臺灣博碩士論文加值系統

本研究的重點，主要包括有對於普魯士藍（Prussian blue）薄膜修飾電極的電化學析鍍及其薄膜物理性質之觀察與討論，並進一步藉由電化學實驗配合同步電化學石英微量天秤（electrochemical quartz crystal microbalance）所獲得關於薄膜氧化還原行為之資訊，建立薄膜電化學反應之機制。另一方面，也利用普魯士藍修飾電極的反應特性，提出一種使用此修飾電極的鉀離子感測方法。
在普魯士藍薄膜析鍍方面，薄膜以定電位法（potentiostatic）析鍍於導電基材上，並提出兩種基礎於不同定義之析鍍效率計算方法。若由析鍍時單位電量做成之質量增加的觀點來看，薄膜的平均析鍍效率為69％，但若由析鍍時注入之電量與析鍍後薄膜可使用電量之比值的觀點來看，薄膜的平均析鍍效率為33.6％。考慮薄膜析鍍所需時間與析鍍之效率等之因素，本研究建議由定電位法析鍍普魯士藍薄膜的最佳施加電位為0.5V（vs. Ag/AgCl）。藉由同步EQCM對於析鍍之薄膜重量測量並配合薄膜厚度之量測，對於平均厚度為1860 ?之薄膜其孔隙度估算為0.39，且薄膜之平均密度為1.52 g/cm3。由SEM與AFM對於普魯士藍薄膜的表面進行觀察，可明顯發現其為多孔性之結構，並且隨著薄膜厚度之增加，薄膜有龜裂的現象發生。
普魯士藍薄膜進行氧化還原反應時，需要配合溶液中水合陽離子的遷出或嵌入薄膜，以維持薄膜的電中性。因此，薄膜之重量隨著反映之進行而改變，還原時因陽離子之嵌入造成質量增加，反之氧化時因陽離子之遷出造成質量減少。薄膜反應時所需之電量及其伴隨之質量變化，會因實驗的操作條件，例如循環伏安法所使用的掃瞄速率，而造成影響。藉由觀察普魯士藍薄膜在不同操作條件下，反應電量變化以及同時發生之質量改變，本研究提出水合陽離子與水分子在薄膜反應時的嵌入/遷出反應機制。薄膜之氧化還原反應進行時，水合陽離子於薄膜與電解質溶液介面間移動，其部分之水合離子被移除，且造成方向相反之水分子相對流動，薄膜之重量也因此造成變化。
普魯士藍的晶格結構具有類似分子篩的作用，所以參與反應之水合陽離子大小會對反應的行為表現有不同的影響。在鹼金屬陽離子中，鉀離子最適合用來參與普魯士藍薄膜之氧化還原反應，反應之可逆性優於使用其他種類之陽離子。在鋰離子與銫離子存在的電解質溶液中，由於其水合離子較大或是離子半徑較大，普魯士藍薄膜的反應可逆性較差，甚至有薄膜溶解脫落的現象於反應進行中發生。若電解質溶液中沒有陽離子只有氫離子存在，則普魯士藍薄膜之氧化還原反應為不可逆，並伴隨發生薄膜之破壞。
鑑於普魯士藍薄膜對鉀離子良好的選擇性，本研究結合電化學感測與同步光譜量測的技術，提出一種新的鉀離子感測方法。感測所使用的方程式基礎於修正後之Nernst equation，利用其描述施加電位與普魯士藍於薄膜中莫爾分率的關係。在普魯士藍還原成普魯士白的反應中，當普魯士藍於薄膜中的莫爾分介於率0.25與1之間時，使用regular solution的理論對Nernst equation進行修正；而當普魯士藍之莫爾分率在0與0.25之間時，Margules equation則用來對Nernst equation進行修正。普魯士藍於薄膜中的莫爾分率則藉由薄膜吸收度的量測換算而得。鉀離子濃度的感測範圍介於3.3x10-4 M 與1.0 M之間。溶液中共存的鈉離子與鋇離子對鉀離子感測所造成之干擾也於本研究中進行觀察與討論。

The main objective of this dissertation is to investigate and discuss the electrodeposition and physical properties of the Prussian blue (PB) thin film modified electrode; moreover, when the mass changes during electrochemical experiments are recorded with the aid of an in-situ quartz crystal microbalance (EQCM), information about redox behaviors and corresponding mass changes of the PB thin films can be obtained. Thus, the redox mechanisms concerning the migrations of hydrated potassium ions and water molecules are proposed. On the other hand, by taking the well selective properties of PB thin films toward potassium ions, a new method for potassium ions sensing based on the PB thin film modified electrode is also proposed.
The PB thin films were deposited on a Pt electrode using a potentiostatic method, and the mass change on the Pt electrode was monitored using an EQCM during the deposition. Two different definitions for the deposition efficiency are proposed; one is based on the mass gain, the other is based on the consumed charge. For the deposition potential in the range 0f 0.3 ~ 0.8 V (vs. Ag/AgCl), the average deposition efficiency is 69.5 % based on the viewpoint of the actual mass gain during deposition; in contrast, the average deposition efficiency is 33.6 % if it is estimated from the ratio of the charge consumption during the reaction of PB to the charge injected during the deposition. Due to the reductive nature of the deposition reaction, the time needed for the reduction increases with the applied potential. The optimal deposition potential was determined to be 0.50 V (vs. Ag/AgCl) by considering the deposition efficiency and the time needed for the complete electrodeposition. The porosity of the PB thin film was estimated to be 0.39 a film thickness of 1860 ?, and the average apparent thin film density is estimated to be 1.52 g cm-3. The porous structures of the PB thin films can be observed from the SEM and AFM images, and thicker films get larger cracks on their surface.
Thin films of PB were reduced to Everitt掇 salt (ES) in solutions containing suitable cations. The redox behaviors with corresponding mass changes were monitored by an in-situ EQCM along with electrochemical measurements. During the redox reactions, electrolytic hydrated cations must be inserted into or extracted out of the PB thin films in order to maintain the electroneutrality, and such an insertion and/or extraction cause mass changes. The migration of hydrated potassium ions is under diffusion control if large scan rate is used in a cyclic voltammetry (CV) experiment. Based on the observations of the redox behaviors and corresponding mass changes, part of the potassium ion掇 hydrated water molecules are stripped off during its migration across the film/solution interface. It is inferred that a counter water molecule flow occurred, which is accompanied by the potassium ion movements. The insertion as well as the extraction mechanisms is proposed.
PB掇 lattice structure act can as a molecular sieve and set a limitation on the sizes of the cations which participating in the redox reactions, thus different alkali-cations exhibit different redox behaviors. Among alkali-cations, K+ and Rb+ could move into or out of the PB lattices much easier than Li+, Na+, and Cs+, because they possess smaller hydrated and ionic radii. However, redox reactions of the PB thin films can still be carried out partially and irreversibly in solutions containing Cs+, Li+, or H3O+ alone, but irreversible reactions or thin film dissolutions was observed.
By combining the electrochemical sensing with an in-situ spectral measurements, a new method for potassium ions sensing is proposed. It is based on the PB modified F-doped tin oxide (FTO) electrode. Governing equations for the potassium ions sensing based on the modified Nernst equations are derivved. By applying either the theory of regular solution (0.25 < x < 1) or the Margules equation (0 < x < 0.25) to the Nernst equation, one can construct a special function, which depends mainly on the mole fraction of PB and the interaction parameters involved. Indeed, such a relationship was observed when K+ concentrations were ranged from 3.3 10-4 M to 1.0 M in this study. The interferences of Na+ and Ba2+ on K+ sensing are also studied.

Abstract.........................................................................................................................................................................I
Chinese Abstract.................................................................................................................................................III
Acknowledgements.............................................................................................................................................V
Table of Contents...............................................................................................................................................VI
List of Tables........................................................................................................................................................IX
List of Figures.........................................................................................................................................................X
Notations..............................................................................................................................................................XIV
CHAPTER 1 Introduction.............................................................................................................................1
1.1 Introduction to Prussian Blue............................................................................................................1
1.2 Motivations......................................................................................................................................................7
1.3 Organization of this Dissertation....................................................................................................9
1.4 References.......................................................................................................................................................12
CHAPTER 2 Experimental ......................................................................................................................15
2.1 Preparation of PB Films......................................................................................................................15
2.2 Preparation of Fluorine-doped Tin Oxide Conducting Glass..................................16
2.3 Cyclic Voltammetry and Potential Step Experiments...................................................16
2.4 In-situ Electrochemical Quartz Crystal Microbalance Experiments .................16
2.5 UV-Vis Spectrophotometry...............................................................................................................17
2.6 Potassium ions sensing........................................................................................................................18
2.7 SEM & AFM................................................................................................................................................19
2.8 References.......................................................................................................................................................19
CHAPTER 3 Electrodeposition and Physical Properties of a PB Thin Film.......20
3.1 Deposition of the PB Thin Films by the Potentiostatic Method..........................22
3.2 Deposition efficiency..............................................................................................................................26
3.3 Porosity and apparent density of the PB film....................................................................34
3.4 SEM Images..................................................................................................................................................35
3.5 AFM Images and Surface Roughness.......................................................................................37
3.6 References.......................................................................................................................................................41
CHAPTER 4 Redox Behaviors of a PB Thin Film...................................................................42
4.1 Cyclic Voltammograms and Corresponding Mass Changes 43
4.2 Dependence of Charge Capacity on Scan Rates 46
4.3 Long-term Cycling Stability 52
4.4 Insertion/Extraction Mechanism...................................................................................................55
4.5 References.......................................................................................................................................................59
CHAPTER 5 Influence of Different Cations on Redox Behaviors...............................60
5.1 Influence of Different Electrolytic Cations............................................................................62
5.1.1 Cyclic Voltammograms....................................................................................................................62
5.1.2 Corresponding Mass Changes of Cyclic Voltammograms....................................63
5.2 Redox Reversibility..................................................................................................................................68
5.3 Recovery Ratio............................................................................................................................................73
5.4 Influence of Different Cations on Potential-Step Experiments..............................77
5.4.1 Mass Change Behaviors in Li+, Na+, K+, or Rb+ Containing Solutions..77
5.4.2 Mass Changes Behaviors in Cs+ Containing Solution.............................................81
5.5 Summary.........................................................................................................................................................83
5.6 References.......................................................................................................................................................84
Chapter 6 Apparent Molar Mass and Hydration Number.................................................86
6.1 Apparent Molar Mass...........................................................................................................................87
6.2 Insertion/Extraction Mechanism for Hydrated K+.........................................................92
6.2.1 Insertion of Hydrated K+ during Reduction....................................................................92
6.2.2 Extraction of K+ during Oxidation........................................................................................93
6.3 Hydration Numbers of K+ During PB掇 Redox Reactions.......................................96
6.4 Summary.........................................................................................................................................................99
6.5 References....................................................................................................................................................100
Chapter 7 Potassium ions sensing....................................................................................................101
7.1 Theory of the K+ Sensing...............................................................................................................102
7.2 Governing Equation for K+ Sensing.......................................................................................105
7.3 K+ Sensing.................................................................................................................................................109
7.3.1 Sensing Limit for K+......................................................................................................................109
7.3.2 Interference of Other Cations on K+ Sensing..............................................................110
7.4 Summary.....................................................................................................................................................115
7.5 References....................................................................................................................................................116
CHPATER 8 Conclusions........................................................................................................................117
8.1 Electrodeposition and Physical Properties of the PB Thin Film.......................117
8.2 Redox Behaviors and Insertion/Extraction Mechanism...........................................118
8.3 Potassium ions sensing.....................................................................................................................120
8.4 Suggestionss..............................................................................................................................................121

Chapter 1
[1] J. H. Buser, D. Schwarzenbach, W. Petter, and A. Ludi, Inorg. Chem., 16, 2704 (1977).
[2] A. Ludi and H. U. Gudel, Struct. Bonding (Berlin), 14, 1 (1973).
[3] M. B. Robin and P. Day, Adv. Inorg. Chem. Radiochem., 10, 247 (1967).
[4] F. Herren, P. Fisher, A. Ludi, and W. H?lg, Inorg. Chem., 19, 956 (1980).
[5] J. F. Keggin and F. D. Miles, Nature (London), 137, 577 (1936).
[6] M. B. Robin, Inorg. Chem., 1, 337 (1962).
[7] G. B. Seifer, Russ. J. Inorg. Chem. (Engl. Transl.), 7, 621 (1962).
[8] J. F. Duncan and P. W. R. Wigley, J. Chem. Soc., 1120 (1963).
[9] B. M. Chadwick and A. G. sharpe, Adv. Inorg. Chem. Radiochem., 8, 83 (1966).
[10] D. Davidson and L. A. Welo, J. Phys. Chem., 32, 1191 (1928).
[11] I. V. Tananaev, M. A. Glushkova, and G. B. Seifer, Zh. Neorg. Khim., 1, 66 (1956).
[12] V. D. Neff, J. Electrochem. Soc., 125, 886 (1978).
[13] D. Ellis, M. Eckhoff, and V. D. Neff, J. Phys. Chem., 85, 1225 (1981).
[14] K. Itaya, H. Akahoshi, and S. Toshima, J. Electrochem. Soc., 129, 1498 (1982).
[15] K. Itaya, T. Ataka, and S. Toshima, J. Am. Chem. Soc., 104, 4767 (1982).
[16] K. Itaya, T. Ataka, S. Toshima, and T. Shinohara, J. Phys. Chem., 86, 2415
(1982).
[17] K. Itaya, I. Uchida, and S. Toshima, J. Phys. Chem., 87, 105 (1983).
[18] K. Itaya, K. Shibayama, H. Akahoshi, and S. Toshima, J. Appl. Phys., 53, 804 (1982).
[19] K. Itaya, T. Ataka, and S. Toshima, J. Am. Chem. Soc., 104, 3751 (1982).
[20] R. J. Mortimer and D. R. Rosseinsky, J. Electroanal. Chem., 151, 133 (1983).
[21] R. M. C. Goncalves, H. Kellawi, and D. R. Rosseinsky, J. Chem. Soc. Dalton Trans., 991 (1983).
[22] J. W. MacCargar and V. D. Neff, J. Phys. Chem., 92, 3598 (1988).
[23] K. P. Rajan and V. D. Neff, J. Phys. Chem., 86, 4361 (1982).
[24] K. Itaya, I. Uchida, and V. D. Neff, Acc. Chem. Res., 19, 162 (1986).
[25] R. J Mortimer and D. R. Rosseinsky, J. Chem. Soc. Dalton Trans., 2059 (1984).
[26] K. Ogura, M. Nakayama, and K. Nakaoka, J. Electroanal. Chem., 474, 101 (1999).
[27] D. J. Beckstead, D. J. De Smet, and J. L. Ord, J. Electrochem. Soc., 136, 1927 (1989).
[28] C. A. Lundgren and R. W. Murray, Inorg. Chem., 27, 933 (1988).
[29] V. Krishnan, A. L. Xidis, and V. D. Neff, Analytic Chim. Acta, 239, 7 (1990).
[30] K. C. Gupta, and M. J. D''Arc, Sensors and Actuators B, 62, 171 (2000).
[31] D. Engel and E. W. Grabner, Ber. Bunsenges. Phys. Chem., 89, 982 (1985).
[32] L. M. Siperko and T. Kuwana, Electrochim. Acta, 32, 765 (1987).
[33] K. C. Ho, J. Electrochem. Soc., 139, 1099 (1992).
[34] N. Leventis and Y. C. Chung, Chem. Mater., 4, 1415 (1992).
[35] M. A. Habib and S. P. Maheswari, J. Appl. Electrochem., 23, 44 (1993).
[36] B. P. Jelle and G. Hagen, J. Electrochem. Soc., 140, 2560 (1993).
[37] K. C. Ho, T. G. Rukavina, and C. B. Greenberg, J. Electrochem. Soc., 141, 2061 (1994).
[38] B. P. Jelle, G. Hagen, and , Birketveit, J. Appl. Electrochem., 28, 483 (1998).
[39] V. D. Neff, J. Electrochem. Soc., 132, 1382 (1985).
[40] M. Kaneko and T. Okada, J. Electroanal. Chem., 255, 45 (1988).
[41] E. W. Grabner and S. Kalwellis-mohn, J. Appl. Electrochem., 17, 653 (1986).
[42] K. Honda and H. Hayashi, J. Electrochem. Soc., 134, 1330 (1987).
[43] M. Jayalakshmi and F. Scholz, Journal of Power Sources, 87, 212 (2000).
[44] P. J. Kulesza, J. Electroanal. Chem., 220, 295 (1987).
[45] F. Li and S. Dong, Electrochim. Acta, 32, 1511 (1987).
[46] K. Ogura and I. Yoshida, Electrochim. Acta, 8, 1191 (1987).
[47] K. Ogura, N Endo, M. Nakayama, and H. Ootsuka, J. Electrochem. Soc., 142, 4026 (1995).
[48] K. Ogura, H. Sugihara, Y. Yana, and M. Higasa, J. Electrochem. Soc., 141, 419 (1994).
[49] K. Ogura, M. Nakayama, and C. Kusumoto, J. Electrochem. Soc., 143, 3606 (1996).
[50] M. Kaneko, S. Hara, and A. Yamada. J. Electroanal. Chem., 194, 165 (1985).
[51] M. Kaneko, K. Takahashi, and E. Tsuchida, J. Electroanal. Chem., 227, 255 (1987).
[52] M. Nishizawa, S. Kuwabata, and H. Yonetama, J. Electroanal. Soc., 143, 3462 (1996).
Chapter 2
[1] R. J. Mortimer, D. R. Rosseinsky, J. Electroanal. Chem., 151, 133 (1983).
[2] R. J. Mortimer, D. R. Rosseinsky. And A. Glidle, Solar Energy Materials and Solar Cells, 25, 211 (1992).
[3] K. Itaya, T. Ataka, and S. Toshima, J. Am. Chem. Soc., 104, 4767 (1982).
[4] K. Itaya, H. Akahoshi, and S. Toshima, J. Electrochem, Soc., 129, 1498 (1982).
[5] G. Z. Sauerbrey, Z. Phys., 155, 206 (1959).
[6] G. Z. Sauerbrey, Z. Phys., 178, 457 (1964).
[7] K. K. Kanazawa and J. G. Gordon II, Anal. Chim. Acta., 175, 99 (1985).
[8] T. Nomura and M. Okuhara, Anal. Chim. Acta., 142, 281 (1982).
Chapter 3
[1] V. D. Neff, J. Electrochem. Soc., 125, 886 (1978).
[2] K. Itaya, H. Akahoshi, and S. Toshima, J. Electrochem. Soc., 129, 1498 (1982).
[3] K. Itaya, T. Ataka, and S. Toshima, J. Am. Chem. Soc., 104, 4767 (1982).
[4] R. J. Mortimer and D. R. Rosseinsky, J. Electroanal. Chem., 151, 133 (1983).
[5] G. Z. Sauerbrey, Z. Phys., 155, 206 (1959).
[6] R. J. Mortimer, D. R. Rosseinsky, and A. Glidle, Sol. Energy Mater. and Solar Cells, 25, 211 (1992).
[7] C. Kuhnhardt, J. Electroanal. Chem., 369, 71 (1994).
[8] C. A. Lundgren and R. W. Murray, Inorg. Chem., 27, 933 (1988).
[9] K. Itaya, I. Uchida, and V. D. Neff, Acc. Chem. Res., 19, 162 (1986).
[10] J. W. McCargar and V. D. Neff, J. Phys. Chem., 92 3598 (1988).
[11] F. Herren, P. Fischer, A. Ludi, and W. Halg, Inorg. Chem., 19, 956 (1980).
[12] A. Ludi and H. U. Gudel, Struct. Bonding (Berlin), 14, 1 (1973).
[13] K. Itaya, H. Akahoshi, and S. Toshima, J. Electrochem. Soc., 129, 1498(1982).
[14] H. Sugimura, N. Shimo, N. Kitamura, H. Masuhara, and K. Itaya, J. Electroanal. Chem., 346, 147 (1993).
[15] H. J. Buser, D. Schwarzenbach, W. Peter, and A. Ludi, Inorg. Chem., 16, 2704 (1977).
[16] A. Hamnett, S. J. Higgins, R. J. Mortimer, and D. R. Rosseinsky, J. Electroanal. Chem., 255, 315 (1988).
Chapter 4
[1] D. Ellis, M. Eckhoff, and V. D. Neff, J. Phys. Chem., 85, 1225 (1981).
[2] K. Itaya, T. Ataka, and S. Toshima, J. Am. Chem. Soc., 104, 4767 (1982).
[3] K. Ogura, M. Nakayama, and K. Nakaoka, J. Electroanal. Chem., 474, 101 (1999).
[4] R. J. Mortimer and D. R. Rosseinsky, J. Chem. Soc. Dalton Trans., 2059 (1984).
[5] D. E. Stilwell, K. H. Park, and M. H. Miles, J. Appl. Electrochem., 22, 325 (1992).
[6] A. Hamnett, S. Higgins, R. S. Mortimer, and D. R. Rosseinsky, J. Electroanal. Chem., 255, 315 (1988).
[7] A. J. Bard and L. R. Faulkner, Electrochemical Methods, 2nd ed., John Wiely & Sons, Inc., New York (2001).
[8] D. Ellis, M. Eckhoff, and V. D. Neff, J. Phys. Chem., 85, 1225 (1981).
[9] V. Krishnan, A. L. Xidis, and V. D. Neff, Anal. Chim. Acta, 239, 7 (1990).
[10] F. A. Cotton, G. Wilkinson, and P. L. Gaus, Basic Inorganic Chemistry, 2nd ed., John Wiley and Sons, Inc., 2nd edition, New York (1987).
[11] B. E. Conway, Ionic Hydration in Chemistry and Biophysics, Elsevier Scientific Publishing Company, Netherlands (1981).
Chapter 5
[1] K. Itaya, T. Ataka, and S. Toshima, J. Am. Chem. Soc., 104, 4767 (1982).
[2] J. W. MacCargar and V. D. Neff, J. Phys. Chem., 92, 3598 (1988).
[3] C. A. Lundgren and R. W. Muarry, Inorg. Chem., 27, 933 (1988).
[4] Z. Jin and S. Dong, Electrochim. Acta, 35, 1057 (1990).
[5] R. J. Mortimer and D. R. Rosseinsky, J. Electroanal. Chem., 151, 133 (1993).
[6] K. Itaya, I. Uchida, and V. D. Neff, Acc. Chem. Res., 19, 162 (1986).
[7] F. Li and S. Dong, Scientia Sinica Ser., B 30, 367 (1987).
[8] S. Dong and Z. Jin, Electrochim. Acta, 34, 963 (1989).
[9] A. L. Crumbliss, P. S. Lugg, and N. Morosoff, Inorg. Chem., 23, 4701 (1984).
[10] K. Aoki, T. Miyamoto, and Y. Ohsawa, Bull. Chem. Soc. Jpn., 62, 1658 (1989).
[11] S. Sinha, B. D. Humphrey, and A. B. Bocarsly, Inorg. Chem., 23, 203 (1984).
[12] A. L. Crumbliss, P. S. Lugg, and N. Morosoff, Inorg. Chem., 23, 4701 (1984).
[13] B. J. Feldman and O. R. Melory, J. Electroanal. Chem., 234, 213 (1987).
[14] S. J. Lasky and D. A. Buttry, J. Am Chem. Soc., 110, 6258 (1988).
[15] M. A. Deakin and D. A. Buttry, Anal. Chem., 61, 1147 (1989).
[16] K. Ogura, M. Nakayama, and K. Nakaoka, J. Electroanal. Chem., 474, 101 (1999).
[17] M. Zadronecki, P. K. Wrona, and Z. Galus, J. Electrochem. Soc., 146, 620 (1999).
[18] K. Kim, I. Jureviciute, and S. Bruckenstein, Electrochim. Acta, 46, 4133 (2001).
[19] A. Ludi and H. U. Gudel, Struct. Bonding (Berlin), 14, 1 (1973).
[20] H. J. Buser, D. Schwarzenbach, W. Petter, and A. Ludi, Inorg. Chem., 16, 2704 (1977).
[21] F. Herren, P. Fischer, A. Ludi, and W. H?lg, Inorg. Chem., 19, 956 (1980).
[22] A. Dostal, B. Meyer, F. Scholz, U. Schr?der, A. N. Bond, F. Marken, and S. J. Shaw, J. Phys. Chem., 99, 2096 (1995).
[23] A. Dostal, G. Kauschka, S. J. Reddy, and F. Scholz, J. Electroanal. Chem., 406, 155 (1996).
[24] F. A. Cotton, G. Wilkinson, and P. L. Gaus, Basic Inorganic Chemistry, John Wiley and Sons, Inc., 2nd edition, U.S. (1987).
[25] B. E. Conway, Ionic Hydration in Chemistry and Biophysics, Elsevier scientific publishing company, Netherlands (1981).
Chapter 6
[1] B. J. Feldman and O. R. Melroy, J. Electrochem. Chem., 234, 213 (1987).
[2] K. Ogura, M. Nakayama, and K. Nakaoka, J. Electroanal. Chem., 474, 101 (1999).
[3] M. Zadronecki, P. K. Wrona, and Z. Galus, J. Electrochem. Soc., 146, 620 (1999).
[4] K. Kim, I. Jureviciute, and S. Bruckenstein, Electrochim. Acta, 46, 4133 (2001).
[5] M. R. Deakin and H. Byrd, Anal. Chem., 61, 290 (1989).
[6] A. Hamnett, S. J. Higgins, R. J. Mortimer, and D. R. Rosseinsky, J. Electroanal. Chem., 255, 315 (1988).
[7] H. J. Buser, D. Schwarzenbach, W. Peter, and A. Ludi, Inorg. Chem., 16, 2704 (1977).
Chapter 7
[1] V. Krishnan, A. L. Xidis, and V. D. Neff, Anal. Chim. Acta, 239, 7 (1990).
[2] D. Engel and E. W. Grabner, Ber. Bunsenges. Phys. Chem., 89, 982 (1985).
[3] L. M. Siperko and T. Kuwana, Electrochimica. Acta, 32, 765 (1987).
[4] K. C. Gupta and M. J. D''Arc, Sensor and Actuators B, 62, 171 (2000).
[5] D. Ellis, M. Eckhoff, and V. D. Neff, J. Phys. Chem., 85, 1225 (1981).
[6] J. W. McCargar and V. D. Neff, J. Phys. Chem., 92, 3598 (1988).
[7] J. M. Prausnitz, R. N. Lichtenthaler, and E. G. de Azevedo, 浢olecular thermodynamics of fluid-phase equilibria, 2nd ed. P T R Prentice Hall, Englewood Cliffs, New Jersey, 213 (1996).
[8] K. Itaya, T. Ataka, and S. Toshima, J. Am. Chem. Soc., 104, 4767 (1982).
[9] C. A. Lundgren and R. W. Muarry, Inorg. Chem., 27, 933 (1988).
[10] R. J. Mortimer and D. R. Rosseinsky, J. Electroanal. Chem., 151, 133 (1993).
[11] B. E. Conway, Ionic Hydration in Chemistry and Biophysics, Elsevier scientific publishing company, Netherlands (1981).