摘要:

132 Analyst, February, 1967, Vol. 92, $$. 132-136 The Automated Analysis of Nitrite and Nitrate in Blood BY M. H. LITCHFIELD (Imfierial Chemical Industries Ltd., Industrial Hygiene Research Laboratories, Alderley Park, Cheshire) A method is presented in which inorganic nitrite and nitrate are deter- mined automatically in blood. The dialysis unit in the automated system separates nitrite and nitrate from blood protein and thus eliminates any pre- liminary manual de-proteinisation procedure. The diazotisation and coupling reactions involving sulphanilic acid and N- ( 1 -naphthyl) ethylenediamine form the basis of the method. Nitrate is reduced to nitrite by a zinc column incor- porated into the system, and this feature enables a rapid change from nitrite to nitrate analysis and vice ~XYSGC.The method is especially suitable for the analysis of a large number of samples. Recovery from blood is reproducible and almost 100 per cent. The limit of detection is 0-1 rug per ml for nitrite, and 0.2pg per ml for nitrate, and less than 1.0ml of blood is needed for complete analysis. Range expansion can substantially increase the sensitivity if needed. THE main difficulties encountered during tlie determination of nitrite and nitrate in blood arise from the initial procedure for removing protein. Several m e t h o d ~ l ~ ~ J ~ * have been suggested for de-proteinising blood before determining the nitrite and nitrate by colorimetric or polarographic procedures. A critical survey of these methods was undertaken in these laboratories in connection with a programme on the metabolism of organic nitrates by experimental animals. It was found that all of the methods suffered drawbacks, such as poor and erratic recoveries and interference by the de-proteinising reagents on metallic columns, when these were used for the reduction of nitrate to nitrite.Moreover, these methods substantially increased the time required for analysis, and the dilutions involved decreased the sensitivity of detection. The Technicon AutoAnalyzer has been used for determining nitrite and nitrate in water,5,6 and it seemed likely that this instrument would be especially suited for the analysis of these components in blood. The dialysis unit enables separation of the nitrite and nitrate from blood protein without any prior complicating procedure, while reduction of nitrate 15-mm flow cell Recorder Fig.1. Flow diagram for the automatic analysis of nitrite and nitrate in blood ILITCHFIELD 133 can be strictly controlled in the automatic system. It was found that a zinc column reduction leads to a simpler manifold with fewer reagents and a more rapid change-over from nitrate to nitrite analysis than a system involving liquid reductants, such as hydrazine and sodium hydroxide. On these considerations the apparatus was set up as described in the following sectim, based upon the well known diazotisation and coupling reactions with sulphanilic acid and N-( l-naphthyl)ethylenediamine.7 METHOD GENERAL DESCRIPTION- The flow diagram for the AutoAnalyzer system is shown in Fig. 1. The .Ampling rate is 40 per hour with a water wash between samples.The modules shown are s-andard, apart from the system containing the zinc reduction column with a by-pass (Fig. 2), which is- described in greater detail later. REAGENTS- All reagents should be of analytical-reagent grade. Sodium chloride solution-A 0.9 per cent. w/v solution of sod :um chloride in distilled water is used. Sodium acetate huger solution-Dissolve 34 g of soYLium acetate trihydrate, CH3COONa.3H,0, in distilled water and make up to 1 litre. .idd 10 ml of K hydrochloric acid and mix. Check that the pH is 6.0, and adjust if neczssary with hydrochloric acid or sodium hydroxide solutions. Sulphanilic acid solution-Dissolve 10 g of sulphanil;,: acid in 2 N hydrochloric acid. Warm to dissolve, make up to 1 litre with 2 N hydroc1,loric acid and filter.Store in an amber-glass reagent bottle. N-( 1-Naphthy1)ethyZenediamine solution-Dissolve '.d g of N-( 1-naphthy1)ethylenediamine dihydrochloride in distilled water and make up to 1 1:tre. Filter and store in an amber-glass reagent bottle. Stock nitrite solution-Dissolve 16000 g of sodium nitrite in distilled water and make up to 1 litre. This is equivalent to 1000 pg per ml of nitrite as NO,-. Preserve with 1 ml of chloroform and keep the solution in the re'rigerator. Working standard nitrate solutions, wh/,n required, are made up as follows: 1-0, 2.0, 3.0, 4.0 and 5.0ml of stock solution are each diluted to 500 ml with distilled water and are equivalent to 2-0, 4-0, 6.0, 8.0 and lG-Opg per ml of nitrite, respectively.Stock nitrate solution-Dissolve 1.63Vd g of potassium nitrate in distilled water and make up to 1 litre. This is equivalent to 1cdOpg per ml of nitrate as NO,-. Working standard nitrate solutins, when required, are made up as follows: 1.0, 2-0, 3.0, 4.0 and 5-0 ml of stock solutic,i are each diluted to 200ml with distilled water, and are equivalent to 5.0, 10.0, 15.0, LO.0 and 25.0 pg per ml of nitrate, respectively. PROCEDURE- Whole or diluted blood is 3ampled directly from the cups on the sample plate and pumped to the dialyser module togFcher with the diluting saline stream. Nitrite and nitrate pass into the receptor stream CL acetate buffer of pH 6.0, and then to the zinc column by-pass system (Fig. 2) of two 2 way taps joined on one leg with transmission tubing, and on the other leg with transmi;sion tubing filled with zinc clippings, the preparation of which is described later.To de- bu b bler Fig. 2. Zinc reduction column incorporating a by-pass134 LITCHFIELD : AUTOMATED ANALYSIS [Artalyst, VOl. 92 L5’hen nitrite is to be determined, the receptor stream from the dialyser by-passes the zinc reduction column, and is then de-bubbled and pumped back through the manifold, re-aerated, and then mixed with sulphanilic acid for the diazotisation step, followed by the introduction of N-( l-naphthy1)ethylenediamine for the coupling reaction. The colour pro- duced is measured in the 15-mm tubular flow-cell with the 550-mp filter. When nitrate is determined, the taps on the zinc column reduction system are turned so that the stream from the dialyser is passed through the zinc column.Here nitrate is reduced to nitrite, while any nitrite originally present passes through unaffected. The stream is then de-bubbled, thus removing any hydrogen formed in the reduction step, and, as described above, it is pumped back through the manifold and then on for diazotisation and coupling. The colour produced is equivalent to the sum of nitrite plus nitrate. Nitrate can, therefore, be determined by subtraction of the nitrite response recorded previously. Each sample of blood is thus sampled twice if both nitrite and nitrate are to be determined. The zinc column is prepared by cutting AnalaR zinc metal (granulated) into pieces small enough to be inserted into a 30-cm length of transmission tubing.The first clipping is pushed to the centre of the tube by a thin piece of wire or by vibration, and other clippings are added from each end until the tube is filled. The column must be conditioned before use by inserting it into the zinc column reduction system and running the reagents through it for half an hour before any sample is passed. The efficiency of the column remains stable throughout a day’s working, although it is always advisable to include standards among the samples to check this. At the end of a day’s run the zinc column is removed and inserted in the line after the de-bubbler, and reagents are pumped through for 5 minutes until all of the air is removed from the column. The column is then stored, filled with this solution and capped off each end to prevent access of air.If this procedure is followed, little loss of efficiency results before the next day’s run. The column should be conditioned for half an hour, as described previously, before each day’s run. RESULTS AND DISCUSSION RECOVERY OF NITRITE AND NITRATE FROM BLOOD- Standard solutions of nitrite or nitrate were added to whole rat blood, the blood itself never being diluted by more than 10 per cent. with the standard solution. Ten determinations were carried out on a bulk sample at each dilution, and theresults of the analyses, corrected for the dilution of the standard solutions, are tabulated (Table I). TABLE I THE RECOVERY OF NITRITE AND NITRATE FROM BLOOD Nitrite or nitrate added, 0.20 0.50 1.00 2.00 5-00 10.00 25.00 r-lg Per ml Nitrite -A- 7 Recovered, Recovery r-lg Per ml range, mean f S.D.per cent. 80 to 110 88 to 102 92 to 100 92 to 100 93 to 101 94 to 101 0.19 f 0.02 0-48 -_t 0.02 0.96 f 0.02 1.92 f 0.04 4.85 f 0.10 9.80 f 0.21 Nitrate 7 - p -7 Recovered, Recovery r-lg Per ml range, mean f S.D. per cent. 78 to 110 85 to 105 89 to 102 92 to 103 92 to 102 93 to 100 - - 0-47 & 0.06 0.96 f 0.06 1.90 f 0.08 4.85 f 0.18 9.70 f 0-30 24.00 f 0-40 LIMIT OF DETECTION- The limits of detection are 0-1 pg per ml and 0.2 pg per ml for nitrite and nitrate, respectively. The control nitrite content of rat blood could not be detected by this method, i.e., it is less than 0-1 pg per ml. The control nitrate value varied between 0-5 and 1.0 pg per ml. The sensitivity of the method was adequate for the analyses carried out in these labora- tories.The use of the range-expander module was investigated, however, and it was found that even on the times 10 range the base-line was steady, and an over-all increase in sensitivity of some 8-fold could be achieved.February, 19671 OF NITRITE AND NITRATE I N BLOOD 135 Fig. 3 shows the reproducibility of peak heights even when lower concentrations follow higher ones. Fig. 3. Recording of peak heights showing reproducibility of nitrite determinations with standard solutions COLLECTION AND PRESERVATION OF SAMPLES- It should be emphasised that adequate precautions must be taken during collection and storage of specimens of blood for nitrite and nitrate analysis. Nitrite can be rapidly oxidised in blood in vitro, as was shown when rat blood, initially containing 52.5 pg per ml of added nitrite and 1.0 pg per ml of nitrate, was incubated at 37" C.After 1 hour the nitrite had fallen to 6.0 pg per ml and the nitrate value had risen to 64pg per ml, an increase in proportion to the loss of 46-5 pg per ml of nitrite. Storage at 4" to 5" C minimises this oxidation, the loss being less than 10 per cent. of nitrite in 1 hour. We have found oxalate - fluoride anti-coagulant (2 mg of potassium oxalate and 1 mg of sodium fluoride per ml of blood) tends to prevent this oxidation rather better than heparin. In any circumstances blood samples taken for nitrite and nitrate determination should preferably be analysed within the shortest possible time. INTERFERENCE- Organic nitrates are reduced on the zinc column to give positive interference in the nitrate determination.It is necessary to remove free organic nitrates from blood samples when their presence is suspected. Fortunately, tney can be easily removed by extraction with ether. Nitroglycerin, ethylene glycol dinitrate and 1,2 propylene glycol dinitrate can be removed completely in concentrations up to 50 pg per ml by one extraction with 10 ml of ether per ml of blood, while ethylene glycol mononitrate requires two such extractions for complete removal. To check that inorganic nitrate was not removed during these extractions the following experiment was carried out. Nitrate was added to rat blood in a concentration of 50.0 pg per ml, and portions of the blood were taken by two operators, one singly extracting with ether, and the other doubly extracting.Duplicate determinations were carried out by TABLE I1 RESIDUAL NITRATE AFTER ETHER EXTRACTION OF RAT BLOOD CONTAINING 50 pg PER ml OF NITRATE Nitrate, p g per ml Single extraction Double extraction A f \ Operator 1 . . . . 4s.5, 47.5 48.0, 48.0 Operator 2 . . . . 48.0, 45.5 48.5, 48.5136 LITCHFIELD each operator who then changed procedures. The residual extracted samples of blood from each extraction were then analysed for nitrate, and the results are shown in Table 11, from which it will be seen that the loss of inorganic nitrate is within the experimental error of the test. CONCLUSIONS The method described has been used for the analysis of nitrite and nitrate in the blood of experimental animals during metabolism studies of organic nitrates. The analyses of large numbers of samples in the minimum of time has been achieved on small amounts of blood containing a wide range of nitrite and nitrate concentrations. Mr. T. Green provided expert technical assistance in preparing the automatic analytical system. REFERENCES 1. 2. 3. 4. 5. 6. 7. Whelan, M., J . Biol. Chem., 1930, 86, 189. Scott, E. W., and Bambach, K., Ind. Engng Chem. Analyt. Edn, 1942, 14, 136. Hasegawa, H., Sato, &I., Yoshikawa, H., Sakabe, H., Jamaguchi, M., and Hotta, K., Bull. Nat. Cass, L. J., Frederik, W. S., and de Lucia, H., Angiology, 1962, 13, 469. Britt, R. D., jun., Analyt. Chem., 1962, 34, 1728. O’Brien, J. E., and Fiore, J., Wastes Engng, 1962, 33, 128. Shinn, -12. B., I n d . Engng Chern. Analyt. Edn, 1941, 13, 33. Inst. Indust. Health, 1962, 8, 10. Received August 23~d, 1966

ISSN:0003-2654    

DOI:10.1039/AN9679200132

出版商:RSC    

年代:1967

数据来源: RSC

摘要:

AnaZyst, February, 1967, Vol. 92, p . 137 I37 The Collection of Uranium (VI) on Cellulose Phosphate BY T. BRUCE AND R. W. ASHLEY (Atomic ETzergy of Canada Limited, Cltallz Rivev, Ontario, Canada) KEMBER~ has shown that the ion-exchange properties of cellulose phosphate can be used for the collection of minute amounts of cations dissolved in water. Campbell, Spano and Green2 have also reported the collection of trace amounts of various metals on ion-exchange resin-impregnated papers and their direct measurement on the paper by X-ray fluorescence. Cellulose phosphate paper can also be used to precipitate, from dilute aqueous solution, ions that form insoluble phos- phates. This property, together with X-ray fluorescence measurement, has been used to determine very low concentrations of uranium in pure aqueous solution.Solutions were passed through discs of Chromedia P81 (effective diameter of 1 cm) by using Kember’s technique. The discs were then dried in a desiccator over silica gel for about 16 hours and the X-ray fluorescence intensity measured. It was assumed that the uranium was held on the surface of the disc and only this side was counted. Solutions were prepared containing 0 to 100 pg of U(V1) in 10 ml of distilled water and treated as described. After correcting for the blank, a calibration graph was plotted for micrograms of uranium against counts per second, and the counting-rate was found to be proportional to the amount of uranium placed on the disc. The standard deviation a t the 95 per cent. confidence level was found to be & 3-5 pg of uranium, and the slope of the calibration graph was equal to 0.14.The procedure was tested as follows. A large volume of solution, containing 5Opg of uranium per litre, was prepared and 1-litre aliquots were taken for each test. The results obtained are shown below- Uranium added, pg . . . . 50 Uranium found, pg . . . . 50.5, 47.5, 49.5, 49-0 Mean, p g . . .. . . 49.1 Difference, pg . . .. -0.9 (-1.8 per cent.) These results show that uranium can be collected quantitatively on cellulose phosphate from solutions as dilute as 50 pg of uranium per litre. In a similar way, uranium was collected on discs of cellulose phosphate, placed in a spectro- fluorimeter and excited at 285 mp. The fluorescence intensity was measured a t 495 mp and found to be approximately proportional to the amount of uranium on the disc in the range 1 to 10 pg of uranium, and was then unaffected by increasing amounts of uranium.Cellulose phosphate fluoresces under the influence of the exciting light, producing a high blank value that makes quantitative measurement of uranium impossible. Washing with dilute phosphoric acid reduces, but does not eliminate, the blank fluorescence. This fluorescence technique can be used to identify uranium in very dilute solution, but jt is not suitable for quantitative work. This paper is an excerpt from CRDC-1250, a report issued by Atomic Energy of Canada Limited, entitled “Collection and Determination of Trace Amounts of Uranium Using Cellulose Phosphate Ion-Exchange Papers,” which is available to those interested in a fuller description of the experimental work, from Atomic Energy of Canada Limited. REFERENCES 1. 2. Kember, N. F., Analyst, 1960, 87, 449. Campbell, W. J., Spano, E. F., and Green, T. E., Analyt. Chem., 1966,38, 987. Received July 20th, 1966

ISSN:0003-2654    

DOI:10.1039/AN9679200137

出版商:RSC    

年代:1967

数据来源: RSC

摘要:

138 BOOK REVIEWS [Analyst, Vol. 92 Book Reviews PRACTICAL HINTS ON ABSORPTION SPECTROMETRY. By J. R. EDISBURY, D.Sc., Ph.D. Pp. xii I would venture to suggest a sub-title for this book, “Practical Hints on Absorption Spectro- metry OY Sfxxtvosco@k?’s Delight.” This is indeed a remarkable work. How often does one pick up a scientific text-book and find oneself enjoying i t ? Stimulated; absorbed; inspired? . . . yes, quite often, but enjoyed? . . . Never . . . well, hardly ever. But in long stretches this book is science-fact that burns the midnight ampkres as if it were science-fiction. Written like an essay and containing many personal reminiscences and reflections told in the first person, it is a truly fascinating book. But it is no lightweight, for it conveys a wealth of practical experience and hard won knowledge that is probably recorded nowhere else.Certainly anyone who has not had the good fortune to have learned his absorption spectroscopy in Dr. Edisbury’s laboratories will learn many new facts about both the technique and the machines with which it is practised. Hints and stratagems abound, but there is much more to it than that, for the author does get across a philosophy-a way of assessing spectra and all things spectroscopic and a way of treating instru- ments with the respect and care that all precision tools require. I know of no parallel elsewhere. The text is concerned principally with ultraviolet - visible range absorption spectrophotometers of all shapes and sizes, and gives special attention to factors such as light sources (“many hands don’t always make the light work”) ; photodetectors ; absorption cells ; preventive maintenance (“I prefer Friday afternoon because all the machinery is nicely warmed up even though the staff are cooling down”) ; stray light; collaborative testing; the quest for accuracy and precision (“raised eyebrows stimulate thought”) ; presentation of results (“you must draw the line somewhere”) .. . and SO on. There are many excellent texts on absorption spectroscopy to which this would act as an admirable companion volume as i t deals with exactly all of the things that they do not. I seriously commend this book to all who take pride in their work whether or not it is absorption spectrophotometry, but above all to students who have to learn the avt as well as the science, the philosophy as well as the theory.No library in any advanced teaching institution can consider being without this book if it has the welfare of its chemists a t heart, and no conscientious spectro- scopist can knowingly dispense with reading it a t least once. Very definitely an “original,” a “must,” a “hit” or what you will. + 266. London: Hilger & Watts Ltd. 1966. Price 50s. Just dare browse through it and see what happens. T. s. WEST KINETIC METHODS OF ANALYSIS. By K. 33. YATSIMIRSKII. Translated by P. J. J . HARVEY. Oxford, London, Edinburgh, New York, Toronto, Paris and Frankfurt: A volume on this topic is timely, especially from so eminent an author, but the reader who expects an account of the work that has recently come into such prominence in analytical chem- istry will be disappointed.Three papers and a book from 1960 represent the most recent references to western literature, while the Russian literature is covered to 1961 with a few references from 1962 ( a book ascribed to 1965 on p. 106 is later correctly dated 1956). The newer work therefore escapes attention. After swallowing this disappointment, what virtues remain ? There are three principal features to this work. First, a practical introduction to the principles and methods of kinetic measurements occupies a little more than half of the text. Second, the remainder of the text offers a fairly comprehensive historical account of analytical methods based on catalytic phenomena, confined to d block elements, together with a few examples of non-catalytic methods.Third, there are numerous citations from Russian and Eastern European literature, much of it in obscure sources difficult of access in the West. Many references are made to proceedings of conferences, reports of official bodies and institutions, theses and the like that normally escape general notice. Nevertheless, however valuable such references may have been in the original Russian version, they are frequently worthless and tantalising in the translation because no detail is given in the text and the source is inaccessible. In many instances they are worse than tvorthless because the reference contains information vital to the understanding, justification or implementa- tion of statements made in the text. Some references (e.g., (8), p.28) to Russian text-books are particularly frustrating. On the other hand, an extensive description is given of a non-available and uninteresting Soviet filter photometer. The spelling of proper names is irritatingly variable : the author’s own name appears in three different transliterations. There is no author index, and the subject index is feeble. Pp. xvi + 154. Pergamon Press. 1966. Price 50s.February, 19671 BOOK REVIEWS 139 The first five chapters are devoted to explication of theory and practice. Many telling points are made with lambent lucidity, but these intermingle strangely with the deeply obscure. The section on the theory of kinetics is superficial: few newcomers to the subject would gain a clear wide grasp from it. The theoretical treatment of catalysis is promising, makes useful points quite clearly, but only introduces the subject and is still rather superficial.Too often is one left hanging by statements such as: “Equation (20) can be integrated” (p. 6), “The application of . . . is so well known . . . the subject is not discussed” (p. 28), “There are also methods used to find the coefficients in equation (10) and in all equations of a similar kind” (p. 81). The transposition of Figs. 7 and 8 makes confusion worse confounded. Repetitions of the obvious instead of the hoped-for pursuit of solution of difficulties (e.g., bottom of p. 45) frustrate. The theory set out is rather approximate, and, apart from the enumeration of certain desirable criteria, its relevance is scarcely indicated and it is put to very little use: the applications given are largely empirical.The translator must be held to blame for many of the faults, obscurities and curious expressions in both the theoretical and experimental sections. Accuracy, sensitivity and precision are confused (p. xiv), “ionic strength of components” (p. xv) is meaningless, the tangent is a curious property of a straight line, “By the very appreciable change in the optical density of the solution the extent of the reaction is found to be negligible” (p. 36), “specified” meaning “measured” (p. 49), the missing reference (7) (p. 51), “orbits” for “orbitals” (p. 58), “Hydrogen peroxide decomposes a t quite a high e.m.f. value a t the cathode” (p. 60), “compounds of these elements catalyse many reactants .. .” (p. 62), “The decomposition of ferrocyanide is catalysed by compounds of silver and gold both of which, on addition of thiourea to the solution, form stable compounds with these elements and sharply increase their catalytic activity” (p. 72), the missing reference (2) (p. 88), “ten parts of a microgram per millilitre” (p. 92), “H,O, twice sublimed under vacuum” (p. 93), “the composition of vanadium in the standard solution” (p. 112), and many other imperfections that could have been avoided. “Luminescence” is used in the Russian sense of the term and “analytical” (p. 33) in the mathematical sense. The author, however, is responsible for lack of clarity in places (e.g., p. 33), the unintroduced a, (p. 48), ignorance of the fact that vanadium(V) oxidises iodide (p.5 6 ) , acidifying a solution to pH 2.1 with 1 0 - 4 ~ nitric acid (p. 92) and other blemishes. In the experimental section, the amount of detail given in the individual methods varies from nil upwards, and is often deficient. The reviewer and his colleagues have attempted to conduct several of the reactions described without success. In some cases the lack of detail is prohibitive (e.g., reaction 3, p. 91) because the reference is not accessible. In others the directions are obscure in some respect or other. Insufficient emphasis is placed on reagent purity in reactions based on catalysis. Methods are given for some 40 elements, many of the methods being of very high sensitivity, and in many cases in sufficient detail for immediate use.Although not up to the author’s usual standard, and marred by poor translation, and having a restricted coverage, this book offers the first collected treatment of an important subject and contains much valuable material. E. BISHOP CHEMICAL KINETICS IN HOMOGENEOUS SYSTEMS. By MOWBRAY RITCHIE. Pp. viii + 115. This admirable and commendably cheap paperback, primarily intended for undergraduates, will be welcomed by those who wish to refresh and up date themselves in a discipline of great industrial significance, and one which is becoming increasingly appreciated in analytical chemistry. It is written by a physical chemist, and chiefly concerns the elucidation of the mechanism of homogeneous organic gas-phase reactions from kinetic studies, but it offers a good background and introduction to the more complex mechanisms and kinetics of analytical processes.PROGRESS IN THE CHEMISTRY OF FATS AND OTHER LIPIDS. Volume 9. POLYUNSATURATED ACIDS. Part 1. Edited by RALPH T. HOLMAN. Pp. iv + 157. Oxford, London, Edinburgh, New York, Toronto, Sydney, Paris and Braunschweig : Pergamon Press. 1966. Price 50s.; $7.75. This paper-backed volume continues the series dealing with the chemistry of fats and related compounds that was started some 14 years ago. The series has dealt exhaustively with many aspects of f a t chemistry, notably with standard methods of analysis in volume 5, with the gas chromatography of lipids in part 1 of volume 7, and with column, thin-layer and paper chromato- graphy in part 3 of volume 8. In the present volume there are four sections devoted to various aspects of the chemistry of the polyunsaturated fatty acids.The first is general, the second Edinburgh and London: Oliver & Boyd. 1966. Price (paper) 13s. 6d.; (cloth) 21s. E. BISHOP140 BOOK REVIEWS [Aizalyst, Vol. 92 deals with the analysis and characterisation of the acids, the third with the determination of their structure by degradative methods and the fourth with the synthesis of the naturally occurring 1,4-acids. The section on analysis and characterisation, by R. T. Holman, occupies some 75 pages and surveys the methods available in detail. Classical methods are included for their historical interest, although the author regards them as of much lesser importance since quick discriminating physical methods were introduced; and by far the greater part of the section is devoted to the latter. The methods employed are not described in detail, but results yielded by them are fully considered.INSTRUMENTAL METHODS OF ANALYSIS. The high standard of the series is amply maintained in this volume. K. A. WILLIAMS By HOBART H. WILLARD, LYNNE L. MERRITT, jun., and JOHN A. DEAN. Fourth Edition. Pp. xviii + 784. Princeton, Toronto, New York and London: D. Van Nostrand Company Ltd. It has been the reviewer’s pleasant task to record that each edition of this book has been a marked improvement on the last, and the fourth edition is no exception. It has been almost completely re-written and brought up to date. There has been some change in style and emphasis, e.g., more stress has been placed on structural identification than previously, which is in keeping with general trends in the application of some of the newer methods.The adverse criticisms recorded against the third edition have all been dealt with, and in particular the directions for use of specific instruments have been largely eliminated. The first two chapters are entirely new and deal with electrical circuits, vaives and semi- conductors. The treatment is, of necessity, brief but sufficient is included to be extremely useful and to do much to obviate the “black-box mentality.” There follow 25 chapters on the various instrumental methods in current use. A final new chapter discusses “on-stream” analysis; this is barely adequate but should whet the appetite of the student for more information.The general arrangement of each topic involves a treatment of general principles, a description of some of the instruments available, and an indication of the range of use; appended are a series of laboratory exercises and a set of problems. The value of the list of laboratory exercises is debatable, but the problems, together with the numerous worked examples that appear in the text, should help to give the newcomer the feel of a method very quickly. No one would cavil a t the amount of space given to spectrophotometry or to the increase in the section on gas chromatography, but it is surprising that whilst circular dichroism warrants a mention, square- wave polarography does not. However, apart from a few such omissions, the over-all picture presented is a fair reflection of present-day practice.The format has again been changed; the printing and the diagrams are first class and the book is a pleasure to handle and to read. This is one of the best books of its kind and can be recommended to all students and young analytical chemists and for surreptitious reading by all chemists ! J. F. HERRINGSHAW ADVANCES IN ANALYTICAL CHEMISTRY AND INSTRUMENTATION. Volume 5. Edited by CHARLES 1965. Price (cloth) 70s.; (paper) 35s. Naturally the balance between the various topics will not suit all readers. N. REILLEY and FRED W. MCLAFFERTY. Pp. x + 398. New York, London and Sydney: Interscience Publishers, a division of John Wiley and Sons Inc. 1966. Price 105s. Reviews of the four preceding volumes of this series have appeared in The A~zalyst, and it is gratifying to report that the high standards of the earlier books are maintained in this present volume.With the exception of the chapters on Automation of the Analytical Process Through Con- tinuous Analysis, and The Solvent Extraction of Metal Chelates, the subjects covered on this occasion may not have the same breadth of appeal as the topics dealt with in the earlier volumes. Collectively, however, the series covers a wide variety of interests for the analyst who wishes to be kept informed on topics that could impinge on his own work. Like the earlier volumes in the series, the contributions are intended to be read from the standpoint of the non-specialist, but the interests of the specialist have not been neglected.Each contribution has received a scholarly treatment by an expert, or experts, in the field, with the chapters well supplemented by literature references. Additional chapters contained in this volume are : Determination of Molecular Weights by Ebulliometry, Interpretation of K-edge X-ray Absorption Spectra of Transition Metal Compounds, Analytical Applications of Microwave Spectroscopy, and The Determination of Molecular Structure by Single-crystal X-ray Diffraction Methods.February, 19671 BOOK REVIEWS 141 As in the previous volumes, Author, Subject and Cumulative (Volumes 1 to 5) Indexes, are included. A Wavning is given, and it is opportune here, to draw this to the attention of readers of Volume 4 who may not see Volume 5. In the Oxygen-flask method (Volume 4, pages 75 to 116) : The analyst should wear safety glasses and u s e a suitable safety screen between himself and the apparatus. The flask must be scrupulously clean.Advances cover a wide field of analytical chemistry and instrumentation, and provide an excellent source of information for the analyst with a broad perspective, especially in an age of problems of increasing complexity. W. T. ELWELL EQUILIBRIA IN SOLUTION. By GEORGE M. FLECK. Pp. xviii + 217. New York, San Francisco, Professor Fleck attempts to provide (at undergraduate level) a “systematic, unified treatment of the major types of solution equilibria-proton transfer, electron transfer, complexation, pre- cipitation-in terms of simple algebraic models based on the equilibrium constants, conservation of mass and electroneutrality.” Topics such as titration curves, isoelectric point, isoionic point, buffer capacity, statistical factors and the distinction between macroscopic and microscopic equili- brium constants are also discussed.The book contains a table of five-place logarithms. The author’s laudable objective has already been achieved in a number of recent books, but his own success is more questionable. The identity of the algebraic treatment of the two series of stepwise equilibria: Chicago, Toronto and London: Holt, Rinehart and Winston Inc. 1966. Price $7.95. A + j H + AH, and M + nA + MA, (charges being omitted) is disguised at the undergraduate level by his treatment of the former as dissociations in Chapter 3 and of the latter as associations in Chapter 7.Moreover, confusion is likely to arise because of the indiscriminate use of symbols. 18, is an over-all association constant on page 122, but a dissociation constant on page 179. Likewise Kk is a stepwise association con- stant on page 122, both a solubility product and a dissociation constant on page 173 and an asso- ciation constant again on page 183. The author uses the electroneutrality principle in treating acid - base equilibria, but not in treating metal - complex equilibria. This is legitimate, but un- necessary, and again disguises the identity of the algebraic approach. How long will it take the undergraduate to realise that the variable F in equation (11.35) is, in fact, the Bjerrums’ n of equation (7.41) 7 It is not apparent why the author did not suggest the standard method of solving equation (11.35) for the two equilibrium constants by using equation (7.42) or (7.43) rather than by inventing an incorrect solution in experiment 3 on page 172.The absence in an American text of any discussion of the excellent types of Scandinavian graphical solution popularised in the United States by the Freiser EQUILIGRApH is regrettable, F. J. C. ROSSOTTI NOMENCLATURE OF ORGANIC CHEMISTRY. Definitive Rules for Section C. Characteristic Groups containing Carbon, Hydrogen, Oxygen, Nitrogen, Halogen, Sulfur, Selenium, and/or Tellurium. Pp. xviii + 260. London: Buttenvorths (Publishers) Ltd. 1965. Price 47s. 6d. For the most part, the I.U.P.A.C. 1957 Rules for organic nomenclature describe the body on which to build.Section C, replacing many of the Liege Rules of 1930, now shows how to supply a wide range of limbs, both fore and aft. Substitutive nomenclature is most widely used and generally preferred. Some characteristic groups, e.g., -NO,, are only named as prefixes; others, e.g., -OH, may be shown either as prefixes (hydroxy-) or as suffixes (-ol), depending on whether or not there is another group present with higher priority for citation as the principal group. In radicofunctional nomenclature the functional class name is expressed as a separate word, e.g., methyl alcohol, diethyl ether. Hydro- is the only example in additive nomenclature to appear as a prefix; in other cases, the added atoms are indicated separately, e.g., hexane ozonide, but for such this method should be limited to a few special cases.Subtractive nomenclature, in addition to -ene and -yne suffixes, includes de- (e.g., dehydro-, deoxy-), nor- (particularly for steroids) and anhydro-. [Note that, in English, des- is only used to indicate loss of, for example, the A ring of steroids.] Conjunctive nomenclature, much used by Chemical Abstracts, has not been generally adopted here ; it has occasional advantages, e.g., ethylenediaminetetra-acetic acid. The preferred substitutive system leads to methanol.146 BOOK REVIEWS [Analyst, Vol. 92 Replacement nomenclature, formerly referred to for heterocyclic compounds as “a” nomen- clature, can be applied to acyclic systems but should only be used when other types are difficult to apply; in general, this means two or more hetero-atoms in a chain of not less than 10 atoms.This system can completely conceal the real nature of a compound, e.g., as a polyester. The rest of this section deals in greater detail with compounds of the elements cited in the title, arranged in nine groups ; for example, that covering carboxylic acid includes derivatives such as amino-acids, peroxy acids, lactones and lactams, acyl halides and anhydrides. Names such as piperidinesulphonic acid and thiazolecarboxylic acids are proper, i.e., the -ine and -ole are not taken as functional suffixes. On the other hand, doubtless because of long usage in the dyestuffs industry, names such as phenolsulphonic acid, naphtholsulphonic acid and naphthylaminesulphonic acid may be used, although systematic names are still preferred. Thiophenol may be used but substitutive nomen- clature is preferred. The use of -carboxyamidine and -carboxamidrazone seems unfortunate as these groups contain no oxygen.Epimino- appears as an analogue of epoxy- and epithio-; these are taken as non-detachable when the alphabetical order of prefixes is used. For use in this country, some anglicising is required, e.g., for sulfenyl, etc., thiophene, ketene. On occasion, guidance by national bodies is needed; for example, “hydro and syllables denoting subtraction . . . may be treated as detachable or non-detachable when the alphabetical order is used.” Listed among a few changes to earlier Rules, benzhydryl-, rejected in 1951, has now been restored to favour. This section by no means completes the work for organic nomenclature; most noticeable among the absentees are silicon and boron compounds, and more is to come on tellurium com- pounds in Section D.The system of nomenclature for organic compounds containing one phos- phorus atom remained just an Anglo - American agreement. A iew points of interest may be mentioned. B. A. ELLIS PESTICIDES IN THE ENVIRONMENT AND THEIR EFFECTS ON WILDLIFE. The Proceedings Of an Advanced Study Institute sponsored by the North Atlantic Treaty Organization, Monks Wood Experimental Station, England, 1-14 July, 1965. Supplement to Volume 3 of The Jowrnal of AppEied Ecology (June, 1966). Pp. xii + 311. Oxford: Blackwell Scientific Publications. 1966. Price 70s. ; $12.00. In July, 1965, seventy-two scientists of various disciplines met for a fortnight a t the Monks Wood Experimental Station of the Nature Conservancy, to listen to thirty-three lectures by their fellows and to join in the ensuing discussions. The scientists came from many countries-not confined to members of N.A.T.0.-and had been invited on an individual basis for their knowledge and experience of the effects of pesticides on wildlife.This volume contains all of the lectures and an assessment of the discussions by the Director of the Advanced Study Group, who also acted as Editor. The range of these lectures is wide and covers the effects of organochlorine and organo- phosphorus pesticides, mercurial and other fungicides on many species, mainly birds and fish. For example, the lecture by Professor J. L. George is an account of his work with the U S . Office of Antarctic Programmes in obtaining and analysing samples of wildlife from the Antarctic, resulting in the detection of small amounts of DDT and DDE in Adelie Penguins and Skua. Dr. F. Schneider reports on attempts to control various pests in Switzerland by using phosphamidon, DDT, endrin and mercury salts. There is an interesting account by Dr. P. L. Ames of his study of DDT residues in Ospreys and their eggs in the north-eastern regions of the United States. This work was part of an investigation into the decline of this species due to embryonic death before hatching, and Dr. Ames discusses experiments with Japanese Quail in captivity as a complementary study. A. V. Holden of the Freshwater Fisheries Laboratory a t Pitlochry reports on his work on determining dieldrin and DDT residues in salmon and trout in Scottish lakes and rivers, and considers the biological significance of the levels found. One of the longest and most interesting to some readers will be a description by Dr. R. E. Warner of his method of treating fish with sub-lethal doses of pesticides and studying behavioural changes. The results show that there may be profound effects on aquatic life a t concentrations far below those producing death or immobility. All of these lectures are eminently readable and full of interest to any scientist who has an interest in pesticides and their effects on wildlife. Edited by N. W. MOORE. These are but four of the lectures picked a t random from this volume. J. O’G. TATTON

ISSN:0003-2654    

DOI:10.1039/AN9679200138

出版商:RSC    

年代:1967

数据来源: RSC