Controlled-Potential and Derivative Polarograph

Kelley, M.T.; Jones, H. C.; Fisher, D. J.

doi:10.1021/ac60153a020

Cited by 94 publications

(66 citation statements)

References 23 publications

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“…The potential of the electrode at time t will be given by E : Ei q-~t [3] where E~ is the initial potential of the electrode, and since ~ is constant dE : vdt [4] and P(,t) : P(E --E~) [5] Equation [2] may thus be rewritten in terms of E Q = kC/v 1/2 [6] I Permanent address: Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California.…”

Section: [2]mentioning

confidence: 99%

Integration of Single-Sweep Oscillopolarograms

Osteryoung¹,

Lauer²,

Anson

1963

J. Electrochem. Soc.

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Integration of the equation for the current-time relationship when a linear potential sweep is applied to an electrode has led to an equation for the number of coulombs passed, Q ~ kCA/~ 1/2, where k is a constant dependent on the potential interval over which the integration is carried out, but independent of sweep rate, C the concentration of the species undergoing reaction, A the electrode area, and ~ the time rate of change of the linear potential sweep. A procedure to distinguish between coulombs due to diffusing and nondiffusing reactants is given. The derived relationships are verified experimentally. Separation of the coulombs due to the reduction of ferric iron and platinum oxide under conditions where both reactions take place concomitantly is described.In the iodide-iodine-triiodide system, it is concluded that iodine, rather than triiodide, is the adsorbed species.) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 142.58.129.109 Downloaded on 2015-06-08 to IP

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Section: [2]mentioning

confidence: 99%

Integration of Single-Sweep Oscillopolarograms

Osteryoung¹,

Lauer²,

Anson

1963

J. Electrochem. Soc.

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“…Scholder and Kolb (3) measured solubilities of Mn(OH)2 in 6.1-18.7M NaOH solution at boiling temperatures (108~176 and found the Mn(II) ion concentration to be 0.211 x 10-2m-13.34 x 10-2m in the concentration range of NaOH. They also isolated Na2[Mn(OH) 4] and Ba2 (or Sr2)[Mn(OH)~] from 50% NaOH (or 19M NaOH) solution saturated with Mn(OH)2.…”

mentioning

confidence: 99%

Solubilities of Mn(II) and Mn(III) Ions in Concentrated Alkaline Solutions

Kozawa¹,

Kalnoki-Kis²,

Yeager³

1966

J. Electrochem. Soc.

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Measurements using a polarographic method of the solubility of Mn(II) in 3-13.5M KOH and 3-19M NaOH at 23 ~ 50 ~ and 70~ as well as solubility of Mn(III) in 5-13.5M KOH at 23~ are reported. The exponential increase in solubility found with increasing KOH and NaOH concentrations is principally due to the formation of OH-coordinated-complex ions; Mn(OH)2 -~ nOH-= [Mn(OH)n+2] n-. Based on the calculation of the equilibrium constant, a likely predominant species of the Mn(II) complexes is [Mn(OH)4] = in 5-12M KOH. Based on measurements for solubility of Mn(II) the heat of dissolution was found to be 6.7 kcal in 9M KOH.It has been shown previously (1) that the cathodic reduction of electrolytic MnO2 in 9M KOH took place in two steps, namely, from MnO2 to Mn2Os (or MnOOH) in the first step and from Mn~O3 to Mn(OH)2 in the second step. It was assumed that the first step was a homogeneous phase discharge through a proton and electron transfer in the MnO2 lattice, and for the second step a new discharge mechanism was proposed (1) based on the presence of dissolved Mn(II) and Mn(III) in 9M KOH. In order to study the details of the second step, solubility values of Mn(II) and Mn(III) oxides or hydroxides in concentrated alkaline solutions were needed. This prompted the present measurements.Few papers have been published on the solubility of Mn(II) in alkaline solutions. Fox et al.(2) in solubility measurements of Mn(OH)2 in neutral solution and up to 4M NaOH solutions found that the solubility increased with increasing NaOH concentration: 7.53 x 10-5m of Mn(II) in 1.924m NaOH and 29.8 x 10-h~q in 4.14m NaOH. They proposed a reaction, Mn(OH)2 + OH-----HMnO2-~-H20, to be a main reaction in this NaOH concentration range. Scholder and Kolb (3) measured solubilities of Mn(OH)2 in 6.1-18.7M NaOH solution at boiling temperatures (108~176 and found the Mn(II) ion concentration to be 0.211 x 10-2m-13.34 x 10-2m in the concentration range of NaOH. They also isolated Na2[Mn(OH)4]and Ba2 (or Sr2)[Mn(OH)~] from 50% NaOH (or 19M NaOH) solution saturated with Mn(OH)2.In the present measurements, by a polarographic method, Mn(II) solubilities in 3-13.5M KOH and in NaOH were obtained at 23 ~ , 50 ~ , and 70~ and Mn(III) solubility was measured in 5-13.5M KOH at 23~The data are discussed to elucidate the equilibrium in the solution and to identify the predominant species of Mn (II) complexes.A polarographic method was selected in the present measurement because the polarographic diffusion current is not only proportional to the concentration of dissolved Mn (II) or Mn (III), but is usually unaffected by the excess solid material suspended in the solution (except colloidal materials , which will be mentioned later). Therefore, the very difficult separation of the excess manganese hydroxide by filtration from viscous alkaline solutions of high concentration was avoided. Experimental General polarographic behavio~ of Mn(II) andMn(III).---In alkaline solutions, Mn(II) ion gives an oxidation wave and Mn(III) ion gives a reduction wave at a droppi...

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“…The past decade has witnessed this field develop from infancy to a state of incipient maturity as a result of rapid evolution of knowledge in three principal areas: instrumental techniques, usable solvents and appropriate schemes for their purification, and electrode reaction mechanisms. The measurement problems attending the high resistance characterizing most aprotic solvent-supporting electrolyte systems (1,2) have been overcome to a large extent by the development of potentiostats and galvanostats which permit automatic potential and current control with threeelectrode cell configurations (3)(4)(5)(6)(7)(8)(9)(10). This development began in the late 1950's with the efforts of Booman (3), DeFord (3, and Kelley and coworkers (6,7).…”

Section: Donald E Smithmentioning

confidence: 99%

“…CHEM., 40,455R (1968 to higher temperatures, sealed containers, and end point detection with reproducible excess of reagent (3-5). Guilbault was the first to use the technique for direct analysis based an kinetics (6). It is the purpose here to present the technique of differential constant-current potentiometry (DCCP) and…”

mentioning

confidence: 99%