Mechanism of Electrodeposition from Aqueous Solutions of Square Planar Complexes

Watt, George W.; Cunningham, James A.

doi:10.1149/1.2425860

Cited by 14 publications

(2 citation statements)

References 8 publications

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“…In addition, a previous paper showed that the mechanism of deposition of this complex did not involve previous dissociation. 32 In short, there is evidence for the surface catalytic activity of electrodeposited Pd black (see Fig. 2).…”

Section: Effect Of the Meoh Concentration-inmentioning

confidence: 97%

Palladium‐Assisted Electrodehalogenation of 1,1,2‐Trichloro‐1,2,2‐trifluoroethane on Lead Cathodes Combined with Hydrogen Diffusion Anodes

Cabot

Centelles

Segarra

et al. 1997

J. Electrochem. Soc.

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In this work, the efficiency and product formation in the electroreduction of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC 113) to obtain completely dechlorinated products has been studied using constant-current electrolysis at different current densities, gas chromatography, scanning electron microscopy, and energy dispersive x-ray. While chlorotrifluoroethene was the main product obtained from CFC 113 in MeOH-water solutions containing NH 4 C1, different and suitable conditions which lead to its complete dechlorination are described in this paper. In the presence of small amounts of Pd 2+ in solution, a very thin film of Pd black was electrodeposited on the Pb cathode and the efficiency of the CFC 113 electroreduction was about 98%. The efficiency was much smaller and the product composition very different in the absence of Pd 2+ in solution, even in the presence of Pd black electrodeposited on the cathode. In the presence of Pd 2+ , the main products in the gas phase were difluoroethene and trifluoroethene. Small amounts of 1,2-dichloro-1,1,2-trifluoroethane, chlorotrifluoroethene, difluoroethane, and fluroethane were also present in the gas phase. The liquid composition was enriched in the less volatile compounds. A possible reaction pathway involving the removal of halides by successive reactions is discussed. The anode employed in these experiments was a thin Pd foil with electrodeposited Pd black, which permitted hydrogen diffusion and its further oxidation to H + . Because of this reaction, contamination of the workingelectrolyte by other oxidation products such as C12 or MeOH derivatives were avoided. This system allows new electrosynthetic processes along with CFC electrodegradation.

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Section: Effect Of the Meoh Concentration-inmentioning

confidence: 97%

Palladium‐Assisted Electrodehalogenation of 1,1,2‐Trichloro‐1,2,2‐trifluoroethane on Lead Cathodes Combined with Hydrogen Diffusion Anodes

Cabot

Centelles

Segarra

et al. 1997

J. Electrochem. Soc.

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“…Other stripping solutions tried were KCN, KCN-NaOH mixtures, NaN02, NH3-NaCl mixtures, NH3-NaOH mixtures, KSCN, HI, KBr, NaOH, and K2S03. They were selected according to the platinum bond strength of the anion (32)(33)(34). None of these solutions showed any indication of platinum dissolution.…”

Section: Methodsmentioning

confidence: 99%

Voltammetric determination of platinum from aqueous solutions and from urine

Schmid¹,

Atherton²

1986

Anal. Chem.

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I t is shown that platinum can be determlned from aqueous solutions o f clsdiamminedicMotopiatinum( I I ) (cisplatin) or of hexachioropiathic acid by differential pulse voltammetry after deposnbn onto a rotating glassy carbon electrode. For cisplatln, deposltlon Is carried out at -0.5 V In 0.15 M NaCi. For hexachloroplatkdc acld best results are obtalned at -0.2 V In 0.1 Y NaHSO,/O.l M Na$04 buffer. The subsequent analysis step is performed In 0.05 M H,SO, after application of a controlled potentlal program to activate the deposlt. During the analysis, the platinum Is not stripped from the electrode. Measured are the currents In the dmerential pulse mode requlred to oxidize the platlnum deposlt. Between samples, the deposlt Is mechanically removed from the electrode. Analysis of clsplatin In urine involves a chelation procedure wlth sodlum dlethyldlthbcarbamate, extractlon of the platbnm chelate wtth chkrdorm, solvent evaporation, and dlgestlon with aqua regla. The resulting hexachioroplatinlc acld is then analyzed for platlnum as described above. Platlnum levels daennhed In ihk work range from 0.1 to 100 ppm. This is sufficient for the monltorlng of patients under treatment wlth cisplatln, where a peak plasma level of 6 ppm is generally expected.

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Über Kaliumtetracyanoplatinat(II), Kaliumtetracyanopalladat(II) und deren Monohydrate

Mühle

Nuß

Dinnebiér

et al. 2004

Zeitschrift anorg allge chemie

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Wir haben die Kristallstrukturen der Kaliumtetracyanoplatinate und ‐palladate sowie deren Monohydrate mittels Röntgen‐Pulverdiffraktometrie und Einkristallstrukturanalyse bestimmt. K2[Pt(CN)4]: orthorhombisch, Pccn, a = 1370.11(2), b = 907.09(1), c = 703.91(2) pm, Z = 4, RF2 = 0.0903 (N(hkl) = 415). K2[Pt(CN)4] · H2O: orthorhombisch, Pnna, a = 715.79(4), b = 977.91(6), c = 1322.46(8) pm, Z = 4, R(F)N′ = 0.027 (N′(hkl) = 1066). K2[Pd(CN)4]: monoklin, P21/c, a = 433.03(2), b = 782.90(3), c = 1328.17(6) pm, ß = 93.069(3)°, Z = 2, Rp = 0.0583 (N(hkl) = 352). K2[Pd(CN)4] · H2O: orthorhombisch, Pnna, a = 721.48(6), b = 976.77(8), c = 1326.4(1) pm, Z = 4, R(F)N′ = 0.048 (N′(hkl) = 1137). In allen untersuchten Vertretern liegen die Anionen übereinander gestapelt, wenn auch teilweise gekippt, vor. Die Ergebnisse werden durch spektroskopische und thermoanalytische Untersuchungen ergänzt.

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Mechanism of Electrodeposition from Aqueous Solutions of Square Planar Complexes

Cited by 14 publications

References 8 publications

Palladium‐Assisted Electrodehalogenation of 1,1,2‐Trichloro‐1,2,2‐trifluoroethane on Lead Cathodes Combined with Hydrogen Diffusion Anodes

Palladium‐Assisted Electrodehalogenation of 1,1,2‐Trichloro‐1,2,2‐trifluoroethane on Lead Cathodes Combined with Hydrogen Diffusion Anodes

Voltammetric determination of platinum from aqueous solutions and from urine

Über Kaliumtetracyanoplatinat(II), Kaliumtetracyanopalladat(II) und deren Monohydrate

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