SCIENTIFIC ABSTRACT BEREZIN, B.D. - BEREZIN, B.I.

• Document Type: CREST
• Collection: Scientific Abstracts
• Document Number (FOIA) /ESDN (CREST): CIA-RDP86-00513R000204820006-9
• Release Decision: RIFPUB
• Original Classification: S
• Document Page Count: 100
• Document Creation Date: January 4, 2017
• Sequence Number: 6
• Publication Date: December 31, 1967
• Content Type: SCIENCEAB

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PERZODZCAL:

ABS~RA C~:

Card ~/4

a~s~m~rckiy, ~. ~,, Berezi~, R. D.

Commu~ica~ ~e mercuro~etr~, ,... ~
~a~arbazon) ' ''~ uarbazone rS^-- ~er,n~rimetrii~
~ ~uosncheniye II.
IZVestiya vysshikh Uche5nykh ZaVe~eni ......

Although ~iphenyl
Publications (Ref carbaZ!~e "
~ ~ -~ acc�re~ng to COrresponding
~,: ~s ~ess suitable
~ the determination icl the Chloride
~ver An the Presen � s as indicater
� s a better ~iZ .... u~ners, ~i~2 ~- ~, methyl t~2_
� '"~CUrometric ~.~-unyi carbazon=~
insufficiently lnve � . ~-ulCa~or. k~ . "-, ~nicn
.... ~ oeen cti11
formed by i~ With =~gated. Biue-viole.
however, is Unknown. Scienti~usi~lon o� which,
" also ~iSagree gs to
the optimum pH_value in the ~e~ermin~tion of halides.
~t woul~ ~e necessary to hnow the solubility product
of mercury diphe~yl car~aZonate end the acid dissociation
Constant of diPhenyl cazbazone in order to find the

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~ndicators of the
Diphenyl Mercurometry.
Carbazone Communication II:
SOV/~ 32_58_4_6/22
optimum concentrati
dilutions , ~ .... One of the indicator, the Pose
o~ ~a~lde Solutions and the ~: ible
the methods Under various
and mercury perohlorato conditions. ~mum accuracy of
Perchl eric acid
Table ~ presents Were Used 1;1 the experiments.

alkaline medium it can be transfer
Carbodiazone (2ef ~% . me at 25 , In an
measured by the n2f; ~. uf di he d int~ diPhenyl
~oAe 2). The data
obtained from the
checked /Table . we_me, hods menti _
the isomo
de+ .... ~ar series ~__ P ~upno~ome%~_ ~ -~ro
{~'m~na~ion of +~_,,~u applied, be...~~u method of
difficult. ~ "~ carhazone ~o ~uu~ or mer~,~ ~tZve
8 ~asoMs~ very
in table 4. The
Product of mercury/dlpheny1 car~zonate
was determined
~a3ter havtn= R,__�rding to
solubili~v ~_~=un mod/fie . ~unev's meth
P~o~ "~ ~'uuuet .... d ~o a cer+.,~- .od, the
~ Practically

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ASSOCIATION:

SUBMITTED:

Indicators of the Nercurometry' Communication
DiPhenyl Carbazone

completely bound by diphenyl Carbazone at a p~ of
approximately. The composition at p~ 2 and 5 .
corresponds to the ratio of diphenyl carbazone.
Hg2+ = 2:1. The dissociation constants of '
after the first s~en ~
0,1 and near zero _~ -t.2~ and at ionia ~iphenyl carbazone
~mounts to f~ ..... ~ S~rengths of
� ~"~--+u~'~0-� and
(~'?~0�1)'~0-8 There are 2 figures, 5 tables, ~nd
rez erences, ~ of which are Soviet.
Ivanovskiy khim~ko tekhnologicheskiy inst~t
Ohemo-Technolog~cal In
A"~Y~c Chemistry)
September 10,

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A ~2~02S,

TITLE

PERIODICALs

ABST~AC$:

Card 1/3

Yatsimirskiy, E. B., Berezin, B. D.
'
IndiCators of Mercurime
II~. ~-Nttroso.~ ...~.~t~Y.~Zndtkator~
' '' ~'a~rozo-a-naftol)
Izvestiya VysshiMh uchebnykh

Among the indicators proposed in the most recent papers
(Refs 1-6) and me~tioned ~n the title, the S~bstance menfioned

,_h~e proved most

1 .... AAA prevent th
' elr fu~^-
practical field ~here are no systematic quantitative investl.
-~un Xnto the
gations into this ~mtter, and the necessity of appropriate
investigations is ,lherefore most obvious.
is struoturallyfal;1 .
~tt?r .as.lnvestttae~sim~ar to B-nitr A~ ~romonitrosol
~2~sx�~�f,: (~ ;J;Z" -ac experimen.~c'~-?aphthol, the
the,o ubi;,: l._ rop.er ies containe dis-
Solutions-' f~a.~F{.~-nttrOSo.a ,. ..... rvso-~-naphtho~.
ex- - ' -'~ '~'~:J~4' -- -~: '--'~ur~-na-h
merXmentall~-ob~,~f2 =~Ae 2 prese m ~noia~ein acid
- - ''"=" values of the
' ' w~u~lon conetan%

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Indicators of Mercurimetry. III. B-Nitroso-a-naphthol SOV/153-58-6-5/22

Card 2/~

of ~-nitroso-a-naphthol. Table 1 shows its solubility in
borate buffer solutions at 25 . From their results, the
authors draw the following conalusions~ The qualitative
characteristics of the substances mentioned in the subtitle
and of the indication product formed by the former with
mcroury-(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 Hg-ions (II), and is therefore more
sensitive. The latter reaction appears instantaneously,
whereas the reaction product of ~-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 ~-nitroso-a-
naphthol (2.15 ~ O.1~) � 10-8 was established. From the data
on the solubility of mercury-~-nitroso-a-naphtholate in dif-
ferent solvents, the equilibrium constant of the indication
reaction of the Hg-(II) ions with ~-nitroso-a-naphthol ~as
obtained (Table 4), and the solubility product (9.7 � 1.2)'10-27
as well as the instability ~nstant of mercury-~-nitroso-a-
naphtholate (~.2 ~ 0.2).~0-20 were determined. There are 4

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Indicators of Mercurimetry. III.~-Nitroso-~-naphthol S0�/15~-58-6-5/22
tables and 14 references, 11 of which are Soviet,

AS$OClATIONI Kafedra analitioheskoy khiaii~ Ivanovskiy khiaiko-
tekhnologioheskiy institut (Chair of Analytical Chemistry;
lvanovo Chemo-technological Institute)

SUB~I~;~ September 10, 1957

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AUTHOH:

TITLE:

PERIODICAL:
ABSTRACT:

Card 1/3;

~erezln, B,D. S0�/15~-2-1-2/25
A Study of Metal Phthalocyanines in Solutions (Izucheniye
ftalotsianinov metallov v rastvorakh). I. Stability of '
Phthalocyanines of Some Metals From th ~ddle )f the IV.
Period (I. UstoyohiVost, ftalotsianinov nekoZorykh metallov
seredlny ohetvertogo perioda)

Izvestiya vysshikh ucheb~kh zavedeniy. Khimiya i khimiches-
kaya tekhnologiya, 1959,'%ol 2, Nr 1, pp 10-14 (USS~)

After a survey of publications (Refs 2-18) the author states
that the thermodynamic properties of metal phthalocyanines
(~Pc) apparently have not yet been investigated. Particularly
interesting are the-determination of the thermodynamic stability
mentioned in the subtitle and a Study of the kind of the
chemical bond in connection with special properties of phthalo-
oyanine as an addendum. Special attention should also be
devoted to the close similarity between phthalocyanine and
biologically important porphyrine derivatives which play a
significant role in the vital action of plant and animal orga-
nisms (Refs 22,2~).~hosephthalocyanines were studied in sulphu-
rid acid solutions. The majority of metal phthalocyanines

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A b~tudy of Metal Phthalooyanines in Solutions. S0�/155-2-1-2/25
I. Stability of Phthalocyanines of 3ome Metals From the~d~tle- of the
IV. Period

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enter an exchange reaction ia such solutions, which is
aocolpanied by the formation of a free phthalocyanine (~2Pc;
Pc denotes the phthalooyanine radical).It has remained un-
known-up till now how far the reaction proceeds according to
the equation (I) in the case of the Co-, NJ,, Cu-, and Zn-
compounds. In the first part of his article the author tried
to determine the relation------'-'--[M2~ = E. It should remain

constant even if the bottom phase consists of MPc and H2Pc.
For this purpose the author studied the solubility' of CoPc,
NiPc, CuPc, and ZnPc by the quantitative method, while that
of FePc was ascertained semi-quan%itatively~' Tables 1 and 2
show the solubility,.nf copper- and cobalt phthalocyanine. The
author found approximate values of the equilibrium constant
of the reaction of dissolution (see equation) for copper- and
cObalt phthaloQYanine. At 20-70� they have the order of

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~tudy of ~etal ?hthalooyanines ~a Solutions. .~�/1~-2-1-2/2~
St~bility of ?hthalooyaniaee off Some Metals From thc ~d~e of the
Period

� ~,i~,de of ~0'6 (,~o,~"~o~). n=t~,~, th, a,~o~ ~o~
that ~ ~reparln8 P~Suent dyes from ph~halocyan~ne
Cu2+. N~2+. and Co2+ by treat%n~ ~ith H2504 eolut~one of up
to 7-8.~ols/1 neither losses ooaur due ~o d~e~olut~on nor
deterioration of the t~n~e due to the accmnulat~on off
phth~l�oyanine or of ~te decomposition product~. The subject
was reoommended by Eo B. Yatsim~rsk[y. ?here are 2 tables and
26 ~efferences~$ off ~h~ch are
ASSOCZATION~ , Z~anovsk~y kh~m~ko.tekhnolo~oheskiy institut~ Ea�edra
oheskoy khim~ (,I~anovo Institute o� Chemical Technology, Ch=ir
of ~Lual~rt~ca! Chemistry)

3U~II~TED: January ~, 1~8

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5(2, 3)
AUTHOR:

TITLE:

PERIODICAL:

ABSTRACT:

Card 1/4

Berezin, B.D. S0V/15~-2-2-4/31'

Investigation of the Metallic Phthalocyaninss in Solutions
(Izucheniye ftalotsianinov metallov.v.rastvarakh).
II. Acidic-alkaline Interaction of the Phthalocyanines of
Some Metals in Sulphurie~acid Solutions (II. Kislotno---osnov.
noye vzaimodeystvlye ftalotsianinQv, nekotorykh matall~v
v sernokislykh rastvorakh)

Izvestiya vysshikhuchehn~kh_.zavadeni~,.Xh~mi~a._t..~b~mt ....
cheskaya tekhnologiya~ 1959~.Vol 2,.Nr 2, pp 165-172 (USSR)

Under the presuppositiOn that the dissolution of stable phthalo-
cyanines in a concentrated H2S04 is accompanied by the reaction:

(MPC)solid * H2so4 0 +, Hso
(an intensely gree~ acid phthalocvaz~tne for-
� n mne solution), the author looked for quantitative Gharac-
teristtcs o$ the dissolution process (II) of the phthalo-
cyanines Cu2+~ Co2+i Ni2+~ Zn~+~ and of the nonmetallic phthalo-
cyanine~ i.e. of those objects which have %he-biggest ~echnical
importance. These characNerietios have a practical value as �

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Investigation of the Metallic Phthalocyanines in 8olutions. II. Acidic-al-
kaline Interaction of the Phthaloayanines of Some Metals in' SulphUric-acid
Solutions
they lead to formulas which are useful for the practical com-
putation of the dissolution of phthaloc~anine dyes in H2SO4
(and other concentrated acids.).in their industrial purification.
The derivation of the mentioned formulas is based on the fact
that 4 peripheral, so'called extracyclic, nitrogen atoms are
present in the molecule, They carry free electron pairs which.
give tho Phthalooyanlnes'the properties of very weak bases.
In the opinion of the author, this.is due. to the participation
of free electron pairs of the extracyclic.nitrogen atoms in
the composition of a metalline molecule (Ref 2). The author
assumes that the metallic phthalocyan~Lnea can. only absorb
one proton in a noticeable deg~ee.-.This, nroton con
weakens the basic pronerti,~ ^~ ~. ,~_j%- ..- siderably
........ ..u~..~. as mt intensely
de�orms the ~-electron cloud aff-thm.c~n~u~te [a~e r~ng in
the direction of the absorbed profess This assumption.was
well conffiraed by the exper'~an~a~..resu~ts of the present paper.
From the data On the solubility, t~e equilibrium constants
XNpo for the reaction,(~)~for the phthalocyanines o~ the

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Ca~ ~/4

Investigation of the Netallie Phthalooyanines in Solutions, II. Acidic-al-
kaline Interaction of the Phthalooyanines of Some Metals in SulPhuric-acid
Solutions
4 metals mentioned before as well as for]t2po' were Computed (1).
Tables 1 and 2 show the indices of these constants (computed
by formula 4). The pENpc;Values keep'a:gOod constancy over
a considerable range of acidity. For a perfect confirmation
of hie assumptions and computations, the author determined
the sOlubility of CuPc and CoPe in 16~?0 m EsSO4 and of
ZnPo in 17.25 m H2SO4, It is in good agreement with the values
comp. ted by equation (4). So i~,can be assumed taat equation (4)
only applies to H2S04 .up to 100~ concentrations. Thin equation
is'useless for oleum since stronge= acids, such as H3SO; et al
(Ref 7), are present in'it. Prom the experimental results of
the present paper, one can make.~hecratical conclusions which
are connected with the dependeneeof the llPc-solubility on
the nature of the metal, On the basis of his investigation
of the phthalocyanine properties, the author-sugges!s modified
structure formulas of the free phthalocyanine and its covalent
complex salts (Pig 2). They are in good agreement with the

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Investigation of the Metallic Phthaloo~anines in Solutions. II. Acidic-al-
kaline Interaction of the Ph~halocyanine~. o� Some. Metals in'Sulphuric.acid
Solutions .
X-ray structural data.as Well as wi~h the chemical and phyaico-
chemical proper~ies ~f the ~hthalocya~ines... K. B. Yat~imirskiy
read the manusoript. �. F. Borodkin supplied the phthalo-
cyanine preparations. ~he~a..a~e.2 figures, 2 tables, and
9 references, 3 of which are Soviet.
ASSOCIATION: Ivanovskiy khimiko-tekh~olSg~cheakiy institut; Kafedra ana-
liticheskoy khimii ,
(Ivanovo Chemical-techmol0giaal.Inst�tute; Chair of Analytical
Chemistry)

SUBMITTED: January 9, 19~8

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TITLE:

2n.
s/155~/61/004/001/003/009
]~ lO/]~2o.~

Berezin, B. D.

Study of phthalocyanines of metals in solutions.
III. Absorption spectra of phthalooyanines in sulfuric
acid solutions

PERIODICAL: Izvestiya vysshikh uchebnykh zavedeniyo Khimiya i
khimicheskaya tekhnologiya, v. 4, no. 1, 1961, 45-52
TEXT: To study photosynthetic and biological reaction chemisms in the
living Organism, the absorption spectra of porphyrine derivatives are
very important for their identification. In the present study, the
author uses strong sulfuric acid solutions of stable metal phthalocyanines:
chemically pure Cu, Zn, Co, Ni salts, R~O4.A1PcC1 (according to Linstead),
CuPcO115, and free H2Pc. Sulfuric acid sOlutions with strong H2SO4 of
known titer were prepared. The absorption spectra in the ultraviolet,
visible, and adjacent infrared spectrum ranges were taken at 22-24�0 by
an C~-4 (SF-4) spectrophotometer. Table 1 gives maxima and intensities

Cara 1/1~

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21124

S/15~/61/004/001/00~/00~
Study of phthalocyanines of .o. B110/B203

of absorption bands. Co, Ni, Cu, and Zn salts dissolved in 8-10 M H2S04
are assumed to have monovalent, basic character: (MePO)dis +
+ H2S04~___ MePcH+ + HS04-. Thus, metal salts protonized in H2SO4
solution can be studied in the spectrum for rules basing on the exchange
of metals and substituents in the complex, on charges in the central
ion, etc. The proton bound in H2SO4 solution to the conjugate ring
system does not change the character of electron transitions but their
probability (bathochromic shift = 80-120 m~, drop in excitation energy;
infrared range 5-6 koal, ultraviolet range = 16 ~cal). This, and similar
conditions for other MePc (Tables 1 and 2), is e~Plained as follows:
n-*x (1) and E-~x ~(2) transitions are possible in the Pc molecule.
In (1), an unbound electron passes from the noncovalent pair of N atoms
to the shell of the E-electron cloud of the macrocycle. In (2), a
E-electron within the conjugate system passes from the electron shell of
one atom to that of another atom. In Pc molecules, probably only (2)
exists, since electron spectra of phthalocyanines and porphyrines are
very similar� In metal pheophytinates, (2) is no longer possible since

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Study of phthalocyanines of

S/~}/6~/004/001/00~/00~
~O/B20~

the intraoyolio N atoms have lost the noncovalent electron pairs by
complex formation. A uC ~mN (3), and a ~N-~UC (4) transition are
likely to occur in MePo. (3) corresponds to minimum exciting energy and
produces the longwave absorption band. In (4), part of the m-cloud
passes from the more electronega~ive N ~o C, which produces the ]ess
intensive, longwave band. The ~0 '*~C~ electron transition from the
conjugate benzene system to the macrooycle system may produce the absorp-
tion band in the adjacent ultraviolet range� Due to the high autonomy
of the two systems, nearly 80 kcal are required to.this end. Besides,
a transition from the macrocycle to the benzene ring, and a mC -* nC~
transition in the substituted benzene ring are also possible. Protoniza-
tion does not interfere with conjugation in the macrocycle, but it
strongly polarizes the u-electron cloud by positive charge. Thus, this
cloud becomes very mobile, and may be even excited by low-energy photons.
Colors are deepened, and maxima are bathochromically shifted according
to the color theory. On introduction of metals in the Pc molecule, the
intensity of maxima drops~ probably due to the formation of a perfectly

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Study of phthalocyanines of .o.

s/ 53/6 /oo4/oo /oo3/oo
~ ~ o/~2 03

symmetric molecule whose x-electron system is stabilized by double
p~-d~ bonds of the central ion with the addendum. New maxima are not
formed, the metal ion is not chromophorous, since the weak transitions
on the d-electron shells do not appear in the spectrum� Thus, the
nature of transitions and the,ionic structure are equal, in principle,
for protonized H2Pc and MePoH . The spectral shift (color change:
deep green-*yellowish broW~) observed in protonized H2Pc after standing
for 48 hr is being studied now.'. On introduction of the covalent metal
ion, 4 c bonds of the contralTi.on a4e formed at the expense of the
completing of ion levels 3d4s~p2 (Co2+, Ni2+, Cu2+); 4d4s4p2 (Zn2+);
3d~s3p2,
or higher levels (Al), by electrons of unbound electron pairs
of intracyclic N atoms. Then, two simple oscillating m-bonds are
formed with the ~-cloud of the addendum by the dzx and dzy electron
orbits of the metal ions unless they have been claimed by o-bonds. The
author had already established an increase of the ~-electron density in
the order: CuPcC115~+A1PoC1 ~ CopO(ZnPc)~ CuPo~NiPc ~H2Pc. The
C~rd 4/~

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s/ 53/6 /oo4/oo /oo3/oo9
Study of Phthalocyanines of ... B110/B203
values for the bonding strength metal - addendum, and for the POSition
and intensity of maxima, are likely to give similar sequences. Table 1
shows for Amax of the MePoN+ the order: E2Pc ~ +A1PcC1 ~ CuPc ~
~CoPc(ZnPc) ~ NiPc, which agrees well with values of 'the mesoporphyrine
complexes: Zn2+ (510 mM) ~ Cu2+ (561 mM) > Co2+ (552 mp)~Nl2+ (550
Also here~ the Ni complex for which maximum stability is assumed shows
the minimum value. The irregularity of ZnPoE+ is explained as follows:
The order of the MePcH+ with respect to the ~-electron density does not
agree with the order of the MePcH+ with respect to X since the same
~-electron density of the macrocycle may result from different fractions
of ~- and ~-bonds, which, in turn, have different effects on the
shift. Also the transition intensity l�g ~ max
electron density. Polarization of bonds of is not simply dependen~ on
benzene nuclei and ~he
macrocycle in CuPcC115 (Fig. 5) effects alleviation of transdtions in
the macrocycle as well as between the conjugate systems maorooyole
benzene nuclei; maxima are bathochromically shifted: CuPoC115 ~s green,
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'"- 21124

'
Study of phthalocyanines of ... B110/B203

CuPCCllsH+ red-brown. Desolvatation of MePcH+ effects a slight change of
~max as well as of the absorption intensities bY interaction of the
proton with nitrogen, and, thus, a stronger polarization effect on the
~-cloud of the macrocycle. This explains the weak bathochromic shift
with increasing H2SO4 concentration. The latter has, however, no
influence on the position of absorption maxima, which excludes the addi-
tion of a second proton to the MePcH+, and proves their existence as
monovalent bases at any acid concentration. In the aluminum complex
(Fig. 4), a dissociation change according to the scheme:
[HSO4.A1.Po< C1]+ [Al'Pa /Cl~ 2+
H J ~ HS04' + is likely to take place.
~ H 2
K. B. Yatsimirskiy is mentioned. There are 5 figures, 2 tables, and
18 references: 8 Soviet-bloc and 10 non-Soviet-bloc. The two refer-
ences to English-language publications read as follows: R. Williams:
Chem. Revs~, 56, 299 (1956); W. Caughey, A. Corwin: J. Amer. Chem. Soc.

Card 6/1~

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s/6 /oo4/oo /.oo;Voop
Study of phthalocyantnes of ... BI 10/B205

Ivanovskiy khimiko-tekhnologicheskiy institut. ~[~fedra
anmliticheskoy khimii (Ivanovo Institute of Chemical
Technology, Department of Analytical Chemistry)

� Ma~ .~1, ~959

Legend to Table 1: Position of electron transitions ~, and their
intensity in sulfuric acid solutions of MePc; (a) phthalocyanine,

(c) electron transitions.
-~ ~ ~ ~ ~ '~ ~ ~'. ~-~ I

SOn moles/liter;
c�ncentrati]n'H�~,~'l t~ ~ ~ ~'~ ~

7/ '�= = &
Card 13 ~

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CTA-RDP86-00513R000204820006-9

2~
................................ '~": ....................... s/~-~/~;~/oo4/oo-~/oo~/oo-~
S~udy of phthalocyanines of ... Bl lO/.B;!03

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s/~/6~/oo4/oo~/oo~/oo~
Study of phthalocyantnes of ... B110/B203 ' :

III I1,*11 II

-III.t~ III Ii

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Study of phthalocyanines of ...

Legend to Table 2: Position
of main electron transitions
in solutions of MePc in
a-CIoH7C1; (a) electron
tran~,itions~ (b) phthalo-
cyanine.

21124

8/15~/61/004/001/00~/00~
3110/3205

b
~,l'a~o.
i
)'mAx,

't
CuPc --
NIPc 676 I
CoPc ' 672'j
ZnPc 6~0 I
Cl' AlPc �9! I

614
6O2
604

622

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Study of phthalocyanines of ...

Legend to Pig. 1: ABsorption
spectra of CuPc and H2Pc;
(1) CuPc in 18 M H2SO4;
(2) Cu?o in 15 M H2S04~
(3) CuPo in ~-OlOHTOl';
(4) H2Pc in ~-C10H7C1.

s/ 53/ /oo /oo /oo3/oo9
3110/3203 '

,.it

Card 11/1~

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s/~ 5~./6 ~/oo4/oo~/003/009
Study of phthalocyanines of'~.. BllO/B203

Legend to Fig. 4: Absorption
spectra of HSO4.AIPcC1;
(~) ~n.~eM H2so~, (2) ~n
14 M H2S04.

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Study of phthalocyanines o� ...

2112/4
s/~ .%V6 ~/oo4/'oo ~/oo.~/Oo9
~ ~ o/~

Legend to Fig. 5: Absorption
spectra CoPc and CuPcC1

(1) CoPc in 18 N H2S04;
(2) CoPc in 15 E H2S04;
(3) CuPcC115 in lS N H2E04.

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cB . .~RL~Z.R;, B.D.
Metal phthalcc~nines in solutions. Part 4: Effect of the
c6ntral ion ek-~ge ,':ud of substituted derivatives on the
properties o� phthaloc2~nines. Izv.vys.ucheb.zav. ;]~-hin.i
khim.tekh. 4 no.3:379-386 '6i. (i!L~A 14:10)

1. Ivanovskiy khi:.~iko-te!~m, olo~icheskiy institut~ kafedrz
analitiehe skoy .'Jxm~.-'~ m.
(?htha!ocyanine)

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~EREZIN, B.D.

Stability of metal phtbalocyanines in solution. Zhur.neorg.khim.
6 no.12:2672-2679 D '61. (MIRA14:12)

1. Ivanovskiy khimiko-te~hnologicheskiy institut, ksfedra analiti-
cheskoy khimii.
(Phthalocyanine)

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s/o7 /6 /oo6/o 2/oo2/o
Bl~O/B147 '

Ab~HOR: Berezin, B. D,

TITLE; Study of the s~abillty of phthalocyanines of metals in
solution

PERIODICAL: Zhurnal neorganicheskoy khimii, v. 6, no. 12, 1961,

TEXT; The author studied less stable phthalocyaniues of metal:s bz the
solubility method, and stable ones by means of isotopic exchange� The
decomposition of lees stable Pc follows the ' + .2+ .. ol
reactzon ~PCsol+2H.O =~a~+H.,~
An exac~ ~4Pc addition was shaken with H2SO~,~ HC1, or HC104 in the thermostat
at 2p + O,2�C. Next, the Ag+ content in the filtrate was nephelometrically
Hg2*
determined as AgC1. was determined with diphenyl carbazono,

de'[;er~lined as rhodanide in an HNO~ medium, ~,-' -' and
~ilonome!;rioally dctcrmined by means of erioch~ome black. Tn~ separation

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3/078/61/o06/0'~ 2/002/oi I
Study of the stability of ,.o BI 10/B147

ol' Be2+ from NPc proceeded more sZowly than that of ~g2+ and ether ions of
less stable Pc except for Fe3+~ since the rates of its hydrolysis au 25�C
i:~ 17~70 and 15~40 moles of H2SO4 are 0.0~5 I 0,008 hr-1 ~nd
1,40 + 0~06 hr''1 respectively� To study the stability of
~nd Zn~Pc were formed from an alcoholic anhydrous so~uti'.;u o~'
ZnC12~65~ and Li Pc in absolute alcohol� They were mixed by
2
equal amounts of titr~ted H2SO4 (1 - 0 moles/liter), at 25 o'.' 50CC and ~he
activity of the solution was determined a�ter cen~rifuging~ ~he activity
of the deposi~ was-~O,O00 pulses/mino A known volume o� a Co
dissolved in H2SO4 cf the ~same concentration (17o20 moles/li~er) wa~ added
to sulfuric Pc soZutions of AZ, Co, NJ, and Zn cont~:!ned in a bulb~
Hydrolysis was conducted according to ~cH++ H20--~ H.~O+ ~ ....
Eeprecipitated dried ~4Pc ;','as diosclvcd in concenr,-r~:te.d H2S04,

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S/078/61/006/012/002/011
Study of the stability of oo~ B110/B147

activity of the solution was determined (T~ble 3). Irreversibility o~
(1) in acid aqueous solutions may be assumed on the basis of examin~zons
by the usual solubility method of the dissociation of less stable Pc of
Ngs Ca~ Cd~ Hgt AS~ Pb, and Feo Even with the stable compound Cl~ePc,
complete "washing out" of the metal with 1 mole of acid occurred after
8 - 10 da~s, with NgPc and PbPc it occurred after 40 - 50 hr, with AgHPc
after 120 hr, with HgPc and CdPc after 12 - 15 hr, and with C~Pc after
2 - 5 hr. The rate of washing depends on the type of central ion. it
increases as the acid concentration increases, but it is quantitatively
indeoendent of the H ion concentration. It probably depends on the
different rates of rupture of the donor - acceptor bond between meta~
and addendum~ Presumably, it is the higher the lower the covalent
character of the metal - addendum bond~ It is due to residual basic
properties of inner-cyclic N atoms of the macro-ring, since the basic
properties of the addendum decrease as the firmness of th~-bond of
metal - nitrogen increases. As regards filling of the hybrid orbit of
the metal ion by electron pairs of nitrogen, the following sequence~ of
bond �irmness are given: Fe3+) Ag+)~g2+, pb2+~ Cd2+, Hg2+~ Ca2+~ The
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Study of the Stability of ooo

S/078/61/006/012/002/0~1
3110/3~47

author studied the isotopic exchange of Co2+-60 v,'ith Pc of Co, ~-~i,
and A1 dissolved in 17~20 moles of H2SO4 following the equations
+ H2PcH+ ~, H2PcH+
~Pctt + 2H+ + ,~,~t (2a) ~aa + C~2+ C~2+ ~
Although insoluble H2Pc and ~drated cations ~able to penetrate

the Pc "~'~indow", are not formed in (2a) and (2b) as in (1)~ H..~"c
separate from (2a) and (2b) due to the slow-rate process, The author
thanks N. I~ Sosnikov~ for help with the experiments~ ~h=.e ~re
figures~ 3 tables, and 22 references~ 12 Soviet and 10 non-Soviet.
three most recent referenoes to English-language public~tions read
i'ollows: B. West. J~ Chem~ Soc~, 5115 (1957); D. Atkin~, C. Garner.
J~ Amer, Chem~ Soc.~ ~*, 3527 (1952); ~',~. Caughey, ,~, Oorwin, j,.
Chem~ Soc~ ~, 150~

AssOCIATION` Ivanovskiy khimiko-tekhnologicheskiy institu~ Kafedra
analiticheskoy khimii (Ivanovo ~nstitute of Chemical
Technolo~, Department of Analytical Chemistry)

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s/oTe/6 /o 5/o
]~140/B147

AUTHOR= ~.

TITLE I A study of metal phthalocyanines in solution, V. The
stability of free phthalocyanine in sulfuric acid solutions

PERIODICALs Zhurnal fizicheskoy khimii, v. ~, no. ~, ~96~, 2494 - 2499

TEXTz The stability of free phthalocyanine (H2Pc) in H2SO4 solution was
studied. Experimental procedurez Free H2Pc is prepared by treating
Na2Pc with ~6% H2SO~ and introducing the mixture intoan ice-bath prepared
from ~istilled water. To remove impurities, H2Pc was heated with acetone.
The st&bility of the H2Pc macroring was studied using weighed portions of
H2Pc and various H2SO~ concentrations. The optical density of the
solutions was measured at regular intervals on a KM(KM) spectrophotometer
(~ = ~20 mB). ~2.~ - ~7~5 M H2SO~ solutions were used for the investiga-
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study of metal phthalocyanines o. o

S/076/61/0~5/011/005/01~
~40/~47:

tion, The decompOsition of H2Pc in acid solution yields the s~e preduc~s
as are obtained by its o~idation (phthalimide and ammonium salts). The
influence of atmospheric oxygen and light (using a 1000 w bulb) on the
decomposition rate of HAPc was also studied. Evaluation of the measure-
meni results showed thai the decomposition rate of H2Pc increases with
increasing H2SO4 concentration up to a maximum and then decreases ~apidly.
A 17.65 M H2SO4 solution-still gave a distinct H2Pc spectrum. Graphic
evaluation yielded the linear function log(Co/C) = f(t), (t = ti4e)~ where
co denotes the intial H2Pc concentratign, and c the concentration in the
Course of the reaction, Therefore this function follows the kinetic
equation -(~c/dt) - krCH2Pc (2), where kr ,= hydrolysis rate constant. The
characteristic decomposition reaction of H2Pc in ~2S04 is assumed to
involve the participation of H~0+, since the H~0+ concentration changes in

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� study of metal phthalooyan~nes ... B140/B147

the same w&y as the decomposition of N2Pc. According to Nammett, the
H~O+ concentration may be calculated as
H - co. et + log ~
o - . H~SO? (~)' where const , -8.56. It was found experi-
mentally that the H~O~ concentration and kr pass through a m~im~ at an
H~SO4 concentration of 14 - 14.5 moles. The author assumes the reaction

mine the r~ction order of the hydrolytic decompo~ition of N2Pc, log k
was plotted wersus lo + r
g H~O . T~us,the author obtaine~, the linear
function log k - lo~ k +-n
. . r ~ .'~ei'xu / ~/, where n - 5 for N~S0.~16
mole's/liter;~d n "~ for N'~ ~f~ . ~ ... , . . ~ 4
Card ~/5' ~ .~-~4/,~ mo~es / ~lter. ~'rom ~5), kr was

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A studY~of metal phthalocyanines ... B140/B147

calculaied and found to be 1.12.10-4 hr-1 which inserted in Eq. (2)

dt = 1 10'4c 04 +
4 protons!.participate, is assuaed to involve the shi�tin; of 2 electrons
from~the;H2Pc macrorin; to 2 protons with ev�lut~on of ~2 ;as. ~he
~hyd~"~lyt~c '~ecompoe$tiO~:o� H2~c is not a��ected by 02 or li�ht,
~2S0~1~ modess,the rate o� solution o� ~2Pc is smaller than f~- r~te of
yaro~y~is"so' thati:the reaction does not reach equ�librium state.
H230~'~ a�~ rate of hydrolysis ~e smaller so that
an equ~libzh~
is reached afteT 1 - 2 hr. It may there�or~ be assumed that in
' a2804'~ ~2Pc8? + ESO~ ie siren ~y- lo� L~270~2504= 1.67 +
+8.~.. ~. ~. $os~o~a ass~eteQ ~n the..e~per~men%so ~here are 4

recent re~erencee ~o ~l~eh-l~e~bl~catio~s read aa
~. Barrett, C. Dent, ~. L~n8tead, ~*~ Chem. Soc., 171~, 1~6t L.
4/5

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S/O ?..~,/~ 1/0.~5/011/00~/01 .~
study of metal PhthalocTanin. es ... ~140/B147
Che~. Revs., 1~, ~, 1~1 W. Cau~hey, A. Co~n, ~. ~er. Chem. Soo.~

ASSOCZATION~

Ivanovskiy khimiko-tekhnologicheskiy institut ( Ivanovo
Institute of Chemical Technology')'

SUBMITTED I March 16, 1960

Card

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~e+.aZ pht2~loc~ee ~n eolutio~o' Pa~t 5zS~btLtty o� free
phthsl~ya~ine ~ sulf~ic acid solutions, ,Zhur~�tzokh~.
~5 no. Ll~2~9~500 N, %1, (I~,.I~ 11:12)

1. Ivanovskiy khimiko.tekhnologicheskih institut,
(~t~oc~e)

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TITLE~

Berezin, B. D.

Methods of lnvesti~atin~ %he e~abil:.;y of phthalocyanine
complex compounds

PERIODIOAL, Akaden~ya nauk 8~8R. Doklady~ v,.

TEXT~ ~he d~seoo~at~on of metal phthalooya~nee ~hlch ~e only noteworthy
in proton e, cid media was studied ~n thee ~aper~
(2)t ~PcH+ + 2H* - H2PoH+ + a2+ (2a)~ where Po is the bivalent anion of
tetrabenzo tetrazaporphin (phthalooyanine)~ and ~' ~s a metal ion.
Process (2) takes plaoe in solid phaee~ and (~a) in H2504 with a concen-
tration of sore than 8 moles/liter. Processes (2) an~ (2a) were found to
be fast and, irreversible with unstable phthalocyan~nes~ ~o e., with those

formed b~ cations of alkalis, alkaline earths,
Be2+, A~+~ Fe2+~ and those containin~ 8b}+~ gn2*~ and Sn2+. The convers~c~

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30702
S/020/6~/141/002/01~/027
Methods of investigatin~oo. ~!0~/Bl!0
of stable Po formed by Cu2+i Zn2+~ Co2+~ Ni~*~ pt2*~ pd2+~ �4+ A1C12+
and partly SnCl~+, according to Eqeo (2) a~d (~) is hardly noticeable.
In aqueotm~ acid ued~a~ stable Pc dissociate ~r~vers~bly acoordin~ to (2)
and ~2a). Despite a marked ionic d~ssocia~ion ~n ~cld me6~a~ Po cannot be
oharaoteri~ed by the eq~ilibrium constant of (2~ o~ (~)o In those oases
�here it is difffioult or impoes~ble to determine ~he in~tab~lity constant,
or where..the binding energy between metal and addenda cannot be measured,
~t is possible to apply~ among others~ the =ethod of determlnin~ the rate
of metal separation under the action of ~eld~~Re~' ~ 10, see below)o This
method was tested on Pc complexes. The fo~me of ?~ existence in H~$~4
at ~arious te2peratures, and the properties o� ~$0~ aes~lzent were studied
in prelim~nary experimentso In an earlier s~uc~y (Khlm, i khim, tekhnol.
A, 165 (1959)~ ~, 45, }79 (1961)) the author pro'~d tha~ Pc in concentrated
H2504 at normal temperatures behaved like mon0acld bases~
MPOs + ~2S~4.~Po~+ + H2SO~ (]). Tabl. ~ ~iv.s equilibrium oonstants of
Eqo (}) at 2]mO. Those of industrially important Po ar~ given in Table 2.

Card 2/g .~'

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~..hods of investigating...

307O�
S/O2q/61/141/O02/01~/027
~10~/BllO

Sxnce the constants remain unchanged at all temperatures~ concentrated
H2SO4 is an ideal solvent. Thus~ the ratio of activity coefficients of
the reactants in (3) also remains constant~ and the reaction product~
(MPcH)HS04~ is completely dissociated. MPcH+ predominates in sulfmric
acid solutions. The equilibrium constants pK of reaction (3) allow con-
clusions as to the formation and durability of d- an~ x-bonds, the
stability of MPc~ the existence of an excessive char,~e on the central ion,
and the induction effect of the substituents in the benzene rin~. The
effect observed is an endothermic one which decreases with increasing
solvation ability of Pc~ either because of the ability of additional co-
ordination of the central ion (ZnPc~ ZnPcC1)e or due to a charge of the
central ion (+A1PcC1), or the polarization of bonds in the chlorination of
benzene rings (CuPcC115)o Pc disintegrates in sulfuric acid solutions
and is completely hydrolyzed on the macroring. {~
~2(CgH4"2)4A+_} + 8~20 + 5~+'--'-~408B502~ + 41IE~ + H2o The coZori.g o~
HPcH+ and H2PcH+ disappears. All unstable Po were found to hydrolyze in
Card ~/~- f

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~0702
Methods of investigating, o.. ~10~/~110
the same manner as free Po. The hydrolysis of H2PoH+ is complicated. The
hydrolysis mechanism of stable ~c was studie~ with the most unstable ~c~
(~04)25~o. ~he hydrol2si, also follows the eq~tion ~n~* + ~' (1),
The limiting stage in unstable Po~ however~ is the hydrol~is of the
H2PoH+ macroring, whereas in stable ~o it ia the metal separation (2a).
Thus, fo~ coordinate bonds between metal and nitrogen are rupt~ed. The
~olysis of stable Pc is only noticeable, at 1OO - 120o0. As to the
readiness of separation~'~eoentral ion in pO, the metals form the order
V4+~Zn2+~Ou2+~Co2+~i2+~pd2+~pt2+. At the same time, the basic
properties of the fou~ ~ at~ms, of'the rings participating in (2) and (2a)
are inoreasingl2.neutralized, Pt2+ has th~ highest stability~ .but~alSO
(~04) AlPc is ver~ stable. The above order reflects the stability order
in porphyria complexes, Ba2+~Mg2+3 Mn2+~ Fe2+> Zn2+)Cu2+~ Co2~i2+~p~
~he~e ~e 6 tables an~ 18 references~ 12 Soviet and 6 non-Soviet. ~he
three ~eferencea to English-la~w;uage publications read as follows~ "

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gethods of investigating..,

~0702
5/020/61/141/002/013/027
~O~/Bl~O

Ref. ?: R. Williams, Chem. Heys, 56, 2~9 (1~56)l ;~,'~f. 101W. Caughey,
A. Corwin, J. Am. Chem. Soc., 77, 1509 (1955)~ Eel. 161 N. Deno, R. Taft,
J. Am. Chem. Soc. 76, 244 (~34~.

ASSOCIATION: Ivanovskiy khimiko-tekhnologicheskiy institut (Ivanovo
Institute of Chemical Technology)

PRESENTED~

Jane 23, 1961, by A. N. Terenin, Academician

SUBMITTED~ June 22, 1961

Table 1. pK of the equilibrium constan~of reaction (5) of stable
phthalocyanins at '25oc.

Legend: (1) Phthalocyanin. .

Table 2. Temperature dependence of pK of phthalocyanins in N2S04.
Legend~ (1) Temperature, �C$ (2) pK of phthalocyanins of metals.

car~ ~/~ ~

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Re~arke on the artiole by I.~.~khtev~ch ~On che~Lcal etab~]ity
of ~-~d ~-~l~oph~ of copper a~d zinc. l~,kh~.~hur. 28

1. IvanoVskiy ~t~k/u~logi~heskiy institut.

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s/ov6/6z/o 6/oo)/oo /o
~101/B108

AUTHOR~

TITLE, Study of metal phthalooyanines in solution. VI. Effect of
the nature cT the central ion on the strength of the phthalo-
cyanine macro-ring in sulfuric acid solutions

PERIODICAL, Zhurnal fi~icheskoy khimii, v. 36, no. 3, 1962, 494 - 501
TEXT: The stability of the compounds MPc of phthalocyanine (H2Pc) with
Cu2+, Ni2+, Co2+, Zn2+, Sn2+, Sn4+, A13+, VO2+, Cd2+, pb2+, Mg2+, Ag+, Fe3+
as well as of the chlorinated compounds C115PoCu in 12 - 17.7 mole/~iter
-H2SO~ was investigated at 25 - 65�j~+,The compounds can be divided into two
groups, (1) stable compounds of 0o2+, Ni2+, Zn2+, A13+, VO2+, which
displayed no noticeable dissociation at room temperature, (2) unstable
compounds of Mg2+, Od2+, Ag+, pb2+, Fei+, Sn2+, Sn4+' The stable ~o's
and C115PcOu had very small constants of. hydrolyzation rate (k~10-4 per
Card' 1_~___ ' '

APPROVED FOR RELEASE: 06/08/2000 C1'A-RDP86-00513R000204820006-9"

"APPROVED FOR RELEASE: 06/08/2000 CTA-RDP86-00513R000204820006-9

Study of metal S/076/62/036/003/00~/011
''' BlO1/B108
hour) at room temperature'even in diluted H2S04. The unstable MPc's had
constants of hydrolyzation rate different from that of H2Pc (0.13720.008
per hour)~.by one order of magnitude. Unlike the unstable I~c,s whose spectra.'
show o~ly the absorption bands of HePeH+, the stable MPc's displayed absorp-
tion bands of their own. H~drolysisproceeds as MPCsd + H2SO4~MPcH+
+ H~o~