Journal of Molecular Liquids 145 (2009) 110–115

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Journal of Molecular Liquids

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Nikolai Izmailov and the electrochemistry of solutions

N.O. Mchedlov-Petrossyan ⁎Department of Physical Chemistry, V.N. Karazin Kharkov National University, 61077 Kharkov, Ukraine

⁎ Corresponding author.E-mail address: mchedlov@univer.kharkov.ua.

0167-7322/$ – see front matter © 2008 Elsevier B.V. Aldoi:10.1016/j.molliq.2008.11.006

a b s t r a c t

a r t i c l e i n f o

Available online 17 November 2008

Keywords:

The paper aims to pay tribchemistry. In the forties–fiftsolutions and considered th

Electrolytes in solutionDissociation schemeAcids strengthDifferentiating influence of solventsSolvation

e problem of the differentiating influence of non-aqueous solvents on the acidsstrength. He also generalized the concept of an unified acidity scale in different solvents, proposed severalnew methods for estimating Gibbs energy of ion solvation, and contributed a lot to the theory of physico-chemical analysis. Beginning from the thirties, Izmailov investigated the possibility to apply various indicatorelectrodes, especially glass electrodes, in organic solvents.

ute to scientific achievements of Nikolai Izmailov (1907–1961) to the solutionies, Izmailov proposed the most detailed scheme of dissociation of electrolytes in

© 2008 Elsevier B.V. All rights reserved.

1. Introduction

The outstanding physico-chemist Nikolai Arkadievich Izmailov(1907–1961) [PhD (1937), ScD, Professor (1948)] headed the Depart-ment of Physical Chemistry of Kharkov State University from 1944 to1961. All his scientific activity was connected with Kharkov Universityand Kharkov Pharmaceutical Research Institute. Over a period ofseveral years (1948-1953) he was Vice-Rector of the University.

On June 26–30, 2007, the International Conference ‘ModernPhysical Chemistry for Advanced Materials’, devoted to the centenaryof the birth of Professor Nikolai Izmailov, took place in V. N. KarazinKharkov National University under the sponsorship of the UkrainianAcademy of Sciences, IUPAC, and European Association for Chemicaland Molecular Sciences, with the financial support of AlumniAssociation of V. N. Karazin National University, Sagmel Inc. (USA),and some other organizations and persons.

Two main directions of scientific interests of Nikolai Izmailovwere (i) the influence of the solvent on dissociation of electrolytes;(ii) statics and dynamics of sorption from solutions. In 1938 in col-laboration with Shraiber, he made a groundbreaking discovery ofthe thin layer chromatography. In the thirties Izmailov investigatedthe possibility to apply various indicator electrodes, especially glasselectrodes, in organic solvents. In the forties–fifties, he proposed themost detailed scheme of dissociation of electrolytes in solutions,considered the problem of the differentiating influence of non-aqueous solvents on the strength of acids, generalized the concept ofan unified acidity scale in different solvents, proposed several newmethods for estimating Gibbs energy of ion solvation, and contributeda lot to the theory of physico-chemical analysis.

Izmailov is the author of over 280 publications; his treatise‘Electrochemistry of Solutions’ (1959) is well known to those working

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in the field of solution chemistry and is still frequently cited. For thisbook, the Academy of Sciences of USSR honored him by theMendeleyev award. 31 persons got PhD degree under Izmailov’ssupervision and 11 of his co-workers later got the ScD degree. In 1955,he received the title ‘Honored scientist of Ukraine’ and in 1957 he waselected to the Ukrainian Academy of Sciences as a CorrespondingMember.

Some additional information about Izmailov’s scientific career,main results and achievements can be found in the essays publishedby the author recently [1,2].1

The aim of the present article is to give a brief review of Izmailov’scontribution to the electrochemistry of solvents.

2. Differentiating influence of solvents

One of themost popular classifications of solvents is based on theirinfluence on the acid-base equilibrium [3–5]. The so-called differ-entiating influence of the solvent can be understood as non-uniformchange of the strength of acids when going from a standard solvent(water) to the given solvent [3–6]. Such ‘resolving’ of the acidicstrength of different acids is now widely used in analytical chemistry[4].

In the course of his work on the analysis of drugs at thePharmaceutical Institute, Izmailov became interested in utilizationnon-aqueous solvents as useful media for acid-base titrations [7,8]. Hetried to rationalize the origin of the concept of the differentiatinginfluence of organic solvents, earlier introduced by Walden andHantzsch. The works of these authors, as well as those of Ogston andBrown [9], Verhoek [10], and few other publications encouragedIzmailov to reveal the driving forces of the solvent effects and to

1 Comprehensive consideration of Izmailov’s scientific heritage, the bibliography,and a set of supplementary materials (mainly in Russian) are available via internet:http://www-chemistry.univer.kharkov.ua/izmailov.

Scheme 1. The general scheme of dissociation of the electrolyte CA in solvent M, proposed by Izmailov. The solvated ionic species are denoted using the ‘solv’ subscript, the stabilityconstant Kstab includes the activity of the solvent.

111N.O. Mchedlov-Petrossyan / Journal of Molecular Liquids 145 (2009) 110–115

give one of the earliest classifications of the differentiating action[7,8,11–15].

The recognized scheme of acid-base equilibria introduced byBrønsted (HA+M⇄MH++A–; M is the solvent) explained the differentchanges in pK on going from one solvent to another, basing on thesolvents’ basicity and relative permittivity, εr, and the charge type ofthe acid-base couple. So, it becomes clear that the medium effects, i.e.,ΔpK=pK (in the given solvent) — pK (in the standard solvent, e.g., inwater), are different for cationic, neutral, and anionic acids. However,this theory was unable to explain the non-uniform medium effectsregistered for acid-base couples of equal charge type but of different‘chemical types’ [10], e.g., carboxylic acids and phenols. Thedifferences in ionic radii are too small to explain the deviations ofexperimental ΔpK values from the theory. This drawback of the theorywas already mentioned by Verchoek [10], who performed his study inthe Copenhagen school in contact with Brønsted.

In the principal review [12], entitled like his Dissertation [11] andrecognized as most complete at that time [16], Izmailov presented acomprehensive and lucid classification of non-aqueous solventsaccording to the character of their levelling and differentiatinginfluence on acid strength.2 He proposed the following groups ofsolvents: (1) amphoteric, such as water and alcohols; (2) mixtures ofalcohols and dioxane with water; (3) acidic solvents, such as formic,acetic, propionic acids, sulfuric acid and its mixtures with water, andliquid hydrogen halides; (4) basic solvents, such as ammonia,hydrazine, pyridine, etc.; (5) ‘aprotic’ (‘inert’) solvents: benzene,chlorobenzene, etc.; (6) ‘differentiating’ solvents.

The latter, namely nitriles, nitrocompounds, aldehydes, ketones,amides,3 had by then been known to differentiate the strength of saltsdue to Walden’s papers. Izmailov significantly developed this conceptand adapted it to acids and bases, taking solvation effects intoconsideration. In order to reveal the peculiarities of the solvation ofmolecules, Izmailov compared interactions between acids (carboxylicacids and phenols) and alcohols, on the one hand, and ketones,nitriles, etc., on the other, using the ‘inert’ solvents as media.Cryoscopy, IR and Raman spectra were used for revealing thecomposition, stability, and structure of molecular compounds ofacids with the ‘active’ solvents [11,15,17]. It was demonstrated that the

2 Though some of the numerical values of dissociation constants, especially inacetone, have afterwards been refined, the general regularities hold.

3 In fact, most of these ‘differentiating’ solvents are now known as protophobic sub-group [4] of dipolar aprotic (according to Parker), or non-hydrogen bond donor (non-HBD, according to Bordwell) polar solvents; acid-base equilibria in protophilic non-HBD solvent dimethyl formamide were studied by Izmailov somewhat later, while thebrilliant solvent DMSO became very popular only in the sixties.

influence of ‘differentiating’ solvents is caused by the specificity ofcomposition and polarity of these molecular compounds, HAMn.

Besides, Izmailov underlined the significance of the degree ofcharge delocalization in conjugated anions (e.g., carboxylate andphenolate) with respect to alterations in the strength of correspond-ing acids in organic solvents [14b,15]; later such ideas grew verypopular [18]. These concepts allowed rationalizing the differentchanges in dissociation constants of acids belonging to the samecharge type but to different ‘chemical types’ on going from water toorganic solvents, despite Brønsted’s theory.

Along with this main kind of differentiating influence, Izmailovrevealed the differentiating influence of basic solvents with low εrvalues, caused by the different stability of MH+A– ion pairs, anddifferentiating influence of acetic acid and some other acidic solvents,where the ‘strong’ acids turn into weak ones.

The concept of solvate formation of ions and molecules resulted ina general scheme of dissociation of electrolytes in solution.

3. General scheme of dissociation of electrolytes in solution

In his Dissertation as well as in his publications during the fifties,Izmailov proposed the scheme of dissociation of electrolytes insolutions [11–15,17], which is recognized bymany authors as probablythe most complete one [3,5,19–26]. This detailed scheme (Scheme 1)was initially proposed by Izmailov for the dissociation of acids, inorder to improve and to extend Brønsted’s scheme. Afterwards, heextended this scheme to the dissociation of any electrolyte.

Izmailov underlined that more complicated species, e.g., dimersformed by carboxylic acids in non-polar solvents, etc., are not shownin the scheme though they can appear in solution. The complexanions, HA2

–, considered in detail by Kolthoff and his pupils [4,27], as

well as A(HA)2– species, were alreadymentioned in earlier publications[28,29], which were cited in Izmailov’s papers. In tautomeric systems,the shift of tautomeric equilibria on going from solvent to solvent canalso contribute the net effects [30,31]. Thus, the Izmailov’s schemeincludes only the most principal, universal stages of dissociation.

From this scheme, simple expressions can be derived for thethermodynamic value of the overall constant:

K−1overall = K−1

stab + 1� �

K−1diss + Kass ð1aÞ

Koverall =Kdiss

K−1stab + 1 + Ktr

=KtrK−1

ass

K−1stab + 1 + Ktr

: ð1bÞ

This overall constant, experimentally determined by conductanceor potentiometry, describes the equilibrium between all kinds of

112 N.O. Mchedlov-Petrossyan / Journal of Molecular Liquids 145 (2009) 110–115

neutral species, on the one hand, and the free ions, on the other.Izmailov named this constant as ‘usual’ (or ‘common’, or ‘ordinary’)one.

Originally, Izmailov used his scheme to interpret the influence ofthe solvent on the dissociation of acids, in particular, to explain thedifferentiating action of solvents [12,13]. For example, in the absenceof ion association, pKoverall=pKdiss+ log(Kstab

−1 +1), while in highly basicsolvents with moderate and low εr value, pKoverall= logKass, and so on.

As a rule, the Kstab values are rather high. In other words, thedissociating species are in fact not the electrolytes (e.g., acids), buttheir complexes with solvent molecules; Izmailov’s concept ofdissociation of electrolytes centered on this point.4

A special case of the dissociation of an acid HA is nowadays oftendescribed by two constants, the ‘ionization’ and ‘dissociation’ ones, K1

and K2 respectively.

HAMn±K1

HMþA−±K2

HMþsolv: + A

−solv:

The overall equilibrium constant, experimentally available bymeans of electrochemical methods, is a combination of these twoconstants:

Koverall =K1K2

1 + K1: ð2Þ

Such approach appeared to be useful for sulfonic, fluorosulfonic[32], and picric [33] acids, etc.; for the product of (HCl+LiClO4) reactionin diethyl ether, Pocker proposed the composition H[(C2H5)2O]n+ClO4

–

[34].However, much earlier Izmailov [11–15,17] supposed the existence

of ion pairs between the solvated proton, i.e., lyonium ion, and theanion of the acid: HM+A–. Eq. (1a) coincides with Eq. (2) (if Kstab

−1 bb1,K1=Ktr, K2=Kass

−1).Accordingly, the species HM+A– are the prototype of the hydrogen-

bond BH+A– associate, which is known to be a product of the trans-formation of B·HA [14].

The generalization of the detailed scheme required to consider thedissociation of ionophores, i.e., salts, in different solvents [14]. Whilethe ionophores, or ‘true electrolytes’, exist as ions already in crystalstate and even more so in solutions,5 the ionogens can be representednot only by protonic acids, but also by such substances as triaryl-chloromethane. In accord with the classical Walden’s works, the latterionogen, as well as related compounds, undergo the following trans-formations in liquid sulfur dioxide: Ar3CCl⇄Ar3C+Cl–⇄Ar3C++Cl–

[5,36]. Actually, Izmailov’s scheme is able to explain these equilibriain terms of dissociation of a molecule into free ions, passing throughthe ‘transformation’ stage.6

In 1956, Izmailov finalized the development of his dissociationscheme [14]. Hedemonstrated thatmanyother schemes scattered in theliterature can be regarded as particular cases of the general scheme.

As early as 1954,Winstein et al. [37], Grunwald [38], and Sadek andFuoss [39] reported the existence of twomain kinds of ion pairs, whichare now named contact (tight, short, intimate, internal) and solvent-separated (solvent-shared, loose, long, external) ones, or CIP and SSIPion pairs [5,40]. They are usually designated as C+A– and C+//A–. Thepapers of Lichtin [41] are also to be mentioned in this connection.

In fact, such different kinds of neutral solvated particles have beenalready foreseen in Izmailov’s scheme. In the case of ionophores, theCAMn species are contact ion pairs, while C+solvA–

solv are solvent-

4 This statement, being evident at first glance, was seemingly underestimated until itwas revealed that the relative acidic (basic) strength of various molecules in the gasphase often differs dramatically [5].

5 However, some amazing exceptions, such as a salt formed of Agranat’s cation andKuhn’s anion [5,35], have been reported later.

6 Interestingly, Izmailov never used the term ‘ionization’ in his works.

separate ones. However, the latter can be considered as contact pairsin the case of ionogens, e.g., acids, where they are designated asassociates of a solvated proton (lyonium) with the (solvated) anion.For example, in 1978 Fuoss underlined: ‘Contact pairs of ionogens mayrearrange to neutral molecules, A+B–⇄AB; e.g., H3O+ and acetate ion’[42]. Evidently, this corresponds to the conversion of HM+A– to HAMn

in Izmailov’s scheme for acids.Of course, since then a huge number of papers dealing with disso-

ciation, ionization, association, multiplicity of ion associates includingpenetrated ones, etc., were published. Besides, the terminology used todesignate the equilibriumconstants is versatile [3–5,36–43]. To considerall these results in the present essay is an impossibility. But it can bestated that Izmailov was one of the first who created the adequateprimary picture of the behavior of electrolytes in solution.

4. General equation for dissociation of acids

In order to explain the non-uniform changes in the strength ofacids, occurring along with variation of the solvent, Wynne-Jones [44]paid attention to the difference of ionic radii and thus in differentalterations of the Born electrostatic term. Gurney [45] put forward theconcept of dividing the changes in the dissociation energy of amolecule in solution into additive ‘nonelectrostatic’ and ‘electrostatic’contributions.

Basing on the general scheme of dissociation, Izmailov derived aset of equations describing the changes of the dissociation constantson going from vacuum to a solvent, and also of the overall constantson going from water to non-aqueous solvents. Neutral, anionic,and cationic acids, as well as salts were involved into consideration[11–15,17,46]. His approach based on deciphering of the transferactivity coefficients, γi, which are also called medium effects, medium(or solvent) activity coefficients, degenerate activity coefficients,distribution coefficients, or solvation coefficients.7

For example, taking into account both dielectric properties of thesolvent and solvation of reactants, the simple equation for the overallconstant in the absence of ion association, i.e., the dissociationconstant of an acid HA

ΔpKoverall =ΔpKoverall in solvent Mð Þ−ΔpKoverall inH2Oð Þ= logγH+ + logγA− −logγHA

ð3Þ

was rearranged in the following manner:

ΔpKoverall =ΔpKoverall in solvent Mð Þ−ΔpKoverall inH2Oð Þ

= ∑i

e2

4:6RTri

1eM

−1

eH2O

� �+ ∑

i

ΔGsolvi

2:3RT+ logKr−log

a⁎Ma⁎H2O

+ log1 + K−1

stab + Ktr� �

M

1 + K−1stab + Ktr

� �H2O

−logka Mð Þka H2Oð Þ

:

ð4Þ

Here, e is the elemental charge, R is gas constant, T is absolutetemperature, ΔGi

solv is Gibbs energy of solvation of an ion, Kr is theconstant of proton exchange (MH++H2O⇄M+H3O+), aM⁎ and a⁎H2O areactivities standardized to infinite dilution in the corresponding sol-vent, the quantities ka(M) and ka(H2O) describe the conversion of HAspecies from vacuum to HAMn and HA(H2O)n in solvents M and H2O,respectively.

Actually, the last two items in the right side of Eq. (4) are equal to− logγHA, while the other ones reflect the (logγH++logγA−) sum.

Hence, in addition to the Born electrostatic term for ion energy in adielectric continuum, already used by Brønsted, the items reflecting

7 For activity coefficients of transfer from water to non-aqueous solvents at zeroionic strength, Izmailov used the term ‘unified zero activity coefficients’ and thedesignation γ0,i. Also, activity coefficients of transfer from vacuum to a solvent, γ0,i' , andfrom a hypothetical media with infinite large permittivity, γ0,i

∞ , were used for derivingvarious relations describing dissociation processes.

8 Interestingly, in his book [15] Izmailov wrote about the usefulness of an electrolyteconsisting of tetraalkylammonium cation and an anion with a similar structure.

9 In turn, discussions of the ‘tetraphenylarsonium–tetraphenylborate’ hypothesispermanently appear in the literature [61].

113N.O. Mchedlov-Petrossyan / Journal of Molecular Liquids 145 (2009) 110–115

other solvation effects were included. In this unified equation, themacroscopic εr values are used disregarding dielectric saturation, andfor simplicity the ions are expected to have a spherical shape.

Actually, Eq. (4) was a synthesis of electrostatic approaches(Brønsted, Wynne-Jones, Gurney) and ‘chemical’ theory of solvation(in the spirit of Mendeleyev and Kablukov) [11]. It is justified callingsuch kind of expressions Brønsted–Izmailov equations.

Some authors reasonably mentioned that the experimentalverification of Eq. (4) and other equations of such kind is hindered,because some quantities included therein are not easily available [24].However, though direct utilization of such equations for exactnumerical calculations is in general case impossible, it vividly showsthe nature of possible contributions to the ΔpKoverall values.

Basing on his equation, Izmailov made a conclusion about thesecondary, though significant role of the relative permittivity in thesolvent’s influence on dissociation of electrolytes [11–15,17]. Furtherpublications on formamide (εr=109.5 at 25 °C) [47] and especiallypropylene carbonate (εr=64.4 at 25 °C) [48] confirm this finding.

The problems of acid-base equilibria in solvents with low εr values,such as benzene, other hydrocarbons and their halogen derivatives, areknown to be complicated by ion association [3–5,16,21,25,34]. Hence,the relative strength of acids depends on the nature of the counterionassociatingwith the anion of the acid. Nowadays, newapproaches havebeen developed in order to avoid this obstacle. For example, dockingthe metal cation into the cryptand cage [49] or utilization of organiccations with extremely delocalized charge [50] seems to be promising.Evenmore, attempts to estimate the relative strength of a set of acids inbenzene, chlorobenzene, tetrachloromethane, and 1,2-dichloroethaneas well as in mixtures of benzene with acetone and ethanol, made inthe fifties by Izmailov in collaboration with Spivak, deserve attention[51]. Both spectrophotometric and potentiometric (with quinhydroneelectrode) techniques were used for revealing the character of thedifferentiating influence of the aforementioned media on the relativestrength of carboxylic acids and nitrophenols.

5. Application to chemical analysis and technology

Izmailov repeatedly applied the general scheme of dissociation andthe equations derived from it, including Eq. (4), to analytical chemistry[52], as a continuation of his early works [7,8,17]. In particular, acid-base interactions in glacial acetic acid and in other acidic solventswere studied [52c-g], as well as titrations of oil products in alcohol–benzene mixtures [52h,i] and acids and drugs in dimethyl formamide[52j], by means of potentiometry in cells with quinhydrone, glass, andantimony electrodes, respectively.

The problem of acidic solvents [20,22,32,43b] is of interest hitherto[53]. As early as 1950 it was demonstrated that mixtures of HClO4 andHCl, of p-toluenesulfonic acid and HNO3, and of HClO4 and H2SO4 canbe successfully analyzed in glacial acetic acid by titrationwith pyridinedimethylaniline (quinhydrone electrode, cell with liquid junction)[52c]. Moreover, the acids were arranged in accord with their strengthin the following sequence

HClO4≫p� toluenesulfonic acid > H2SO4ðIÞ > HCl > HNO3;

which agrees with the conductivity data of Hantzsch and Langbein. Atthe same time, it was shown that theobromine and caffeine, which areextremely weak bases in water, can be titrated with p-toluenesul-phonic acid in formic acid, which levels the strength of bases [52d,e],etc.

The comparison of various acidic solvents is of especial interest.Indeed, formic acid does not possess the differentiating influence inrespect to mineral acids owing to its high εr value [52f]. Such levellingrole of the relative permittivity was also observed within the course ofstudies in mono- and dichloroacetic acids (at 70 °C): only CCl3COOH

manifests itself as a solvent which differentiates the strength ofmineral acids [52 g].

Izmailov also adapted his general scheme and equations derivedfrom it to explain the regularities of ion exchange on ionites in organicsolvents [15,17,54] and for optimization of the extraction of sub-stances, mainly morphine and other drugs, from solutions bymeans ofadsorption technique [55].

6. Solvation of molecules and ions

In accord with Eq. (3), the total medium effect can be divided intothe ionic and molecular contributions. For the latter, the aforemen-tioned spectral and cryoscopic research was performed. Simulta-neously, Izmailov developed some aspects of the theory [56] andpractice [57] of physico-chemical analysis.

The solvation of ions was also carefully studied. Izmailov con-secutively proposed a set of extrathermodynamic assumptions forestimating transfer activity coefficients fromwater to solvent for singleions, especially for the proton [58]. The aim was to create a unifiedacidity scale pA for different solvents:

pA = pH−logγH+ ð5Þ

Some of Izmailov’s methods were discussed by Bates [59]. This wasstill the ‘pre-tetraphenylborate era’;8 the modern selected values arecompiled by Marcus et al. [60].9

A series of Izmailov’s studies were devoted to both, concentrationand transfer activity coefficients of hydrogen chloride [58c,d,62] andsalts [63]. Themainmethodwas based on e.m.f. measurements in cellswith quinhydrone, hydrogen, and various amalgam electrodes.Solubility of silver and cesium salts as determined by using isotopes[64] was also utilized for the same purpose.

In 1960, Izmailov published a significant work describing themethod to calculate energies of ion transfer from vacuum to thesolvent, basing on e.m.f. data in cells with and without liquid junction[65]; the paper also includes an interesting discussion concerningenergies of cavity formation in the solvent continuum. This publica-tion must be considered in parallel with some other papers of Sovietphysico-chemists [66]; an example of recent results in this field givesthe work of Kelly, Cramer, and Truhlar [67].

Further, considering ion solvation as complex formation, Izmailovapplied quantum chemistry to estimate proton affinities and ionicsolvation energies at the end of the fifties [68].

Shortly after the pioneering publication of Rabinovich et al. [69],Izmailov started utilization of Volta-cells for determining realsolvation energies and activity coefficients of single ions [70].Afterwards this method appeared to be very fruitful [71].

A set of reports devoted to the estimation of free energies of iontransfer both from solvent to solvent and fromvacuum to solutionwaspublished by Izmailov in the Proceedings of the Soviet Academy ofSciences [68a,72].

7. Indicator electrodes in non-aqueous media

Indicator electrodes are powerful tools for both studying acid-baseequilibria in solutions and analytical purposes. Taking into accountthe difficulties arising for using the hydrogen electrode in somenon-aqueous media, Izmailov already in the thirties started studyingself-fabricated antimony [73] and glass electrodes [74] in organicsolvents.

114 N.O. Mchedlov-Petrossyan / Journal of Molecular Liquids 145 (2009) 110–115

Examining the hydrogen function of the glass electrode in aqueousand, in particular, in non-aqueous media continued after the WorldWar II [75] and was extended in order to clarify the origin of ‘alkaline’and especially of ‘acidic’ errors of the glass electrodes [76]. Investiga-tions of the ion adsorption processes on the surface of glass electrodesby using isotopes [77] were of especial interest. Izmailov’s works inthis field are discussed in the literature [78].

For various purposes some other electrodes, e.g., silver andtungsten ones, were used. These results, as well as studies demon-strating the usefulness of organic solvents in polarography, and a lot ofother information concerning electrochemistry of solvents, weresummarized up in the voluminous 958-page monograph [15].10

In 1973, in recognition of his achievements in the field of glasselectrode studies, Izmailov was posthumously included into the groupof State prizewinners of the USSR.

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(b). A. Marichetti, C. Preti, M. Tagliazucchi, L. Tassi, G. Tosi, Can. J. Chem. 69 (1991)509.

[34] Y. Pocker, R.F. Buchholz, J. Am. Chem. Soc. 92 (1970) 2075.[35] K. Okamoto, T. Kitagawa, K. Takeuchi, K. Komatsu, T. Kinoshita, S. Aonuma, M.

Nagai, A. Miyabo, J. Org. Chem. 55 (1990) 996.[36] (a). P. Walden, Berichte 35 (1902) 2018;

(b). N.N. Lichtin, P.D. Bartlett, J. Am. Chem. Soc. 73 (1951) 5530.

10 It is certainly impossible to mention here all the work carried out by Izmailov andhis pupils. It must be only noted that Izmailov’s publications are well referred to inChemical Abstracts.

[37] S. Winstein, E. Clippinger, A.H. Fainberg, G.C. Robinson, J. Am. Chem. Soc. 76 (1954)2597.

[38] E. Grunwald, Anal. Chem. 26 (1954) 1696.[39] H. Sadek, R.M. Fuoss, J. Am. Chem. Soc. 76 (1954) 5905.[40] J.E. Gordon, The Organic Chemistry of Electrolyte Solutions (Russian translation).

Mir, Moscow, 1979.[41] (a). N.N. Lichtin, H.P. Leftin, J. Phys. Chem. 60 (1956) 160;

(b). N.N. Lichtin, H.P. Leftin, J. Phys. Chem. 60 (1956) 164.[42] R. Fuoss, J. Phys. Chem. 82 (1978) 2427.[43] (a). C.R. Witschonke, C.A. Kraus, J. Am. Chem. Soc. 69 (1947) 2472;

(b). I.M. Kolthoff, S. Bruckenstein, J. Am. Chem. Soc. 78 (1956) 1;(c). G. Boche, Angew. Chem. Int. Ed. Engl. 31 (1992) 731.

[44] W.F.K. Wynne-Jones, Proc. Roy. Soc. London. Ser. A 140 (1933) 440.[45] R.W. Gurney, J. Chem. Phys. 6 (1938) 499.[46] N.A. Izmailov, V.N. Izmailova, Zh. Fiz. Khim. 29 (1955) 1050.[47] (a). M. Mandel, P. Decroly, Trans. Faraday Soc. 56 (1960) 29;

(b). M. Mandel, P. Decroly, Nature 210 (1964) 290.[48] K. Izutsu, I.M.Kolthoff, T.Kujinara,M.Hattori,M.K.Chantooni,Anal.Chem.49(1977)503.[49] (a). I.S. Antipin, A.N. Vedernikov, A.I. Konovalov, Zh. Org. Khim. 22 (1986) 446;

(b). I.S. Antipin, R.F. Gareev, A.N. Vedernikov, A.I. Konovalov, J. Phys. Org. Chem. 7(1994) 181.

[50] (a). I. Leito, T. Rodima, I.A. Koppel, R. Schwesinger, V.M. Vlasov, J. Org. Chem. 62(1997) 8479;

(b). K. Abdur-Rashid, T.P. Fong, B. Greaves, D.G. Gusev, J.G. Hinman, S.E. Landau, A.J.Lough, R.H. Morris, J. Am. Chem. Soc. 122 (2000) 9155.

[51] (a). N.A. Izmailov, L.L. Spivak, Zh. Fiz. Khim. 36 (1962) 757;(b). N.A. Izmailov, L.L. Spivak, Zh. Fiz. Khim. 36 (1962) 1158.

[52] (a). N.A. Izmailov, Zh. Anal. Khim. 4 (1949) 267;(b). N.A. Izmailov, Zh. Anal. Khim. 4 (1949) 275;(c). A.M. Shkodin, N.A. Izmailov, Zh. Obsh. Khim. 20 (1950) 38;(d). A.M. Shkodin, N.A. Izmailov, N.P. Dzyuba, Zh. Obsh. Khim. 20 (1950) 1999;(e). A.M. Shkodin, N.A. Izmailov, N.P. Dzyuba, Zh. Anal. Khim. 6 (1951) 273;(f). A.M. Shkodin, N.A. Izmailov, N.P. Dzyuba, Zh. Obsh. Khim. 23 (1953) 27;(g). A.M. Shkodin, N.A. Izmailov, N.P. Dzyuba, Ukr. Chem. J. 20 (1954) 595;(h). S.R. Sergienko, N.A. Izmailov, L.L. Spivak, P.N. Galich, Zh. Anal. Khim. 10 (1955)

315;(i). S.R. Sergienko, P.N. Galich, N.A. Izmailov, L.L. Spivak, Zh. Anal. Khim. 11 (1956)

785;(j). N.P. Dzyuba, N.A. Izmailov, Ukr. Chem. J. 31 (1965) 403.

[53] Á. Buvári-Barcza, L. Barcza, Pharmazie 60 (2005) 243.[54] N.A. Ismailow, Z. phys. Chem. 215 (1960) 314.[55] N.A. Izmailov, Yu. V. Shostenko, S. Kh. Mushinskaya, Usp. Khim. (Russ. Chem. Rev.)

24 (1955) 346.[56] (a). N.A. Izmailov, Zh. Fiz. Khim. 27 (1953) 807;

(b). N.A. Izmailov, Zh. Fiz. Khim. 25 (1956) 1070.[57] (a). N.A. Izmailov, K.P. Partskhaladze, Ukr. Chem. J. 22 (1956) 167;

(b). N.A. Izmailov, A.K. Franke, Ukr. Chem. J. 22 (1956) 557;(c). N.A. Izmailov, M.N. Tzarevskaya, Ukr. Chem. J. 26 (1960) 688.

[58] (a). N.A. Izmailov, Zh. Fiz. Khim. 23 (1949) 639;(b). N.A. Izmailov, Zh. Fiz. Khim. 23 (1949) 647;(c). N.A. Izmailov, V.V. Aleksandrov, Zh. Fiz. Khim. 24 (1950) 1004;(d). N.A. Izmailov, V.V. Aleksandrov, Zh. Fiz. Khim. 31 (1957) 2619.

[59] R.G. Bates, in: J.F. Coetzee, C.D. Ritchie (Eds.), Solute-Solvent Interactions, NewYork, 1969, pp. 45–96, Ch.2.

[60] (a). Y. Marcus, M.J. Kamlet, R.W. Taft, J. Phys. Chem. 92 (1988) 3613;(b). C. Kalidas, G. Hefter, Y. Marcus, Chem. Rev. 100 (2000) 819;(c). G. Hefter, Y. Marcus, W.E. Waghorne, Chem. Rev. 102 (2002) 2773.

[61] (a). R. Schurhammer, G. Wipff, New J. Chem. 23 (1999) 381;(b). R. Schurhammer, G. Wipff, J. Phys. Chem. A 104 (2000) 11159;(c). J. Schamberger, R.J. Clarke, Biophys. J. 82 (2002) 3081;(d). L.I. Krishtalik, Russ. J. Electrochem. 42 (2006) 1006.

[62] N.A. Izmailov, I.F. Zabara, Zh. Fiz. Khim. 20 (1946) 165.[63] N.A. Izmailov, E.F. Ivаnоva, J. Chimie Phys. et de Phys.-Chim. Biol. 55 (1958) 354.[64] N.A. Izmailov, V.S. Chernyi, Zh. Fiz. Khim. 34 (1960) 127.[65] N.A. Izmailov, Zh. Fiz. Khim. 34 (1960) 2414.[66] (a). V.A. Pleskov, Usp. Khim. (Russ. Chem. Rev.) 16 (1947) 254;

(b). V.P. Vasil’ev, E.K. Zolotarev, A.F. Kapustinskii, K.P. Mishchenko, E.A. Podgornaya,K.B. Yatsimirskii, Z. Fiz. Khim. 34 (1960) 1763.

[67] C.P. Kelly, C.J. Cramer, D.G. Truhlar, J. Phys. Chem. B 111 (2007) 408.[68] (a). N.A. Izmailov, Yu. A. Kruglyak, Doklady AN SSSR 134 (1960) 1390;

(b). N.A. Ismailov, J.A. Krugliak, R. Gáspár, I. Tamássy-Lentei, Acta Phys. Acad. Sci.Hung. 13 (1961) 203.

[69] V.A. Rabinovich, A.E. Nikerov, V.P. Rotstein, P.N. Sokolov, Leningrad Univ. Bull. 4(1960) 101.

[70] (a). N.A. Izmailov, Yu. F. Rybkin, Dopovidi AN URSR (Proc. Acad. Sci. of UkrainianSoviet Soc. Rep.), 1962, p. 69;

(b). N.A. Izmailov, Yu. F. Rybkin, Dopovidi AN URSR (Proc. Acad. Sci. of UkrainianSoviet Soc. Rep.), 1962, p. 1071.

[71] (a). V.A. Rabinovich, A.E. Nikerov, V.P. Rotstein, Electrochim. Acta 12 (70) (1967) 155;(b). B. Case, R. Parsons, Trans. Faraday Soc. 63 (1967) 1224;(c). R. Parsons, B.T. Rubin, J. Chem. Soc., Faraday Trans. 1 (1974) 1636;(d). Yu. F. Rybkin, Usp. Khim. (Russ. Chem. Rev.) 44 (1975) 1345.

115N.O. Mchedlov-Petrossyan / Journal of Molecular Liquids 145 (2009) 110–115

[72] (a). N.A. Izmailov, Doklady AN SSSR 126 (1959) 1033;(b). N.A. Izmailov, Doklady AN SSSR 127 (1959) 104;(c). N.A. Izmailov, Doklady AN SSSR 149 (1963) 884;(d). N.A. Izmailov, Doklady AN SSSR 149 (1963) 1103;(e). N.A. Izmailov, Doklady AN SSSR 149 (1963) 1364;(f). N.A. Izmailov, Doklady AN SSSR 150 (1963) 120.

[73] N.A. Izmailov, V.P. Pivnenko, Materials of Research Work of the Ukrainian Instituteof Soviet Commerce, Kharkov 1 (1940) 14.

[74] N.A. Izmailov, M.A. Belgova, Zh. Obsh. Khim. 8 (1938) 1873.[75] N.A. Izmailov, T.F. Frantsevich-Zabludovskaya, Zh. Obshch. Khim. 16 (1946) 501.

[76] (a). N.A. Izmailov, A.M. Aleksandrova, Zh. Obsh. Khim. 19 (1949) 1403;(b). N.A. Izmailov, A.M. Aleksandrova, Doklady AN SSSR 71 (1950) 311;(c). N.A. Izmailov, A.M. Aleksandrova, Zh. Obsh. Khim. 20 (1950) 2127.

[77] (a). N.A. Izmailov, A.G. Vasil’ev, Zh. Fiz. Khim. 29 (1955) 2145–5471;(b). N.A. Izmailov, A.G. Vasil’ev, Zh. Fiz. Khim. 30 (1956) 1500;(c). N.A. Izmailov, A.G. Vasil’ev, Doklady AN SSSR 95 (1954) 579.

[78] (a). A.T. Cheng, R.A. Howald, D.L. Miller, J. Phys. Chem. 67 (1963) 1601;(b). R.G. Bates, Determination of pH. Russian transl, Khimiya, Moscow, 1972.