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AbstractThe kinetics of the formation of sodium chlorate during electrolysis of chloride solutions with use
of dimensionally stable anodes is studied. An analysis and calculations suggest that the experimental results are
well described by the proposed set of differential equations under the assumption that the homogeneous chem-
ical reaction of chlorate formation has second, rather than third, order by active chlorine.
c, M CE, %
0.20 150
1
0.15 100
0.10
50
2
0.05
0 50 100 150 200 250
t, min
0 50 100 150 200 250
t, min Fig. 3. Time dependence of overall CE for AC and NaClO3
for 300 g l1 NaCl + 0.2 g l1 K2Cr2O7; pH 8 to 9, 90.
1
50
2
5 7 9 pH
0 50 100 150 200 250
t, min
Fig. 6. The pH dependence of steady-state AC concentra-
tion (based on data given in table) in 300 g l1 NaCl +
Fig. 5. Time dependence of CE for AC for 300 g l1 NaCl + 0.2 g l1 K2Cr2O7 at 90: (symbols) experiment and (solid
0.2 g l1 K2Cr2O7; pH 8 to 9, 90. line) calculation.
This implies that the effective rate constant of the pH. This conforms to relation (31), from which it fol-
NaClO3 formation is pH-dependent lows that the effective rate constant increases with [H+]
by first order, provided [H+ ] KD. At [H+ ] KD , a fur-
k0 K D[H ]
+
ther decrease in solution pH will make the rate constant
k = -------------------------------
-2 . (31) of the NaClO3 formation decrease (our estimate yielded
([H ] + KD)
+
KD = 6.6 108 at 90).
As follows from (16) and (31), at [H+ ] KD, the pH
COMPARING THE CORRECTED MODEL dependence of the logarithm of the steady-state AC
WITH EXPERIMENT concentration is linear, with a slope of 0.5. To verify
this conclusion, the relevant experimental dependence
When calculating dependences of concentrations of (Fig. 6) was approximated with the equation
AC and NaClO3 with (15) and (18), we employed the
optimum constant 3k = 0.055 mol l min1, which had log [ Cl* ] 1 = a + bpH. (32)
been found using a nonlinear programming method.
The curves thus calculated coincided with relevant The optimum coefficients, found with a linear regres-
experimental and calculated curves (Fig. 2). Figure 5 sion method, are a = 3.726 and b = 0.36. When deter-
shows time dependences of CE for AC: experimental mining these parameters, we ignored the first point,
(symbols) and calculated with (20), (22) and (24) (solid because [Cl*] is pH-independent at pH 66.5. The
line) and demonstrates good agreement between the slope value 0.36 we obtained is in a reasonable agree-
model and experiment. Similar kinetic measurements ment with its expected theoretical value of 0.5.
were taken at lower pH values of 7.47.8 (table). Similar non-steady-state measurements were car-
The calculations we performed showed that, in a ried out at pH 6 to 7. The conclusion was that a steady-
chlorate electrolysis, the rate constant of the NaClO3 state AC concentration occurs in this case much sooner,
formation increases to 3k = 1 with decreasing solution which makes it difficult to study the NaClO3 formation
kinetics. That is why we performed all the measure-
ments in this work at higher pH and tested basic proce-
Time dependences of concentrations and CE of AC and dural questions connected with the obtaining of exper-
NaClO3, measured in 300 g l1 NaCl + 0.2 g l1 K2Cr2O7; imental results and their subsequent mathematical
pH 7.47.8, 90C treatment.
CE(Cl*), CE(NaClO3),
t, min [Cl*], M [NaClO3], M
% % ACKNOWLEDGMENTS
10 1.75 102 1.83 103 83.75 26.3 The author thanks E.V. Kasatkin for useful critical
30 4.75 102 6.8 103 69.70 30.1 advice aired when discussing this work.
60 4 102 2.8 102 28.10 58.6
120 4 102 6.75 102 13.40 67.8 REFERENCES
180 4.5 102 1.23 101 9.57 78.4 1. Evdokimov, S.V., Elektrokhimiya, 1999, vol. 35, p. 366.
240 4.5 102 1.54 101 7.18 73.8 2. Evdokimov, S.V., Elektrokhimiya, 1999, vol. 35, p. 202.
3. Kokoulina, D.V. and Krishtalik, L.I., Elektrokhimiya, An Introduction), Moscow: Vysshaya Shkola, 1975,
1971, vol. 7, p. 346. p. 319.
4. Kheifets, L.I., Goldberg, A.B., and Mazanko, A.F., Itogi 8. Bagotzky, V.S., Osnovy elektrokhimii (Fundamentals of
Nauki Tekh., Ser.: Elektrokhimiya, 1983, p. 244. Electrochemistry), Moscow: Khimiya, 1988, p. 272.
5. Yakimenko, L.M. and Seryshev, G.A., Elek-
9. Antropov, L.I., Teoreticheskaya electrokhimiya (Theo-
trokhimicheskii sintez neorganicheskikh soedinenii (The
retical Electrochemistry), Moscow: Vysshaya Shkola,
Inorganic Electrosynthesis), Moscow: Khimiya, 1984,
1984, p. 324.
p. 35.
6. Vetter, K., Elektrochemische Kinetik, Berlin: Springer, 10. Rotinyan, A.L., Tikhonov, K.I., and Shoshina, I.A., Teo-
1961. reticheskaya elektrokhimiya (Theoretical Electrochem-
7. Damaskin, B.B. and Petrii, O.A., Vvedenie v elek- istry), Leningrad: Khimiya, 1981, pp. 268, 302.
trokhimicheskuyu kinetiku (Electrochemical Kinetics: 11. Evdokimov, S.V., Elektrokhimiya, 2001, vol. 37, p. 420.