摘要:

Proceedings of the Society for Analytical Chemistry CONTENTS Reports of Meetings . . . . 147 “Sugar Analysis” . . . . .. 148 “Infrared Spectroscopy”. . .. I50 Proc. SOC. Anal. Chem. Vol. 2 NQ. 10 Pages 147-162 Publications Received . . .. 159 Papers accepted for The Analyst 160 Notices .. - . .. .. 161 Forthcoming Meetings Back cover October 1965 Vol. 2 No. 10 PROCEEDINGS OF October 1965 THE SOCIETY FOR ANALYTICAL CHEMISTRY President of the Society A. A. Smales. O.B.E. Hon. Secretory of the Society S. A. Price Hon. Treasurer of the Society D. T. Lewis C.B. Hon. Assistant Secretaries of the Society 9. S. Cooper; D. W. Wilson Secretary Miss P. E. Hutchinson 14 BELGRAVE SQUARE LONDON S.W.1 Telephone BELgravia 3258 Editor J. 6. Attrill Proceedings is published by The Society for Analytical Chemistry and distributed t o members and all subscribers t o The Analyst without charge Single copies may be obtained direct from the Secretary The Society for Analytical Chemistry a t the above address (NOT through Trade Agents) price 2s.6d. post free. Remittances payable to “Society for Analytical Chemistry” MUST accompany orders REPORTS OF THE ANALYTICAL METHODS COMMITTEE Reprinted from The Analyst dditives in Animal Feeding Stuffs The following six Reports dealin Additives in Animal Feeding Stuffs may be obtained direct from the Secretary The Society for Analytical Chemistry 14 Belgrave Square London S.W. I (not through Trade Agents) price Is. Od. t o members of the Society and 2s. 6d. t o non-members. A remittance made out t o “Society for Analytical Chemistry” MUST accompany every order. The Determination of Penicillin Chlortetracycline and Oxytetracycline in The Determination of Stilboestrol and Hexoestrol in Compound Feeding Stuffs. The Determination of Nitrofurazone in Cornpound Feeding Stuffs. The Determination of Water-soluble Vitamins in Compound Feeding Stuffs. The Determination of Fat-soluble Vitamins in Diet Supplements and Com- The Determination of Amprolium in Animal Feeding Stuffs. Diet Supplements and Compound Feeding Stuffs. pound Feeding Stuffs.

ISSN:0037-9697    

DOI:10.1039/SA96502FX035

出版商:RSC    

年代:1965

数据来源: RSC

摘要:

THE SOCIETY FOR ANALYTICAL CHEMISTRY Forthcoming Meetings-conztiizued November Friday 12th f-frzr STOL Thursday 1 8th COV 12 K ‘r R Y ,- I uesclay 231-d 1,Oil‘l)ON Wednesday 24th 1,ONImN Tuesday 30th I ,OK DO N WESTKI~N S I ~ C T I ON Ordinary Meeting. Kristol; 6.30 p.m. MTrlLANIE SiscwoN- jointly with the Hirmingham and Midlancls Scctioiis of the ICoyal lnstitute of Cheniistry and the Society of Chemical Industry. “Analytical Aspects of Molecular Biology,” by I). G. Smyth H.Sc. Ph.1). Ixcturc ‘Theatre 1131 7 Ianchester College of Technology Covcntry ; 7 p.m. H N I ~ U E S GriouP Annual General Meeting followed by the the Retiring Chairman Dr. I,. Hrealey €+.Sc. I;. I<. L.C. Meeting lCoorn of the Chemical Society Hurlington HOUSC Picc:adilly Idondon w.l; 7 p.m. MTCAL Me-raoiis GROUP Iliscussion Meeting.Ijiscussion on “The Optimal Environment for hlicrochcmical Analysis” “The Feathers,” Tudor Street London E.C.4; 6.30 p.m. “Separate or Calculate,” by A. I,. Glenn E.Sc. H.Yharm. Ph. I). lT.l’.S. [Jniversity of Strathclyde Glasgow ; 5.30 p.m. ATOMIC-ABSORPTION SPECTROSCOPY GROUP Annual General Meeting. “ Atomic-fluorescence Spectroscopy,” by G* I. Goodfellow. Meeting LCoom o f the Chemical Society E3urlington House Piccadilly London will be opened by A. J. Cross t3.S~. SCOTTISH SIiCTION. w.1. THE SOCIETY FOR ANALYTICAX- CHEMISTRY Forthcoming Meetings October Thursday 21st EDINBURGH Thursday 2 1 st LONUON Friday 22nd CAMBRIDGE Tuesday 26th SHEFFIELI) Friday 29th LONDON November Tuesday 2nd HUDDERSFI ELU Wednesday loth LONDON SCOTTISH SECTION. “The Application of High-voltage Paper Electrophoresis to Some Analytical Problems with Special Reference to Carbohydrates,’> by 1).Gross B.Sc. Ph.D. Heriot-Watt College Edinburgh; 7.30 p.m. BIOLOGICAL METHODS GROUP Discussion Meeting. Discussion on “Use and Abuse of Statistics in Biological Assays” to be intro- “The Feathers,” Tudor Street London E.C.4; 6.30 p.m. ATOMIC-ABSORPTION SPECTROSCOPY GROIJP jointly 7~ith the Cambridge University Chemical Society. “An Introduction to Atomic-absorption Spectroscopy,” by W. J. Price B.Sc. F.K.I.C. “The Application of Atomic Absorption in the Study of Magnesium Metabolism in Man,” by L. Watson M.B. M.K.A.C.P. “The Use of Atomic-absorption Spectroscopy in British Non-ferrous Metals Research Association Laboratories,” by R. A. White. Cambridge University Department of Chemistry Lensfield Road Cambridge ; 8.30 p.m.NORTH OF ENGLAND SECTION and SPECIAL TECHNIQUES GROUP jointly witJz the Modern Methods of Analysis Group of the Sheffield Metallurgical Association on “The Determination of Oxygen in Steel.” “An Automatic Spectrographic Method for the Determination of Oxygen in Steel,” by M. S. W. Webb B.Pharm. F.P.S. F.R.I.C. and I<. J . Webb. “The Determination of Oxygen in Steels by the l 6 0 ( y n) 1 5 0 Reaction,, by C. A. Baker M.A. D.Phi1. “The Determination of Oxygen in Steels by measurement of the prompt y- Radiation emitted during deuteron bombardment,” by T. H. Pierce. Conference Room of the British Steel Castings Research Association 5 East Bank Road Sheffield 2; 7 p.m. MICROCHEMICAL METHODS GROTJP 21st Anniversary Celebration.Meeting on “Microchemistry-Past Present and Future.” Speakers Professor 1%. Belcher Ph.D. D.Sc. F.R.I.C. F.1iist.F.; C. Whalley B.Sc. F.R.I.C.; and Professor C. I,. Wilson Ph.D. D.Sc. F.R.I.C. F.I.C.T. Imperial College South Kensington London S.W.7; 4.30 p.m.; followed by Dinner at 7 p.m. for 7.30 p.m. duced by K. L. Smith M.P.S. NORTH OF ENGLAND SEc’rIoN jointly with the Huddersfield Section of the Royal Institute of Chemistry and the Huddersfield Region of the Society of Dyers and Colourists. “Colouring Matter in Food,” by J. B. Aldred M.A. F.K.I.C. Lecture Theatre (Catering Block) Huddersfield College of Technology AUTOMATIC METHODS GROUP Inaugural Meeting. Followed by an Ordinary Short Introductory Talk by H. E. Stagg. “Process Control with Gas Chromatography in Chemical Industry,” by H. Won-radiometric Instruments for Process Control in the Windscale n’uclear “Data Processing Systems Incorporating Automatic Analysis,’’ by C. W. “Some Applications of Radioisotopes in Chemical Analysis,” by J. K. Skrebow- Wellcome Building Euston €toad London N.W. 1 ; Inaugural Meeting 3 p.m. Continued inside back covey Huddersfield ; 7.30 p.m. Meeting of the SOCIETY on “Automatic Analysis.” Kienitz. Fuel Reprocessing Plant,” by C. K. McGowan. Munday . ski. and Society Meeting 3.15 p.m. PRINTED BY W. HEFFER & SONS LTD. CAMBRIDGE. ENGLAND.

ISSN:0037-9697    

DOI:10.1039/SA96502BX037

出版商:RSC    

年代:1965

数据来源: RSC

摘要:

October 1965 PROCEEDINGS OF THE SOCIETY Vol. 2 No. 10 FOR ANALYTICAL CHEMISTRY Reports of Meetings ORDINARY iClEETING AN Ordinary Meeting of the Societj. was held at 7 p.m. on Wednesday October Gth 1965 in the Meeting Room of the Chemical Society Rurlington House London lV.1. The Chair was taken by the President Dr. A. A. Smales O.B.E. F.R.I.C. A lecture on “Some Special Sensitive and Selective Reactions in Inorganic Trace Analysis” was given by Professor T. S. West Ph.D. D.Sc. F.R.I.C. NORTH OF ENGLA4ND ~ Z N D SCOTTISH SECTIONS JOINT Meeting of the North of England and Scottish Sections was held at 2.30 p,m. on Fridav September loth 1965 in the Central Hotel Carlisle. The Chair at the afternoon session was taken by the Chairman of the Scottish Section Mr. J. K. McLellan M A . B.Sc. F.K.I.C.The following papers were presented and discussed “The Use of Thin-layer Chromatography in the Pliarmaceutical Industry,” by J . S. IZ’ragg R.Sc. F.R.I.C. ; “Some Applications of Chromatography at the U.K.A.E.A. li’indscalc 1,aboratories” by D. M’. Ockenden K.Sc. P1i.L). The Chair at the evening session was taken by the Chairman of the North of England Section Dr. J. F. Clark &I.&. A.R.C.S. D.I.C. F.R.I.C. F.K.S.H. and the paper presented and discussed was “Combination of Gas Chromatography and Mass Spectrometry,” by IY. Kelly E.Sc. Ph.D. MIDTANDS SECTION .I JOINT Meeting of the Midlands Section of the Society and the Birmingham and Midlands Section of the Royal Institute of Chemistry wa5 held at 3 p.m. on Wednesdav September 15th 1965 at the Hills Lecture Theatre The University Birmingham 15.The subject of the meeting was “Thermometric Titrimetry (Enthalpimetry) .” The Chair at the afternoon session was taken by the Chairman of the Birmingham and Midlands Section Professor J. C. Robb R.Sc. Ph.L). I).Sc. F.R.I.C. The following papers ivere presented and discussed “Introduction to Thermometric Titrimetry,” by L. S. Bark K.Sc. F.K.I.C. ; “Thermodynamic Background and Possible -4pplication to Analytical Yroblems,” by H. J. V. Tyrrell K.Sc. M.A. P1i.D. ; “An Apparatu.; for Recording Thermo- metric Titration Curves,” by W. S. Sebborn B.Sc. A.R.I.C. The Chair at the evening session was talteri bv the Chairman of the Midlands Section Mr. W. T. Elwell F.EC.1.C. The following papers were presented and discussed “Develop- ment of an Automatic Titrator with IXgital Read-out,” by Y . J . Priestley R.Sc. and M. Smith; “Thermometric Titrations of Sorne Precipitation Reactions,” by R. J. N. Harries R.Sc. Dip.Ed. A.K.I.C. ; “Acetone as Solxwit in the Thermometric Titration of Acidic Substances,” by G. A. I’aughan F.R.T.C. 147

ISSN:0037-9697    

DOI:10.1039/SA9650200147

出版商:RSC    

年代:1965

数据来源: RSC

摘要:

148 SUGAR ANALYSIS lProc. SOC. Anal. Chem. Sugar Analysis The following are summaries of two papers presented at the Joint Meeting of the North of England and Midlands Sections held on March 30th 1965 and reported in the May 1965 issue of Proceedings (p. 71). The Analysis of Sugar Mixtures and Some Problems Encountered BY R. BUTLER (James Pascall Stveatham Road Mitcham Suvvey) IN defining ‘‘sugar mixtures” reviewed in his paper Mr. Rutler listed raw materials (sugar glucose syrup and invert sugar; as single ingredients in mixtures or with other substances such as milk) end-products (e.g. boiled sweets caramels fondants jam centres and marsh- mallows) and effluent. He referred to moisture content as an important figure in control analysis and owing to the need for various techniques to be employed depending on the nature of the material being examined the results obtained were not necessarily an indication of the “true moisture content.” They should be regarded simply as the results obtained by subjecting the samples to a standard set of conditions.Mr. Butler continued by discussing direct drying both in air and in vacuum drying after dispersal on a support medium (sand or Celite) refractometric measurement and the use of the semi-automatic Karl Fischer method. He claimed that the latter method gave reproducible results at the usual level of 1.5 to 3-5 per cent. and had been used down to levels of 0.3 per cent. Reliability was better than that obtained by the specific gravity refractive index or infra red techniques. Turning from the low levels of moisture in mixtures to a consideration of low levels of solids Mr.Butler referred to the routine examination of effluent. In addition to the need for ensuring compliance with the requirements of the local Rivers Board it was a matter of economic importance to ascertain the rate at which valuable raw materials were going “down the drain.” Although not an official method satisfactory results were obtained by hydrolys- ing an aliquot of the effluent and determining the total carbohydrates by a semi-micro Lane - Eynon titration with Fehling’s Solution. This method had been accepted by the Rivers Hoard concerned and was found to be accurate at levels up to 1000 p.p.m. Sugar was examined for traces of invert sugar as this had an effect on the colour texture and keeping qualities of many confectionery products.The invert sugar could be determined colorimetrically by digestion with methylene blue in an alkaline medium or by titration with EDTA using murexide as an internal indicator. One important characteristic of both glucose syrup and mixtures containing it was the development of a yellow colour on heating. This was measured by heating a sample,under strictly-controlled conditions and determining the colour of the resultant candy with a tintometer or a spectrophotometer. Research into the causes of this colour was being conducted and the presence of short-chain amino-acids sulphur dioxide and trace metals (copper iron zinc and possibly magnesium and molybdenum) appeared to be significant factors. Mixtures of sugar glucose syrup and invert sugar used as ingredients could be resolved by the determination of total reducing sugars before and after inversion by a Lane - Eynon titration and of invert sugar by the Luff-Schoorl method.Roiled sweets were examined by the same methods as were all other products after defecation. Techniques involving specific gravity refractive index and polarimetry could be employed in certain instances but owing to the need to apply various corrections dependent on assumed approximate compositions these methods were not entirely suitable. With the increasing use in confectionery of glucose syrups of different conversions the standard methods had been found unreliable unless the identity of the syrup was known. This could not be the case when a competitor’s product was being examined and new tech- niques such as paper thin-layer and carbon-column chromatography were required.These methods were either qualitative only or time-consuming and even these could not be used to distinguish between the dextrose present in glucose syrup and dextrose monohydrate as an additional ingredient. October 19661 SUGAR ANALYSIS 149 The Application of Modern Techniques to Special Problems in Sugar Analysis BY D. GROSS (Reseavch Labovatovy Tate G. Lyle Hefinevies Ltd Keston Kent) DK. GROSS pointed out that the main problems in sugar analysis were presented by products at the extreme ends of the purity scale. Those approaching 100 per cent. puritssuch as sucrose of reagent grade and those a t the other end of the scale such as molasses with up to 40 per cent. impurities had to be analysed in different ways. It was generally accepted that the determination of trace impurities in pure sugar products and the estimation of total sugars in impure products gave the most useful information on the composition and quality of the product.Although conventional procedures (H. C. S. de Whalley I.C.U.M.S.A. Methods of Sugar Analysis Elsevier Publishing Co. Amsterdam 1964) were perfectly adequate for the determination of total sugars (sucrose and invert sugar) and total ash more specific and selective methods were required for detection and determination of trace or rare components of both organic and inorganic nature. The last 16 years had seen an increasing adaptation and use in the sugar industry of modern separation techniques such as paper and thin-layer chromatography paper electro- phoresis and of ion-exchange and enzymic methods for the purpose of detecting and deter- mining carbohydrate compounds at extremely low concentration-levels e.g.0.002 per cent ~ (I). Gross Frances J. Gardiner and K. W. Butters Ifit. Sugar J. 1962 64 69.) It was thus possible to detect traces of other sugars in the sucrose used for fundamental polarimetric measurements and the necessary corrections could be applied for optically-active impurities present. The development and application of high-voltage paper electrophoresis (U. Gross Lab. Practice 1961 10 622) in the lecturer’s laboratory had materially helped in the analysis of such diverse groups of compounds in sugar products as rare sugars amino-acids amines volatile fatty acids non-volatile carboxylic acids polyhydric alcohols alkali and alkaline- earth metals and inorganic acids.I t had been possible to use electrophoresis in conjunction with paper and column chromatography to investigate the occurrence in varying concentra- tions of raffinose and stachyose in beet-sugar products and later (Gross Gardiner and Butters idem,) surprisingly also in cane-sugar products of reducing sugars other than glucose and fructose e.g. mpsicose or allulose of galactinol planteose and an entirely new family of isomeric trisaccharides the kestoses compounds synthesised by the action of yeast or mould invertase on sucrose. As a result a chromatographic test for raffinose had been officially adopted and was used in the sugar industry all over the world. A similar test had been proposed for 6-kestose and 1-kestose although 1-kestose had to be separated electro- plroretically from neo-kestose before the determination could be carried out.The concentra- tion of raffinose and kestoses in molasses could be as high as 7 per cent. the kestoses accounting for more than half of this figure. The speaker went on to say that another problem was that of the heat-degradation pro- ducts some of which were reducing but not fermentable and consequently were liable to be de- termined as invert sugar by conventional analysis. Research into these compounds and others produced by the mild acid-hydrolysis of sucrose revealed a multitude of mostly-unknown compounds although some were identified as anhydrides of monosaccharides such as the di-fructose dianhydrides the diheterolevulosans and colour precursors such as 5-hydroxy- methylfurfural. The determination of sugar colour apart from optical density and visual comparison measurements had up till now been the toughest problem.It had not been possible to adapt conventional analysis techniques to this task chromatographic procedures having been tried in the past without complete success and these had given ambiguous results. It now looked as if a combination of gel-filtration with Sephadex columns and high- voltage paper electrophoresis particularly in borate buffer might provide a break-through in this notoriously difficult field. Separation by methods involving molecular size and elec- trical mobility was the first step in disentangling the complex mixture of coloured com- pounds which ranged in hue from dark brown to bright yellow. When separation had been achieved a qualitative and later perhaps a quantitative assessment of the composition of the colour in sugar products could then be made.Some progress in this direction had already been made and this was illustrated by some colour slides. 150 INFRARED SPECTROSCOPY [Proc. Soc. Awal. Chzem. Of the enzymic methods that had been used in sugar analysis the invertase method took precedence. The enzymic hydrolysis of sucrose to glucose and fructose before the deter- mination of invert sugar by either polarimetric or chemical (copper-reduction) methods was often preferred to that with hydrochloric acid on account of its mildness. If the sugar product contained raffinose a second hydrolysis with melibiase an enzyme converting meli- biose to glucose and galactose had to follow. This was best done on a second aliquot with a mixture of invcrtase and melibiase obtained from bottom yeast.This mixture converted all sucrose and rafinose to fructose glucose and galactose. By this method 3 polarimetric readings before and after partial and complete hydrolysis enabled the sucrose and raffinose contents to be calculated. This was the elegant Paine and Ralch method which had been officially adopted for molasses but which was not suitable for raffinose concentrations below 0.5 per cent. Another enzymic method which had tentatively been taken into use recently was the glucose oxidase method. The enzyme specific for D-glucose was also known as notatin penatin and glucose dehydrogenase. As in the bromine oxidation glucose was converted to the delta-lactone of gluconic acid directly liberated hydrogen combining with dissolved oxygen to give hydrogen peroxide.Horse-radish peroxidase was added to a suitable reagent an oxygen acceptor such as o-toluidine anisidine or di-anisidine ; the enzyme’s action was to decompose hydrogen peroxide and the liberated oxygen was determined colorimetrically. The titration of gluconic acid after opening the lactone ring constituted an alternative pro- cedure. The method was extremely useful in that it could give accurate figures for the proportion of fructose and glucose in invert sugar. These had been difficult to obtain up till now necessitating somewhat lengthy chromatographic procedures. A complication might arise owing to the presence of traces of invertase or maltase or both in glucose oxidase which affected the accuracy of analysis of sugar and glucose products; it had been reported that maltase activity could be suppressed by the addition of “Tris” (2-amino-2-hydroxymethyl-propane-l 3 diol) . Finally with regard to the determination of moisture in sugar products by the Karl Fischer method which Mr. Butler the previous speaker had mentioned an improved pro- cedure in the lecturer’s laboratory had made it possible to make reliable determinations of the moisture content down to a level of 0.002 per cent. and the moisture included in the crystal itself by dissolution in forrnamide under rigorously standardised conditions. Laevulose could be determined after the oxidation of glucose.

ISSN:0037-9697    

DOI:10.1039/SA9650200148

出版商:RSC    

年代:1965

数据来源: RSC

摘要:

150 INFRARED SPECTROSCOPY [Proc. Soc. Awal. Chzem. Infrared Spectroscopy The following are summaries of papers presented at the Joint Meeting of the Micro- chemical Methods and Special Techniques Groups held on April 9th and loth 1965 and reported in the June 1965 issue of Proceediwgs (p. 83). Some Advances and Trends in Infrared Spectroscopy 13Y r). 14. w. .kNDERSON (Department of Chemistvy Univevsity of Edidmvgh) DR. A;vu~riso;v said that modern infrared spectroscopy offered great scope as a microchemical method of analysis. In the belief that a joint meeting of this type could reasonably be expected to attract both novices and experts he began by outlining very briefly the basic analytical t echni (1 ues involved. He considered that the most interesting of the recent developments in analytical infrared- spectroscopy had been (a) the exploitation of new applications and techniques which had resulted from the introduction of attenuated total reflectance ( b ) the development of special cells and auxiliary instrumentation together with refinements in handling techniclues which had achieved increased sensitivity and (c) the realisation by inorganic chemists that the application of infrared spectroscopy was not by any means limittd to organic systems.Since each of these major advances was to be covered adequately by the other speakers Dr. Ander- son said that his object was to avoid any possible duplication and that he would therefore give an account of some of the other developments made recently in instrumentation tech- niques and applications. October 19651 INFRARED SPECTROSCOPY 151 With regard to instruments he considered that the near future would see the introduc- tion of more specialised spectrometers in contrast to the flexible general-purpose instruments currently marketed.This trend had already begun in the United States of America where older spectrometers due €or replacement were being “upgraded” and modified to perform some limited specific analytical function. Rapid-scan instruments which were capable of producing a complete spectrum in 16 seconds had been developed for examining fractions eluted from gas - liquid chromatography columns. The same trend could be expected to result in the production of much cheaper spectrometers than were currently available. Such instruments could not be expected to match the generally high specification of current models but they could nevertheless prove to be adequate for basic instructional purposes and for answering many of the routine and frequently simple questions such as whether a carbonyl group was present or whether compounds A and R were identical.Questions oi this nature currently engaged wastefully the operating-time of an expensive top-grade instrument. Dr. Anderson suggested that in the future spectrometers would be used in the same numbers as balances; the average laboratory used “rough” balances weighing to the nearest gram as well as micro-balances and balances weighing to the fourth place oi decimals. A t present 2 grades of spectrometer were available the E3000 to F5000 grade and the El400 to @000 grade; an instrument in the FGiOO to &SO0 range was now overdue.With regard to cells specialised designs continued to be published regularly and it was essential that this be maintained as difficult and new analyses which would require improvisa- tion or modification to an existing technique would continuc to arise. The introduction of the “Irtran” range of optical glasses had greatly facilitated work with vapour-phase and aqueous systems although their high cost at present limited the extent to which they could be used. Considering some of the more conventional methods of sample preparation the speaker suggested that operators had now to be prepared to depart from the basic methods of pre- paring mulls and discs when faced with difficult substances; the literature contained many descriptions of novel useful methods. Thus the replacement in the pressed-disc technique of potassium bromide by polyethylene could be of advantage and the examination of aqueous solutions could often be simplified by the use of polyethylene foil windows solvent extraction with liquid resins or silver chloride discs.The use of matched thickness “Millipore” filters could simplify many sampling and sample-preparation difficulties and this new technique could be expected to become widely used. Infrared spectroscopy offered a valuable auxiliary service to gas chromatography and this application was now being extended to thin-layer chromatography. Ilr. Anderson stressed the need for spectroscopic verification of chromatographic evidence in basic research on uncharacterised systems. The lecturer concluded by making brief reference to the advantages of using polarised radiation and of investigating spectra in the “near” or “far” regions.Use of the far infrared region had increased in recent years and the “polythene-enrichment” technique that had heen proposed recently was worthy of note. The Study of Chelate Compounds by Infrared Spectroscopy* BY ROBERT J. MAGEE (Defiavtment of Cheunistvy Queefl’s Uvzivevsity Belfast) T h . MAGEE said that the modern analyst had at his disposal a wide range of techniques by which a material could be satisfactorily analysed. However most of thcse techniques gave no indication of the form in which elements were bound in the material. Infrared spectroscopy was one of the few techniques by which this information could be obtained. As opposed to the field of inorganic compounds this feature had long been recognised with organic compounds and infrared spectroscopy had become well established in this field.The application of infrared methods to inorganic materials was made difficult by problems created by the use of solutions. With inorganic compounds and particularly inorganic corriplexes it was not possible to select a suitable solvent. Water the usual solvent for * I>r. Magee presented a similar paper under the title “Inorganic Applications of lnirared Spcctroscopy” at t h e Joint Meeting of the North o f England and Midlands Sections on April Bth 1965 as reported in t h e May 1965 issuc o i Pvoceedings (p. 71). 152 INFRAREL SPECTROSCOPY [PTOC. SOC. A%aE. Chsptz. inorganic compounds absorbed very strongly in the infrared and most non-polar liquids were poor solvents.Some salts were soluble in partially-chlorinated solvents e.g. methylene chloride but interaction between solvent and solute was often considerable. Covalent inorganic compounds might be studied in solution but it was necessary to chose a solvent whose spectrum did not interfere with that of the solute molecule. Because of these clif7ii- culties most inorganic compounds were examined in the solid state. Much of the early work on solids usually by means of reflectance spectra had been carried out on single crystals or sections but this technique was not particularly suitable for routine work. Absorption spectra might also be recorded for very thin films or sheets hut considerable difficulty was encountered in the preparation of thin sheets as many substances could not be sliced thinly enough to be transparent to infrared radiation.In some instances sublimed thin films had been used. The impact of these techniques had been very small in the inorganic field. Apart from these minor techniques there were 3 principal methods-the powder method the mull technique and the pre d-disc method-for the preparation of inorganic materials. In all these methods a layer of randomly-orientated small particles was placed in the beam of the spectrophotometer - Dr. Magee said that for the study of inorganic substances it was useful to have an instru- ment capable of use down to about 250 cm-l. The infrared spectra of inorganic substances tended to be broad but both in the pressed-disc method and the mull technique the spectra could be made much sharper by cooling the sample.Infrared spectroscopy was very useful for investigations on cis - trans isomerism metal - ligand site attachment and in the determination of bond types in complex molecules. The lecturer then referred to structural isomerism giving the isomerism of nitropwt- ammine cobalt(m) [C”O(NH,),XO,]~++ and nitritopentarnmine cobalt(IrI) j Co(NH,),ONO j2+> as an example. By analogy with the colours of compounds known to contain M-0 or M N links the stable yellow-brown form had been considered to have a Co-N link while the unstable red form was considered to have a Co-0 link. This liad been verified by an infrared technique the growth of peaks a t 1430 1315 and 825 cm-l and the lessening of the ahsosp- tions at 1460 and 1065cm-3 being observed as a freshly prepared red nitritopentammine cobalt(rI1) chloride sample aged.Eventually the peaks at 1460 and 1065 cm-I had dis- appeared and the spectrum had become that of the yellow-brown nitropentammine cobalt (m) chloride. In chelates involving thiourea and urea as ligands it was important to know whether there were metal - nitrogen bonds or for urea metal - oxygen bonds. To investigate a metal - urea chelate the infrared spectra of the complexes were compared with that for frce urea. It had been concluded that strong bands at 1603 and 1683 cm-1 were caused by C - - 0 stretching and symmetrical NH bending. The urea molecule was probably a resonance hybrid of the following structures- NH +NH - / / 0 - c c” 0-c a NH ‘“Fig NH - / \ 0 .- c +NH If co-ordination involved M-’N bonds the electron demand by nitrogen ought to be increascd a tendency to block the above resonance would be noticed.Both these effects tended tcr raise the C=O stretching frequency. The NH stretching region ought consequently to have bands in the frequency range for free amido groups with some absorption several hundred wave numbers lower caused by the bound NH group. As a result of the blocking of resonance the CN stretching frequencies should be lowered. Thus the spectrum ought to differ signi- ficantly from that of urea and the effects outlined had been observed in platinum(I1) - and palladium(i1) - urea complexes. If the co-ordination involved M - 0 bonds however the spectrum ought to differ little from that of urea as these had no great effect on the NH stretching frequencies. The C=-O absorption ought to shift to lower frequencies owing to enhancement of resonance and this occurred in chromium(irI) iron(IIr) zinc(11) and copper(iz) chelates.Where a group M-H formed a hydrogen bond there was a great change in the strength of the M-H bond which was reflected in the vibrational frequency of that bond. When a group Qctober 19651 TNFKARED SPECTROSCOPY 153 was hydrogen-bonded its frequency of absorption was lowered considerably. The lecturer illustrated this by referring to the nickel - dimethylglyximate complex in which the OW stretching usually found near 3100 cm-l was shifted to much lower frequencies. Dr. Magee next spoke about infrared methods in inorganic analysis. He said that the application of infrared techniques to the analysis of inorganic material was not widespread the mull and powder methods having been used in a limited way.There was evidence that these techniques were not ideal for the quantitative analysis of inorganic substances and they were consequently mainly used qualitatively. The pressed-disc method was suitable for quantitative work and seemed more promising analytically. An interesting application of the infrared technique had been the quantitative analysis of condensed phosphates with the pressed-disc method. Commercial sodium triphosphate was often contaminated with small amounts of sodium pyrophosphate and sodium tri- metaphosphate. Each constituent was determined with an accuracy of within &0.5 per cent. and this compared favourably with X-ray and chemical methods. A novel approach which permitted the application of infrared methods to samples present in aqueous solution was that of combining the potassium bromide disc technique with freeze-drying.This method had been applied to the determination of traces of sulphate and was satisfactorily accurate at this level Potassium bromide was added to the solutions before freeze-drving and the residue obtained from the freeze-drying tubes was finely divided and pressed into discs. The method was slow because of the freeze-drying but this could be carried out overnight. The same technique had also been applied to the determination of small amounts af sulpfiate nitrate and nitrite in water samples and chlorate in the presence of other oxy- halogen anions. Another approach which had been applied to the analysis of a wide range of inorganic substances was that of incorporating ionically-bonded inorganic material into a covalent- bonded complex stronger and sharper absorption bands being obtained ; in conjunction with the potassium bromide disc technique qualitative and quantitative analysis could be pcr- formed.This technique had been used to identify I4 polyatomic anions all of which formed compounds of the type (phenyl) AsX X being the anion after reaction with tetraplrenyl arsonium chloride. The precipitated compound was made into a disc with potassium bromide and examined on the infrared spectrometer characteristic bands attributable to metal or non-metal to oxygen stretching frequencies for the polyatomic anions being obtained. The reagent itself exhibited a relatively simple infrared spectrum with few strong absorption bonds none of which interfered.‘The same reagent had been used for the quantitative determination of rhenium and technetium and for the determination of perchlorate in sea water. With 8-hydroxyquinoline reagent and the potassium bromide technique it had been found that characteristic bands occurred in the spectrum of the aluminium gallium and zinc complexes that were suitable for the quantitative determination of the three elements. The complexes of niobium tantalum and associated metals had been examined in the infrared region and a method for the determination of niobium and tantalium had been developed and applied to the determination of both elements in steel. The complexes of molybdenum vanadium and tungsten had been used for quantitative determination of these three elements singly or in pairs with an error of about 3 per cent.For the detection and determination of anions the reagent nitron had been found suitable it being possible to detect 13 anions singly or in admixture including amongst others ferro- cyanide ferricyanide nitrate and nitrite. The Infrared Spectra of Small Samples RY H. A. WILLIS ( 1 mfevial Chemical I.lzd.ustvies Ltd. Plastics Division Welwyn Garden Cit,? Elevts.) MR. WILLIS said that a sample of about 10 mg of solid liquid or gas could be easily handled in the infrared spectrometer. In many instances unfortunately this sample size was far too large especially when chromatographic separation methods were used and the spectroscopist was continually being asked to deal with samples of one tenth one hundredth or even one thousandth of this size. 154 INFIiARED SPECTROSCOPY [€>roc.SOC. Anal. Chem. A simple calculation based on the size of the spectrometer beam and the sample thick- ness required to obtain a reasonably intense spectrum showed that if the sample could be efficiently transferred to the instrument about 100 pg of material would suffice for a satis- factory measurement without necessitating significant modification to the spectrometer. If reasonable allowance was made for losses on transfer of the sample there should be no great difficulty in handling 500 pg of rnaterial in the conventional spectrometer. A lead washer could be used to reduce the aperture of a halide disc press permitting discs of about 2 x 7 mm to be prepared. These were left in the lead washer which acted as a holder and stray-radiation screen in the spectro- meter.For gaseous samples the most satisfactory cell wa3 a rectangular-section light pipe. For most commercial spectrometers cross-sectional dimensions of 4 x 10 mm were suitable with a cell having a path-length of 10 cm. T t was found in practice that ;I simple glass tube formed an effective light pipe and it was not necessary to apply a metallic coating to the walls to increase reflectivity. Small liquid samples presented the greatest difficulty mainly because of the substantial losses that occurred on transferring the sample to the absorption cell. Commercially avail- able microcells were probably best for these samples but it was as well to use a moderately thick cell (about 0.25 mm) and to handle liquid samples in solution as transfer losses could then be reduced.Experience with these micro methods in which the conventional spectrometer was used would soon reveal that micro work required substantial effort in sample preparation ; with small samples the risk of contamination was greatly increased. Stringent precautions had to be taken to exclude air from gaseous samples water from liquid samples and grease or inorganic impurities from solids. Since traces of impurity in air were often lost in the collecting process it might be pre- ferable to collect the air with the sample in a multi-reflecting gas cell. The efficiency of such cells (path lengthlunit volume) was much the same as that of the light-pipe gas cell hut with a cell specially designed to match a particular spectrometer it was possible to obtain a good spectrum from a sample diluted one hundred or even one thousand times with air.This method of treating a sample was however confined to those samples in which the diluent did not absorb in the 2.5 to 15 p region and generally methods of separating the sample from extraneous material were required. Of these the most satisfactory for liquids and gases was probably vapour-phase chromatography and several traps and much associated equipment had been described for collecting fractions from a column and transferring these to an infrared spectrometer. A particular instance that had received much attention was the identification of thin surface layers on a substrate "g. coatings on metal surfaces or synthetic films sut:h as regenerated cellulose polythene or polypropylene. These might have very thin coatings to reduce water-vapour permeability or to impart anti-static properties or ink adhesion.The attenuated total reflection method particularly the multi-reflection method was very valuable for coatings on metal surfaces but was of little use for coatings on organic films wl-1er.e attenuation of the radiation beam by the substrate outweighed the attenuation produced by the surface layer. In these instances the speaker had found the surface-scraping method originally suggested by Johnson to he very reliable. Surface layers of only 500 A thickness could be easily examined by this method. When a sample was too small to make a layer of adequate thickness and still cover a large enough area of the spectrometer beam modifications to the instrument were necessary. A method frequently advocated was to reduce the beam area at the sample position by using a beam condenser.Although some form of optical beam condenser had been in existence for perhaps 20 years the device had never become very popular. The common form of reflecting condenser was optically inefficient and the micro focus formed at the sample position unless careful attention was paid to optical alignment was of such poor quality that any advantage of beam condensation was outweighed by radiation losses. The most satisfactory condenser that would achieve a magnification of about x6 was probably the double off-axis ellipsoid system. All beam condensers however concentrated thermal radiation on a small sample and this raised a serious problem since the sample might decompose or evaporate. The very The simplest samples to handle were solids.These separation methods were not suitable for relatively involatile solids. October 18661 INFRAKEL) SPECTROSCOPY 155 large aperture necessary to obtain a microfocus made this method fundamentally unsuitable for use with small volumes of gas. Thus the beam condenser was largely restricted to work with small solid specimeiis. A more promising approach for most samples was to leave the optical system alone and to concentrate on the methods of increasing the apparent intensity of weak absorption bands. Ordinate-scale expansion by either mechanical or electronic methods was often satis- factory and the signal-to-noise ratio of most commercial instruments would permit ordinate expansion of up to 10 times with a sample of average optical quality. To obtain greater expansion of a weak spectrum the time-averaging computer seemed to hold considerable promise.In this method the spectrum of the sample was measured a large number of times and the ordinates of successive spectra were added together. Because noise was randomly negative or positive it was effectively cancelled by summation while the true signal built up. Although several hours running time might be necessary to build up a weak spectrum involving the summation of one hundred or more separate runs apparatus was commercially available by which this might be done automatically and no attention was required after the apparatus had been set up to record a particular sample. Infrared Spectra of Inorganic Materials BY I). F. EVANS (Impevial College of Scievzce and Technology South Kensivzgtoa I.ondon S .W.7.) DR. EVANS said that although infrared spectroscopy had been extensively used in inorganic chemistry specific applications to analysis were comparatively rare. One difficulty en- countered in the infrared spectra of inorganic compounds was that very often only solid samples could be studied. For a fairly simple isolated molecule or ion the number of infrared or liaman-active vibrations could be derived from the symmetry oi the molecule or ion as given by its point group and the selection rules for infrared and Iiaman radiation. For a crystalline solid however one ought strictly to consider the site symmetry i.e. the symmetry of the environment around the centre of gravity of the molecule in the unit cell and this might well be less than the symmetry of the isolated molecule.For example the isolated planar carbonate ion (D,h point group) had 4 vibrational frequencies of which vl the totally sym- metric stretch was infrared jnactive. In the calcite lattice the site symmetry was D3 while in aragonite the site symmetry was only C,. Theoretically calcite ought to show the three expected vibrational frequencies in the infrared while in aragonite v1 ought to become infrared active and v3 and v4 ought to split. The lecturer said that this was in fact observed. Unresolved splittings of this kind and also vi hrational coupling with lattice modes were two factors that contributed to the large breadth often found in the infrared bands of inorganic solids. Infrared spectroscopy had been used to determine the carbonate content of phosphate minerals and from the observed spectra it had been concluded that the carbonate ions were not present in the form of calcite or aragonite but were in solid solution replacing phosphate ions in the crystal lattice (W.M. Tuddenham and K. J . P. Lyon A.tzaZ. Chew. 1960 32 1630). A number of other applications of infrared spectroscopy to the analysis of minerals had been reported. However in view of the complicated structures of many minerals much of this work had necessarily been purely empirical. In a compound with the empirical formula A (H20)n the hydrogenic species present might be H,O (latticed or co-ordinated) OH- or M-OH H,O+ and (probably) H,O,+ and H,04+ (R. 11. Gillard and G. Wilkinson J . Chew. SOC. 1964 1640). In a true hydrate the symmetric and asymmetric 0-H stretches occurred at approxi- mately 3300 cm-l (although this value was very dependent upon the degree of hydrogen bonding) and the €I-0-H bend occurred at 1600 to 1630 cm-1.These assignments could be readily checked by deuteration both frequencies being reduced by a factor of approximately 2-:. In co-ordination hydrates of the type M(OH,), there were also frequencies which involved the motion of the water molecule relative to the central atom M. Deuteration studies were also very useful since the M-OH stretch would be little affected whereas the Infrared spectroscopy had been very useful in structural studies of hydrates. 156 INFRARED SPECTROSCOPY [Proc. SOC. Anal. Chem wagging and rocking vibrations which involved predominantly hydrogen motions would be considerably reduced in frequency.In compounds such as K,[Sn(OH),] containing the M-OH grouping the 0-H stretch would again occur a t approximately 3300 cm-l but there would be no band at approximately 1600 cm-l. This band was replaced by an MO-H deformation (which might be quite weak) at approximately 1000 cm-l. The H,O+- ion was isoelectronic with NH and had 4 fundamental vibrations all active in the infrared- v1 VZ v3 v4 m3200 cm-1 -1 100 cm-1 -2600 cm-1 -1700 cm-1 S y mine trical Symmetrical Asymmetrical Asymm etrical stretch bend stretch bend The H,O* ion occurred in hydrates of strong acids such as H,O+.Cl- H,0+.C104- and H,0+.NQ3- and also chloromolybdic acid Mo,Cl1,.2HCl.2H,O which from its infrared spectrum ought to be formulated as (H,O),+(Mo,Cl,)Cl,. The detection of an 0-H or N-H stretching frequency could obviously be used as an analytical technique.An exarnplc of this was given by the compound originally formulated as K,[Os(NO,),j on the basis of the analytical figures. However the infrared spectrum showed a strong hand at 3240 cm-l and a weaker one at 970 cm-l. Hence it ought to be formulated as IS,[ Os(N0) (OH)(N0,)4J> which only differed from the above structure by one hydrogen atom. The characterisation of an 0-H or N-H stretching frequency was usually straightforward but diffrculties could occur with compourids containing very strong hydrogen bonds. For example in anhydrous cyanide acids of the type H,Pt(CN), HAu(CN) and H,Co(CN), the N-H stretch occurred not at about 3000 cm-l but as an extremely broad and intense band centered at about 1000 cm-l. It had been concluded that symmetrical N-H-N hydrogen bonds were present in these compounds.Similar spectra had been observed in substances such as potassium hydrogen diaeetate where there was X-ray and neutron diffraction evidence for symmetrical 0-H-0 hydrogen bonds. The author concluded by saying that the far infrared region (below approximatcly 400 cm-l) had recently attracted considerable attention especially since commercial instru- ments were now available with low-frequency limits of 50 cm-l or lower. It was not clear how useful the far infrared region would be for analytical purposes. However in structural studies an important application had been the location of metal - ligand stretching fre- quencies involving comparatively heavy ligands. In compounds of the general formula MXmLn where L was a ligand such as pyridine assignments could be made by making the reasonable assumption that if X were l-tr instead of C1 the metal - ligand vibrations would not be appreciably altered (13.J . H. Clark and L. S. Williams IYLOY~. Chem. 1965 4,351.) The Application af Long-path (4091) Gas Cells to the Analysis of Atmospheric Pollution BY L. C. THOMAS ~ M i ~ i ~ ~ ~ y of Defence Chemical Defence Exfieuimental Establishment Povton. I)ozon Salisbuvy Wiltsf MR. THOMAS said that the long-path cells used in this work were a matched pair of Perkin Elmer Model 198 multi-reflection cells. The optical design was based on that of White and permitted the absorption path to be varied from 4 to 40 metres in steps of 4 metres. The cells were normally used at their maximum path of 40 metres.They were fitted to a Perkin Elmer Model 21 spectrophatometer which was equipped with electronic ordinate-scale expan- sion with multiplication factors of up to twenty. Use of the full multiplication factor for low absorbances was equivalent to an absorption path of 800 metres. The cells were fitted to a sample-handling and evacuation system constructed in 1-inch diameter copper pipe which enabled the cells to be filled and emptied either together or October 19651 INFRARED SPECTROSCOPY 157 independently. A vacuum of better than 0.1 mm of mercury was readily attained and this was adequate for the work. For the measurement of extinction coefficients a dynamic-flow system was used to avoid adsorption losses in the cells. A constant gas concentration was set up and this was passed through the cell until constant absorbance was recorded by the spectrometer.The effluent concentration was then estimated chemically. For field samples whose volume was too limited to allow a dynamic system to be used the cells had to be calibrated. This was achieved either by collecting and re-introducing samples from the dynamic calibration or by introducing small known volumes of gas into the cell. A convenient method of doing the latter was by the use of a gas-chromatograph gas-sampling valve. With such a valve gas volumes of 0.25 1 5 and 25 ml could be introduced. After raising the pressure to 760 mm of mercury with nitrogen this resulted in nominal concentrations of 5 20 100 and 500 p.p.m. by volume. Lower concentrations were prepared by successively halving the pressure in the sample cell by sharing the contents of this cell between the identical sample and reference cells raising the pressure in the sample cell to 760 mm of mercury with nitrogen and re- evacuating the reference cell.This was the method used to determine the minimum detect- able concentration of a gas. Atmospheric samples were collected with a battery-operated diaphragm-pump which was used to inflate a plastic sample bag. This bag was made from a laminate consisting of four layers polyester aluminium foil poly(viny1idene chloride) and polyethylene with a total thickness of 0.005 to 0.006 inch. This laminate had a very low permeability and con- centration variations in 24 hours were within the experimental errors of the measuremcnts. Before use these hags had to be purged with nitrogen to remove any volatile constituents from the plastics.The spectrum of nitrogen from an unpurged bag had shown the presence of ethyl methyl ketone acetone P-xylene 1,1 1-trichloroethane and an unidentified constituent absorbing at 11.55 p. Mr. Thomas continued by saying that qualitative analysis presented some problems. Absorption bands arising from atmospheric water vapour masked a wide region of the spec- trum. Although i t was possible to compensate for this absorption by introducing an equal amount of water vapour into the reference cell it would be preferable to remove the water if this could be done without also removing other components. Even after compensating for the water it was often difficult to identify the bands which could then be detected. This was due to the lack of adequate data on gas-phase absorption spectra the only readily access- ible collection being that of Pierson et al.(Aaal. Chem. 1956 28 1218). The early stages of this work had been concentrated on the measurement of the extinction coefficients and the minimum-detectable concentrations of those compounds reported as liable to be present in the atmosphere at concentrations of 0-1 p.p.m. or above. Samples of exhaust fumes from both diesel and petrol engines had been examined to indicate which compounds were likely to be found in the spectra of traffic atmospheres. An air sample taken in traffic had been shown to contain 31 p.p.m. of methane 4p.p.m. of acetylene 20 p.p.m. of propene 18 p.p.m. of butadiene 21 p.p.m. of isobutylene 36 p.p.m. of saturated hydrocarbons (calculated as hexane) 0.4 p.p.m.of nitrogen dioxide and 72 p.pm. of carbon monoxide. Some difficulties had been encountered during his work as a result of reactions occurring between samples and gas apparently adsorbed on the cell surfaces. A sample of pure hydrochloric acid vapour had been found to contain nitric acid formic acid water carbon dioxide and hydrocyanic acid in addition to hydro- chloric acid. Similarly the spectrum of a sample of ethylene oxide had shown the pro- gressive devdopment with time of absorption bands due to 2-chloroethanol as a result of reaction between the ethylene oxide and hydrochloric acid still adsorbed on the cell surfaces after repeated evacuation. To date these undesirable syntheses had only been found to occur after high concentrations of gas had been examined in the cell.Finally the lecturer gave a word of caution. 168 INFRAREI) SPECTROSCOPY IPYOC. SOC. A.tzal. Chem. Infrared Analysis by Attenuated Total Reflectance BY N. A. PUTTNAM (Colgate-Palmoliiie Lld. Manchestev 6) Tln. PUTTNAM said that in tlie past infrared analyses had been carried out by transmission since in general reflection spectra were weak and lacked detail. The recent introduction of the method of attenuated total reflectance (A .T.R.) which was a special reflection technique developed simultaneously by Fahrenfort S$ectmchiwz A cia 1961 17 698) and Harrick (Plzys. Rev. Lett. 1960 4 224) had greatly reduced these disadvantages. Since A.T.R. depended upon attenuation of the reflected radiation at an interface between the sample and an analys- ing crystal of higher refractive index it was essentially independent of sample thickness.Hence it was possible by A.T.R. to obtain high-contrast spectra from bulk samples which were equivalent to those obtained by transmission through thin films. For this reason ,4.T.R. was preferable for samples that were not suitable for preparation as thin films e.g. polymers or were only characteristic as thick layers. Since it was a surface technique it was also ideally suited for the examination of samples which were only available on a non-transparent support e.g. lacquers. Amplification of weak absorptions was made possible by multi- reflection where the surface was sampled many times. Samples containing suspended matter such as dispersed solids or emulsions that produced high backgrounds in transmission spectra due to scatter also gave better results by A.T.R.Advantage could also be taken of using bulk samples to obtain spectra which were equivalent to those obtained by transmission through thin films for samples that showed very strong absorptions e.g. aqueous solutions. Such a technique eliminated the difficulties encountered in filling and cleaning short-path- length cells and the troublesome interference patterns found with such cells. For aqueous solutions there was no need to compensate for the very strong solvent-absorptions. In theory there was a unique A.T.K. spectrum for each angle of incidence and the inten- sity of absorptions increased as the angle of incidence approached the critical angle. The thickness of the sample could also in the case of solid samples influence the resulting A.T.R.spectrum. For each type of sample i t was necessary to carry out a preliminary study to determine the angle that gave adequate resolution of the highest intensity. ‘The choice of analysing crystal would depend upon the nature of the sample to bc examined. From the quantitative aspect Beer’s law although not valid for reflection spectra was still a fair approximation and various reports had appeared of relationship between formal “absorbance” and concentration. Since “absorbance” varied with angle of incidence it was essential to obtain reproducible angles the requirement being that the angle could be repro- duced to within IJr_O*S”. The determination of alcohol sulpliates in shampoos based on the sulphate absorption at 1220 em-1 could be readily carried out with A.T.R.and the standard deviation was found to be 17.0 & 0.16 per cent. A similar standard of accuracy was found for tlie determination of phosphate and sulphonate in a liquid detergent product with the absorptions at I090 cm-l and 11 80 cm-l respectively. Owing to non-reproducible contact between the sample and the analysing crystal in the analysis of solids with the technique errors as large as +I2 per cent. were introduced it was necessary to employ a ratio of absorbances. Such a procedure based on the ratio of the intensity of the hydroxyl absorption at 3400 cm-l to that of the methylene absorption at 28000 cm-l had been used to determine the moisture content of soap. At the 13 per cent. moisture-level the standard deviation was -toe2 per cent. Examination of the polymeric material precipitated by acetone from butadiene - styrene copolymer latexes showed there was a linear relationship between the bound styrene content of the latex and the ratio of the “absorbances” a t 740 and 900 cm-1. A.T.R. had also been applied to phthalate-plasticised poly(viny1 chloride) affixed to a cellulose backing. It was found that there was a linear relationship between the phthalate content and the ratio of the “alxorbancc” of phthalate at 1460 cin-l and that of poly(viny1 chloride) at 1430 cm-l.

ISSN:0037-9697    

DOI:10.1039/SA9650200150

出版商:RSC    

年代:1965

数据来源: RSC

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ISSN:0037-9697    

DOI:10.1039/SA9650200159

出版商:RSC    

年代:1965

数据来源: RSC

摘要:

160 PAPERS ACCEPTED FOR PUBLICATION [Proc. SOC. Anal. Chem. Papers Accepted for Publication in The Analyst THE following papers have been accepted for publication in The A~calyst and are expected to appear in the near future. “The Quantitative Determination of Renzoic Acid in Soft Drinks by Ion-Exchange “Detection and Determination of Ethylene Glycol in Propylene Glycol by Thin-layer ““The Determination of Residues of Dimethoate by Use of Multi-band Chromatoplates,’2 “Recent Developments in the Measurement of Nucleic Acids in Biological Materials “The Analysis of Titanium Dioxide Pigments by Spark-source Mass Spectrography,” “Replacement of Renzidine by Copper Ethylacetoacetate and Tetra Base as Spot-test “Analysis for Residues of Chlorinated Insecticides and Acaricides A Critical Review,” “The Determination of Residual Anionic Surface-active Agents in Mineral-flotation Chromatography,” by M. A. Ford. Chromatography,” by H. B. S. Conacher and D. 1. Rees. by I). C. Abbott J. A. Bunting and J. Thomson. A Supplementary Review,” by H. N. Munro and A. Fleck. by P. F S. Jackson and ,J. Whitehead. Reagent for Hydrogen Cyanide and Cyanogen,” by P. Feigl and V. Anger. by I(. I. Reynon and K. E. Elgar. Liquors,” by G. R. E. C. Gregory.

ISSN:0037-9697    

DOI:10.1039/SA9650200160

出版商:RSC    

年代:1965

数据来源: RSC

摘要:

October 19651 NOTICES 161 Notices BRITISH STANDARDS INSTITUTION DRAFT SPECIFICATIONS A FEW copies of the following draft specifications issued for comment only are available to members of the Society and can be obtained from the Secretary The Society for Analytical Chemistry 14 Belgrave Square London S.W.S. Draft Specification prepared by Sub-committee TSE/58/2-Analysis of Iron and Man- ganese Ores. I> 65/8563-Draft R.S. Methods for the Analysis of Iron Ores. Part 1 Iron Draft Specification prepared by Sub-committee NFE/-/S-Sampling and Analysis of D 65/8564-Draft R.S. Methods for the Analysis of Aluminium and Aluminium Draft Specification prepared by Technical Committee LRC/2-Glasswarc for Medical and 11 65/9015-1>raft R.S. Specification for Tubes for the Measurement of the Draft Specification prepared by Technical Committee LKC/ LS-Laboratory Autoclaves.1> 65/9254-Draft B.S. Specification for Laboratory Autoclaves (Revision of K.S. Draft Specifications prepared by Sub-Committee NFE/22/6-Sampling and Analysis D 65/9009-1_)raft H.S. Method for the Sampling and Analysis of Lead and Lead Part 2 Determination of Arsenic in Lead and Lcad Alloys. 65/9010-Draft R.S. Methods for the Sampling and Analysis of Lead and Lead Part 3 Determination of Bismuth in Lead and Lead Alloys. D 65/9011-1>raft B.S. Methods for the Sampling and Analysis of Lead and Lead Part 4 Determination of Copper in Lead and Lead Alloys. I> 65/9012-Draft I3.S. Methods for the Sampling and Analysis of Lead and Lead Part 10 Determination of Antimony in Lead arid Lead Alloys. Aluminium and Aluminium Alloys.Alloys. Bacteriological Use. Erythrocyte Sedimentation Rate. Part 15 Nickel (Photometric). 2646). of Lead and Lead Alloys. Alloys. Alloys. Alloys. Alloys. Draft Specifications prepared by Technical Committee ClC/26 --Reagent Strengths. D 65/9296-Draft R.S. List of Preferred Chemical Indicators. I3 65/9297--Draft B.S. Recommended Strength for Solutions Used in Chemical Analysis. ASSOCIATION OF CLINICAL BIOCHEMISTS SCIENTXPIC COMMITTEE T H E ,4ssociation of Clinical Biochemists is publishing a series of TTecEinical Bulletins prepared by some of its members for the Scientific Committee of the Association. To date five have apye ared- “Data. Sheet on Control Sera,” July 1964 (price 1s.) “A Report on the Enzyme Questionnaire Circulated by the Scientific Committee,” by A .H Gowenlock December 1964 (price 1s.) ““on-recording Spectrophotometers for the Visible and Ultra-violet Ranges A Comparative Table of Instruments Available in Great Britain,” by A . H. Gowenlock P. C. Nicholas and J . H. Wilkinson May 1965 (price 1s. 6d.) “Control Solutions for Clinical Biochemistry,” by 1’. M. C. Hroughton and A. W. Gowenlock June 1965 (price 1s. 6d.) “Recording Spectrophotorneters A Comparative List oi Low-priced Instruments Readily Avail- able in Britain,” by P. Sewell July 1965 (price 2s. 6d.) 162 NOTICES [PYOC. SOC. Anal. Chew. In addition the Association has just published its Scientific Report No. 1 “Colorimeters with Flow Through Cells A Critical Assessment of Four Instruments,” at a price of 13s. 6d. A review of this Report will appear in due course in The AYtaZysl.These publications can be obtained from Mr. J. T. Ireland Biochemistry Laboratory Alder Hey Children’s Hospital Liverpool 12 England. Prices quoted include postage. THE ROYAL INSTITUTE OF CHEMISTRY ME,J,DOLA MEIIRI FOX 1965 THE medal is the gift of the Society of Maccabaeans and is normally awarded annually. The next award will be made early in 1866 to the chemist who being a British subject and under 30 years of age a t 31st December 1965 shows the most promise as indicated by his or her published chemical work brought to the notice of the Council of the Royal Institutti of Chemistry before December 3 I st 1965. No restrictions are placed upon the kind of chemical work or the place in which it is conducted. The merits of the work may be brought to the notice of the Council either by persons who desire to recommend the candiclate or by the candidate himself by letter addressed to The President ?‘he Royal Institute o f Chemistry 30 Russell Square London \&’.C.1 . the envelope being marked “Meldola Medal.” Applications made by the candidate himself should include the names of two referees. Where the application is made by another person the candidate will subsequently be requircd to furnisti the name of a secorid referee. The letter should be accompanied by six copies of a short statement on the candidate’s career (date of birth education and experience degrees and other qualifications special awards etc. with dates) and of a list of titles with references of papers or other works published by the candidate independently or jointly.Candidates are also advised to forward one reprint of each published paper of which copies are available. THE INSTITUTE OF PHYSICS AN11 THE PHYSICAL SOCIETY CONFEliENCE ON THE TNTEGTIATION OF PHYSICS AND CHEMISTRY TEACHING SHEFFIELI) APNII 1 3 ~ ~ TO ETH 1966 THE Education Group of The Institute of Physics and ‘The Physical Society is arranging a conference on ‘The integration of pttysics and chemistry teaching” to be held at the Univcr- sity of Slteflfield from April 13th to lfith 1966. liesidcn tial accommodation will be available in the University Halls of Residence and advance registration will be necessary. Further details and application forms will be avail- able in January 1966 from the Meetings Officer The Institute of Physics and ’The Physical Society 47 lSelgrave Square London S.W.I . Correspondence about the programme should cd to the Honorary Secretary of the Education Group T>r. P. J . Black Department of Physics The University nirmingham 15. XXXVITH INTEIINATIONAIJ CONGRESS ON INDUSTRIAL CHEMISTRY 13RUSSEI23 SEPTEMRBR IOTH TO 21ST 1!)66 THE XXXVIth International Congress on Industrial Chemistry under the auspices of the “Soci4t6 de Chimie Industrielle,” will be held in Rrusscls from September loth to 21st 1966. One of the 31 sections of the scientific programme deals with analysis methods and apparatus. Any further information may 1x1 obtained from the General Secretariat of the XXXVIth International Congress on Industrial Chemistry 49 Square Marie-Louise ISrussels 4 13 el g i 11 m . THE SOCIETY FOR ANALYTICAL CHEMISTRY XIIITH INTERNATIONAL SPECTROSCOPY COLLOQUIUM AT the XIIth International Spectroscopy Colloquium held in Exeter in July this year the offer of the Canadian Association for Applied Spectroscopy to sponsor the XIIIth Colloquium in 1967 was officially accepted.A preliminary announcement of the XI11 th Colloquitim Spectroscopicurn Internationale will be sent to all members of the major Spectroscopic Societies; it will be held in Ottawa Canada from June 19th to 23rd 1967 and spectroscopists are invited to contribute papers in any of the fields of spectroscopy to be covered in the technical sessions. The Colloquium will be held on the modern campus of Carleton University. Accommodation will be available in the University’s new residences. The official languages of the Colloquium will be English French and German ; multilingual guides will be available. Tours of laboratories and research centres in Ottawa Montreal and Toronto will be arranged. There will be a full programme of social events and excursions of recreational and cultural interest for wives of delegates are planned. Requests for information and offers of papers should be sent to the Secretary XI11 Colloquium Spectroscopicum Internationale National Research Council Ottawa 7 Canada. UNIVERSITY OF OTTAWA CANADA JUNE 19TH TO 23RD 1967

ISSN:0037-9697    

DOI:10.1039/SA9650200161

出版商:RSC    

年代:1965

数据来源: RSC