Czasopismo | RUDY I METALE NIEŻELAZNE | Rocznik 2016 - zeszyt 8

Kinetics of the Reaction of Platinum(IV) Chloride Complex Ions in Aqueous Solution, in the Presence of C2H5OH

10.15199/67.2016.8.2

nr katalogowy: 100347
10.15199/67.2016.8.2

In this work, the kinetic studies of the reaction of platinum (IV) chloride complexes ([PtCl6 ] 2-) with ethyl alcohol in aqueous solution were carried out. Obtained data suggest the complex character of the reaction which is sensitive to pH of the solution. It was found that in the alkaline solution two parallel reaction paths are present: hydrolysis and the redox reaction of [PtCl6 ] 2-. It leads to [PtCl5 (H2O)] - and [PtCl4 ] 2- ions formation in the system. Both reactions has bimolecular character and at 55oC and at pH =12, are described by the second-order rate constants: k1 = 0.085.10 -3 [M -1s -1] (for the hydrolysis) and k2 = 3.55.10 -3 [M -1s -1] (for the redox reaction). Experimentally determined values of enthalpy and entropy of activation for the hydrolysis reaction are equal to 23.654 [kJ·mol -1] and -187.16 [J·mol -1·K -1], respectively. The same parameters for the redox reaction are as follows: 24.016 [kJ·mol -1] and -166.591 [J·mol -1·K -1], respectively. As a result of data analysis it was also suggested that the ethyl alcohol may play a catalytic role during [PtCl6 ] 2- hydrolysis. Its presence leads to slight acceleration of this reaction and to slow Pt 4+ reduction. Keywords: kinetics, mechanism, redox reaction, platinum, ethanol, rate law Kinetyka reakcji kompleksów chlorkowych pla tyny(IV) w roztworze wod nym, w o becności C2H5OH W pracy przedstawiono wyniki badań kinetycznych reakcji kompleksów chlorkowych platyny (IV) ([PtCl6 ] 2-) z alkoholem etylowym, w roztworach wodnych. Otrzymane dane sugerują złożony charakter reakcji, czuły na pH roztworu. Wykazano, że w roztworach alkalicznych obecne są dwie równoległe ścieżki reakcji: hydroliza i reakcja redoks [PtCl6 ] 2-. Prowadzi to do utworzenia jonów [PtCl5 (H2O)] - i [PtCl4 ] 2- w układzie. Obydwie reakcją mają charakter dwucząsteczkowy i w temperaturze 55oC oraz przy pH = 12 są opisane przez drugorzędowe stałe szybkości reakcji: k1 = 0,085[...]

Bibliografia

[1] Applied Photophysics Ltd., 21 Mole Business Park, Randalls Rd, Leatherhead KT22 7BA, Wielka Brytania.
[2] Baigent C. L., G. Muller. 1980. "A colloidal gold prepared with ultrasonics". Cellular and Molecular Life Sciences 36: 472-473.
[3] Belskaya Olga, T. I. Gulyaeva, A. B. Abruzov, V. K. Duplyakin, V. A. Likholobov. 2010. "Interaction between Pt(IV) and Pd(II) Chloro Complexes in Solution and on the γ-Al2O3 Surface". Kinetics and Catalysis 51: 105-112.
[4] Chen C. W., D. Tano, M. Akashi. 1999. "Synthesis of platinum colloids sterically stabilized by poly(N-vinylformamide) or poly(N -vinylalkylamide) and their stability towards salt". Colloid. Polymer Science 277: 488-493.
[5] Chen C. W., M. Akashi. 1997. "Synthesis, Characterization, and Catalytic Properties of Colloidal Platinum Nanoparticles Protected by Poly(N-isopropylacrylamide)". Langmuir 13: 6465-6472.
[6] Gaussian 0.3 software, Gaussian Inc., USA.
[7] Gordon R. B., M. Bertram, T. E. Graedel. 2006. "Metal stocks and sustainability". Procceding. National Academy of Science of the United States of America 103: 1209-1214.
[8] Hindmarsh Kathryn, Donald A. House, Rudi van Eldik. 1998. "The redox kinetics of platinum(II)/(IV) complexes". Inorganica Chimica Acta 278: 32-42.
[9] Ingelsten H. H., R. Bagwe, A. Palmqvist, M. Skoglundh, Ch. Svanberg, K. Homlberg, D. O. Shah. 2001. "Kinetics of the Formation of Nano-Sized Platinum Particles in Water-in-Oil Microemulsions". Journal of Colloid and Interface Science 241: 104-111.
[10] Jorgensen A. O., K. P. Campbell. 1984. "Evidence for the Presence of Calsequestrin in Two Structurally Different Regions of Myocardial Sarcoplasmic Reticulum". Journal of Cell Biology 98: 1597-1602.
[11] Jorgensen C. Klixbüll. 1956. "Complexes of 4d- and 5d-Groups. II. Crystal Field and Electron Transfer Spectra of Ruthenium(II) and (III), Iridium(IV) and Platinum(IV)". Acta Chemica Scandinavica 10: 518-534.
[12] Kameo A., T. Yoshimura, K. Esami. 2003. "Preparation of noble metal nanoparticles in supercritical carbon dioxide". Colloids and Surfaces A. Physicochemical and Engineering Aspects 215: 181-189.
[13] Lemma Kelemu, Donald A. House, Negussie Retta, Lars Elding. 2002. "Kinetics and mechanism for reduction of halo- and haloam( m)ine platinum(IV) complexes by L-ascorbate". Inorganica Chimica Acta 331: 98-108.
[14] Mehrotra U. S., M. C. Agrawal, S. P. Mushran. 1970. "Reduction of hexachloroplatinate by ascorbic acid". Journal of Inorganic and Nuclear Chemistry 32: 2325-2329.
[15] Mishra B., C. D. Anderson, P. R. Taylor, C. G. Anderson, D. Apelian, B. Blanpain. 2012. "Recycling of Strategic Metals". Journal of Metals 64: 441-443.
[16] Murray Pieter, Klaus R. Koch, Rudi van Eldik. 2014. "Mechanism of tetrachloroplatinate(II) oxidation by hydrogen peroxide in hydrochloric acid solution". Dalton Transactions 43: 6308-6314.
[17] Patrushev V. V. 1998. "Reduction of platinum group metals in phosphoric acid solutions by formalin". Hydrometallurgy 50: 89- 101.
[18] Perrin D. D. Dissociation Constants of Organic Bases and Aqueous Solution. 1965. London: Butterworths.
[19] Perrin D. D. Dissociation Constants of Organic Bases and Aqueous Solution. Supplement. 1965. London: Butterworths.
[20] Reck Barbara, T. E. Graedel. 2012. "Challenges in Metal Recycling". Science 337: 690-694.
[21] Siiman O., W. P. Hsu. 1986. "Surface-enhanced Raman scattering (SERS) enhancements and excitation profiles for 3,5-pyridinedicarboxylate and dabsyl aspartate on colloidal gold". Journal of the Chemical Society. Faraday Transactions 1 82: 851-867.
[22] Toshima N., T. Yonezawa, K. Kushihashi. 1993. "Polymer-protected palladium-platinum bimetallic clusters: preparation, catalytic properties and structural considerations". Journal of the Chemical Society. Faraday Transactions 1 89: 2537-2543.
[23] W. Yu, H. Liu, M. Liu, J. Zheng. 1999. "Preparation of Polymer-Stabilized Noble Metal Colloids". Journal of Colloid and Interface Science 210: 218-221.
[24] Wang Q., H. Liu, H. Wang. 1997. "Immobilization of Polymer-Stabilized Noble Metal Colloids and Their Catalytic Properties for Hydrogenation of Olefins". Journal of Colloid and Interface Science 190: 80-386.
[25] Wesdemiotis C., A. Fura, F. W. McLafferty. 1991. "Protonated Ethanol and Its Neutral Counterparts". American Society for Mass Spectrometry 2: 459-463.
[26] Wu M. L., D. H. Chen, T. C. Huang. 2001. "Preparation of Pd/Pt Bimetallic Nanoparticles in Water/AOT/Isooctane Microemulsions". Journal of Colloid and Interface Science 243: 102-108.

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