Zinc reaction with diphenylantimony and diphenylbismuth chlorides in aprotic solvents

Article abstract of DOI:10.1134/S1070363206100136

Products of zinc oxidation with diphenylantimony and diphenylbismuth chlorides in aprotic solvents are established. The effective adsorption constants of the reagents on the metal surface and the rate constants and activation energies of the processes und

Full text of DOI:10.1134/S1070363206100136

ISSN 1070-3632, Russian Journal of General Chemistry, 2006, Vol. 76, No. 10, pp. 1581 1583.
Pleiades Publishing, Inc., 2006.
Original Russian Text
Ya.V. Losev, S.V. Klement’eva, S.V. Maslennikov, I.V. Spirina, 2006, published in Zhurnal Obshchei Khimii, 2006, Vol. 76,
No. 10, pp. 1648 1651.
Zinc Reaction with Diphenylantimony
and Diphenylbismuth Chlorides in Aprotic Solvents
Ya. V. Losev, S. V. Klement’eva, S. V. Maslennikov, and I. V. Spirina
Research Institute of Chemistry,
Lobachevskii Nizhny Novgorod State University, State Educational Institution of Higher Professional Education,
ul. Gagarina 23, korp. 5, Russia, 603950, Nizhny Novgorod, 603950 Russia
e-mail: spirina@ichem.unn.runnet.ru
Received April 11, 2006
Abstract Products of zinc oxidation with diphenylantimony and diphenylbismuth chlorides in aprotic
solvents are established. The effective adsorption constants of the reagents on the metal surface and the rate
constants and activation energies of the processes under study are calculated.
DOI: 10.1134/S1070363206100136
Inspite of the numerous studies connected with re-
activity assessment of oxidant ligand systems in the
course of metal solution in aprotic solvents [1],
quantitative correlation of the rates of such reactions
and the physicochemical parameters of the reagents
calls for further experimental data. In particular, ki-
netic regularities of zinc oxidation with diphenylanti-
mony and diphenylbismuth II chlorides (I, II) are
quite necessary.
Langmuir Hinshelwood scheme that assumes reagent
adsorption on similar-in-nature active centers of the
metal surface [5].
In this case, the reaction scheme can be described
by the following equations:
ads
KOx
(
4)
Ox + S
L + S
Ox(S),
L(S),
ads
KL
(5)
(6)
k
According to [2], the oxidation of zinc powder
with trifluoromethylstibine iodide gives tetra(trifluo-
romethyl)distibine in nearly quantitative yield. This
compound slowly decomposes at room temperature.
Wiberg and Modritzer [3] found that tetra(diphenyl)-
Ox(S) + L(S)
Products.
ads
Ox
and K aL ds are the equilibrium adsorption
K
constants of the oxidant and ligand; and COx and CL,
their concentrations.
dibismuthine is unstable and converts into Ph Bi,
3
The reaction rate has the following equation:
(
PhBi) , Ph , and Bi in solutions. Analogous data on
n 2
the transformations pathways of (Ph Bi) and (Ph Sb)
2
2
2
2
ads
kK COx
Ox
ads
L
ads
K
CL
formed by magnesium oxidation with Ph SbCl (I) and
V =
,
2
(7)
2
ads
(
1 + K COx + KL C )
Ox L
Ph BiCl (II) were reported in [4].
2
Analysis of the composition of the intermediate
and final products of the oxidation of compact zinc
with compounds I and II allows the following reac-
tion mechanism to be suggested.
2
where k = k S ; k is the rate constant; and S , number
0
0
of active adsorption centers of the metal per its unit
surface.
Transformation of experimental data in the
Ph ECl + Zn
PhEZnCl,
(1)
(2)
(3)
2
COx/V = f(COx) and C /V = f(C ),
L
L
PhEZnCl + Ph ECl
(Ph E) + ZnCl ,
2
2
2
2
CL= const, COx = const.
(
Ph E)
Ph E + Ph + (PhE) + E,
3 2 n
2
2
E = Bi, Sb.
coordinates at C = const and C = const, respect-
L Ox
ively, with subsequent combined solution of the result-
ing equations allowed us to calculate effective
equilibrium reagent adsorption constants and reaction
rate constants. From the temperature dependences of
The kinetic curves of zinc oxidation with com-
pounds I and II in a DMF p-xylene mixture (Figs. 1,
) show that both processes can be described by the
2
1581

1582
LOSEV et al.
CDMF, M
CDMF, M
0
5
10
0
5
10
8
8
6
8
6
1
1
6
6
4
2
2
2
4
2
0
3
4
2
0
3
4
4
2
0
4
0
0
0.1
COx, M
0.2
0
0.1
COx, M
0.2
Fig. 2. Dependence of the rate of zinc oxidation with
Fig. 1. Rate of zinc oxidation with diphenylantimony
chloride in the DMF p-xylene mixture: (1, 3) C
diphenylbismuth chloride in the DMF p-xylene mixture
on the concentration of the (1, 3) oxidant (C 13 M)
0,DMF
0
,DMF
1
3 M and (2, 4) C
0.1 M. T, K: (1, 2) 343 and
and (2, 4) ligand (C
0.1 M). T, K: (1, 2) 303 and
0
,Ox
0,Ox
(
3, 4) 323.
(3, 4) 283.
these values, effective adsorption enthalpies and
entropies were found (see table).
conditions: 3000 2.3-mm glass column packed with
10% of Reoplex-400 on Cellit-545, katharometer
bridge current 180 mA, carrier gas helium (flow rate
1
EXPERIMENTAL
60 ml min ), injector, oven, and detector tempera-
tures 180 C. Kinetic measurements were carried out
by the resistometric procedure [6] modified for
operating with easily hydrolyzed and oxidized com-
pounds.
Chromatographic analysis of benzene and diphenyl
was carried out on a Tsvet-104 instrument. Analysis
Effective adsorption equilibrium constants, enthalpies, and
entropies and rate constants and activation energies of zinc
oxidation with diphenylbismuth chloride in the DMF
p-xylene mixture
Zink wire (Technical Specifications 6-09-5294-86),
d 0.36 mm, was used as received. Organic solvents
were purified and dried according to conventional
procedures [7]. Bismuth, antimony, zinc, and chlorine
contents of the starting compounds and reaction
products were determined according to [8, 9]. Liquid
mixtures were degassed by repeated freeze pump
thaw procedure. Diphenylantimony and diphenylbis-
muth chlorides were prepared according to the pro-
cedures in [5]. The purity of the samples was control-
led by their melting points and main substance con-
tents that were no less than 99.5%.
5
T, K
KOx
KL 102 k 10 , molcm 2 min 1
a
Ph SbCl
2
323
333
343
19
17
15
57
45
37
2.1
3.3
4.0
a
Ph BiCl
2
283
293
303
12.1
9.5
6.9
1.8
0.83
0.42
11
34
87
Analysis of products formed by zinc oxidation with
compounds I and II was carried out as follows. A
fivefold molar excess of compact zinc was placed
under an inert atmosphere in a flask containing a THF
oxidant solution (0.1 M). The reaction mixture was
kept at 20 C for a time necessary for complete reac-
tion. Therewith, a black precipitate accumulated on
the flask bottom. Note that in the course of zinc oxi-
a
1
Ph SbCl:
H
10.5 0.5 kJmol
,
S
Ox
9.2
67
2
Ox
,
1
1
1
0
5
.2 Jmol
K
1
H
28.3 0.5 kJmol
1
,
S
L
L
1
Jmol
K
, E 29 3 kJmol ; Ph BiCl:
H 20.2
a
2
Ox
1
1
1
1
kJmol
;
S
50.5 5.5 Jmol
K
;
H 36 1 kJmol
1
.
;
Ox
Jmol
L
1
1
S
K ; E 63 3 kJmol
a
L83
8
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 10 2006

ZINC REACTION WITH DIPHENYLANTIMONY
1583
dation with compound II metal mirror appeared on
the reactor walls. After reaction completion, the black
precipitate was separated from the liquid phase and
unreacted metal. It was several times washed with
THF, dried, and weighed. The results of chemical
with water. The aqueous extracts were combined and
analyzed for Zn2 and Cl [10]. The Zn and Cl
+
2+
contents corresponded to 0.497 mol of ZnCl per
2
1 mol of compound II. The organic phase was divided
in two parts. One of them was dried over sodium
sulfate and evaporated to leave a yellow oil that crys-
tallized on cooling. After two crystallizations from
toluene, the product melted at 76.5 C {published data
[7, 8] and gravimetric analysis show that oxidants I
and II react with zinc in a 2:1 ratio.
Analysis of products of zinc oxidation with
diphenylantimony. The liquid phase of the reaction
mixture was separated from the dark brown powder.
The latter was repeatedly washed with THF, dried at
for Ph Bi [11]: mp 76 77 C). The second part of the
3
organic phase was treated with conc. HCl to form,
3+
according to [11], benzene and BiCl . The Bi
3
content [8] of the HCl solution was 0.485 g-ion per
1 mol of compound II. Chromatography of the
toluene solution showed that it contained 1.47 mol of
benzene and 0.078 mol of diphenyl per 1 mol of
compound II.
reduced pressure, dissolved in 20% nitric acid, and
the solution was analyzed for Sb3+ [9]. The Sb3+
content corresponded to 0.485 g-ion per 1 mol of
compound I.
The liqid phase was evaporated, and toluene was
added to the oily residue. A white precipitate formed.
It was separated and dissolved in water, and the solu-
REFERENCES
2
+
tion was analyzed for Zn and Cl [10]. Their con-
1. Maslennikov, S.V., Doctoral (Chem) Dissertation,
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Nizhny Novgorod, 2006.
2
of compound I. The organic layer was divided in two
2
3
4
. Dale, J., Emeleus, H.J., Haszeldine, R.N., and
Moos, J.H., J. Chem. Soc., 1957, no. 8, p. 3708.
equal parts. One part was evaporated, and the residue
2
+
was mineralized by oxidation with HNO . The Sb
3
. Wiberg E. and Modritzer K., Z. Naturforsch. B, 1957,
vol. 12, p 132.
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pressure. The residual solution was cooled to isolate
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3
5
. Kocheshkov, K.A., Skoldinov, A.P., and Zemlyan-
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istry. Antimony, Bismuth], Moscow: Nauka, 1976.
melts at 52 54 C. Chromatography detected traces of
diphenyl in the reaction products.
Analysis of products of zinc oxidation with di-
phenylbismuth chloride. After reaction completion,
the black precipitate was separated from the liqiud
phase, washed with THF, dried at reduced pressure,
cooled, and dissolved in acetic acid. The solution was
6. Zhukov, S.A., Lavrent’ev, I.P., and Nifontova, T.A.,
React. Kinet. Catal. Lett., 1977, vol. 7, p. 405.
7
8
9
. Gordon, A.J. and Ford, R.A., The Chemist’s Compa-
nion, New York: Wiley, 1972.
3
+
3+
analyzed for Bi
[9]. The Bi
content was
. Bremer, H. and Wendlandt, K.-P., Heterogene Kata-
lyse, Berlin: Akademie, 1978.
0
.314 g-ion per 1 mol of compound II. By chroma-
tographic analysis, 0.238 mol of benzene per 1 mol
. Marczenko, Z., Kolorymetryczne oznaczanie pier-
wiastkov (Photometric Determination of Elements),
Warsaw: Wyd. Naukowo-Techniczne, 1968.
of oxidant II was determined. The metal mirror
formed on the flask walls was dissolved in 20% nitric
acid. The Bi3+ content [9] of the resulting solution
1
0. Charlot, G., Les methodes de la chimie analytique,
was 0.171 g-ion per 1 mol of compound II. The liquid
phase was evaporated, and the residual yellowish
green material was treated with toluene. A white pre-
cipitate formed. The mixture was repeatedly shaken
Paris: Masson, 1966.
11. Considine, W.L. and Ventura, J.J., J. Organomet.
Chem., 1965, no. 3, p. 420.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 10 2006