Cr～（3+）电化学氧化生成Cr_2O_7～（2-）过程研究
摘要
本文研究了Cr~(3+)在硫酸介质中电化学氧化生成Cr_2O_7~(2-)的过程，提出了Cr~(3+)电化学氧化生成Cr_2O_7~(2-)的反应历程。采用循环伏安法和稳态法测定了该体系的循环伏安曲线和稳态极化曲线；恒电流条件下，在两电极体系中采用整体电解法，研究了操作电流密度、Cr~(3+)浓度、温度、硫酸浓度以及超声对Cr~(3+)电化学氧化生成Cr_2O_7~(2-)过程电流效率的影响，实验结果验证了提出的反应历程的正确性。本文还研究了自制的Ti/SnO_2+Sb_2O_3/PbO_2电极对Cr~(3+)硫酸溶液阳极氧化过程电流密度和Cr~(3+)电化学氧化生成Cr_2O_7~(2-)过程电流效率的影响。并针对以Cr_2O_7~(2-)/Cr(3+)为媒质间接电化学氧化蒽制蒽醌过程，采用整体电解法研究了活性炭吸附、超声和电极材料对Cr~(3+)循环液电化学氧化生成Cr_2O_7~(2-)过程电流效率的影响，为实现该过程的工业化提供理论指导和技术参数。研究表明：
(1)硫酸介质中Cr~(3+)电化学氧化生成Cr_2O_7~(2-)经过下列反应历程：
其中反应②为电化学反应控制步骤，反应③是Cr~(3+)氧化生成Cr_2O_7~(2-)的反应，其中OH_(ad)与Cr~(3+)的反应是Cr~(3+)氧化生成Cr_2O_7~(2-)过程的速率控制步骤，反应④是O_2的生成反应。由上述反应历程推导可得Cr~(3+)氧化过程的反应速率r_3、电流效率η和反应选择性β的表达式：
陈吕平:
cr3十电化学氧化生成crZo户过程研究
几=
d【er3+
=k3厚裔ICr’‘’
几
巧+残
:_r户_3+，
=入3L、IJ=
k3[Cr3+]
k3[Cr，+]+k4[oHod]，，。。_3+1.{不不丁
“，卜‘”V一币不
叭A飞(Eor、fer，+1
一=下，一exPI一二云.厅二丁了一万
r4 A4\Kl/IUnadJ
一一一一
nn尸
(2)操作电流密度、反应温度、超声及cr3+、H十、50互一的浓度均对cr3+电化
学氧化过程的电流效率有影响。提高操作电流密度和50且一的浓度，cr，‘电化学氧
化过程的电流效率减小;提高反应温度、增大Cr3十和H十的浓度，过程的电流效率
会增大;超声的存在亦使Cr3+硫酸溶液电解时的电流效率增大。
(3)用聚合前驱体通过热分解法自制的Ti/SnOZ+SbZO3lPbO:电极比PbO:电极
的抗剥蚀性好，使用寿命长，可以提高Crs+硫酸溶液阳极氧化过程的电流密度和
Cr3+电化学氧化过程的电流效率。
(4)cr，十循环液电解时的电流效率低于纯cr3+硫酸溶液电解时的电流效率:cr，+
循环液经活性炭吸附后进行电解，或Cr3+循环液在超声下电解，均可提高其电化
学氧化过程的电流效率。以自制的Ti/s n02+sbZO3?bo:电极为阳极电解cr，十循环
液时的电流效率也低于用该电极电解纯Cr3+硫酸溶液时的电流效率。
The electrochemical oxidation of Cr3+ to Cr2O72- in sulfuric acid solution was studied. The formation mechanism of Cr2O72- in sulfuric acid solution was theoretically analyzed. The cyclic voltammograms and steady-state polarization curves of the electrochemical oxidation of Cr3+ in sulfuric acid solution were determined using three-electrode cell. The influences of operation current density, the concentration of Cr3+ and sulfuric acid, temperature as well as ultrasound on the current efficiency of the electrochemical oxidation of Cr3+ to Cr2O72- in sulfuric acid solution were studied. The effects of electrode materials on the current density and the current efficiency of the electrochemical oxidation of Cr3+ were also studied. The influences of active carbon, ultrasound and electrode materials on the current efficiency of the electrochemical oxidation of the contaminated Cr3+ solution in the process of indirect oxidation of anthracene to anthraquinone by Cr2O72- were investigated too.
(1) The theoretical analysis and experimental results showed that the formation mechanism of Cr2O72- in sulfuric acid solution was
In the above mechanism, the reaction (2) was electrochemical reaction determining step, the reaction (3) which was the oxidation of Cr3+ to Cr2O72- and the
reaction (4) which was the evolution of oxygen reaction proceeded simultaneously. The reaction of OHad with Cr3+ was considered to be the rate-determining step of the oxidation of Cr3+to Cr2072-.
According to the above mechanism, the relation of the rate of the oxidation of Cr3-
to Cr2O732- with the concentration of Cr3+ and H+ as well as temperature in sulfuric acid solution was represented as follows:3+
The current efficiency of the electrochemical oxidation of Cr3+ to Cr2072- in sulfuric acid solution can be described as:
The relation of the selectivity of the reaction (3) and (4) with the operation current density, temperature as well as the concentration of Cr3+ can be expressed as:
(2) The experimental results showed that the current efficiency of the electrochemical oxidation of Cr3+ to Cr2O72- in sulfuric acid solution increased with decreasing operation current density or the concentration of SO42- . The current efficiency increased with increasing temperature or the concentration of Cr3+ or the concentration of H+ at the same reaction condition. The current efficiency also increased when the electrolytic oxidation of Cr3+ was carried out in the presence of the ultrasound.
(3) The experimental results also showed that the current density and the current efficiency of the electrochemical oxidation of Cr3+ in sulfuric acid solution with Ti/SnO2+Sb2O3/PbO2 as an anode were much higher than that with PbO2 at the same reaction condition. The Ti/SnO2+Sb2O3/PbO2 electrode had a better resistance to denudation and a longer lifetime than PbO2 electrode in the electrochemical oxidation process of Cr3+
(4) The current efficiency of the electrolytic oxidation of the contaminated Cr3+ solution was lower than that of the un-contaminated Cr3+ solution with PbO2 as an anode or Ti/SnO2+Sb2O3/PbO2 as an anode. The current efficiency of the electrochemical oxidation of the contaminated Cr3+ solution was improved when the contaminated Cr3+ solution was treated by activated carbon before electrolysis. The current efficiency also increased when the electrolytic oxidation of the contaminated Cr3+ solution was carried out in the presence of the ultrasound.
(1)硫酸介质中Cr~(3+)电化学氧化生成Cr_2O_7~(2-)经过下列反应历程：
其中反应②为电化学反应控制步骤，反应③是Cr~(3+)氧化生成Cr_2O_7~(2-)的反应，其中OH_(ad)与Cr~(3+)的反应是Cr~(3+)氧化生成Cr_2O_7~(2-)过程的速率控制步骤，反应④是O_2的生成反应。由上述反应历程推导可得Cr~(3+)氧化过程的反应速率r_3、电流效率η和反应选择性β的表达式：
陈吕平:
cr3十电化学氧化生成crZo户过程研究
几=
d【er3+
=k3厚裔ICr’‘’
几
巧+残
:_r户_3+，
=入3L、IJ=
k3[Cr3+]
k3[Cr，+]+k4[oHod]，，。。_3+1.{不不丁
“，卜‘”V一币不
叭A飞(Eor、fer，+1
一=下，一exPI一二云.厅二丁了一万
r4 A4\Kl/IUnadJ
一一一一
nn尸
(2)操作电流密度、反应温度、超声及cr3+、H十、50互一的浓度均对cr3+电化
学氧化过程的电流效率有影响。提高操作电流密度和50且一的浓度，cr，‘电化学氧
化过程的电流效率减小;提高反应温度、增大Cr3十和H十的浓度，过程的电流效率
会增大;超声的存在亦使Cr3+硫酸溶液电解时的电流效率增大。
(3)用聚合前驱体通过热分解法自制的Ti/SnOZ+SbZO3lPbO:电极比PbO:电极
的抗剥蚀性好，使用寿命长，可以提高Crs+硫酸溶液阳极氧化过程的电流密度和
Cr3+电化学氧化过程的电流效率。
(4)cr，十循环液电解时的电流效率低于纯cr3+硫酸溶液电解时的电流效率:cr，+
循环液经活性炭吸附后进行电解，或Cr3+循环液在超声下电解，均可提高其电化
学氧化过程的电流效率。以自制的Ti/s n02+sbZO3?bo:电极为阳极电解cr，十循环
液时的电流效率也低于用该电极电解纯Cr3+硫酸溶液时的电流效率。
The electrochemical oxidation of Cr3+ to Cr2O72- in sulfuric acid solution was studied. The formation mechanism of Cr2O72- in sulfuric acid solution was theoretically analyzed. The cyclic voltammograms and steady-state polarization curves of the electrochemical oxidation of Cr3+ in sulfuric acid solution were determined using three-electrode cell. The influences of operation current density, the concentration of Cr3+ and sulfuric acid, temperature as well as ultrasound on the current efficiency of the electrochemical oxidation of Cr3+ to Cr2O72- in sulfuric acid solution were studied. The effects of electrode materials on the current density and the current efficiency of the electrochemical oxidation of Cr3+ were also studied. The influences of active carbon, ultrasound and electrode materials on the current efficiency of the electrochemical oxidation of the contaminated Cr3+ solution in the process of indirect oxidation of anthracene to anthraquinone by Cr2O72- were investigated too.
(1) The theoretical analysis and experimental results showed that the formation mechanism of Cr2O72- in sulfuric acid solution was
In the above mechanism, the reaction (2) was electrochemical reaction determining step, the reaction (3) which was the oxidation of Cr3+ to Cr2O72- and the
reaction (4) which was the evolution of oxygen reaction proceeded simultaneously. The reaction of OHad with Cr3+ was considered to be the rate-determining step of the oxidation of Cr3+to Cr2072-.
According to the above mechanism, the relation of the rate of the oxidation of Cr3-
to Cr2O732- with the concentration of Cr3+ and H+ as well as temperature in sulfuric acid solution was represented as follows:3+
The current efficiency of the electrochemical oxidation of Cr3+ to Cr2072- in sulfuric acid solution can be described as:
The relation of the selectivity of the reaction (3) and (4) with the operation current density, temperature as well as the concentration of Cr3+ can be expressed as:
(2) The experimental results showed that the current efficiency of the electrochemical oxidation of Cr3+ to Cr2O72- in sulfuric acid solution increased with decreasing operation current density or the concentration of SO42- . The current efficiency increased with increasing temperature or the concentration of Cr3+ or the concentration of H+ at the same reaction condition. The current efficiency also increased when the electrolytic oxidation of Cr3+ was carried out in the presence of the ultrasound.
(3) The experimental results also showed that the current density and the current efficiency of the electrochemical oxidation of Cr3+ in sulfuric acid solution with Ti/SnO2+Sb2O3/PbO2 as an anode were much higher than that with PbO2 at the same reaction condition. The Ti/SnO2+Sb2O3/PbO2 electrode had a better resistance to denudation and a longer lifetime than PbO2 electrode in the electrochemical oxidation process of Cr3+
(4) The current efficiency of the electrolytic oxidation of the contaminated Cr3+ solution was lower than that of the un-contaminated Cr3+ solution with PbO2 as an anode or Ti/SnO2+Sb2O3/PbO2 as an anode. The current efficiency of the electrochemical oxidation of the contaminated Cr3+ solution was improved when the contaminated Cr3+ solution was treated by activated carbon before electrolysis. The current efficiency also increased when the electrolytic oxidation of the contaminated Cr3+ solution was carried out in the presence of the ultrasound.
引文
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[2] 马淳安．有机电化学合成导论[M]．北京：科学出版社，2002：5-6，241～246
[3] 郑录，罗兰．应用媒质的间接电有机合成[J]．大学化学，1988，3(2)：8～15
[4] 何龙．焦油加工过程中Cr_2O_7~(2-)／Cr~(3+)电化学再生研究．硕士毕业论文．太原理工大学，1998：5～18
[5] Blasiah E, Piszczek L, Baranek W. Electrochemical oxidation of chromium (Ⅲ) to chromium (Ⅵ) [J]. Przem. Chem.,1967, 46(8): 447～451
[6] 张忠诚，刘嘉丽，王信东．间接电解氧化合成邻硝基苯甲醛的研究[J]．精细化工，1995，12(1)：52～54
[7] 赵崇涛，朱则善．间接法电合成2-甲基丁酸的研究[J]．电化学，1999，5(3)：310～313
[8] Gross,R.F. J, Hickling, A. Studies in electrolytic oxidation. Part Ⅸ. The anodic oxidation of chromic salts to chromate[J]. J.Chem.Soc. 1937, 6:325～330
[9] Lee J S, Sekine T. Electrolytic oxidation of chromium (Ⅲ) on lead dioxide in the cell without diaphragams[J]. Denki Kagakn Oyobi Kogyo Butsuri Kagaku, 1976, 44(2): 135～137
[10] Lee J S, Sekine T. Anodic processes of oxidation of chromium (Ⅲ) sulfate in aqueous sulfuric acid solution[J]. Denki Kagakn Oyobi Kogyo Butsuri Kagaku, 1974, 42(12): 642～649
[11] Lee J S. Mechanism for the electrochemical oxidation of chromium (Ⅲ) sulfate in sulfuric acid solution[J]. Chosen Shogakkai Gakujutsn Rombunshu, 1976, 6:155～186
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