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Supplement to official, standardised and recommended methods of analysis
563
SHORTCOMMUNICATIONS
The authors are grateful to Dr. S. M. F. RAKMAN for providing research facilities. One of us (K.N.M.) received financial assistance from CSLR, (India) which is gratefully acknowledged. MOHSIN
I 1. M. xgG1,
KOLTHOFF
AND
I?. 1. ELVING,
TreuIise ma AnaZyficaZ
Chemislry,
Part
K.N.
QURESHI MATHUR
It,
John Wiley,
p. 156.
z I).F. BOLTZ, Colo~itn~l~ic p.326.
(Received
Decemberzrst,
Uelcrminafion
of Nonmdnts,
Vul.
III,
Lntcrscicncc, EJcw York, 1958,
x967) AmzZ.Ct~im. Adz, 4x (1968)560-563
BOOK
REVIEWS lntevacliom in Electrolyte Solutions, Topics in Inorganic and General Vol. 8, Elsevicr, Amsterdam, x966, x +2x4 pp., price Z)fl+ 40,-.
G. I-I. NANCOLLAS,
Chemistry,
Information concerning complexes in solution forms an important branch of coordination chemistry, and fundamental work in this field has influenced the development of titrimetry, biochemistry, ocean chemistry and nuclear fuel rcprocessing. Analytical chemists, biochemists and nuclear chemists have made important contributions to solution chemistry, especially in elucidating the nature of species formed by chemical equilibria in electrolyte solutions (ionic equilibria). NANCOLLAS is well known for his research in the field of solution chemistry and belongs to the British “zero ionic strength” group, which emanates from C. W. DAVIES. The other group, predominantly Scandinavian, make their measurements in media of high and constant ionic strength. As the reviewer belongs to the latter group, this will be reflected in his criticism of NANCOLLAS' book. The book deals mostly with very simple equilibria, in which one species is formed from two (M+A+MA). This is due to the fact that, if one limits the investigation to an ionic strength less than 0.1: M, the concentrations of the metal ion and the ligand cannot be varied over very wide ranges. Thus polynuclear complexes, MmAn, or complexes with many ligands, MAn, may not always be detected, Furthermore, the British group are of the opinion that thermodynamic calculations can only be performed for pure water (zero ionic strength), which is, of course, not true, and activity factors for reacting components X may very well be defined for other media, e.g., fx+x when [X]+o in 3 IU NaC104. The British group have spent much time in considering the values of the AG (-RTlnK), AH and TAS terms of complex formation, while the Scandinavians have directed their research towards finding all possible species that can be formed from M and A in solution. This is then illustrated by distribution diagrams of which the reader willfindnonein NANCOLLAS'~~~~. It is therefore natural that Chapters 4 and 5 of the book, which deal with relaAnaZ.Clrim. Ada, 41 (rg68) 563-564
564
BOOK REVIEWS
tionships between association constants, cnthalpy and entropy changes, are cxccllent. The reviewer especially enjoy&l the parts dealing with the polyamine, carboxylic, amino acid and nminol,olyc~trl,oxylate coml~le,xes. Tile problem of inner- and oqtersphere co’mplex formation of ion-pairs is also treated very well, but the book does not deal with equilibria in mixed or non-aqueous solvents. Chapter 3 deals with experimental methods for determining association (stability) constants and Chapter 4 treats the problem of calculating the constants from experimental data. The division of the material in these two chapters into experimental techniques, primar$ data, relationships between primary data (e.g. cmf) and concentrations of different species, and, finally, calculation of the parameters in the relationships, is, however, not very strict, Some experimental methods have been treated briefly (e.g. solvent extraction) or omitted altogether (e.g. vapour pressure osmometry), while other methods (c.g:. conductance, solubility measurements, and determination of the heats of association) are treated in more detail. k warning should have been given for the possibility of the formation of mixccl solid complexes in solubility measurements, and for the variation of the ion-cxchnnge constants at low (trace) concentrations. SUNNET{, well-known for his work in calorimetry, should have had his name spelt correctly, It is irritating to see electroneutrality (11.39, 41, 79, 87, 89) still in use instead of the analytically known total concentrations of all components (total TlI03 on p, 39, total M on p. 4r, total H on p. 79, 87 and 89). Chapter G gives a limited hut very enjoyable treatment of the kinetics and mechanism of metal comples formation and the structure of the complex. The Appendix contains tables of thermodynamic functions, which are discussed further in Chapters 3 ancl 4. GEORGE NANCOLLAS has written a very useful book, which can be recommcmled as an introduction to the field, I have on several occasions examined students at the University of Gothenburg on NANCOLLAS book with good result, and it is furthermore important that Scandinavian chemists become acquainted with the British way of thinking in the field of ionic equilibria. I). DYRSSEN (Gijteboq)
Supplement to Off-r:cial, Standar&sed and Recmrwended Methods of Aotnlysis, Compiled and edited by S. C. JOLLY, for the Analytical Methods Committee of The Society for Analytical Chemistry, London, 1967. Society for Analytical Chemistry, London, x967, xiv +424 pp., price 147 s (126 s to Society members). The main publication to which this Supplement is attached was reviewed in this journal (Attal, Cl~inz..4&a, 30 (1964) IOG) and the samecomplimentarycomments .are equally applicable to this extension. For a publication with this coverage to be of maximum benefit to the analyst, it must be reasonably up-to-date, and this prime objective of the A.M.C. has been commendably’achieved with the appearance of this Supplement. RVUZ~. C/rim, A ckt, 4x (rgG8)564-5G5
SHORTCOMMUNICATIONS
The authors are grateful to Dr. S. M. F. RAKMAN for providing research facilities. One of us (K.N.M.) received financial assistance from CSLR, (India) which is gratefully acknowledged. MOHSIN
I 1. M. xgG1,
KOLTHOFF
AND
I?. 1. ELVING,
TreuIise ma AnaZyficaZ
Chemislry,
Part
K.N.
QURESHI MATHUR
It,
John Wiley,
p. 156.
z I).F. BOLTZ, Colo~itn~l~ic p.326.
(Received
Decemberzrst,
Uelcrminafion
of Nonmdnts,
Vul.
III,
Lntcrscicncc, EJcw York, 1958,
x967) AmzZ.Ct~im. Adz, 4x (1968)560-563
BOOK
REVIEWS lntevacliom in Electrolyte Solutions, Topics in Inorganic and General Vol. 8, Elsevicr, Amsterdam, x966, x +2x4 pp., price Z)fl+ 40,-.
G. I-I. NANCOLLAS,
Chemistry,
Information concerning complexes in solution forms an important branch of coordination chemistry, and fundamental work in this field has influenced the development of titrimetry, biochemistry, ocean chemistry and nuclear fuel rcprocessing. Analytical chemists, biochemists and nuclear chemists have made important contributions to solution chemistry, especially in elucidating the nature of species formed by chemical equilibria in electrolyte solutions (ionic equilibria). NANCOLLAS is well known for his research in the field of solution chemistry and belongs to the British “zero ionic strength” group, which emanates from C. W. DAVIES. The other group, predominantly Scandinavian, make their measurements in media of high and constant ionic strength. As the reviewer belongs to the latter group, this will be reflected in his criticism of NANCOLLAS' book. The book deals mostly with very simple equilibria, in which one species is formed from two (M+A+MA). This is due to the fact that, if one limits the investigation to an ionic strength less than 0.1: M, the concentrations of the metal ion and the ligand cannot be varied over very wide ranges. Thus polynuclear complexes, MmAn, or complexes with many ligands, MAn, may not always be detected, Furthermore, the British group are of the opinion that thermodynamic calculations can only be performed for pure water (zero ionic strength), which is, of course, not true, and activity factors for reacting components X may very well be defined for other media, e.g., fx+x when [X]+o in 3 IU NaC104. The British group have spent much time in considering the values of the AG (-RTlnK), AH and TAS terms of complex formation, while the Scandinavians have directed their research towards finding all possible species that can be formed from M and A in solution. This is then illustrated by distribution diagrams of which the reader willfindnonein NANCOLLAS'~~~~. It is therefore natural that Chapters 4 and 5 of the book, which deal with relaAnaZ.Clrim. Ada, 41 (rg68) 563-564
564
BOOK REVIEWS
tionships between association constants, cnthalpy and entropy changes, are cxccllent. The reviewer especially enjoy&l the parts dealing with the polyamine, carboxylic, amino acid and nminol,olyc~trl,oxylate coml~le,xes. Tile problem of inner- and oqtersphere co’mplex formation of ion-pairs is also treated very well, but the book does not deal with equilibria in mixed or non-aqueous solvents. Chapter 3 deals with experimental methods for determining association (stability) constants and Chapter 4 treats the problem of calculating the constants from experimental data. The division of the material in these two chapters into experimental techniques, primar$ data, relationships between primary data (e.g. cmf) and concentrations of different species, and, finally, calculation of the parameters in the relationships, is, however, not very strict, Some experimental methods have been treated briefly (e.g. solvent extraction) or omitted altogether (e.g. vapour pressure osmometry), while other methods (c.g:. conductance, solubility measurements, and determination of the heats of association) are treated in more detail. k warning should have been given for the possibility of the formation of mixccl solid complexes in solubility measurements, and for the variation of the ion-cxchnnge constants at low (trace) concentrations. SUNNET{, well-known for his work in calorimetry, should have had his name spelt correctly, It is irritating to see electroneutrality (11.39, 41, 79, 87, 89) still in use instead of the analytically known total concentrations of all components (total TlI03 on p, 39, total M on p. 4r, total H on p. 79, 87 and 89). Chapter G gives a limited hut very enjoyable treatment of the kinetics and mechanism of metal comples formation and the structure of the complex. The Appendix contains tables of thermodynamic functions, which are discussed further in Chapters 3 ancl 4. GEORGE NANCOLLAS has written a very useful book, which can be recommcmled as an introduction to the field, I have on several occasions examined students at the University of Gothenburg on NANCOLLAS book with good result, and it is furthermore important that Scandinavian chemists become acquainted with the British way of thinking in the field of ionic equilibria. I). DYRSSEN (Gijteboq)
Supplement to Off-r:cial, Standar&sed and Recmrwended Methods of Aotnlysis, Compiled and edited by S. C. JOLLY, for the Analytical Methods Committee of The Society for Analytical Chemistry, London, 1967. Society for Analytical Chemistry, London, x967, xiv +424 pp., price 147 s (126 s to Society members). The main publication to which this Supplement is attached was reviewed in this journal (Attal, Cl~inz..4&a, 30 (1964) IOG) and the samecomplimentarycomments .are equally applicable to this extension. For a publication with this coverage to be of maximum benefit to the analyst, it must be reasonably up-to-date, and this prime objective of the A.M.C. has been commendably’achieved with the appearance of this Supplement. RVUZ~. C/rim, A ckt, 4x (rgG8)564-5G5