磷酸—硫酸溶液中铜阳极电流振荡及其调控研究
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摘要
对电化学振荡行为的研究，可以加深我们对电极反应过程机理的认识；对
电化学复杂振荡的耦合及同步的研究，则能使我们了解同一电解池中两个研究
电极之间如何通过相互作用而形成不同的振荡行为；而对电化学复杂振荡的混
沌控制研究，则可以丰富化学与混沌学的交叉研究，对改善电化学反应也很有
帮助。铜作为阳极在电溶解过程中能产生丰富复杂的振荡行为，近年来，针对
Cu／H_3PO_4体系的研究很多，但对铜阳极溶解过程机理的认识还有待于加强添
加物对振荡行为影响的研究，H_2SO_4作为一类特殊的添加剂，对H_3PO_4体系中
铜阳极溶解电流振荡的影响尚未见报道。为此，本论文研究了铜阳极在磷酸-
硫酸混合溶液中的电流振荡行为。
本论文采用线性电位扫描法，通过改变扫描速度、反应温度、串入外电阻
以及采用不同形状的电极(环电极与线电极)进行实验。并着重探讨了H_2SO_4
作为添加剂对铜阳极电溶解所产生振荡行为的影响。发现振荡的产生是电极表
面膜的生成，溶解与一定液相传质作用耦合的结果。另外，发现随着添加剂
H_2SO_4含量的增大，电流振荡先增强后逐渐减弱。
通过恒电位方法，在实验中观察到小幅振荡、周期振荡、混合振荡、准周
期振荡等行为。发现，相对于没有添加剂的情况而言，适量加入添加剂H_2SO_4
可以使振荡形式更丰富。
利用延迟反馈控制法对铜阳极在磷酸-硫酸溶液中所产生的复杂电化学振
荡行为进行控制，研究表明，延迟反馈控制法应用于上述体系是行之有效的。
我们在实验中实现了将混沌振荡控制为周期运动，将周期-1振荡控制为周期
-2、周期-4振荡的形式。我们还研究了延迟时间和控制因子对控制效果的影响。
最后我们研究了双铜电极振荡行为的耦合作用及同步现象，结果表明，两
铜电极的振荡互相影响，可以形成同相，锁相等同步行为。物质转移作用对同
相同步的形成起决定性作用。添加剂H_2SO_4的适量加入，使得1：1形式同步
较多。
The study of electrochemical oscillations can make us know the mechanism of electrochemical reactions and the research of coupling and synchronization of electrochemical oscillations make us realize that different oscillations can be made by two work electrodes acting each other. The study of chaos control in electrochemical oscillations can not only combine the research of chemistry and chaos, but also improve electrochemical reactions. There are abundant oscillations in electrochemical system with copper being the anode. These years, there are many reports of the study of Cu/H3PO4 system. We can know further the mechanism of the anodic dissolution of copper by studying the influence of additives put into the above system. There is no report about the influence of H3PO4, a special additive, on Cu/H3PO4 system. In this paper, the anodic dissolution of copper in phosphoric and sulphuric acid was studied.
Through sweep voltammograms, we study the results of changing the rate of sweep, temperature, electrodes of different shapes and connecting a resistance .We pay much more attention to the influence of H2SO4.It is found that the oscillation is the result of the breaking and forming of film coupling with the mass transport. It also shows that the oscillation amplitude increases at first, then decreases gradually with the increase of the amount of H2SO4 addition.
We find many types of oscillations during the experiments. Compared with the system without additive, there are more kinds of oscillations with H2SO4 as additive in the experiments.
Means of the delay feedback is used to control the chaos in the electrochemical oscillations during the process of the anodic dissolution of copper. The result proved that the method is effective. We control the chaos to period and control the period one to period two and period four. We also study the effect of the control-factors.
Last, we study the coupling and synchronization of electrochemical oscillations. The results show that the synchronization is determined by mass transport. With suitable amount of H2SO4 put in the system, there are more 1:1 synchronizations discovered.
电化学复杂振荡的耦合及同步的研究，则能使我们了解同一电解池中两个研究
电极之间如何通过相互作用而形成不同的振荡行为；而对电化学复杂振荡的混
沌控制研究，则可以丰富化学与混沌学的交叉研究，对改善电化学反应也很有
帮助。铜作为阳极在电溶解过程中能产生丰富复杂的振荡行为，近年来，针对
Cu／H_3PO_4体系的研究很多，但对铜阳极溶解过程机理的认识还有待于加强添
加物对振荡行为影响的研究，H_2SO_4作为一类特殊的添加剂，对H_3PO_4体系中
铜阳极溶解电流振荡的影响尚未见报道。为此，本论文研究了铜阳极在磷酸-
硫酸混合溶液中的电流振荡行为。
本论文采用线性电位扫描法，通过改变扫描速度、反应温度、串入外电阻
以及采用不同形状的电极(环电极与线电极)进行实验。并着重探讨了H_2SO_4
作为添加剂对铜阳极电溶解所产生振荡行为的影响。发现振荡的产生是电极表
面膜的生成，溶解与一定液相传质作用耦合的结果。另外，发现随着添加剂
H_2SO_4含量的增大，电流振荡先增强后逐渐减弱。
通过恒电位方法，在实验中观察到小幅振荡、周期振荡、混合振荡、准周
期振荡等行为。发现，相对于没有添加剂的情况而言，适量加入添加剂H_2SO_4
可以使振荡形式更丰富。
利用延迟反馈控制法对铜阳极在磷酸-硫酸溶液中所产生的复杂电化学振
荡行为进行控制，研究表明，延迟反馈控制法应用于上述体系是行之有效的。
我们在实验中实现了将混沌振荡控制为周期运动，将周期-1振荡控制为周期
-2、周期-4振荡的形式。我们还研究了延迟时间和控制因子对控制效果的影响。
最后我们研究了双铜电极振荡行为的耦合作用及同步现象，结果表明，两
铜电极的振荡互相影响，可以形成同相，锁相等同步行为。物质转移作用对同
相同步的形成起决定性作用。添加剂H_2SO_4的适量加入，使得1：1形式同步
较多。
The study of electrochemical oscillations can make us know the mechanism of electrochemical reactions and the research of coupling and synchronization of electrochemical oscillations make us realize that different oscillations can be made by two work electrodes acting each other. The study of chaos control in electrochemical oscillations can not only combine the research of chemistry and chaos, but also improve electrochemical reactions. There are abundant oscillations in electrochemical system with copper being the anode. These years, there are many reports of the study of Cu/H3PO4 system. We can know further the mechanism of the anodic dissolution of copper by studying the influence of additives put into the above system. There is no report about the influence of H3PO4, a special additive, on Cu/H3PO4 system. In this paper, the anodic dissolution of copper in phosphoric and sulphuric acid was studied.
Through sweep voltammograms, we study the results of changing the rate of sweep, temperature, electrodes of different shapes and connecting a resistance .We pay much more attention to the influence of H2SO4.It is found that the oscillation is the result of the breaking and forming of film coupling with the mass transport. It also shows that the oscillation amplitude increases at first, then decreases gradually with the increase of the amount of H2SO4 addition.
We find many types of oscillations during the experiments. Compared with the system without additive, there are more kinds of oscillations with H2SO4 as additive in the experiments.
Means of the delay feedback is used to control the chaos in the electrochemical oscillations during the process of the anodic dissolution of copper. The result proved that the method is effective. We control the chaos to period and control the period one to period two and period four. We also study the effect of the control-factors.
Last, we study the coupling and synchronization of electrochemical oscillations. The results show that the synchronization is determined by mass transport. With suitable amount of H2SO4 put in the system, there are more 1:1 synchronizations discovered.
引文
[1] Irving R.Epstein, Kenneth Showalter. J.Phys. Chem.100,1996, 13132-13147
[2] 幸厚文，《化学中的非线性问题》，中国科技大学，109
[3] Peter，Coveney．时间之箭[M]．江涛，等．译．长沙：湖南科学技术出版社，1995
[4] 黄闻新等，《化学中的白组织反应及其应用前景》，海南师范学院学报，第15卷，第2期(2002年)
[5] Prigogine I. Structure, Dissipation and Life[C]. Communication Presented at the First International Conference "Theoretical Physics and Biology",Versailles.1967; North-Holland, Pub,Am.1969
[6] 郝柏林，分岔、混沌、奇怪吸引子、湍流及其他[J]．物理学进展，1983，3(3)：329-416
[7] 程极泰，混沌的理论与应用，上海，上海科学技术文献出版社，1992，12-89
[8] 吴祥兴等，《混沌学导论》，57
[9] 郝柏林，《从抛物线谈起-混沌动力学引论》，119
[10] 王东生，曹磊，《混沌、分形及其应用》，55
[11] Ott E, Grebogi C, York J A. Controlling chaos. Physics Review Letters,1990,64(11):1196-1199
[12] Peng B, Petrov V, Showalter K. Controlling chemical chaos. J Physical Chemistry,1991,95(13):4957-4959
[13] Hunt E R. Stabilizing high-periodic orbits in a chaotic system: The diode resonator. Physical Review Letter, 1991,67(15):1953-1955
[14] Huberman B A, Lumer E L.Dynamics of adaptive system. IEEE Trans on CAS, 1990,37(4):547-550
[15] Chen G, Dong X. On feedback control of chaotic nonlinear dynamical systems. Int J of Bifurcation and Chaos, 1992,2(2):407-411
[16] Pyragas K. Continuous control of chaos by self-controlling feedback. Physics Letters A,1992,170:421-428
[17] 黄润生，混沌及其应用[M]．武汉，武汉大学出版社，1999
[18] 兰祝刚，彭巍，混沌同步方法的研究[J]．通信技术，2000，(1)：28-31
[19] 赖建文，周世平，李国辉，间歇驱动混沌同步法[J]．物理学报，2001，(1)：39-41
[20] 方锦清，非线性系统中混沌同步控制方法-同步原理及其应用前景(二)[J]．物理学进展1996(3)，11-13
[21] 高金峰，潘秀琴，自适应方法控制混沌超混沌系统同步的研究[J]．计算技术与自动化 1999．18(4)：7-12
[22] L.Kocarev et al, Experimental demonstration of secure communications via chaotic synchronization[J].Int J .Bifucation and Chaos, 1992,2(3):709-713
[23]K.S.Halle et al. Spread spectrum communication through modulation of chaos[J]. Int J.Bifucation Chaos, 1993,3(4):469-477
[24]Koper M.T.M..Adv. Chem. Phys.[J],1996,92:161-298
[25]Edited by TANG You-Qi (唐有祺主编).Frontier of Modern Chemistry [M], Beijing:Zhigong Press, 1997:604-605
[26]谢复新，许志强，贾晓颖，《高等学校化学学报》，[J]，1993，14(10)：1439-1441
[27]傅宏刚，余海涛，王俊东，《高等学校化学学报》，[J]，1999,20(3)：445-449
[28]J.L.Hudson and T.T. Tsotsis, Chemical Engineering Science, Vol.49. No.10, 1994,1493-1572
[29]田昭武，《电化学研究方法》，科学出版社，207-230
[30]李学良，等《铜阳极在磷酸与硫酸混合溶液中溶解的电流混沌振荡行为》，[J]．有色金属Vol，55，No．1(2003)
[31]李学良，鲁道荣等，表面部分成膜金属阳极溶解模型及其振荡与混沌行为[J]，金属学报，2001，37(5)：496
[32]Mauricio U.Kleinke. J.Phys,Chem,99,1995,17403-17409
[33]Glarum S H,Marshall J H. The anodic dissolution of copper into phosphoric acid [J]. Electrochem Soc, 1985,132(12):2872
[34]Glarum S H,Marshall J H. The anodic dissolution of copper into phosphoric acid ⅡImpedance behavior[J]. Electrochem Soc, 1985,132(12):2878
[35]Albahadily F N,Schell M. An experimental investigation of periodic and chaotic electrochemical oscillations in the anodic dissolution of copper in phosphoric acid[J].Chern Phys, 1988,88(7):4312
[36]李学良，何建波，鲁道荣，等，金属阳极溶解中的电化学混沌及其研究[J]．Chemistry Online,2000,2(3)：00027
[37]Minotas J C,Djellab H,Ghali E. Anodic behavior of Cu electrodes containing arsenic or antimony as impurities[J].Appl Electrochem, 1989,19:777
[38]李学良，何建波，鲁道荣，等，恒电位下铜阳极电流振荡的延时控制[J]．物理化学学报，2002，18(3)：218
[39]Williams E.C.,Barlett M.A..J.Electrochem. Soc., 1958,103:363
[40]Kojima K., Tobias C.W..J.Electrochem Soc.,1973,120:1026
[41]Tsitsopoulos L.T., Tsotsis T.T..Surface Science, 1987,191:225
[42]Hoar T.P.,Farthing T.W.. Nature, 1952,169:324
[43]Pearlstein A rne. J,Lei H.P., Nobe Ken.J.Electrochem.Soc 132, 1985,2159-2165
[44]雷惊雷，罗久里，《铜电极刚极溶解过程恒电位电流振荡的动力学模型》，高等学校化学学报，Vol．21，No．3(2000)，453-457
[45]J.L.Hudson and T.T. Tsotsis, Chemical Engineering Science, Vol. 49. No.10, 1994,
1493-1572
[46]徐远航，化学通报，1993(1)，13-17
[47]小泽昭弥主编，吴继勋等译，《现代电化学》 化学工业出版社，1995
[48]陆兆锷编，《电极过程原理和应用》，高等教育出版社，1992
[49]查全性，《电极过程动力学导论》，科学出版社，1987，449-483
[50]Parmananda P, Jiang Yu.J.Phys. Chem., 1998,102:4532
[51]Kiss I Z,Gaspar V, Nyikos L,Parmananda P.J.Phys. Chem.A,1997,101:8668
[52]Hohmann W, Schinor N, Kraus M, Schneider FW. J.Phys. Chem.A,1999,103:5742
[53], Baba R.,Shiomi Y, Nakabayashi S. Chemical Engineering Science,2000,55:217
[54]方锦清，物理学进展，第16卷，第2期，1996，137-201
[55]K. Pyrags. Phys Lett .A 170,1992,421
[56]T. Lcarroll, J. Triandaf, J.Schwattz, Pecora, Phys. ReV. A46,1992,61-89
[57]幸厚文，《非线性化学》，187
[58]W. Hohmann,N.Schinor, et al.J.Phys.Chem.A, 103,1999,5742-5748
[59]Nadia Mazouz, Georg Flatgen,Katharina Krischer, and Ioannis G. Kevrekidis. The Impact of the Operation Mode on Pattern Formation in Electrode Reactions,, J,.,Electrochem,, Soc, 1998,145(7):2404-2411
[60]Antonis Karantonis ,Yuka Shiomi, Seiichiro Nakabayashi,Voherence and coupling during oscillation metal electrodissolution, J. Electroana. Chem, 2000,493,57-67
[2] 幸厚文，《化学中的非线性问题》，中国科技大学，109
[3] Peter，Coveney．时间之箭[M]．江涛，等．译．长沙：湖南科学技术出版社，1995
[4] 黄闻新等，《化学中的白组织反应及其应用前景》，海南师范学院学报，第15卷，第2期(2002年)
[5] Prigogine I. Structure, Dissipation and Life[C]. Communication Presented at the First International Conference "Theoretical Physics and Biology",Versailles.1967; North-Holland, Pub,Am.1969
[6] 郝柏林，分岔、混沌、奇怪吸引子、湍流及其他[J]．物理学进展，1983，3(3)：329-416
[7] 程极泰，混沌的理论与应用，上海，上海科学技术文献出版社，1992，12-89
[8] 吴祥兴等，《混沌学导论》，57
[9] 郝柏林，《从抛物线谈起-混沌动力学引论》，119
[10] 王东生，曹磊，《混沌、分形及其应用》，55
[11] Ott E, Grebogi C, York J A. Controlling chaos. Physics Review Letters,1990,64(11):1196-1199
[12] Peng B, Petrov V, Showalter K. Controlling chemical chaos. J Physical Chemistry,1991,95(13):4957-4959
[13] Hunt E R. Stabilizing high-periodic orbits in a chaotic system: The diode resonator. Physical Review Letter, 1991,67(15):1953-1955
[14] Huberman B A, Lumer E L.Dynamics of adaptive system. IEEE Trans on CAS, 1990,37(4):547-550
[15] Chen G, Dong X. On feedback control of chaotic nonlinear dynamical systems. Int J of Bifurcation and Chaos, 1992,2(2):407-411
[16] Pyragas K. Continuous control of chaos by self-controlling feedback. Physics Letters A,1992,170:421-428
[17] 黄润生，混沌及其应用[M]．武汉，武汉大学出版社，1999
[18] 兰祝刚，彭巍，混沌同步方法的研究[J]．通信技术，2000，(1)：28-31
[19] 赖建文，周世平，李国辉，间歇驱动混沌同步法[J]．物理学报，2001，(1)：39-41
[20] 方锦清，非线性系统中混沌同步控制方法-同步原理及其应用前景(二)[J]．物理学进展1996(3)，11-13
[21] 高金峰，潘秀琴，自适应方法控制混沌超混沌系统同步的研究[J]．计算技术与自动化 1999．18(4)：7-12
[22] L.Kocarev et al, Experimental demonstration of secure communications via chaotic synchronization[J].Int J .Bifucation and Chaos, 1992,2(3):709-713
[23]K.S.Halle et al. Spread spectrum communication through modulation of chaos[J]. Int J.Bifucation Chaos, 1993,3(4):469-477
[24]Koper M.T.M..Adv. Chem. Phys.[J],1996,92:161-298
[25]Edited by TANG You-Qi (唐有祺主编).Frontier of Modern Chemistry [M], Beijing:Zhigong Press, 1997:604-605
[26]谢复新，许志强，贾晓颖，《高等学校化学学报》，[J]，1993，14(10)：1439-1441
[27]傅宏刚，余海涛，王俊东，《高等学校化学学报》，[J]，1999,20(3)：445-449
[28]J.L.Hudson and T.T. Tsotsis, Chemical Engineering Science, Vol.49. No.10, 1994,1493-1572
[29]田昭武，《电化学研究方法》，科学出版社，207-230
[30]李学良，等《铜阳极在磷酸与硫酸混合溶液中溶解的电流混沌振荡行为》，[J]．有色金属Vol，55，No．1(2003)
[31]李学良，鲁道荣等，表面部分成膜金属阳极溶解模型及其振荡与混沌行为[J]，金属学报，2001，37(5)：496
[32]Mauricio U.Kleinke. J.Phys,Chem,99,1995,17403-17409
[33]Glarum S H,Marshall J H. The anodic dissolution of copper into phosphoric acid [J]. Electrochem Soc, 1985,132(12):2872
[34]Glarum S H,Marshall J H. The anodic dissolution of copper into phosphoric acid ⅡImpedance behavior[J]. Electrochem Soc, 1985,132(12):2878
[35]Albahadily F N,Schell M. An experimental investigation of periodic and chaotic electrochemical oscillations in the anodic dissolution of copper in phosphoric acid[J].Chern Phys, 1988,88(7):4312
[36]李学良，何建波，鲁道荣，等，金属阳极溶解中的电化学混沌及其研究[J]．Chemistry Online,2000,2(3)：00027
[37]Minotas J C,Djellab H,Ghali E. Anodic behavior of Cu electrodes containing arsenic or antimony as impurities[J].Appl Electrochem, 1989,19:777
[38]李学良，何建波，鲁道荣，等，恒电位下铜阳极电流振荡的延时控制[J]．物理化学学报，2002，18(3)：218
[39]Williams E.C.,Barlett M.A..J.Electrochem. Soc., 1958,103:363
[40]Kojima K., Tobias C.W..J.Electrochem Soc.,1973,120:1026
[41]Tsitsopoulos L.T., Tsotsis T.T..Surface Science, 1987,191:225
[42]Hoar T.P.,Farthing T.W.. Nature, 1952,169:324
[43]Pearlstein A rne. J,Lei H.P., Nobe Ken.J.Electrochem.Soc 132, 1985,2159-2165
[44]雷惊雷，罗久里，《铜电极刚极溶解过程恒电位电流振荡的动力学模型》，高等学校化学学报，Vol．21，No．3(2000)，453-457
[45]J.L.Hudson and T.T. Tsotsis, Chemical Engineering Science, Vol. 49. No.10, 1994,
1493-1572
[46]徐远航，化学通报，1993(1)，13-17
[47]小泽昭弥主编，吴继勋等译，《现代电化学》 化学工业出版社，1995
[48]陆兆锷编，《电极过程原理和应用》，高等教育出版社，1992
[49]查全性，《电极过程动力学导论》，科学出版社，1987，449-483
[50]Parmananda P, Jiang Yu.J.Phys. Chem., 1998,102:4532
[51]Kiss I Z,Gaspar V, Nyikos L,Parmananda P.J.Phys. Chem.A,1997,101:8668
[52]Hohmann W, Schinor N, Kraus M, Schneider FW. J.Phys. Chem.A,1999,103:5742
[53], Baba R.,Shiomi Y, Nakabayashi S. Chemical Engineering Science,2000,55:217
[54]方锦清，物理学进展，第16卷，第2期，1996，137-201
[55]K. Pyrags. Phys Lett .A 170,1992,421
[56]T. Lcarroll, J. Triandaf, J.Schwattz, Pecora, Phys. ReV. A46,1992,61-89
[57]幸厚文，《非线性化学》，187
[58]W. Hohmann,N.Schinor, et al.J.Phys.Chem.A, 103,1999,5742-5748
[59]Nadia Mazouz, Georg Flatgen,Katharina Krischer, and Ioannis G. Kevrekidis. The Impact of the Operation Mode on Pattern Formation in Electrode Reactions,, J,.,Electrochem,, Soc, 1998,145(7):2404-2411
[60]Antonis Karantonis ,Yuka Shiomi, Seiichiro Nakabayashi,Voherence and coupling during oscillation metal electrodissolution, J. Electroana. Chem, 2000,493,57-67