SCIENTIFIC ABSTRACT YATSIMIRSKIY, K. B. - YATSIMIRSKIY, K. B.

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• Collection: Scientific Abstracts
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• Publication Date: December 31, 1967
• Content Type: SCIENTIFIC ABSTRACT

Card 2/2
5W_
Influence of Ionic Force on the Instability Ponstants of
Halogen and PBeudo-Halogen Complex Compounds. (Cont*.)
the Davies(9) equation can similarly be used for converting
the constant to zero ionic- force if this latter is below
values of the order of OA. The instability constant for
the ZnCNS'~ complex has-also been found by the equilibrium-
shift method in the system Fe3+_ - CNS- electrolyte.
There are twenty five references, four of them kassian.
Ref.9 is CA.Davies, J',Amer'. Chem'. Soo., 2093, (1938)'.
5 Tableaq 5 Figures, 19 Equations'.
Ivanovskiy Chemical Tecbnology Institute,
Received 11 September, 1956.
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AUTHOR: Yatsimirskiy., t.1B. 78-3-2/35
TITLE: Thermodynamics of Complex-Formation Reactions
in Solutions. (Termodinamika Reaktsiy
Kompleksoobrazovaniya v Rastvorakh).
PERIODICAL: Zhurnal Neorganicheskoy Khimii, 1957, Vol.II,
Nr.3, pp. 491-501. (USSR)
ABSTRACT: This is a report presented at the Seventh All-Union
Conference on the chemistry of complex compounds,
hold 12th October, 1956. Starting from a brief review
of methods used recently for the investigation of
equilibria in solutions of complex compounds, the author
goes on to show in a tabular form the relative amount of
effort devoted to the study of the stability of various
complex compounds in solution.# Attention is drawn to
the importance of the question as to whether all inter-
mediate stepa are realised in step-wise complex formation.
This question is fundamental to the mathematical methods
used for treating experimental data and for the relation-
Card 1/2 ships between the stepwise instability constants. It is

.thermodynamics of Complex-Formation Reaetions in Solutions.
shown that best agreement between experimental and
calculated data for aluminiumfluoride complexes was
obtained with the use of the equation proposed by Van
Fanthaleon(13); this equation also gives good results
for other fluoride complex compounds and also for several
complexes with ammonia, imidazole and other substances.
The data presented show that careful study must be made
not only of the composition of the*intermediate complex
particles, but also of their stereochemical features.
Thermodynamic functions for step-wise complex formation
are tabulated for different series of compounds, and a
table is also presented showing the distribution of
electrons by energy levels in an octahedral field. it
is shown that the ideas used can lead to explanations of
observed regularities in the changes of the stability of
complex compounds and also of apparent discrepancies.
There are 11 figures, 5 tables and 27 references, 10
of which are Slavic.
SUBMITTED: 29 October, 1956.
Card 2/W
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Y,4TS 0'ril psi~l /, ~Z, Z.
YATSIMIRSKIY, K.B.; GUSIKOVA, L.V.
Thermochomistry of thloaulfate complexes of cadmium and zinc.
Zhur.neorgokhims 2 no#9;2039-2042 S 157. (MIRA 10:12)
1.Ivanovskiy khimiko-tekhnoloitichaskiy- institut im. D.I. Mendeleyeva.
(Thermochemiitry) (Cadmium thiosulfate)
(Zinc thiosulfate)
r
A, 33

TATSIM
The entropyof polyatomic ions [with summary in English]. Zhur.
fiz.khim. 31 no.9:2121-2126 S 157. (MM 11:1:
I.Khimiko-tekhnologicheakiy Institut, g. Ivanovo.
(Entropy) (ions)
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AUTHORS: Y;:.tsimirsld~y, K.B. Alekseyeva, 1.1. 153 --58-1..8/29
- - ----------
TITLE: The Investigation of Absorption Spectra and the Determination
of the Dissociation Corstants of Molybdio Acid (Izuoheaiye
spektrov pogloshcheniya i opreaeleniya konstant dissotsiataii
molibdenovoy kisloty)
PERIODICAL: Izvestiya vysshikh uchebnykh zavedeniy Khimiya i khimicheskaya
tekbnolog*&, 1958, Nr 1, pp. 53-58 (USSR)
ABSTRACT: A process of depolymerization is assumed to take place during the
dilution of molybdio acid solutions, and it is believed that
highly diluted solutions contain nearly only monomeric particles.
The correctness of this asswnption is confirmed also by the study
Of complex molybdenum compounds (by the application of the kinetic
method). The authors were therefore interested in investigating
these diluted molybdio acid solutions by the optical method. They
obtained the following results: Highly diluted molybdic acid solu-
tions contain no polymerized particles, which pr*ves the constancy
of the molar extinguishing coefficient within t fairly Wensive
interval of the molybdenum ooncentrates (2~10- to 2-10 . M). By
Card 1/2 the kinetic method it waa established that in acid solutions and

The Inve tigation of Absorption Spectra and the Determinatir-
3"
of the Dissociation Constants of Mo2,ybdic Acid 153 ~58-1-8/29
in the case of a high degree of dilution mainly non-dissociated
molecules of molybdio acid exist. It may therefore be expected
that in the case of low pH--values non-disaociatea molecules, buti
at higher pH-values hyaromolybdate- and molybdate ions will be
found (as dissociation products of molybdic acid). For the de-
termination of the H2MoO47disaociation constants and for the pur-
pose of investigating the absorption spectre, the dependence of
the optical dowity of the solutions upon the concentration of
the hydrogen ions vai studied. According to the aourve taken by
the curve (fig.1) the existence of 3 kinds of parUcles with
diverse molar extinguishing coefficients according to pH values
must be expected. On the strength of the experimental data ob-
tainea absorption spectra of molybdic acid as well as of dissooi-
ation products were obtained (fig.3). There are 3 figures, 3
tables, and 6 referenceB: 2 of which an Soviet.
I
ASSOCIATION: Wedra'analiticheskoy khimii (Chulr,of Analytical
Chemistry) - I
SIMMITTED: Sc-ptct.,-bcr 101 1957
Card 2/2

5M
AUTHORS:
TITLE:
PERIODICALs
ABSTRACT:
Card 1/3
Yasinskene, E. I., Y4,tsimirskiy, K. B. SOV/153-58-2-6/330
Examination of the Complex Compounds of Iron (III) and
Titanium (III) With Ursa (Issledovaniye komplekanykh
soyedineniy zheleza (III) i titaniL (III) a mochevinoy)
Izvestiya vysshikh uchebnykh zavedehiy. Khimiya i khimicheakaya
tekhnologiya, 1958t Nr 2, PP 31-35 (USSR)
When mixing a diluted iron (III) nitrate solution with urea
there is no perceptible change of color. This prevents a
direct examination of such systems by measuring the optical
density of solutions with different urea concentrations. On the
other hand, it has been stated that the color intensity of
solutions of the iron rhodanide complexes decreases more
distinctly by an addition of urea solution than by a dilution
with-equal quantities of water. This could only be explained by
the formation of an iron urea compound. Therefore, the
iron (III) compounds with urea have been studied by means of
decolorizing the solutions which contain iron rhodanide
complexes. A literature survey on the latter is given (Refs 1-6).
J,

Examination of the Complex Compounds of Iron (III) SOV/153-56-2-6/30
and Titanium (III) With Urea
From this, it has become obvious that it is pos3ible to make a
solution in which the complex FeSCN2+ will be predominantly
present. For their calculations, the authors required a
knowledge.of the instability constant of the iron (III)
rhodanide complex K FeSCN2+ *
C o n o 1 u a i o n a i The authors have studied the system
Pe3+-SCF- -CON2H4 by means of the optical method. They
determined the formation of complex compounds in the solution:
FeCON2H4 3+ and Fe(CON2H4)23+ . The instability constants of
these complexes were determined as 1.01 and 2.00, respectively;
the ionic strength being 0-103 and the temperature 18-200 .
2) Urea-containingg diluted, acid TiC13-solutions have been
studied. The formation of a complex compound Ti(CON2H4 )3+ in
the solution was determined; its instability constant at the
ionic strength 0.261 and. at 18-200 was k 2.69
Card 2/3
of

Examination of the Complex Compounds of Iron (III) SOV/153-58-2-6/30
and Titanium (III) With Urea
There are 4 figures, 2 tables, and 11 references, 5 of which
are Soviet.
ASSOCIATION: Vilfnyusskiy gosudarstvennyy universitet im. V. Kapsukasa i
IvanoVBkiy khimiko-tekhnologicheskiy institut
(Vilnyus State.University imeni.V. Kapsukas and Ivanovo
Chemical-Technological Institute)
Kafedra analiticheskoy khimii
(Chair of Analytical Chemi'stry)
SUBMITTED: September 10, 1957
Card 3/3

5 2
AUTHOPS:
D. S0V/157-'-,8-2-8/3o
Berozin, B.
,
TITLE: The Indicators of Mercurimetry (Indikatory merkurimetrii)
Communication I. Sodium Nitroprusside (Soobshcheniye I.
I
ilitroprussid natriya)
PERIODICAL: Izvestiya v-js..-,hikh uchebnykh zavedeniy. Khimiya i khimichec-
kaya tekhnologiya, 1958, Nr 2, PP 43 - 50 (USSR)
ABSTRACT: The method of mercurimetric analysis is used at
present in the determination of various substances
on a large scale. It is based on the capability
of the ions of bivalent mercury of forming stable
complex compounds with several anions and molecules
according to the reaction
Hg 2+ + nAz------~' HgA 2-nz M. This method increasingly
n
,replaces the argentometric method, as it has a
number of advantages over the latter. The mercurimetric
method is, however, hardly known-in quantitative
Card 1/4 respect. The limits of its applicability with various
i F7 ~,T--M I 'M;lt
Y
ji
4'~

The Indicators of Mercurimetry. Communication I. SOV/153-58-2-6/30
Sodium Nitroprusside
indicators an well as the most important quantitative
characteristics of the letter are not known. The
present paper deals first of all with the investiCation
of the solubility of Hg~Fe(CN) 51103. In the experimental
part first the solubility of this Indicator is
studied in water. Table 1 gives the results. Further-
more its solubilit is investigated by the pre-
cipitation method ~Table 2). From the data of
table I the authors at'empted to calculate the
solubility product A. 4gl,',pr of mercury nitroprusside
fron the following relation: $ 92+ 3~~`Npr 2-j(1).
11411pr -'[H ,
From the observation of the process of atepwise
complex formation (IV) the expression of the correction
for the stepwine complex formation is determined. After
this correction is introduced, and after the
simplification and insertion of knovin quantities, the
following equation is obtained:
r1-1 OIA

The Indicators of Mercurimetry. Communication 1. SO'1/153-55-2-8/30
Sodium Ritroprusside
1
5 ~Vend 1HgCl 21
2
-r,-, 1 g c7
&V 2.64-010- . - . 1:1)
m -17 0 2-j
11p,
CHg2+ Npr
F
1
where 41 Vml denotes the correction (in Mr-) of the
titration liquid mercury nitrate of a concentration
Co 2+; it is alwz.ys detracted from the final volume
H9
of the mercury nitrate solution used for the titration;
Vend denotes the final volume of the solution after
Npr 2-j denote the con-
the titration;c HgCl 211 andc,
centrations of mercuric chloride or nitroprusside,
respectively in the solution after the titration. To
.provd that the equation (5) fully reflects the nature
of the correction in the merc~rimetric determination
of the chloric with the ni-troprusfjide indicator under
normal.titration.conditions t-ble 4 giveo a conparioon
of the correction s calculated according to (5) vrith
Card 3/4 those experimentally found. The experimental data

The Indicators of Mercurimetry. Communication 1. 51GV1;::7-z'-3-2-9 /;ts
Sodium Nitroprusside
of table 4 permit the conclusion that the equation (5)
;can be used for a sufficiently accurate calculation
of the mentioned corrections if the titration is
carried out fairly slowly and under con2tant
stirring (by hand). These possibil.ities make sodium
nitroprusside one of the 'best indicators of morcuri-
metry. There are 1 figure, 4 tables, and 13 references,
4 of which are Soviet.
ASSOCIATION: Ivanovskiy khimiko-tekhno--10gL.-eskiy institut (Ivanovo
Chemical Technological IrE~titlute) Kafedra analiticheskoy
khinii (Chair of Analytical Chemictry)
SUBMITTED: September 10, 1957
Card 4/4
!M40

50), 5(2)
AUT11011IS: Yatainirokiy, K. B. f Fed-)rova, T. 1. J
TITLE: Inveati-ation of For.-.ja'41-e and Thiocyanate Complexes
Z
A
.
of Bivalent Chroi-AU1.1 (Izucheniye formiatnyk1h i
rodanidnyk-h komple!-sov dvukhvalontnogo khrona)
PERIODICAL: Izveatiya vyoi3hij',h Lich(.,Ijnykh zavadeniy. Khiz.-Aya i khi-lichc~o-
kaya takhtiolo-iyat 19589 Ur 3, PP 40 - 4~
U

ABSTRACT; In continuation of the papers hitherto published
(Ref 1) the authors decided to study the composition
and stability of the complexes under review. The
measure-ients of the optical density were carried
out by means of the photometer jt4'. Titrated
solutions of chromium (II) chloride, sodium formate
and potassium thiocyanate were used for that purpose.
Preliminary experiments already demonstrated a
variation of the color and its intensity, respectively,
in pouring together the first and second (Refs 2-4),
colution, respectively.
and the first and third c
Card 1/3 For the investi,-ation of the complex chromium (II)

Inv estiGation of Forn-te and Thiocyanate Complexes of SOY/153-5-0-7-71/3c
Bivalent Chromium
compounds with forinate by the optical method light
absorption curves of chromium (II) chloride
without and with formate were plotted (Fig 1). The eOM-
position and stability of the complex compounds
formed were determined by mixing the chromium
chloride oolutione (with a constant concentration
0.47 mols/t) with sodium formato solutions of
variable, concentration (from 0.05 to 10 molsM.
The optical density of these solutions wan then
determined by means of a light filter (transmission
range at 618mv). The results are presented in table 1
and fi-ure 2. The chromium thiocyanate complexes
were studied with two light filters: 619 and 574 mg.
The results (for'A,= 574 mg) are given in table 3 and
figure 2. It was proved by.these investia--.tions
that bivalent chromium forms with formate and
thiocyanate in solutionscompl x compounds of the
following composition: CrHCOC~,, Cr(HCOO) , CrC1115,,
Card 2/3 Cr(CNS )2 The inotability constants of tKese complexes
-777777777777777M77MM77

Investiga-tion of Formate wnd Thiocy=ate Complexes of SQ7/ z 7r: P- 7-7 /:Z
Bivalent Chromium
at 25' and at a ionic strength 0 were calculated
an'd are given. There are 6 figures, 4 tables, and 7
references, 4 of which are Soviet.
ASSOCIATION; Ivanovskiy khiniko-tekhnolo,-iciieskiy institut (Ivanovo
Institute.of Chemical Tochnolob"Y) Kafedra analiticheskoy
khimii ( Chair of Analytical Chemistry)
SUBMITTED: September 10, 1957
Card

5W SOV/153-58-3-29/30
AUTHOR: Yatsimirskiy, K. B.
TITLE: Calculation of the Stabilization Energy on a Splitting of the
Main Level in the Crystalline Field (Raschet energii
stabilizatsii za schet rasshchepleniya osnovnogo urovnya v
kristallicheskom pole),
PERIODICAL: Izvestiya vysshikh uchebnykh zavedeniy. Xhimiya i
khimi'cheskaya tekhnologiya, 1958, Nr 3, PP 170-172 (USSR)
ABSTRACT: On the action of the crystalline field on an ion Yrith ex-
ternal d-electrons the main energy level is split up into sev-
eral new ones. The electron redistribution to these levels is
accompanied by an increase in energy & (Ref I - only for spe-
cial cases). The author tries to find a general solution of
the problem of the calculation of A. After various steps he
arrives at the general equation for the calculation of the in-
crease in energy due to the action of the crystalline field on
an ion with d-electrons:
Z n (E E (6)1
1)
5 1
Card 1/3 where 5 denotes the average electron number for one cell,

SOV1153-58-3-29130
Calculation of the Stabilization Energy on a Splitting of the Main Level in
the Crystalline Pield
Card 2/3
911 92 teaegm the number of cells for each level, n1l n2 ... nil
nM the electron number in Ithese Cells, and E1' E2 ... Em the
energies of the newly formed levels. The author discusses some
special cases: octahedral field, tetrahedral and tetragonal
field, and derives the corresponding equation for each of
them. Among the tetragonal field two extreme cases were dealt
with: a) The tetragonal bipyramid represents an only slightly
deformed octahedron, and b) The tetragonal bipyramid is
maximally expanded along the axis of the fourth order. In the
table the values of the multiplier befor;e (E 4 -Ej) as well as
those before (E2 - Ej) in the equations (7a), (a), and (12) are
men'tioned for the series of ions with two oharges. The data
mentioned show that the position of the 'stability maximum due
to the action of the crystalline field depends on the spatial
arrangement of the surrounding particles: in an octahedral
surrounding the maximum decreases to V2+ and Ki 2+ , and in a
2+ 2+
tetragonal one to Ti and Co The author had arrived at the
4

SOV/ 153-58- 3-29/30
Calculation of the Stabilization Energy on a Splitting of the Ya-n 7eyej ir,
the Crystalline Field
same conclusions, now proved by experimental results, already
at some earlier time on the basis of other considerations
(Ref 3). There are 1 table and 3 references, 1 of which is
Soviet.
,16"OCIATION: Ivanovskiy khimiko-tekhnologicheskiy institut (Ivanovo Insti-
0
tute of Chemical Technology) Kafedra analiticheskoy khimii
(Chair of Analytical Chemistry)
SUBMITTEDs danuary 18, 1958
3/3

5W
AUTHORSt Vasil'yev, V. P., Korableva, V. D.1 SOV/153-58-3-30/30
Tatsimirskiy. K. B.
TITLEt Conference Discussion on the Methods of Investigating the
Complex Formation in Solutions (soveshohaniye-diskussiya
po metodam izuoheniya kompleksoobrazovaniya v rastvorakh)
PERIODICAL: Izvestiya vysshikh uohebnykh zavedeniy. Khimiya i
khimiohBakaya tekbnologiya, 1956P Hr 3P PP 173 - 174 (USSR)
ABSTRACTs From February 18 to 21, 1956 a conference discussion took
place at the town of Ivanovo; it dealt with the subjects
mentioned in the title. It was called on a decision of the
VIIth All-Union Conference on the Chemistry of Complex
Formations. More than 200 persons attended the conference,
among them 103 delegates from various towns of the USSR.
At the conference methods of determining the.oomposition of
the 'complexes in solutions were discussed, as well as the
methods of calculating the instability codstants according
to experimental data and problems concerning the influence
of the solvent upon the processes of complex formation.
I. I. Chernyayev, Memberp Academy of Sciences, USSJR, stressed
Card 1/16 in his inaugural lecture the great importance and actuality

Conference Discussion on the Methods of SOT/153-58-3-30/30
Investigating the Complex Formation in Solutions
of the problems to be dealt with, and wished the conference
all the best in Its work# I* Ve Tananayev, on behalf of the
Orgkomitet (Organization Oommittec) hold a lecture ont "The
Method of Determining the Composition of Compounds Formed in
Solutions", In hie 199turel V. N. Tolmaohev dealt with the
problem of the graphical interpretation of the method by
ostromyslenskiy-Zhob. It was proved that this method can
also be used in such oases where the equilibrium of complex
formation was turned complex by the hydrolysis or dimerization
of the central ion. In the lecture by A. K. Babko and
M. M. Tananayko, "Physical and Chemical Analysis of the
Systems With 3 Colored Complexes in the Solution", the reBUltS
of a systematic investigation in copper-quinoline-salicylate,
as well as in oopper-pyridine-salicylate systems by means of
the optical method were dealt with. In the lecture by Ya. A.
Fialkov the idea of a further investigation of the complex
formation processes in solutions was developed. Besides the
determination of the composition and stability of the complexes
also the physical and chemical properties, the chemical nature
Card 2/16 and the structure of the complex compounds must be investi-

Conference Discussion on the Methods of SOV/153-58-3-30/30
Investigating the.Complex Forma.tio.n in Solutions
gated. The lecture by K. B. Yatsimirskiy dealt with the
conditions of checking '1R-e_u_s-eTU71_n_es~ o:rthe method of isomolar
aeries in the determination of the complex composition. To
be able to obtain objective results the position of the
maximum at various concentrations of the components must be
checked. A. K. Babko made several critical remarks concerning
the lecture by L V. Tananayev. He pointed out that such a
method of investigation must be chosen that is connected with
the characteristic properties of the system investigated.
A. P. Komar' mentioned in his lecture that for the time being
the method by Ostromyslenskiy-Zhob is the best for determining
the complex composition, and should be employed as often as
possible. This demands, however, that,all instructions con-
cerning this method are strictly obeyed. L S. Mustafin,
L. P. Adamovich and V. I. Kuznetsov took part in the discus-
sion. K._A ~Yat&imirskiy proved in his lecture "Hydrolytic
Equilitrl7a and tKe ~Polya_erization in Solutions" that, if the
hydrolysis products are polymerized, the "inclusion into the
complex" and the "formation function" at a constant pH value
Card 3/16 are varied with the modification of the total concentration of
R
a- PUM
r -5. 61,
e" R U
V K

Conference Discussion on the Methods of SOY/153-58-3-30/30
Investigating the Complex Formation in Solutions
the metal. Therefore all those methods may be employed for
investigating the polymerization of this type which make the
determination of at least one of the two functions mentioned
possible. It was proved that the hypotheses on the existence
of complexes of the type "nucleus + chain members" can also
be founded from the viewpoint of structural conceptso particles
the charge of which does not exceed unity can occur as "chain
members". The usefulness of the characterization of areas of
existence of pclymers by means of surface diagrams: "total
concentration of the metal - pH11 was proved as well. L I.
Alekseyevs, and K. B. Yatsimirokiy in their lecture "Investiga-
.tion of the Polymerization of Iso-Poly Acids in Solutions"
mentioned experimental results of the investigation of the
polymerization in solutions of molybdio acid. The authors
proved that especially the molybdic acid within a certain
range of the pH values and the concentrations exists as a
number of compounds that can be expressed by an overall formula
m004 (amoo4)n-2, In the lecture by N. V. Aksel'rud and V. B.
Card 4/16 Spivakovskiy investigation,reaulto on basic salts taking into

Conference Discussion on the Methods of SOV/153-58-3-30/30
Investigating the Complex Formation in Solutions
account the complex formation in solutions by means of the
potentiometrie method were mentioned for systems with zinc,
cadmium and indium. In the evaluation of their results the
authors employed the method of the table difference. The
calculation of the consecutive constants was carried out
according to the interpolation formula by Newton. M. A.
Chepelevtokiy held -a lecture on 11pH Measurement Method of
the Solutions in Combination With t4j_System Analysis of the
Solubility Diagram of the System Oul-F-EC1 - H 20 in Investiga-
ting'Complex Copper Compounds in Saturated Solutions". It
was found that the substance at the bottom of the liquid is
more basic than the solutions furthermore, the increased
acidity of the solution from the viewpoint of the formation
of hydroxy-ohloro complexes in the solutiorf was explained.
Y. 11. Kuzneteov opened the discussion with his lecturej he
pointed 'but the necessity of utilizing the concepts worked
out in the investigations of the polymerization in organic
chemistry in the chemistry of polynuclear complexes. A. A.
Card 5/16 Grinberg thinks that the new approach of the hydrolysis

Conference Discussion on the Methods of BOY/153-58-3-30/30
Investigating the Complex Formation in Solutions
Card 6116
investigation as developed by the Scandinavian school is of
high value. He also pointed to the necessity of studying
the kinetics of the polymerization process and a quantitative
determination of the strength of the polymerse A. K. Babko
pointed out that the study of the polymer structure was
necessary. N. P. Komar' mentioned in hie lecture that the
rather widely spread polymerization type according to the
scheme "nucleus + chain members" is not obtained in all cases.
The following scientists took part in the discussion: V. N.
Tolmaohev, A. V. Ablov, I. S. Mustafin, I. V. Tananayev and
J. B. Yatsimirskiy. A. K. Babko then discussed in his lecture
T%deitlibde` -of Deiisrimining the Dissociation Constant of the
Complex Groups in Solutions" the main principles of determining
the instability constants. N. P. Komar' discussed in his
lecture "Calculation Methods of the Instability Constants of
the Complex Compounds According to Experimental Data" the
possibilities of using the known calculation methods of the
instability constants for various oases of the complex forma-
tion in solution. If'oeveral mononuolear complexes are formed
the displacement method by Abegg and Bodlender (completed by

Conference Discussion on the Methods of SOV/153-58-3-30/30
Investigating the Complex Formation in Solutions
A. K. Babko) cannot be recommended for the calculation of
the instability constant. The lecturer discussed the dis-
solution methods of the polynomials proposed by B'yerrum,
leden, Rossoti, Sketaharcl, Edsolloy and other authors. The
constants calculated in this way are not very accurate. It
was proved that the method of successive approximations can
lead to wrong conclusions as to the chemical processes taking
place in the system investigated. The most probable value
of the physical constanta can be obtained by the method of
the least squares. B. V. Ptitsyn, Ye. N. Tekster and L. I.
Vinogradova described the determination methods of the
instability constants of the oxalate complexes of niobium,
uranium and iron which are based on the investigation of the
equilibrium displacement of the complex formation by silver
ions. N. k. Bol'shakova, I. V. Tananayev and G. S. Savch&nko
h6ld'a lecture on "The Role of the Time Factor in the Investiga-
tion of the Complex Formation". In the discussion on the
lectures A. A.. Grinberg mentioned that due to the slow
adjustment of the equilibria the methods discussed of
Card 7/16 determining the instability constants (palladium and cobalt

Conference Discussion.on the Methods of SOV/153-58-3-30/30
Investigatingthe Complex Formation in Solutions
complexes) can often not be employed. A. V. Ablov pointed
out the necessity of devising direct methods of proving the
existence of intermediate forms in a step-wiae complex forma-
tion. K. B. Yatsimirskiy mentioned that the instability
constanis-ot--S,io-w-l-y--&issooiating complexes can be calculated
from thermochemical data. L. P. Adamovich, A. R. Golub
among others took part in the discussion on the lectures.
A. K. Babko requested inclusion in the next conference on the
chemistry of complex compounds a lecture in which various
calculation methods of the instability constants should be
discussed by the example of actual cases. This should clarify
to which divergencies of the values of the constants dif-
ferent methods of evaluating the experimental data can lead.
N. P. Komaro stressed that in the determination of the
instability constants.all chemical equilibria should be taken
into account that render complex the complex formation process
in the solution, especially the hydrolysis processes of the
central ion and the addendum. In the lecture delivered by
V. M. Peshkova and A. P. Zozulya "Application of the DiBtribu-
Card 8/16 tion Method to the Investigation of the Stability Constants
Y~

Conference Discussion on the Methods of SOV/153-58-3-30/30
Investigating the Complex Formation in Solutions
of Some Thorium Complex Compounds" results obtained from the
experimental investigation of the distribution of thorium,
compounds in the systems: acetylacetone benzene - water, and
2-oxy-1,4,-naphthoquinone - chloroform water were given.
From these data the instability constants of the thorium
complexes with aoetyl-acetone and 2-oxy-1,4-naphthoquinone
were calculated. 1. V. Tananayev, G. S. Savchenko and Ye. V.
Goncharov held a lecture on the application of the solubility
method in the determination of the stability of complex
compounds in solutions. In this lecture also other methods
of investigating complex formation processes in the solution
were discussed (PH measurement, measurement of the optical
density, as well as of the heat of mixing). B. D. Berezin
hold a lecture on the "Application of the Sol-ability Method
in Studying the Fhthalocyan~ne Complexes of Metals". He
used the determined quantitative characteristics of the
reaction of the transition of the phthalocyanides of cobalt,
nickel, copper and zinc, as well as of the free phthalo-
cyanine into the sulfuric acid solution for the theoretical
Card 9116 reasoning, and as an experimental proof of the existence of

Conference Discussion on the Methods of
Investigating the Complex Formation in Solutions
SOV/153-58-3-30/30
g-bonds in the complexes investigated. These characteristics.
also served him as a proof of new electronic formulae of
phthalocyanine and its complex derivatives. In the lecture
delivered by 1. L. Krupatkin on "The Method of the Two Solvents
as a Method of Investigating the Formation and Propertieo of
Organic Complexes" it was proved that this method makes it
possible to determine-the number of complexes formed in the
system, their composition and relative stability. V. I.
Kuznetsov, A. K. Babko, N. P. Komar', I. S. Mustafin and
Ya. I. Tur'yan took part in this discussion. In the lecture
delivered by A. A. Grinberg and S. F. Kiseleva on the complex
palladium compounds (II) with a coordination number above
four it was proved that in the case of a targe chlorine and
bromine ion excess complexes with the coordination number 5
are formed. The instability constants of these complexes
were estimated. L. P. Adamovich mentioned a new manipulation
in the spectrophotometric investigation of the complex com-
pounds that can be used in systems with the formation (or
predomination) of one single complex. This method makes it
possible to determine the composition and instability constant

Conference Discussion on the Methods of SOY/153-58-3-30/30
Investigating the Complex Formation in Solutions
Card 11116
of the complex. In the lecture delivered by K. B. Yatsimirskiy
and V. D. Korableva the application of the theory of crystal-
line fields for the determination of the composition and
structure of the chloride complexes of cobalt, nickel and
copper according to the absorption spectra of these complexes
was discussed. It was proved that in a hydrochloric acid
concentration above 5 mole/liter in the solution there exists
an equilibrium between the tetrahedrio and octahedric form
of the cobalt chloro complexes. Yu. P. Nazarenko proved in
his lecture "The Application of Radioactive Isotopes in the
Investigation of the Solvation Equilibrium in Solutions of
Complex Compounds" the possibility of using data on the
isotope exchange to clarify the structure of the complex and
mechanism of the hydration processes. V. Klimov mentioned
in his lecture the use of radioactive isotopes in the study
of tin and antimony complexes in non-aqueous solutions. k. V.
Ablov, V. N. Tolmachey, V. I. Kuznetsov and A. M. Golub took
part in the discussion of the lectures. The usefulness of
employing the theory of the crystalline fields in explaining
the results obtained from the absorption spectra of the com-

Conference Discussion on the Methods of SOY/153-58-3-30/30
Investigating the Complex Formation in Solutions
plex compounds was stressed. In the lecture delivered by
I. A. Shek on "The Investigation of the Complex Formation
by the Method of the Dielectric Permeability and the Polariza-
tion" the principles of the methods mentioned were presented.
This method was employed for investigating the compounds of
the type of the "affiliation" products. The lecture delivered
by 1. A. Shek and Ye. Ye. Kriss "Employing the Method of the
Dielectric Constant for Investigating Complex Compounds of
the Type of Crystal Solvates in Solutions".dealt with the
investigation of the solvates of lanthanum and cerium chlorides
with ketones, as well as with the study of the compounds
formed in heterogeneous systems with tributyl phosphate and
nitric acid. V. F. Toropova gave in her lecture "The Polaro-
graphic Method of Investigating the Complex Formation in
Solutions" a survey of the applications of the polarographic
method in the study of the complex compounds, and illustrated
several fine characteristic features of this method. In the
lecture delivered by T. N. Sumarokova "The Cryoooopic Method
of Investigating the Complex Formation Reactions" a survey of
Card 12/16 the possibilities of the cryoscopic method was given, and its
Malt,
3-7
-4.

Conference Discussion on the Methods of SOV/153-58-3-30/30
Investigating the complex Formation in Solutions
Card 13/16
applicability in the study of several complex compound:s of
stannic chloride with organic substances was proved. A. M.
Golub described the results of his investigations of thio- '
cyanate complexes of several metals. A vivid discussion took
place on the lectures hold. Ya. A. Fialkov, and Yu. Ya.
Fialkov considered the aryoscopic method of investigating
complex compounds to be of considerable value. K. B.
Yatsimirskiy pointed out that the publication of -the surveys
a- -inaviTuil methods of investigating the complex formation
reactions would be desiredi this concerns especially the
polarographio method. The oryoscopic method should be brought
to a level that makes the calculation of the equilibrium
constants of the processes to be investigated possible. The
problem of the method of evaluating the,experimental results
becomes more and more important. Many scientists use the
instability constants without taking into account the way
in which.they had been obtained. The calculation methods
employed by A. M. Golub are one step back, as compared to
those employed at present. In his lecture N. P. Komar'
pointed out the extremely great importance of the mathematical

Conference Discussion on the Methods of
Investigating the Complex Formation in Solutions
Card 14/16
SOT/153-58-3-30/30
evaluation of.the results obtained, as well as of the plotting-
of-ourves. A. K, Babko suggested helecting one or two systems
that are experimentally well investigated, and to evaluate
the results obtained according to different methods so that
it is possible to check and evaluate them. Ya. I. Tur'yan
took part in the discussion. Ya. As Fialkov discussed in
his lecture "The Effect of the Solvent on the Complex Formation
Process as Vell as on the State of Equilibrium in the Solutions
of Complex Compounds" the influence exerted by the solvents
upon the molecular stateg upon the solvation of the system'
components, upon the stabilization of the COMDlexes formed
in the system, upon the step-wise dissociation of the complexes
and upon a number of other processes. The influence exercised
by the dielectric constant upon the complex formation process
was discussed. It was concluded that a direct relation does
not exist, and that the chemical nature of the solvent must
be taken into account. A. V. Ablov and L. V. Nazarova held
a lecture on "The Spectroscopic Investigation of Nickel Cobalt
'Pyridinatest in Various Solvents". The instability constants
of the complexes were determined and it was proved that the
~-,~..7777

Conference Discussion on ~Ae,Methods of BOY/153-58-3-30/30
Investigating the Complex Formation in Solutions
stability of the 1pyridinateal is changed in dependence on
the solvent. Ya. I. Tur"yan in his lecture t'The Influence
of the Solvent Upon the Composition and Stability of Complex
Iona" discussed the polarographic investigation method of
the chloride and thiooyanate complexes of lead in aqueous
ethanol solutions at different content of the non-aqueous
solvent and at a constant ionic strength. A step-visa
character of the complex formation was found as well as the
instability constants of the complexes. The influence of
the dielectric constant of the solution on the stability of
the investigated complexes was proved. In the lecture by
V. P. Vasil yev on the "Investigation of Aquo Complexes in
Mixed Solvents" the main attention was devoted to the neces-
sity. of the qualitative recording of the dolvation effects
in the complex formation. The applicability of the polaro-
graphic method in the determination of the composition and
stability of the &quo complexes in mixed solvents was proved
and experimental material on the thermodynamics of the
dissociation of the cadmium-aquo complexes in aqueous ethanol
Card 15116 solutions was mentioned. V, N. TolmachaT, V. 1. Kuznetsov

Conference Discussion on the Methods of SOV/155-58-3-30/30
Investigating the Complex Formation in Solutions
and 1. V. Tananaysy stressed in their lecturas the necessity
of a more complete and general investigation of the solvation
processes. A. K. Babko and A. M. Golub pointed out the
great importance of the investigations of the complex forma-
tion equilibria in non-aqueoue solutions, and made several
oritioal oo=ents on the leoture.by Ya, L Turoyan, The
following scientists took part in this disoussiont L. P.
Adamovich, 0. 1. Khotayanovskiy, 1. P. Moskvin and A. G.
MuetakhOT. At the final meeting of tho'conforenoe A. A.
Grinberg, Corresponding Member, AS USSR, said in his speech
that suoh a oonferenoe was very urgent, A detailed disous-
eion of the determination methods of the composition of the
complexes, as well as of the method used in the study of the
quantitative characteristics of the otepwise complex forma-
tion was extremely useful for all who attended this conference.
Card 16/16
uSWj&_Dc_4o976
ill*~141'~U&' ni -7-P-4I
_2: :L
Vti T
z1r
'R~
.4

.5(2,4)
AUTHORS
TITLE:
PERIODICAL:
ABSTRACT:
yatsimirskiy, K. B., Korableva, V. D. SOV/1 53-:/8-4-4/22
Absorption Spectra of Cobalt, Hickel and Cop-,,,er-Salts
,in Concentrated Hydrochloric Acid (Spektry pogloshcheniya
rastvorov soley koballtal nikelya i medi v kontsentriro-
vannoy khloristo-vodorodnoy kislote)
Izvestiya vysshikh uchebnykh zavedeniy. Khim-4ya i khimiches-
kaya tekhnologiya, 1956, Nr 4, pp 19 - 28 (USSR)
The above mentioned spectra have not yet been investigated
as carefully as those in aqueous solutions (Refs 1-8).
Previous investigations are continued in the present
paper (Refs 13,14). On the basis of the spectra and
fundamental ideas of the theory of crystalline fields
the authors tried to ascertain the composition and
structure of the complex compounds formed in solutions.
The spectra were taken by means of the spectrophotometer in
aqueous and HC1-solut4ons between 220 and 1200 mg. The
solutions used in the tests were obtained by corresponding
dilution from initial solutions containing cobalt,
Card A
/4

Absorption Spectra of Cobalt, Nic~el and Copper-Salts SOV/1513-58-4-4/22
in Concentrated Hydrochloric Acid
n4ckel, copper nitrate and cobalt chloride. The
sp~-ctra taken are shown in figures 1-3. A band with
an absorption maxinum at 300 mv can be seen clearly
in the s-oectra of the aqueous solutions of the above
nitrates. The band is character-*Lstic of the nitrate
ion (7ef 17). It Pay be assumed that the formation
of the band is connected with the transition of
electrons within the ion itself, with the tra-:1,sition
of electrons from the nitrate ion to the meta' ion, or
vice versa. The maximum at 300 mg is shifted with in-
creasing HC1-concertration, and a new one is for.-ied
with its center at 270 mi, for hydrochloric cobalt,
at 300 mp for nickel, and at 380 mV approx-i-iately for
copper. The new maximum is apparently conditioned by
the traraition of electrons irom the chlorine ion
to the metal ion. The foriation of the new shifting
band in the ultraviolet spectral ran~-e le,~ds to the
ascumition that chlorine complexes of tlhecc rrietrila
exist in the hydrochloric colutions of ~he above
Card 2/ mentioned three metals. Then the spectra of each of
7777777777

Absorption Spectra of Cobalt, Nickel and Copper-Salts SOV/153-58-44/22
in Concentrated Hydrochlori-C Acid-
those notals are dincusoed individually. The absorption
spectra obtaineO may be interpreted accordinE; to the
theory of the crystalline fieldo, if it is presupposed Vnat
a) cobalt forms octahedral pink-colored chlorine complexes
and various tetrahedral lightblue-colored complexes from
the M-concentration op 5 MOO, onward; b) nickel
forms various octahedr0 complexes [NiCl(H 0) and
2 5T
Incl. 2(H20)41 in Hfl-solutions; c) the copper chloride
complexes are formed step-like, being probably of
tetragonal structure. There are 9 figures, 2 tables, and
30 references, 4 of wihich are Soviet.
ASSOCIATION: Ivapovskiy khimiko-tekhnoloLricheakiy inotitut (Ivanovo
Institute of Chemical lbehnologY) Y,;,-.fedra anpliticheskoy
khimii (Chair of Analytical' Chemistry)
!XXIIITTED: October 14, 1957
31f

5(2)
A.FTHORS: Yats-imirckiy, K.
TITLE: --I -tors of tile
Communication II:
Difenilkarbanzon)
B., Berezin, B. D. SOV/1 -1--8-"-6/22
u -if,
rc rot. -try (Iridil-ttory merktirimetrii)
Diphenyl Carbazone (Soobshchaniya II.
PERIODICAL: Izvestiya vysshikh uchebnlrkh zavedeniy. Khimiya i 'r--himiches-
kaya tekhnologiya, 19513, TIr 4, pp 35 - 42 (USSR)
ABSTRACT: Although diphenyl carbazide, according to corresponding
publications (Ref 11), is less suitable as indicator
for the determination of the chlorides of thallium (Ref 4),
silver in the presence of copper (Rcf' 5), methyl thio-
uracil (Ref 6), and others, diphenyl carbazone, which
is a better mercurometric indicator, has been !,till
insufficiently investigated. Blue-violet compounds are
formed by it with Hg2+, the composition of which,
however, is unknown. Scienticts also disagree as to
the optimum, pH-value in the determination of halides.
It would be necessary to know the solubility product
of mercury diphenyl carLazonate and the acid dissociation
Card I/ constant of diphenyl carbazone in order to find the

Indicators of the MercurometrY. Communication II: SO V/1 J,13-58-4-6/22
Diphenyl Carbazone
optimum concentrations of the indicator, the possible
dilutions of halide solutions and the optimum accuracy of
the methods under various conditions. Perchloric acid
and mercury perchlorate were used in the experiments.
Table 1 presents the solubility of diphenyl carbazone
in bortito buffor colutiono doterminod at 250 -# bi an
alkaline medium it can be transformed into diphonyl
carbodiazone (Ref 2). K a of diphenyl carbazone vias
measured by the spectroPhotometer (Table 2). The data
obtained :from the two methods mentioned above were
checked (Table 3). The spectrophotometric method of
the isomolar series was applied, because the preparative
determination of the indication product of mercury ions
(II) with diphenyl carbazone is, for various reasons, very
difficult. The results are given in table 4. The
solubility product of mercury,'diphenyl carbazonate
was determinod according to Gorbachev'r, method, the
latter having been modified to a certain extent. Th 26
solubility product amounts to (Ref 17)(6.7+0,'7).10- -
Card 2/0 First a calibration curve was plotted. 11927 is practically

Indicators of the Mercurometry. Communication II: SC)V//l',3-',P,-4-6/22
Diphenyl Carbazone
conpletely bound by diphenyl carbazone at a pH of 5
approxi.mately. The composition at pH 2 and 5
corrooponds to the ratio of diplienyl carba-zone:
Hg 2+ . 2:1. The dissociation constants of diphenyl carbazone
after the first step at 250 and at ionic strengths of
0,1 and near zero amounts to (304�-O~3)-10- a and
(1.1+0.1).10 -8 . There are 2 figures, 5 tables, and 18
reierences, 9 of which are Soviet.
ASSOCIATION: Ivanovskiy khimiko-tekhnologicheskiy institut (Ivanovo
Cheno-Technological Inotitute) Kafedra analiticheskoy
khimii (Chair of Analytic Chemistry)
SUBMITTED: September 10, 1957
Card 31#
ga
R"

5W 153-58-
AUTHORS: Yatsimirskly, Y. B., Karacneva, f;.
TITLE: On the Change of the Entropy in Complex Forming Reactions With
Complexons (0b izmenenii entropii pri reaktsiyakh komplekso-
obrazovaniya s kompleksonami)
PERIODICAL: Izvestiya vysshikh uchebnykh zavedeniy. Khimiya i khimicheskaya
tekhnologiya, 1958, Nr 5, Pp 13-21 (USSR)
ABSTRACT: The reactions mentioned in the title concerning mono and bi-
valent cations of the metals with ethylene diamine tetra-
acetate, are characterized by relatively low thermal effects
and by considerable positive entropy changes (Refs 1,2). Thus,
the entropy changes in these reactions play an important role
and to a high degree determine the stability of the metal
complexonates in the solutions. There are, however, no reliable
data on the entropy char-gee in the affiliation reaction of
the proton to the anions of the complexons as well as in the
reactions of the complexonate formation of the trivaleiit metals.
As for the calculation of the entropy changes besides data
on the equilibria also exact data on the enthalpy change during
Card 1/3 the said-process are necessary it became necessary to determine
4~
"~,ilQ m
- -T --, N
R~' -`M.44

On the Change of the Entropy in Complex Forming Reactions With Complexons
calorimetrically the thermal effects of the mentioned reaction!3
under the participation of complexons. For this purpose the
authors decided 'to determine by direct calorimetric measure-
ments the reaction heat in the addition of the protons to the
anLons of ethylene diamine tetraacetate and of hexamethylene
diamine tetraacetate, as well as the formation heat of the
combination of aluminum with the former acetate and of calcium
with the lattez. The hexamethylene diamine tetra acetic acid
was synthesized at the IREA (Institut khimicheskikh reaktivov
Institute for Chemical Reagents) and supplied by Professor
R. P. Lastovskiy, The results obtained are given in tables
1-5, 7, B. Data concerning-the change of the heat content and
of the entropy in the dissociation of the ethylene diamine
tetraacetic acid and of hexamethylene diamine tetraacetic
acid were obtained. With the former acid the entropy in the
dissociation of the acid is changed under the separation of
the two last protons Ord and 4th step of dissociation) by a
much higher absolute value than is the case with the first two
protons. With the last mentioned acid it may be assumed that
the entropy in the corresponding dissociation is changed in
Card 2/3 about the same degreep i. e. in the case of the separation of
.5,
R
.-P

SOV/153-5a-5-2/26
On the Change of the Entropy in Complex Forming Reacticn~- Wit- Co=nlexcni-
one of the protons AS will be equal to half of the entropy
change in the separation of two protons. Furthermore the
changes of enthalpy and entropy in the formation of the
aluminum complex with the ethylene diamine tetraacetic acid
and of the calcium complex with the hexamethylene diamine
tetraacetic acid are determined. The factors were revealed
which determine the value of the-entropy change in the re-
actions of the complexonate formation in aqueous solutions.
Corresponding equations 'mere suggested@ There are 2 figures,
9 tables, and 12 references, 4 of which are Soviet.
ASSOCIATION: Ivanovskiy khimiko-tekhnologicheskiy institutj Kafedra ana-
liti--heskoy kh-imii (-rvanovo Chemo-Technological Institute,
Chair of Analytical Chemistry)
SUBMITTED: November 19, 1957
Card 3/3
.j M '1'

5 (2"t 3)
AUTHORS: Yatsimirskiy, K. B., Berezin, B. D. sov/153-58-6-5/22
TITLE: Indicators of Mercurimetry (Indikatory merkurimetrii).
III. B-Nitroso-a-naphthol (III. B-nitrozo-a-naftol)
PERIODICAL: Izvestiya vysshikh uchebnykh zavedeniy. Khimiya i khimicheskaya
tekhnologiya, 1958, Nr 6, pp 28-33 (USSR)
ABSTRACT: Among the indicators proposed in the most recent papers
(Refs 1-6) and mentioned in the title, the siubstance mentioned
in the subtitle and its monobromine derivative, bromonitrosol
Ref 4), have proved most useful for various applications
Refs 4,7-9) in practical work. However, a number of dif-
~
ficulties still prevent their further introduction into the
practical field. There are no systematic quantitative investi-
gations into this matter, and the necessity of appropriate
investigations is therefore most obvious. As bromonitrosol
is structurally fairly similar to 8-nitroso-a-naphthol, the
latter was investigated. The experimental part contains dis-
cussions of: (1) Acid properties of 0-nitroso-a-naphthol,
(2) the solubility of B-nitroso-a-mercury-naphtholate in acid
solutions (Tables 3,4). Table 2 presents the computed and
Card 1/3 experimentally obtained values of the dissociation constant

Indicators of Mercurimetry. III. B-Nitroso-u-naphthol SOV/153-58-6-5/22
of 2-nitroso-u-naphthol. Table I shows its solubility in
borate buffer solutions at 25 0. From t heir results, the
authors draw the following conclusions: The qualitative
characteristics of the substances mentioned in the subtitle
and of the indication product formed by the former with
mercury-(II) ions are very close to the corresponding values
of diphenyl-carbazonium (Ref 14). Consequently, the two
indicators can be regarded as equivalent in this respect.
Diphenyl-carbazonium does, however, yield a more vividly
colored product with lig-ions (II), and is therefore more
sensitive. The latter reaction appears instantaneously,
whereas the reaction product of 2-nitroso-naphthol tends to
form oversaturated solutions with the Hg-(II) ions. Thus
diphenyl-carbazonium is to be more highly recommended. In the
course of work, the acid dissociation constant of B-nitroso-a-
naphthol (2-15 t 0.13) - 10-8 was established. From the data
on the solubility of mercury-B-nitroso-a-naphtholate in dif-
ferent solvents, the equilibrium constant of the indication
reaction of the Hg-(II) ions with 0-nitroso-a-naphthol was 27
obtained (Table 4), and the solubility product (9-7 t 1-2) .10
as well as the instability_ Hnstant of mercury-B-nitroso-a-
Card 2/3 naphtholate (1.2 t 0.2)-10 were determined. There are 4

Indicators,of Mercurimetry. III.B-Nitroso-a-naphthol SOV/153-58-6-5/22
tables and 14 references, 11 of -which are Soviet.
ASSOCIATION: Kafedra analiticheskoy khimii; Ivanovskiy khimiko-
tekhnologicheskiy institut (Chair of Analytical Chemistry;
Ivanovo Chemo-technological Institute)
SUBMITTEDi September 10, 1957
Card 3/3
. . . . . . . . . .
-F
0

AUTHOR:
TITLE:
7 :5 //W /A~ ~i~/
PERIODTCAL:
Udalltsova, N.I. 26-58-6-16/56
Complexons in Analytical Chemistry (Kompleksony v analitiche-
skoy khimii) International Conference in Moscow (Mozhdu-
narodnyy simpozium v Moskie)
Priroda, 1958# Nr 6, P 74-75 (USSR)
ABSTRACT: The use of complexons in analytical chemistry and the prospective
development of this new field was the subject of an international
conference in November 1957 in Moscow. It was convened at the
Institut geokhimii i analiticheskoy khimii imeni V.I. Vernad-
skogo Akademii nauk SSSR (Moskva) (Institute of Geochemistry
and Analytical Chemistry imeni V.I. Vernadskiy of the USSR
Academy of Sciences)(Moscow). The Conference heard reports on;
Theoretical questions in the chemistry of com~lexons; the use
of new indicators in complexonometric titration; the application
of complexons in the analytical chemistry of rare elements; the
synthesis, properties and prospective use of new complexons.
Professox-X,B-._Yatsimirskiy-lectured on "The Thermochemistry of
Complex Compounds with Complexons", Professor P.N. Paley on
"Complexon III, as a Reducing Agent" and Professor R.P. Lastov-
Card 1/2 skiy on "Research Work in the Field of the Synthesis of New

26-50-6-16/56
Complexons in Analytical Chemistry. InternAtional Conference in Moscow.
Complexons and Their Investigation". In the discussion the
following prominent Soviet scientists pnrticipatedt I.P.
Alimarin, I.V. Tananoyev, V.I, Kuznetsov, A.K. Babko, N.P.
Card 2/2 Komar' and others.
1. Chemistry-Conference 2. Chemistry-Reports

YATSIMIRSIjY' I.B. jous in kinetic method of analYBis Trudy kom i analil: 8)
Main variat MM
khim',- '8-.82-87 !58-
(Chemical reaction, Rate, Of)
ai
U,

YATSD(IRSXIY, K.B.; ROSLYANDVA, Ye.N,
Radiometric titrations using solutions of cobalt-60 complexen.
Trudy kom.anal.khIm. 9:194-199 '58. (Titration) (MIRA 11: U)
(Cobalt compounds) (Radiochermistry
Effln,
2t -J.

If ~ '0-2-14/43
'AUTHORSi Yatsimirskiy, X. B.
I Korableva, V.
TITLEt The Th~ocyanate Complexes of Manganese, Iron, Cobalt and
Nickel (Rodanidnyye kompleksy margantsa, zhelezal koballta
PERIODICALs Zhurnal Hoorganicheskoy Khimii, 1958, Vol- 3, Hr 2, pp#339-345
(USSR)
ABSTRACTt The equilibrium of the complex-formation of the following
systems was investigated by the colorimetric indioator-moth-
.odtM2+ - CNS_ M2+ . Mn 2+ , Fe 2+ , Cc 2+ , X12+.
In all tests the concentration of thiocyanate-ion amounted
to 0,0004965 mol/l and the concentrations of the metal-solu-
tions 0,02 - 1 mol/l. By the calculation of the'stability
constant of the co*plexes it is proved that only complexes
of the type M(CNS) r exist. The stability constant of FeCNS +
is 0,048,'Of MnCNS + - OP058, of CoCNS - 0,031 and o Ni~NS +
'0,021. The comparison of these values shows that NiCNS
Card 1/2 represents the most'unstable complex. For the determination

78-2-14/43
The Thiocyanate Complexes of Manganese, Iron, Cobalt and ITIckel
of the stability of the CuCNS +- complex the colorimetric indi-
cator-metbod is unsuitable, as the copper-thiocyanate com-
plex is very unstable. There are 1 figurej 1 table, and 19
references, 4 of which are Slavic.
ASSOCIATIONt IYandwo * abruical-t4dbno~ogical -Tijetittite-
(Ivanovsky khimiko-tekhnologichosky institut)
SUBMITTEN March 25, 1957
AVAILABLEv Library of Congress
Card-2/2
WN M Sh !

AUTHORSs
TITLEs
PE11101DICALs
ABSTRAM
Card 113
M;\ 1;i~ s V,,% A ) \< , ,
Yataimirskiy, K. B. , ffaryshki;ia, 7PL-2-15/A
The Kinetics of the Oxidation of Thio8ulfate With Hydrogen
Peroxide in the Presence of Tungstic Acid (Kinetika reaktsii
okieleniya tiosullfata perekislyu vodoroda Y prioutstvii
vollframovoy kisloty)
Zhurnal Neorganichoskoy Xhimii, 1956i,vol- 3, Nr 2,
pp, 346-351 (USSR)
The kinetics of the oxidation of thioaulfato with hydrogen
Peroxide in an acetic-aoid solution in the presence of tungstic
acid was investigated. The reaction velocity was performed by
the phototurbidimetric method with a photocolorimetero3K-M
with a green filter. Between the concentration of sulfuric
acid and the optical density of the solution a linear depen-
dence.was found to exist which may be expressed by the follow-
ing formulat D wo( 11S,04 2]. In this formula D denotes the optic-
al density andotthe proportionality factor. From this equat-
ion follows that the modification of the optical density in
the solution is proportional to the reaction velocity and can
be used for the determination of the reaction velocity of the
catalytic oxidation of thiosulfate. The authors investigated
31~
7

The Kinetics of the Oxidation of Thiosulfate With Hydrogen 78-2-15/43
Peroxide in the Presence of Tungetic Acid
the dependence of the reaction velocity on the sodium-
-tungstate concentration in a quantity of 1,o.lo-7 - 5,0.1o-7
mol/i and on the concentration of H202 in a quantity of
0,8.io 3 - 792.1o-3 mol/i as well as on the concentration of
sodium thionulfate in a quantity of 0,8.10-3 - 316,1o-3 mol/l.
The reaction velocity of the concentration of hydrogen ions
was also investigated as well as the influence exerted by
various additions,.-The reaction velocity of the catalytic oxi-
dation of thiosulfate with H202 may generally be expressed
by the following equationt
d[S042-]
-
m
q
P
. . J(. C
. C
2
;C
In this equation denotes k
W S
203 H202 '.
dt
the catalytic coefficient and qv m, and p are the power expon-
ents. The performed tests show that the reaction velocity
shows a linear dependence on the sodium-tungBtate concentrat-
ion and the hydrogen-peroxide concentration, But the depen-
dence on sodium thiosulfate is of a complicated nature. The
reaction velocity of the catalytic oxidation of sodium thio-
aulfate with hydrogen peroxide increases with an increase in
Card 2A the concentration of hydrogen ions. In a+cid medium tungstic

The Kinetics of the Oxidation of Thiosulfate With Hydrogen 78-2-15/43
J'aroxide in the Preeence or Tungstic Acid
Acid _ i s,;c onverted to varicuq cationidio forms, 0.9.1
A. + 2+
U2wo4 + n` - wo 2' OR + H20 , if2WO4+ 2H , W02 + 2 H20.
The catalytic oxidation of sodium thiosulfate with H20 in
an acid medium probably is a reaction between ions witi oppo-
site poles. At first the.oationidio forms of tungstic acid re-
act with hydrogen peroxide under comDlex-formation ana then the
slow reaction between this complex rW62 ORR 202+j and hydrothio-
sulfate IRS203-3- There are 10 figures, 1 table and 10 re-
ferences, 5 of which are Slavic.
ASSOCIATION: Ivanovo Chemilcal-technological Institute (Ivanovskiy
khimiko-tekhnologicheski institut)
SUBMITTEDs April 24, 1957
AVAILABLE:, Library of Congress
Card 3/3

78-2-16/43
AUTHORS: YatsimirskiY9 K. B. Karacheva, G. A,
TITLEt The Kinetics of the Oxidaiion Reaction of Iodide With Rydro-
~en Nroxide in the Presance of Iron-AW-Compounds
l(inetika reaktaii okisleniya yodida perekielyu vodoroda v
prieutstvii soyedineniy zheleza (III))
PERIODICAM Zhurnal'Neorganicheskoy Khimiiq 19581 Vol-3t Nr 21 PP-352-359
(USSR)
ABSTRACTs The authors determined the kinetics between hydrogen peroxide
and potassium iodide in the presence of iron salts in HC1-
and H2 SO -solutions. The investigation of the kinetics of
this rea9tion was performed by the optical method. The photo-
metric investigations were performed on a universal photo-
meter of the type( r and at 533
,PM with green filte pA and
19-200C and 21-220C. The inclination between the tangent
angle and the abscissa of the iron-concentration is propor-
tional to the reaction velocity.
Card 1/3 tg o(. dD do E# ~sv
dt dt

78-2-16/43
The Kinetics of the Oxidation Reaction of Iodide With Hydrogen Peroxide in
the Presence of Iron-/III/-Compounds
d - optical density, t - timet E a molar coefficient,
- thickness of layer, v a reaction velocity# The dependence
of the reaction velocity on the iron-concentration, the con-
centration cC hydrogen ions, the concentration of potassium
iodide and the ECl-concentration was illustrated by experi-
ments. Analogoustests were also performed with sulfuric acid
and iron-/III/-sulfate as catalysts. The kinetic equation of
the catalytic reaction is as followst
doi k
2 zom 0 a 3+
dt H202 * j Fe
In this formula X - the catalytic coefficient, C 12 9 CH 2021
CJ_ and CFe3+ signify concentrations of the corresponding ions
in the reaction mixture. The reaction intermixture increases
with an increase in the concentration of hydrochloric acid.
The reaction velocity in the case of H 2SO is complicated, as
sulfuric-acid complexes form on these confitions. The stabili-
ty of trivalent imn with ethylene-diamine-tetraacetic acid
was also determined by the kinetic method. For pK, Ve, EDTA
Card 2/3 at,* 0 a value of 26.,5 270 was found4 There are 9 fi-

78-2-16/43
The Kineticq of the Oxidation Reaction of Iodide With 4drogen Peroxide in
the Presence of Iron-/III/-Compounds
gures, 3 tables, and 12 references, 2 of which are Slavic.
ASSOCIATIONt IvAnoto Chemical-technological Institute.
(Ivanovskiy khimiko-tekbnologicheskiy institut)
SUBMITTEDs April 24, 1957
AVAILABLEs Library of Congress

SOV/78-3-8-46/48
AUTHORS: Vasiltyev, V. P., Korableva, V. D., Yatsimirskiy, K. B.__'
TITLE: Conference Discussionon the Methods of Investigating Complex
Formations in Solutions (Soveshchaniye-diskussiya po metodam
izucheniya kompleksoobrazovaniya v rastvorakh)
PERIODICAL: Zhurnal neorganicheskoy khimii, 19589 Vol. 3, Nr 8, pp. 1982-
1986 (USSR)
ABSTRACT: From February 18 - 21, 1958 a conference with discussions took
place at Ivanovo, which dealt with the methods of investigating
the complex formations in solutions.
At this conference the methods of determining the composition
of the complexes in solutions2 the methods of calculating the
stability constants on the basis of experimental data, as well
as the influence exerted by the solvonto on the process of com-
plex formation were discussed. Numeroub experimental and theo-
retical papers were submitted to the conference, which dealt
with the process of complex formation in aqueous and non-aqueous
solutions. Especially methods concerning the composition of the
complexes as well as methods of investigating step-wise complex
Card 1/0 formations were dealt with in detail.

AUTHOR:
TITLE:
PERIODICAL:
Yatsimirskiy, K. B.
SOVI/78-3-10-5/35
The Thermochemistry of the Compounds of Transition Metals and
the Theory of the Crystal Fields (Termokhimiya.soyedir-eniy
perekhodnykh metallov i teoriya kristallicheskikh poley)
Zhurrial neorganicheekoy khimii, 1958, Vol 3, Nr 10, pp 2244-2252
(USSR)
ABSTRACT: The thermochemistry and the theory of the crystal field were used
for the thermochemical characterization of the solid compounds
of transition metals. An analysis was carried out of the struc-
ture and energetic curve of some ions of transition metals, as
well as of the lattice energy of the chlorides of elements of
the fourth and fifth group of the pe-riodic system. The effective
eneray of this compound is A = Q(E 2-El) (6). The difference
between the value of lattice energy determined by experiments
and that calculated by linear interpolation is represented by the
magnitude A. The magnitude 6 shows constant values for most of
the salts of iron-(II), cobalt-(II), nickel and copper. The
values of A calculated by the thermochemical analysis are
higher than those obtained by bhe optical analysis. The magnitude
Card 1/2 qhows higher values for trivalent element3 than for biva-lent
M, ------ ARM

SOV/78-3-10-5/35
The Thermochemistry of the Compo*jndn of Tra.r.sitior, lietals and t'---- Theory of
the Crystal Fields
ovies. A is higher for the compounds of elements of the fifth
period than for those belonging to the fourth period. The
values of lattice energy for many compounds of the fourth Group
of the periodic system are indicated in the tables 3 and 4. The
increase of lattice energy of fluorides, sulfides and sulfates
of the fourth group of the periodic system was calculated and
indicated in table 6. It was shown that chlorides, bromides,
iodides, oxides, hydroxides and acid salts of elements of the
fourth group of the periodic system (11n, Fe, Co, Ni, Cu, Zn)
show a constant difference of heat of formation for one metal
and one pair of anions. This r-ale was used for the calculation
of the unknown heat of formation of Fe(HCO 2)2' Fe(NO 3)2 and
NiCO 3' There are 2 figures, 9 tables, and 18 references, 5 of
which are Soviet.
ASSOCIATION: Ivanovskiy khimiko-tekhnologicheskiy institut (Ivanovo Institute
of Chemical Technology)
SUBMrMD: August 6, 1957
Card 2/2

Y~. 7-S1m1'PSKjY,
AUTRORS: Yatsimirskiy, K. B., Rigin, V. 1. 75-1-18/26
TITLE:- Kinetic Methods of Quantitative Analysis
(Kineticheskiye metody kolichentyennoGo analiza).
Report' 4, Determination of Small Amounts of
Tungsten (Soobsolieni 0 4. opredeloniye malykh
kolichestv vollfrwna~
PERIODICAL: Zhurnal Analitichoskoy Khimii, 1958, Vol. 13, Nr 1,
pp. 112-115 (USSR)
ABSTRACT: A number of elements ian be quantitatively determined by
utilizino- their catalytic action upon reactions whose
velocities are comparativele low and conveniently measurable.
The oxidation of iodides with hydrogen peroxide in acid
solutions:
9 202+ 2J- + 2H+ - J 2 + 2H 20 (1)
at room temperature in the absence of catalysts proceeds
very slowly. It was found that the reaction velocity
in the presence of traces of hexavalent molybdenum and
Card 1/5 tungsten compounds, but also of compounds of iron, uranium

Kinetic. Methods of Quantitative Analysis. 75-1-18/26
Communication 4- Determination of Small Amounts of Tungsten
and chromium is higher. The catalysis of the reaction by
molybdates can be used for the determination of molybdenum
(ref, 5)- In the present paper a method for the quantitative
determination of small amounts of tungsten is described.
On the basis of experimental results the following equation
was set up for the velocity of the catalyzed reaction (1):
c. -. c CW (2)
d j H202
il.is the coefficient of the catalysis and is dependent on
acidity. This may be explained by the fact that only forms
with tungsten as cation are catalytically active and that
an increase in the acid concentration increase the
concentration of these forms and possibly also modifies
their structure. For 0,1 molar acid concentration
according to equation (2) is equal to 1,0-108 (time in minutes,
contentration in moles per liter).
Card 2/5 On the basis of theoretical considerations

Kinetic Methods of Quantitative Analysis. 75-1-10/26
RePort 4. Determination of Small Amounts of TunEsten
the minimum tungsten concentration can be dutorminud
which can be found by this method. For this the v~~locity
constant k of the non-catalyzed reaction is needed. Under
the same conditions it ia according to published data
(ref. 2) equal to 1,89. Consequently the followin- ap-
LI plies
for the minimum concentration of tungsten (c Vi ):
min
Op I !~, V 2.10-9 mol/liter
X
min
There-fore, regarding sensitivity, this method surpasses
all hitherto known methods of determining tunC:5ten. By
this method tungsten can also be determined in the presense
of a number of other elements. Calcium, aluminum, zinc,
nickel, cobalt and manganese at the concentrations
investigated (ratio c foreign ion : atunGsten m 106) exercise
no essential influence on t reaction velocity. On the basis
Card 3/5 of the reaction 2Cu2* + 4J- -6. Cu.2 J2 + j2 copper sliChtly

Kinetic Methods Of Quantitative Analysis. 75-1-18/26
Report Determination of Small Amounts of Tungsten
Card 4/5
accelerates the separation of iodine. Lead, mercury und
cadmium slow down the reaction, because they form complex
ions with the iodide and thereby diminish the effective
concentration of the iodide. Phosphate retards the reaction.
Fluoride, citrate, tartrate, oxalate, arsenate and silicate
at the investiGated concentrations (ratio 0 - 0
forcien ' tuncsten
103) completely prevent the catalytic action of tun,,sten.
The solubility of tungstic acid H 21704 and mercury W -
tunestate was also determined according to this kinetic
method. Only scarce and contradictory data exist on the
solubility of these compounds which forn the precipitate
in the gravimetric determination of tun-sten. For the
solubility of tungstic acid in 1-normal hydrochloric acid
the authors found (1,0 + O,j).jo-4 mole/liter and for the
solubility of mercury (Y)-tungstate in 1-norrial hydrochloric
acid they found (2,2 + 0,2) jo-4. In an experimental part
the investigations of-the dopendence of the reaction
velocity of the catalyzed reaction(l) on the concentrations
of tungsten, iodide, hydroGen peroxide as vell as hydro-

Kin,itia ,',othodB of Quantititive Analysis. 75-1-18/26
Report 4. Determination of Small Amounts,of Tungsten
chlorio acid are described in detail. The experiments on
the influence of foreign ions upon the determination and
the experiments for the determination of the solubility
of tungstic acid and its mercury (I)-salt are also
described.
There are 5 figures, 4 tables, and 8 references, 3 of which
are Slavic.
ASSOCIATION: Ivanovo, Chemical and Technological Institute
avanovskiy khimiko-tekhnolo6icheskiy institut)
SUBMITTED: March 2, 1957
AVAILABLE: Library of Congress
1. Tungsten - Jetermination 2. Quantitative
analysis - kiethods
Card 5/5

75-13-2-24/27
AUTHOR: Pozdnyakov, A.A.
TITLE Syriposium on the Theory and Use of Complexons in
Analytical Chemistry (Simnoziiin po toorii i primeneniyu
ko-mpleksonov v araliticheskoy khi!3ii)
PERIODTCAL: Zhurnal A"aliticheskoy Klhintii, 1950, Vol. 13, Ur 2,
pp. 261-262 (USSR)
ABSTRACTt A symposium on the theory-and the use of complexons
in analytical chemistry which was called by the Commission
for Analytical.Chomiictry at the Institute for Geoche-
mistry and Analytical Chemintry imeni V.I. Vernadskiy
AS USSR, took place in I'loscow from November 28 to
November 30, 1957- 11.1ore t1han 50 specialists of comPlcxo-
metry, amonirst whom were. also representatives from peoplole
democracies, attended this symposium. 13 lectures were
attended and judged. Part.of the reports was devoted to
theoretical problems, another part dealt with the synthesis
Card 1/4

75-13-2-24/27
Symposium on the Theory and Use of Complexons in Lnalytuical Chen;-stry
of now complaxons and color indicators and with the
use of complexons, especially of complexon III,for the
separation and determiriation of olomento.
K.B. Yat2jajEa~jy (Ivanovo) roportod on the results of
thermochemical investig-ations of complex compounds.
R. Prshibil (Prague) reported on metallochromic indicators
of the phthalein-series and on 2 new indicators: Glycine-
thymol-blue and Clycine-cresol-red. I.Kerbl (rr_-Ir-Ue)
renorted on the results obtained by the investi7ation of
melallochromic derivatives of amino acids and on the
mechanismn of the indicator effect of metallochromic
indicators. One of the articles by this author dealt
with errors in titration in complexometry. The rerorto
delivered by L. Erdei (Budapest) and 1.11. I,Tusta-fin
(Saratov) were devoted to the use of some new indicators
,Card 2/4

75-13-2-24/27
Symposium on the Theory and Une.of Complexona in Analytical Chemistry
Card 3/4
,in complexonetry. R, Prshibil re~,orted on the complexo-
metric determination of oxydizinC,and reducing compounds.
P.H. raley (moscow) reported about the reducinG properties
of eomplexon III. R.P. Lastovskiy ( ~';,~oscow) reported on
investi.n-ation word:* in the field of the synthesis of now
complexons and their invezti.-ation. Lyan' Shi-tsyuan' and
Tsen' In'-tsao (Peking) reported on the possibility of
the use of the,complaxes of pyrocatechol with trivalent
iron for theaetermination.of fluorine.M.M. Senyavin
(Moscow) delivered a lecture 'on the use of complexons
*in the ion exchange c1hromatography. Yu.Yu. Lurlye
(Moscow) reported on some methods of analysis in the
metallurgy of nonferrous metals which are based on the
use-of comnlexon III. In the course of a discussion,
A.R. Babko proposed to use complexon III for the retardation
of crystallization processes*

75-13-2-24/27
Symposium on the Theory and Use of Complexons in Analytical Chemistry
I.P. Alimarin, I.V. Tananayev-'V.I Kunnetsov, A.K.
Babko, N.P. Kozzarl and.others took an active part in the
Symposium.
1. Chemistry--USSR
Card 4/4

5(2
AUTHORS: -fatsimirskiy, K.B., Alekseyeva, I.I. SOV132-24-12-2145

TITLE: Spectrophotometric and Kinetic Methods for Determining Molybdenum
0
in Alloys (Spektrofotometricheakiy i kineticheskiy metody opre-
deleniya molibdena v splavakh)
PERIODICAL; Zavodskaya Laboratoriya, 1958, Vol 24, Nr 12, PP 1427-1429 (USSR)
ABSTRACT: A method for determining molybdenum in steels and nickel alloys was
developed which is based upon the absorption of light by molybdic
acid in the wave-length region 220 - 240 m,,K(Ref 2). It is carried
out in alkaline medium, The sensitivity of the method is givei as
7- 10-7 g/ml Mo. The measurements were made with a SF-4 spectrophoto-
meter. The molybdenum content is determined on the basis of' a standard
curve. Molybdenum alloys of Ni base Nr 3 and 4 as well as E.1401 and
KHOS2Msteels were analyzed (Table 1). The relative error of ~-he meths..
is 2-5 %- The kinet4e method of determining molybdenum is ten times
more sensitive than the spectrophotometric method. The principle of
the kinetic method is the catalytic effect of molybdic acid in the
oxidation of iodide with hydrogen peroxide. The method was pre-
viou.siy reported in an earlier paper (Ref 5).
Card 1/2 Since FP.3+, Cu 2+ , and other ions interfere in the analysis the iron

SOV/32-24-12-2/45
Spec tropho tome trio and Kinetic Methods for Determining Molybdenum in Alloys
(Fe2+) in the present analysis was oxidized with Trilon B to FP3+
and then bound in a complex compound. A FEK-M apparatus was ii-sed
to analyze Kh 10S 2 M steel (Table 2) and iron oxide (Fe 203) (Table 3).
The sensitivity of the method is about 10-8 g/ml Mo.- There are 3
tables and 7 references, 6 of which are Soviet.
ASSOCIATION. Ivanovskiy khimi-ko-tekhxiologicheskiy institut
(Ivanovo Chemical Technological Institute)
Card 2/2
.7 -a-;:i

50) PHASE I BOOK EXPLOITATION SOV/2032
Yatsimirskiy, Konstantin Borisovich..,and Vladimir Pavlovich
_Vas11'yev
Konstanty nestoykosti komplekonykh soyedineniy (Instability
Constants of Complex Compounds) Moscow, Izd-vo AN SSSR,
1959. 205 p. 4,500 copies printed, Errata slip inserted.
Sponsoring Ageney: Akademiya nauk SSSR. Institut obshchey i
neorganicheakoy khimii.
Reap. Ed.: I.I. Chernyayev, Academician; Ed. of Publishing
House: D.N. Trifonov; Tech. Ed.: S.G. Markovich.
PURPOSE: The book is intended for chemists,, engineer!~and
technicians concerned with analytical chemistry, electro-
chemistry, technology of nonferrous and rare metals, and
related fields.

Instability Constants (Cont.) SOV/2032
COVERAGEt The authors claim that this book is the first
attempt to make a complete compilation of the instability
constants of complex compounds. Instability constants of
3,,381 complex c.ompounds are given. Methods,of calculating
instability conB'%"ants are described in an introductory
chapter. The book was compiled chiefly on the basis of
literature published up to 1954. No personalities are
mentioned. There are 79 referencespof which 35 are
Soviet, 28 English, 6 German, 4 French, and 6 Swedish.
TABLE OF CONTENTS:
Foreword 3
THEORETICAL PART
Cho I. Some Functions Characterizing the Stepwise Complex
Formation in Solution 7
Bibliography 15,
""'il NU
N:F
0,
-4
R
01,

zciE 1:1 W; F113MIa t RM
Pr (Y)lKsk-iy--
0 a,
A 2 T 19 t; A 1; &1 5
a Ou a 0 1. a 00.4
Oo
.114 1.
A.4
0 00
g wr
31
A~j
0 ON
2
2' PHI OM,
'o -a log
SAO
Id 14
a o
o a
WWI -2 4.
laoc 2 o ch r a
I.
tal H,

5(4) S011/ 153-2 -4 -2/3?
AUTHOR! Yatsimirskiy, Y. B.
TITLEs Thermochemistry cf tho Dij~!ociati,.;% ~-,f Hydro--en Peroxide
PERIODICAL: Izveotiya vysshikh. uchobnylk'n za-edeniy. Khimiya I, kh"micheskaya
tekhriologiya, 1959, Vol 2, Nr ~-j n 4'8(- -- 4841 (USSR)
ABSTRACT: The author compute.3 the fo=-.aticn heats of the lons and radi~.Uls
formed with the dissociation mentioned in th- -.1tle, according
to various schemes. Depending on the b-,arstlng polnt (-J the ch'a-
mical borkd, the following groups may form with the dissociation
of the H 202molecule~ IV-, 02H-' H'11-' 00Hj 02H'~ 1 011-1 1104ani Off
(Ref 1). If the dissociation of the latter continues, new atoms
and ions may'appear: 0., 0-, 0,- and 02-. In order to compute
2
the heat effects of the dissociation reactions of If 202 in the
gaseous phase and an aqueous solution, the formation heats of
the particles mentioned above have to be known. The data on
aqueous H 202- solutions are rather scarce. However, these values
can be estimated on account of the present laws and rules together
Card 1/3 with thermochemical. data. Table 1 shows the formation heats of
4,
U~

,0 .1
Thermochemistry of the Dissociation of Hydrogen Peroxide SOV/15-A-2-4-2/'12
0+'011+ , 02H2and 02- , in addition to most particles mentioned
above. The formation heats of the gaseous ions 0 and 02- can be
2 2
determined (Table 2) from the formation heats of the correspond-
ing crystalline compounds of alkali metals (Ref 3) as well as
from the values of the lattice energy (Refs 7 and 10). The values
of proton affinity computed by the author are shown in table 1.
It is necessary to know the hydration heats of the respective
particles in order to compute the heat effects of the dissociation
reactions of H 02 in aqueous solution. The hydration heats of
only four of tKe groups mentioned are given in publications. In
order to estimate the hydration heat, the dimensions ot the re-
spective particles have to be determined and, occasionally, their
shape has to be considered. Since the size of the anions 02-
and OH- is approximately equal, the author assumed that the
particle size OHm and 02Hm depends only glightly on their charge.
Thus the effective cationic radii of. OH+ and 0,,H+ were equated
to 1.3 and 1.7 R, respectivelyl their hydratio'n heats, however, to
those of -K+ and Gs+. A round value of 10 kcal/mol was assumed
for OH and 02H, and of 4 kcal/mol for the hydration heats of U
Card 2/3 and 0. The hydration heat of H- was determined by interpolation

Thermochemistry of the Dissociation of Hydrogen Peroxide SOV/153-2-4-2/32
by using the values of the ionic radii of F-,J1- ar," Cl- as w,-rll
as of the hydration heats of F- and Cl-. The average value of the
heats of P- and OH- was assumed to be the value of the hydration
heat of 0-. The hydration heats of the ions 0 - and 02-was also
2 2
determined by interpolation. The formation heat of particles in
an aqueous solution could be computed according to equation (3)
since there were data available on the formation and hydration
heats. The last column of table 1 shows these values for all
particles mentioned. These values can be used for computing the
heat effects of the dissociation of H,O, and of several ions and
radicals. Table 3 shows a summary arra4nged accordin g to various
.schemes in the gaseous phas- and in'aqueous solution. All H202
reactions are endothermal according lo these schemes. There
are 3 tables and 12 references, 5 of which are Soviet.
ASSOCIATION: Ivanovskiy khimiko-tekhnologicheskiy instiltutj Kafedra analitiches-
koy khimii (Ivanovo Institute of Chemical Technology., Chair of
Analytical Chemistry)
SUBMITTED: December 27, 1957
Card 3/3

5(4) sov/63-4-2-8/39
AUTHOR: Yatsimirskiy #B-,$. sor
ZV S
TnU: Kinetic Methods of Chemical Analysis
PMODICAL: Eb-imicheskaya nauka i promyshlennost', 1959, Vol 4, Nr 2,
pp 186-190 (USSR)
ABSTRACT: The rate of chemical reactions can be used t& determine the concentration
of the reacting substances. This kinetic method is very sensitive and
selective. Quantities of 10-11-10-12 g and concentrations of 10-8-10-9 M
can be determined. Drawbacks are the high relative error of 5 - 7%, the
effect of temperature admixtures, the surface of the reaction vessel, eta.
A formula is given for determining the concentration of a substance B
by obtaining the rate of change of the substance A. The reactions used
in the kinetic method are usually of the homogeneous catalytic oxidation-
reduction type. Some substances are determined by their ability to form
inactive compounds which stop the catalytic reaction Z-Ref 9, 1~_7.
The reaction rate is measured according to the law Lambert-ITA;ger-Baer.
Reactions in which light-absorbing substance forms or disappeax-s ai-e.
especially useful, because the optical density changes during the re-
'Card 1/2
action. Reactions in which gases are formed Z-Ref Pi 7 are'used in the
777

Kinetic Methods of Chemical Analysis sov/63-4-2-8/39
kinetic method by obtaining the volume of the gas at certain time in-
tervals. If the concentrations of the tested substances vary only
slightly, the differential method of kinetic analysis must be applied.
If the variation is considerable, the integral method is used. For-
mulae are given. In a table the various methods for determining dif-
ferent elements and ions are compiled. The absence of catalytic ac-
-Livity in various complex metal compounds, the simple compounds of which
are catalytically active, is used in the study of complex formation
~ Ref 32, 43, 63, 69, 70L,7-
There is 1 tableand 72 references, 24 are Soviet, 21 Japanese, 10
Geman, 6 American, 4 English, 3 Italian, 1 Hungarian, 1 Yugoslav,
I Polish, and 1 Czechoslovak
Card 2/2
7,

5 M' SOV/78-4-2-9/40
AUTHORS: Yatsimirskiy, K. B., Karacheva,.G. A.
TITLE: on the Influence of Ionic Strength on the Heat
Effect in the Formation Reaction of th, ;omplexonates of
Calcium and Nickel (0 vliyanii ionnoy sily na teplovoy effekt
reaktaii obrazovaniya kompleksonatov kalltsiya i nikelya)
PERIODICAL: Zhurnal neorganicheskoy khimii, 1959, Vol 4, Ur 2,
pp 294-300 (USSR)
ABSTRACT: The influence of.the ionic strength an the change of the
entropy and heat content during the uomplex forming reactions
of calcium and nickel was investigated by ethylenediamine
tetraacetic acid. The complex formation proceeds quantitatively
at pH 10-11 and is shown in the following equations:
2+ 4--.,- CaEDTA 2-
Ca ~ + EDTA M
Ni 2+ + EDTA 4" NiEDTA 2-;- (2)~
The change of the ionic strength from 0.06 tc 1.58 brings
about a considerable change of.--'SH and nZ whereas the entropy
changeZIS almost remains constant. It was found that at low
Card 1/3 ionic strengths (up to 0.15) the entropy change decreases with

SOV/78-4-2-9/40
On the Influence of conic Strength on th Eeat. Effect in the
Formation Reaction oi the ComplexonateE of Calcium and Nickel
an increase in ionic power. The 2average entropy change on the
formation of the complex CaEDTA is 30.6 + 0.2 cal/mol degrees.
For 6 H of the formation of CaEDTA2- the following equation
was found:
4 H - f (~t) - B. 16 (10) w.... ionic strength
On the change of the thermodynamic functions analogous
regularities of the formation of the complex NiEDTA2- were
found. Here, the average entropy change is 59.2 _+ 0-5 cal/mol
degrees.
The following equation was found for A H: -
LH - f ()4) - 10.08 (11)
The AH values found experimentally and the AH values cal-
culated from eqikations (10) and (11), of respective ionic
strengths, are in accordance. The differdnee between experi-
mental values and values calculated does not exceed
+ 0.1 kcal/mol in the case of complex CaEDTA 2- and
2-
Card 2/3 + 0.2 kcal/mol in the case of NiEDTA There are 3 figures,

SOV/78-4-2-9/40
On the Influence of ..., Ionic Strength in th Heat Effect in the
Formation Reaction of the Complexonates of Calcium and Nickel
6 tables, and 11 references, 2 of which are Soviet.
ASSOCIATION: Ivanovskiy khimiko-tekhnologicheskiy institut (Ivanovo
Chemo-technological. Institute)
SUBMITTED; August 62 1957
Card 3/3

5W

J',,UTHORS s SOV/78-4-4-6/44
Yatsimirskiy; X. B., Orlova~ LT. N~
TITLE% The T--rl ~jjer-,- nt Goid Compounde on the Velocity of the
3ubstii;uM,;m leaction in Cyanide Complexes of Iron (II)
ziuyedinenly zolota na skorost' reaktsii
zameshchenlya v tsianidnykh kompleksakh zheleza (W
PERIODICALs Zhurnal neorganicheskoy khJ.mii, 1959, Vol 4, Nr 4,
Pp 741-746 (USSR)
ABSTRACT: The kinetics of the reaction between ferrocyanide and
nitro5o bprzene ir, the presence of gold compounds was
invest-igated by using optical methods. The light
absorption of the complex compound formed between iron
aquopentacyanide and nitroso benzene was investigated.
The absorption spectrum was plotted at a wave length of
530 mpusirg a FEK-N-54 nephelometer, It was found that
the reaction between -the ferrocyanide ions and the
nitroso benzene in the pre3ence of gold salts is not
a catalytic reaction. The reaction proceeds at first
through an oxidation of the ferrocyanide and a
simultaneous reduution of the gold (III) to gold (I).
Card 1/4

The Influ-o- of Go."d C-,)mpounds In the Velocity of SOV/78-4-4-6/44
the in Cyanide Complexps oil ircz: (II)
In the second stage of the reaction the farrocyanide
and go4'.d chloride form an intermediate complex, which
jr. aqueous aolut4cn decomposes into th F 3-
- e ions I' e(CNI5 if 26J
a:& The fe._rroaq-.iz)ponta-.yanJde i1or- reacts
1. k )21
rapidly with nitrosQ benzene to form the colored complex
[Fe.(C.,~I),.C H=NO13-
6 The folloring mechanism is suggested
for the reactiont
)4- 3--
2Fe(C-N, + AUC! 2Fe(CNl + 2C1 (4)
+ AAC~2
NrG 1 9-
C"I
[Aur,121 2 [Ps (C-N) 6 NC-Pe-.CN.,..A IU....NC-Fe-C (5)
NC CN Ci NCI"\ CN
NC,\ CN C NC."'"'.' CN 9
NG-- Fa -- C11, . Au. . . NC-- Fr- --CN + 2H 0
N /'-, r,Iy 1-, 1 2
Card 2/4 C CIT HC/ CNO

The Tnfluence of Gold Compounds on the Velocity Of SOV/7e-4-4-6/44
the Substitution Jeaction in Cyanide Complexes of Iron (II)
- [JLu(CN)21- + 2C1- + 2[Fe(CN) 5H20]3- (6)
[Fe(CN) 5H'O] 3- + C6H5 NO - [Fe(CN) 5C 6H 5N0] 3- + H 20 (7)
The rate of the reaction between the ferrocyanide and
the nitroso benzene was investigated at various
concentrationa of gold salts and ferrocyanide ions
and at various PH values. The results are given in figure
1. Thm maximum rateof reaction occurs in the PH
I range
4.2 to 5. In more strongly acidic and basic solution
the rate of reaction is slower. The intensity of the
violet color of the complex [Fe(CN) 5C 6H5NO]3- is
dependent upon the gold concentration. The influence of
various salts upon the reaction was investigated. The
salts XNO,1 KCI, and KBr do not influenca the formation
of the complei. The presenue of KCN and KCNS disturbs
Card 3/4 the reaction, since in this case the gold ion is bound

The Tnfluence of Gold Compounds on the Velocity SOV/78-4-4-6/44
the Substitution Aeaction in Cyanide Complexes of iror. (II)
in very stable complexes. rate constants of the
reaction were determineQ for various pH .-alues. blercury
and platinum ions disturb this dett -...Lnation of gold.
There are 7 figures and 9 references,
ASSOCIATTON: Ivanovskiy khimiko-tekhnologicheskiy institut
(Ivanovo Chemical Technological Institute)
SUBMITTED% January 13, 1958

..........
5(4)
SOV/78-4-4-18/44
AUTHORS: Alekseyeva, I. I.
TITLE: State Molybdic' Acid in Weal Acid Solutions
molibdencvoy kisloty v s--,bokislykh rastvorakh)
PERIODICAL: Zhurnal neorganicheskoy khimii,,-1959, Vol 4, Hr 4, pp 818-822
(TJSSR~)
ABSTRACT: The conditions under which molybdic acid polymerizes were in-
vestigated at different concentrations (2.0.10-4 to 8.0.10-2
molar) and,at. various pH 1,ralues (1-6-5). In order to ascertain
the pas6ib ility of the exist-ence of the monomeric fc= off
paolybdic acid,and.to determine-the nature of the polymerization
pr cess the light absorption.of solutions of molybdates and
molybdic acid wiis studied at wavelengths from 270 to 350 mtt.
~
Th6aetermination,.of th6
optiGal densities was carried out
using a SF-4 spectrophotometer. The dependence of the molar
absorption coefficients upon
the moly~dateconcentration was
.
wavelength. The curv;a
investigated at constant pH and constant
.
cbtained-sh6w that at lower 'm'olybdate concentrationa the
molybdic acid.is present in the monomeric form. The polymezic
form exists also at higher concentrations. The phase diagram
Card 1/2 of molybdic acid In solution was constructed (log C 'An

SOV/78-4-4-18/44
State Molybdic Acid in Weakly Acid Solution
dependence upon the pH value). In the pH range I to 4 the
10
polymerizatlon begins at a molybdic acid concentration of
molar. With an increase in the pH value the polymerization
boundary shifts to the side of the higher concentration.
Finally at pH 6-5 no more polymerization occurs. The fcllowir-g
polymerization schemes are suggested-for molybdic acid:
nMoO 2- + (n-1)HOH...._t(HMoO )'moo(n+l)-+ (n-l)OH-
4 4 n-1 4
(at,pH values 4 to 6) and
Moo n+
k 0- (H Moo
(n+l)H~' + (HMoO 4)n-1 4 2 4)rl
(at pH values 1-4).
There are 5 figures and 7 references, 1 of which is Soviet.
ASSOCIATION: Ivano*skiy khimiko-tekhnologicheakiy inatitut. (Ivano-i-,~ Chemio'3~1
Technological Institute)
SUBMITTED: April 24, 1956
Card 2/2

AUTHORS:
TITLE:
SOV/713-4-7-13/44
Yatsimirskiyft. 13., Nar,7shkinaf Yes F.
--------------
The Kinetics of the Oxidation Reaction of Thiosulohate by
Hydrogen Peroxide, in the Pri3pence of 'Vanadate (Kinetika reaktaii
okisloniya tiosullfata,,perekisty''u,vlodoroda y prisutstvii Yana-
data)
Zhurnal_neorganiche3koy khimiis 1959, Vol 4o Nr 7,
PP 1548 1551 (USSR)
The kinetics of the reaction mentioned in the title has already
been quantitatively investigated~ but in the presence of tung-
state (11ef 2). The said reaction develops according to the
equation S 0 2- + 4H 0 M 2SO2- + 2H+ + 3H 0, The reaction rate
2 3 2 2 4 2 2
was photometrically measured by the increase of the optical
density of a suspension of barium sulfate, The results nbtained
are shown by the,following diagrams: Figure 1. - Dependence of
the reaction rate on the concentration of ammonium vanadate.
Figure 2. - Dependence of the reaction rate on the concentration
of hydrogen peroxide and thiosulfates Figure 3* - Dependence of
the reaction rate on hydrogen ion concentration. Figure 4. -
Dependence of reaction rate on ionic strength (by the addition
PERIODICAL:
ABSTRACT:
Card 1/ 3
T777

SOV/78-4-7-13/4#4
The Kinetics of the-Oxidation Reaction of Thiosulphato by Hydrogen Peroxide
in the Presence of Vanadato
of. NaC104 or KNO3). For the connection between the reaction
rate 'and the concentration of the reacting substances the
following equation is given:
d[SO42-] c . 9C c 2-, where V= 3-8,10 7 mol/-'.min.
dt ITH4VO3R202* S203
However, this equation holds only for a certain concentratior.
interval. At very low concentrations of thiosulfate the de-
pendence of the reaction rate on concentration is no longer
linear. Table I mentions the influence exercised by various
foreign ions upon the development of the reaction. By the
formation of catalytically inactive complei compounds the
reaction is interrupted by the addition of fluorides, citrates,
tartratesq phosphates, etc. Univalent cations exercise no
noticeable influence upon the development of the reaction.
Copper-- and ferrous ions accelerate the reaction by their
Card 2/3 catalytic effect. There are 5 figures, 1 table, and 5 ref-

SOY/70-4-7-13/44
~
h
T
K
The Kinetics of the Oxidation Rea,c.tion of Thiopulphate by Hydrogen Peroxide
ne
i
t
in the j?resence of Vanadate
n
h
e
P
erences, 3 of which are Soviet.
S CI
A AT
So IC
ASSOCIATION: Ivanavskiy khimiko-tekhnologicheskiy institut (Ivanovo Chemico-
technological Institute),,Stalingradskiy mekhanicheakiy institut
(Stalingrad Institute for Mechanics)
SU IT T_"-
B11 ,D.
SUBMIT". D: April 7, 1958
Card.3/3

5(2),5(4)
AUTHORS: XaLaizt- -1-11/32
rzki4t,~~ SOV/75-14
Drobysheva, 0. M*, RiCing V. I.
TITLE: Kinetic Methods of Quantitative Analysis
(Kineticheskiye metody kolichestvennogo analiza).
Communication 5. A Kinetic Method for the Quantitative
Determination of Tantalum (Soobshcheniye 5. Ki-petichoskiy
metod kolichestvennogo opredeleniya tantala)
PERIODICAL:
AB~9TIIRACT:
Card 1/3
Zhurnal analiticheskoy khimii, 1959, Vol 14, Nr 1, pp 60-62
(USSR)
In the present paper the catalytic effect of tantalum (V)
compounds on the oxidation of iodides with hydrogen peroxide:
in acid solution is made use of for the elaboration of a
kinetic method for the quantitative determination of small
quantities of tantalum. All the reagents used were carefully
cleaned from heavy metals. The tantalum solution was treated
with certain quantities of potassium iodide and starch
solutions and carefully intermixed. The required quantity of
hydrogen peroxide was then added. After renewed intermixing the
solution was measured in a photo-colorimeter FEK-M at regular