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ISSN 1063455X, Journal of Water Chemistry and Technology, 2017, Vol. 39, No. 3, pp. 143147.
Allerton Press, Inc., 2017.

Original Russian Text S.Yu. Bashtan, R.D. Chebotareva, S.V. Remez, 2017, published in Khimiya i Tekhnologiya Vody, 2017, Vol. 39, No. 3, pp. 261269.
PHYSICAL CHEMISTRY
OF WATER TREATMENT PROSESSES
The Synthesis of Activated Chlorine in an Electrodialyzer

with a Tube Ceramic Membrane and a TitaniumDioxide
Manganese Anode
S. Yu. Bashtan, R. D. Chebotareva*, and S. V. Remez
Dumanskii Institute of Colloid and Water Chemistry,
National Academy of Sciences of Ukraine, Kiev
*email: [email protected]
Received April 5, 2016
AbstractThe article has investigated the impact of the design of an electrodialyzer with a little
soluble
titaniumdioxidemanganese anode and a ceramic membrane separating electrode spaces, on the con
centration of chlorateions when producing sodium hydrochlorite. It has been shown that the location of
the anode inside a ceramic membrane makes it possible to obtain sodium hypochlorite without an impu
rity of chloriteions.
DOI: 10.3103/S1063455X17030043
Keywords: activated chlorine, sodium hypochlorite, membrane electrodialyzer, ceramic membrane,
titaniumdioxidemanganese anode.
INTRODUCTION
The most mass consumption of electrochemically synthesized activated chlorine takes place in water treat
ment. Activated chlorine, having large oxidizing potential, is used as an oxidant of organic and mineral impu
rities and also for decontamination and conservation of water [13]. In this connection of great importance
is a purity of the reagent obtained by the electrolysis of chloride of chloride salts of alkaline metals. The use
for this process of barely soluble anodes not containing noble metals makes it possible to create a unit acces
sible for a consumer thanks to low cost of anodic materials.
In electrolysis of solutions of sodium chloride on the anode two main processes may take placeoxidation
of water and oxidation of chlorine ions [4]:
H2O 1/2O2 + 2H+ + 2e, 0 O2 = 1.23 V; (1)
Cl 1/2Cl2 + e , 0Cl2 = 1.36 V. (2)
Despite a greater negative potential of the reaction of water decomposition (1) due to high overtension of
oxygen release on most anodic materials, in aqueous solutions of sodium chloride it is mostly reaction (2)
oxidizing of chlorine ions. The direction of the reaction depends both on the nature of anodic material and
the parameters of the process of electrolysis (the concentration of the solution of salt, current density, etc.).
Therefore, when building new units it is important to determine conditions of their effective operation.
One of the accessible and cheap is a titaniumdioxidemanganese anode (TDMA) featuring high corro
sion resistance in the given process [4].
To exclude the formation of sodium chlorate, which is a harmful impurity for warmblooded animals [5],
the electrolysis is conducted in units having division of electrode spaces. In recent years for this purpose
ceramic membranes [6, 7] have been used on a wide scale. These membranes have a high resistance for a long
operation in an aggressive medium, which advantageously stand out compared with polymer membranes [8].
The objective of the present research is production of activated chlorine free of chlorate, in an electrolyzer
with a partition ceramic membrane and an anode of titanium covered with dioxide manganese.
EXPERIMENTAL
The electrolyzer is a flowtrough cylindrical unit (Fig. 1), whose cathodic and anodic spaces are separated
by a ceramic membrane made of aluminum and zirconium oxides in the form of a tube with an external diam
eter 12 and wall thickness 1 mm.
Three versions of the complete equipment were investigated: Athe anode of titanium wire 2 mm in
diameter covered with dioxide manganese (TDMA) was wound in the form of a spiral on the external surface
of the ceramic membrane with a pitch 3 mm, the cathode of a steel wire 2 mm in diameter in the form of a
rod of a spiral 6 mm in diameter is located inside the membrane; Breverse location of electrolytethe
cathode is wound on the membrane, TDMA is a rod of a spiral 6 m inside the membrane; Cthe electrodi
alyzer without separation of the electrode compartments (the location of electrodes just as in unit, type A, but
without ceramic membrane. The ratio of the volumes of electrode chambers inside and outside the membrane
constituted 1 : 8. The flows outcoming of electrode chambers were united outside the limits of the electrodi
alyzer.
For obtaining TDMA the titanium wire (titanium of brand BT1) was treated by the melt of manganese
nitrate at 120130C held in it for 13 min and then submitted to thermal treatment at 200210C for one
hour to the formation of black mass of manganese dioxide. For improving regularity of the cover the operation
of immersion into the melt of manganese salt and subsequent thermotreatment were repeated 45 times.
Prior to the experiment upon obtaining sodium hypochlorite preliminary preparation anode for stabiliza
tion of its characteristics was carried out. Then anode polarization was carried out at current density 0.5
3.0 A/dm2 on h, In this case one could observe an increase of the anode potential by 20 mV, which most likely
is determined by the change of the degree of oxidation of the surface layer of the active cover [9, 10]. Corrosion
tests of TDMA were conducted in the solution of sodium chloride with the concentration 50 g/dm 3 in the
range of current density 0.63.2 A/dm3.
Activated chlorine was analyzed iodometrically presented in terms of hypochlorite ions; the concentration
of chlorateions was determined using the permanganate method.
RESULS AND DISCUSSION
As can be seen from Fig. 2 at an increase of the value of polarizing current the destruction degree of the
oxidemanganese covering decreases, which may be caused by the growth of oxygen overtension and corre
sponding decrease of the pH of anolyte observed in this case is also conducive to the reduction of corrosion rate.

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ISSN 1063455X, Journal of Water Chemistry and Technology, 2017, Vol. 39, No. 3, pp. 143147.

Allerton Press, Inc., 2017.

The Synthesis of Activated Chlorine in an Electrodialyzer

RESULS AND DISCUSSION

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