local grammar school where he had a distinguished career and was soon showing his aptitude for chemistry and sport. At the age of 17 he came south and embarked on a career which in fact became his life interest for he joined the staff of Dr.Ernest J. Parry Barrister-at-Law Consulting Chemist and author of “The Chemistry of Essential Oils,” the standard work in English of its day. Parry was quick to appreciate a good man when he saw one and encouraged George Ferguson to pursue his studies and it was not long before he was made a partner and upon Parry’s death the sole proprietor. So with characteristic enthusiasm and without any delay in 1925 he enrolled as an evening student at Birkbeck College Breams Buildings in the City. Those of us who were there at the time knew immediately that an exceptionally brilliant young man had come amongst us. Under the careful tuition of Senter Barrow Sugden and Myddleton he quickly became an outstanding student. So much so that within 4 years he had graduated with a First Class Honours degree in Chemistry as an internal student of the University of London.This in itself was a remarkable achievement because in those days all students at Birkbeck College were studying in the evening after a long day’s work including Saturday mornings However this was not enough for George Ferguson for without delay he embarked on a 4 year Ph.D. course and was seconded to that brilliant Organic Chemist and pillar of strength in the Chemistry Department at Birkbeck the late Dr. Fred Barrow. In 1933 he submitted a thesis “The Stereo Chemical Relationship of the a-Amino Acids The Configuration of Natural Valine” and received his Doctorate another remarkable achievement for an evening student. Those of us who were there at the time knew a Ph.D. did not tell us everything about George Ferguson.We saw in him an outstanding Preparative Chemist and a man whose manipulative ability at the working bench and attention to detail singled him out as a brilliant analyst. I t was not a case of all work and no play with George Ferguson because he was always a very lively member of that small party that repaired to the local at the end of the evening’s work for the usual conviviality. In the summer he was to be seen regularly on the sports ground at Greenford either batting or fielding and wearing an old faded cap the colours of which we could never quite place for which he developed an extraordinary affection. His College days also brought him great happiness for it was there he met a young demonstrator Maude Cole whom he subsequently married. May 19701 PUBLICATIONS RECEIVED 87 Most men with a thesis behind them would now have relaxed in their spare time but not so George Ferguson for almost immediately he was appointed a demonstrator in the depart- ment and quickly displayed another facet of his character namely an extraordinary flair for imparting knowledge to the students around him by his inexhaustable patience and kindness.He was a great inspiration to his students who were at that time living through a period of terrible economic depression and we soon realised that we had in George Ferguson a man who had a kindly word for everyone and was completely dedicated to his profession. Apart from George Ferguson’s work in the chemistry laboratory he devoted much of his time to the non-academic side of the College. Upon graduation he joined the Court of Electors and before very long was one of the four members elected to the Governing Body of the College.In 1966 he became chairman of this court but modestly declined all entreaties to stand as one of the Governors of the College. In addition to all this George Ferguson became Secretary of the Association of Consulting Chemists. He joined our Society in 1935 and was a member of the Essential Oils Sub-committee for 20 years; for 14 of those years he was its Chairman until the very day he was taken ill. With Dr. Fred Barrow as his co-author he published a paper on the “Stereo Chemistry of Amino Acids” in the Journal of the Chemical Society 1935. He had been a member of the Chemical Society for 40 years when he was appointed a life member in 1967. In 1966 he translated Suchard and Bobaranski’s Semimicro Methods of Organic Com- pounds (1936). The Funeral Service was held at St. Mary Magdalene Enfield on Thursday December 18th’ and was attended by many prominent members of the chemical profession. He is survived by his widow Maude and a son and a daughter to whom we extend our sincere sympathy. J. H. SEAGER He was a member of the Faraday Society and a Fellow of the R.I.C. Changes in the Register of Members DEATHS WE record with regret the deaths of William George Burgess Leon Ganellin Oscar Lazar John Ralph Nicholls.

ISSN:0037-9697    

DOI:10.1039/SA9700700086

出版商:RSC    

年代:1970

数据来源: RSC

摘要:

May 19701 PUBLICATIONS RECEIVED 87 Publications Received The publications listed below have been received by the Editor of The Aqzalyst in which journal Book Reviews will continue to appear. Cambridge University Press. 1970. Price 85s. Edited by BENTON JONES JUN. 1970. Price $20.00. 6 issues per volume. AN INTRODUCTION TO X-RAY CRYSTALLOGRAPHY. By M. M. WOOLFSON. Pp. x + 380. London COMMUNICATIONS IN SOIL SCIENCE AND PLANT ANALYSIS. Volunie 1. Number 1. January 1970. New York and London Marcel Dekker Inc Pp. iv + 62. A New Journal MODERN MICROCRYSTAL TESTS FOR DRUGS THE IDENTIFICATION OF ORGANIC COMPOUNDS BY MICROCRYSTALLOSCOPIC CHEMISTRY. By CHARLES C . FULTON. Pp. xvE + 466. New York London Sydney and Toronto Wiley-Interscience. 1970. Price ;514 5s. DISSOCIATION CONSTANTS OF INORGANIC ACIDS AND BASES IN AQUEOUS SOLUTION.International Union of Pure and Applied Chemistry. Analytical Chemistry Division Commission on Electroanalytical Chemistry. By D. D. PERRIN. Pp. vi + 133-236. London Butter- worths. 1970. Price 44s. 88 PUBLICATIONS RECEIVED [Proc. SOC. Analyt. Chem. ANCILLARY TECHNIQUES OF GAS CHROMATOGRAPHY. Edited by LESLIE S. ETTRE and WILLIAM H. MCFADDEN. Pp. xii + 395. New York London Sydney and Toronto Wiley-Interscience. 1970. Price 165s. By M. T. BECK D.Sc. Translation Editor R. A. CHALMERS. Pp. 285. London New York Toronto and Melbourne Van Nostrand Reinhold Company. 1970. Price 90s. DIFFERENTIAL THERMAL ANALYSIS. Edited by R. C. MACKENZIE. Volume 1. Fundamental Aspects. Pp. xvi + 775. London and New York Academic Press. 1970. Price LlZ. Nineteenth Series.Edited by J. A. GAUTIER and P. MALANGEAU. Pp. iv + 207. Paris Masson et Cie. 1970. Price 8OF. ELEMENTS DE POLAROGRAPHIE. THEORIE TECHNIQUE INSTRUMENTALE APPLICATIONS ANALY- TIQUES. By R. POINTEAU and J . BONASTRE. Pp. viii + 396. Paris Masson et Cie. 1970. Price 120F. CHEMICAL SEPARATION METHODS. By JOHN A. DEAN. Pp. xiv + 398. New York Cincinnati Toronto London and Melbourne Van Nostrand Reinhold Company. 1970. Price 126s. AKALYTICAL METHODS FOR PESTICIDE RESIDUES IN FOODS. Compiled and Edited by H. A. MCLEOD P. J. WALES R. A. GRAHAM M. OSADCHUK and K. BLUMAN. Pp. ii + 247. Ottawa The Queen’s Printer. 1969. Price $5.00. Monographs in Organic Functional Group Analysis. Volume 4. Oxford London Edin- burgh New York Toronto Sydney Paris and Braunschweig Pergamon Press. 1970. Price 50s. By D. J . DAVID and H. €3. STALEY. Pp. xii + 627. Kew York London Sydney and Toronto \T-iley-Interscience a division of John Wiley & Sons. 1970. Price jtT13 10s. LUMINESCENCE OF BIOPOLYMERS AND CELLS. By GRIGORII M. BARENBOIM ALEKSANDR N. DOMANSKII AND KONSTANTIN K. TUROVEROV. Translation Editor RAYMOND I;. CHEN. Pp. viii + 229. New York and London Plenum Press. 1969. Price $12.50. Pp. xii 4- 130. London Adam Hilger. 1970. Price 60s. CHEMISTRY OF COMPLEX EQUILIBRIA. MISES AU POINT DE CHIMIE ANALYTIQUE ORGAKIQUE-PHARMACEUTIQUE ET BROMATOLOGIQUE. THE DETERMINATION OF ORGANIC PEROXIDES. By R. M. JOHNSON and I. W. SIDDIQI. Pp. x + 119. ANALYTICAL CHEMISTRY OF THE POLYURETHANES. Part 111. VACUUM TECHNOLOGY AN INTRODUCTION. By L. G. CARPENTER M.A. B.Sc. F.1nst.P.

ISSN:0037-9697    

DOI:10.1039/SA9700700087

出版商:RSC    

年代:1970

数据来源: RSC

摘要:

88 PUBLICATIONS RECEIVED [Proc. SOC. Analyt. Chem. Notices INTERNATIONAL UNION OF PURE AND APPLIED CHEMISTRY REPORT ON THE WORK OF I.U.P.A.C. 1957-1967 A REPORT on the work of the International Union of Pure and Applied Chemistry 1957-1967 by Wilhelm Klemm President of I.U.P.A.C. 1965-1967 has recently been published (Butter- worths London 1969 20 pp.). A few copies are available to members of the Society on request to the Executive Secretary The Royal Society 6 Carlton House Terrace London S.W.1. I.U.P.A.C. FINAL RECOMMENDATIONS ON NOMENCLATURE SYMBOLS UNITS AND STANDLARDS THE following reports of interest to analytical scientists have recently been published for the Analytical Chemistry Division of I.U.P.A.C. in Pure a.nd Applied Chemistry and reprints are available from Butterworth and Co.(Publishers) Ltd. 88 Kingsway London W.C.2 at the prices indicated- “Recommended Nomenclature for Titrimetric Analysis,” report prepared by E. B. Sandell and T. S. West (reprinted from Pure A$$. Chem. 1969 18 429436; price 5s.). THE SOCIETY FOR ANALYTICAL CHEMISTRY “Recommendations for the Presentation of the Results of Chemical Analysis,” report prepared by R. W. Fennel and T. S. West (Pure A$@. Chem. 1969 18 439-442; “Sodium Carbonate and Sulphamic Acid as Acid - Base Primary Standards,” report prepared in conjunction with the Society for Analytical Chemistry -4nalytical Methods Committee (Pure A$$. Chem. 1969 18 445455; 5s.). “Recommended Symbols for Solution Equilibria,” report prepared by Y. Marcus (Pure Appl. Chem. 1969 18 459-464; 5s.). 5s.). BRITISH STANDARDS INSTITUTIOS DRAFT SPECIFICATION ,4 FEW copies of the following draft specification issued for comment only are available to members of the Society and can be obtained from the Secretary The Society for Analytical Chemistry 9/10 Savile Row London IVlX 1AF. Draft Specification prepared by Technical Committee CIC/21-Xmmonia and Nitric Xcid. 70/7735-Draft B.S. Methods of Test for Ammonia Solution (Metric Cnits).

ISSN:0037-9697    

DOI:10.1039/SA9700700088

出版商:RSC    

年代:1970

数据来源: RSC