Obtaining of trialkylphosphates in anodic dissolution of copper phosphide

Article abstract of DOI:10.13005/ojc/300413

Due to obtain trialkylphosphate is suggested to use anodic solution of copper phosphide in alcohol solutions. At this, it can use copper phosphide, obtained at the processing of wastes of phosphorus production. Moreover, it is presented ways of obtaining of tri-n-butylphosphate and tri-izo-butylphosphate.

Full text of DOI:10.13005/ojc/300413

ISSN: 0970-020 X
CODEN: OJCHEG
2014, Vol. 30, No. (4):
Pg. 1553-1556
ORIENTAL JOURNAL OF CHEMISTRY
An International Open Free Access, Peer Reviewed Research Journal
www.orientjchem.org
Obtaining of Trialkylphosphates in
Anodic Dissolution of Copper Phosphide
A.P. AUESHOV1, S. SATAYEV2 and A.S. TUKIBAYEVA3*
Laboratory of Physico-chemical methods of researches1, Department of Chemical
Technology of inorganic substances2, Department of Nanotechnology3, M.Auezov
South Kazakhstan State University, South-Kazakhstan region, Republic of Kazakhstan .
*Corresponding author E-mail: tukibayeva@inbox.ru
http://dx.doi.org/10.13005/ojc/300413
(Received: July 26, 2014; Accepted: September 10, 2014)
ABSTRACT
Due to obtain trialkylphosphate is suggested to use anodic solution of copper phosphide in
alcohol solutions. At this, it can use copper phosphide, obtained at the processing of wastes of
phosphorus production. Moreover, it is presented ways of obtaining of tri-n-butylphosphate and
tri-izo-butylphosphate.
Key words: trialkylphosphate, tri-n-butylphosphate, tri-izo- butylphosphate,
Copper phosphide, electrosyntheses, sacrificial anodes.
INTRODUCTION
was found that three alkyl phosphates
corresponding to the three possible combinations
of substituents bound to phosphorus in phosphate
are formed.
In the research1,2 are shown the
possibilities of obtaining of trialkylphosphate by the
electrolysis of suspensions of red phosphorus. The
authors of work3 used dialkylphosphoric acid as
the initial phosphorus containing compounds for
synthesis of trialkylphosphate. Next authors4
studied the process of synthesis of tryalkyl
phosphates, i.e., derivatives of methanol, butanol,
and diethylene glycol, by anodic oxidation of
dimethyl phosphite in the corresponding alcohol. It
In this regard, it was interesting to
investigate the possibilities of obtaining of
trialkylphosphates by the using of sacrificial copper-
phosphorus anode as a donor of phosphorus. The
copper-phosphorus alloys are produced by
industries, in addition, these alloys are formed at
the processing of phosphorus sludge5.

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AUESHOV et al., Orient. J. Chem., Vol. 30(4), 1553-1556 (2014)
Mechanism of anodic dissolution of Electrolysis was performed at current
copper-phosphorus alloys in the alcohol solutions density of 0.25-0.30 A/m2’”10-4 during 5 hours.
of hydrogen chloride can be represented by the Temperature of an electrolyte was 65-70oC. The
following equations:
Cu + Cl ® CuCl + e
Cu3P + Cl-  3CuCl+ P + 3e
voltage on the bath was not exceeding 20-22 W.
The passed current, which was measured by copper
...(1) coulometer, was 35 ampere hour (A·h). At this, in
the results the electrolysis was dissolved 29.6 g of
...(2) copper phosphide anode. 25.2 g of copper powder
was isolated on the cathode, the part of which fell to
3CuCl + 3 ROH  P (RO)3 + 3HCl + 3Cu, where
R - Alkyl radical ...(3)
the bottom of the electrolysis.
After filtration, the solution was subjected
The formed phosphides are subjected to to vacuum distillation. The unreacted butyl alcohol
further oxidation. This process may proceed on the was distilled off at the temperature 32-35oC and the
anode or in solution with the participation of oxygen pressure 2.66’”103 Pa. The white deposit of copper
or copper compounds. In the latter case, the reaction monochlorides was precipitated in the remains,
may be in the form
which it was filtered off. Weight of precipitate after
drying was 3.1 g. The volume of filtrate was 30 cm3.
2CuCl+ P (RO)3 + 2ROH ® OP (RO)3 +2HCl + ROR Moreover, to this filtrate 60 cm3 of benzene were
+ 2Cu
...(4) added and were mixed for 5-6 minutes, after that
the solution was poured into the separating funnel
Trialkylphosphates are the efficient and washed out with 40 cm3 of distilled water until
complex forming reagents.Particularly, in this regard the disappearances of blue color of copper ions in
the valuable substances are tri-n-butylphosphate the aqueous layer. The benzene layer was filtered
and tri-izo-butylphosphate, which are used for through anhydrous sodium sulfate. After distillation
selective extractions of uranium, thorium6.Currently, of benzene from liquid leavings by the vacuum
these reagents are used in nuclear fuel engineering, distillation at a temperature of 159-165°C (1.60’”103
therefore the development of new methods of the Pa) 20 cm3 of liquid containing phosphorus was
obtaining of trialkylphosphate presents practical obtained.
interest.
Electrosyntheses of tri-izo-butylphosphate.
MATERIALAND METHODS
Electrolysis with 300 cm3 of isobutyl alcohol
(2-methyl-3-propanol), also previously saturated by
hydrogen chloride was performed on the above
Electrosynthesis of tri-n-butylphosphate
In glass electrolyzer, equipped by water presented procedure, the electrolysis performed at
jacket and return refrigerator 200 cm3 of n-butane the current density of ia = (0.2-0.25) ’”10-4 A/m2 and
alcohol was loaded. Previous of electrolyzing the U = 20 -24 W. At these conditions 60 A/hours of
alcohol was saturated by dry gaseous hydrogen electricity was passed through the electrolyte. The
chloride. In this purpose it is very convenient to loss of anode mass was 46.1 g.
obtain the dry hydrogen chloride by the action of
concentrated sulfuric acids on concentrated
Further processing of electrolyte was
hydrochloric acid with the followed passing of conducted same ways, as tri-n-butylphosphate.
hydrogen chloride through a flask with concentrated After distillation of benzene, 35 cm3 of tri-izo-
H2SO4.
butylphosphate was remained, which has been
subjected to vacuum distillation5
A plate of copper – phosphorus alloys
(phosphorus content is 10 mass %) weighing 112 g
with the total area 3.5’”10-3 m2, and working surface
RESULTSAND DISCUSSION
2.5’”10-3 m2, the copper plates cathodes with Electrosyntheses of tri-n-butylphosphate
analogous size were used in electrolysis.
The density of tri-n-butylphosphate was

AUESHOV et al., Orient. J. Chem., Vol. 30(4), 1553-1556 (2014)
determined by State standard 18995.1-73 p.27.The
trialkylphosphate.
1555
analysis of phosphorus in trialkylphosphate was
conducted by Kjeldahl8. Determination of the
refractive index was implemented according to
State standard 18955.6-739.
Thus, 29.6 g of copper-phosphorus alloy
was dissolved at the electrolysis, and 26.9 × 0.098
= 2.90 g of phosphorus passed into the solution.
Theoretical amount of tri-n-butylphosphate was
266×2.90/31 = 24.88 g
The boiling point of tri-n-butylphosphate
was determined according to State standard
18995.6-73, p.1. IR-specters are taken by the
«SPEKORD-IR», of Germany Company “Carl Seis,
Iena”.
The measured weight of 20 cm3 of tri-n-
butylphosphate was equal to 19.40 g, i.e., the output
of tri-n-butylphosphate was 77.9%.
Quantitative analysis indicated, that the
liquid contains about 11.09 % of phosphorus.
Determination the boiling point, density, refractive
index and take IR-spectra are gave the following
results:
Electrosyntheses of tri-izo-butylphosphate
In the result of distillation under pressure
of 1.064’”102 Pa, at the corresponding temperatures
(T) were obtained the following (G) substances.
1) T = 86-87 oC, G-10 g
2) T = 110-112 oC, G-7 g
Boiling point – 289.6 oC (at 9,806.104);
Density, g/cm3 - 0.9720
3) T = 120-130 oC, G-12 g
Refractive index – 1.4261
In each of these fractions were determined
the content of phosphorus (P) and refractive index
(n20).
Character absorptions in the IR-specter
-1000 - 1100 cm-1 P-O-C (valent)
- 1274 cm-1 P=O (valent)
1) P = 10.3 %, n20 =1.4198
- 730 cm-1 P-O (sym.valent).
2) P = 10.6 %, n20 =1.41983
3) P = 12.1 %, n20 =1.4222
These data allowed us to identify the
product as tri-n-butylphosphate.
As it is evident from the cited data, that first
and second fractions have similar values by the
contents of phosphorus and same refractive indixes.
The third fraction is different by phosphorus content.
However, all three fractions gave exactly the same
IR-spectra, identical IR-specters of tri-izo-
butylphosphate10.
We conducted the calculation the yield of
tri-n-butylphosphate containing phosphorus, as
well as other trialkylphosphates by the following. In
each experiment the amount of phosphorus, which
passed into the solution, was analytically
determined. In general, this value was about 9.8%
of the total amount of copper - phosphorus alloys.
Then, on the basis of reaction of formation, we
determined the theoretical amounts of
On the basis of these data, we got product,
which was identified as tri-izo-butylphosphat.
Output of the amount of phosphorus was 71.11%.
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