The response of cation-sensitive glass electrodes to alkali metal ions in partially aquated media

Rechnitz, G. A.; Zamochnick, S. B.

doi:10.1016/0039-9140(64)80136-3

Cited by 17 publications

(7 citation statements)

References 8 publications

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“…Maintaining constant ionic strength by replacing H+ with Na+ may not result in sufficiently constant activity coefficients at these concentrations. Moreover generation of Ag(II) Rate constants are tabulated in Tables II and III for 75 kinetic runs, as a function of ionic strength (7), [H+], and temperature. For 41 of the runs, the values of ki and ki were determined by a Runge-Kutta numerical integration26 of the pair of simultaneous differential equations ford[Ag(II)]/dí andd[H3P03]/d( within a kinetic run, systematically adjusting the rate constants to give the best fit, in the least-squares sense, with observed A values.…”

Section: Resultsmentioning

confidence: 99%

“…The equilibrium lies far to the left. 1,6,7,[11][12][13] The silver(H)-silver(I) exchange reaction also proceeds via this disproportionation.14,16 One limiting form of the rate law for the silver(Il)-thallium(I) reaction suggests a similar mechanism in which thallium (I) reacts with silver (III) in the rate-determining step. However detailed analysis supports a more elaborate mechanism involving thallium(II) and N03 radical, but not silver (III), as intermediates.16 The purpose of the present research is to study the kinetics and mechanism of another redox reaction of silver(II) with particular attention to possible involvement of silver (III).…”

Section: Introductionmentioning

confidence: 99%

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Kinetics and mechanism of the silver(II)-phosphorous acid reaction

Viste¹,

Holm²,

Wang³

et al. 1971

Inorg. Chem.

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The oxidation of phosphorous acid by silver(I1) in perchloric acid solution takes place by two independent paths. Aside from acid dependence, the rate law is -0.5d[Ag(II)]/dt = k~[HaPOsl + ka[Ag(II)]2[Agf] -l [HaPOa]. The rate-determining step proposed for the first path involves the dissociation of H + from a P-H bond, generating a reactive intermediate with a lone pair of electrons on phosphorus. The value of kl is in reasonable agreement with the previously known rate constant for deuterium exchange with the P-H bond of phosphorous acid. For the second path the reaction of silver(II1) with phosphorous acid is suggested as the rate-determining step. However the reaction of silver(I1) with a monomeric phosphorus(1V) species, as an alternative possibility for the rate-determining step, is not completely ruled out. Introduction Silver(I1) is a particularly strong oxidizing agent in aqueous solution (Ag2+-Ag+ reduction potential E o =

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Kinetics and mechanism of the silver(II)-phosphorous acid reaction

Viste¹,

Holm²,

Wang³

et al. 1971

Inorg. Chem.

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“…News, June 12, 1967, p metal ions by a tetraphenylboron titration (9, IO). Rechnitz (11) has studied the response of the cation-sensitive electrode to alkali metal ions in nonaqueous solution, and Jacobson (12) has developed a method for the continuous assay of potassium in the presence of ammonia with the Beckman cation electrode.…”

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confidence: 99%

Use of ion selective electrodes in enzymic analysis. Cation electrodes for deaminase enzyme systems

Guilbault¹,

Smith²,

Montalvo³

1969

Anal. Chem.

117

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Diverse Ions. The effect of many diverse ions was studied using the procedure described in the experimental section for the analysis of 4 ppm of bismuth. An error of less than 2.5 was considered negligible. The results of this study are summarized in Table 111.Iron(II1) and mercury(I1) are reduced by the ascorbic acid and can be tolerated only in small amounts. Iron(I1) slowly reduces the heteropoly acid to heteropoly blue, but if the samples are measured very soon after preparation, small amounts of iron(I1) can be tolerated. Apparently the reduction by iron is considerably slower than that by ascorbic acid and has only a small effect on the rate. Fluoride interferes seriously, probably by complexing with the Mo(V1). Chloride is the only other important anion interference but no explanation for its interference can presently be offered.Advantages of the Rate Method. The reaction rate method has many advantages over conventional spectrophotometric methods using similar chemical systems. In the rate method it is not necessary to make absorbance measurements at a very carefully selected time in order to avoid or compensate for blank absorption. The presence of other materials that absorb at the measurement wavelength or that impart a turbidity to the solution will not normally interfere in the reaction rate method. These advantages coupled with the excellent precision and good sensitivity obtainable should make this a very useful method.The response, selectivity, and use of the 3 9 0 4 7 and 39137 Beckman cationic electrodes for the determination of NH 4+ activity are reported. Both electrodes were found to respond to NH4: in the concentration range 10-1 to lO-5M with a deviation of f 0.5 mV in the 10-1 to 1O-M region and =t 20 mV at 10-4 to lo-5M region. The response characteristics of the micro 3 9 0 4 7 electrode were found to be Ag+ > H+ > K+ > NH4+ > Na+ > Li+>>Mg*, Ca2+. Those of the 39137 electrode were Ag+ > K+ > H+ > NH4+ ? Na+ > Li+ > Mgz+, Ca2+. At a pH of 7 the only serious interferences in the assay of [NH 4+] are Ag+ and K+. Both electrodes were used for the assay of deaminase enzyme systems: u rea-u rea se, g luta m i ne-g I u ta m i n a se, as pa ragi neasparaginase, D-and L-amino acids-amino acid oxidases. All substrates and enzymes could be assayed with a precision and accuracy of about 2.5%. 2) are finding widespread use in analytical chemistry. Excellent reviews on ion selective electrodes and their applications have been prepared by Rechnitz (3, 4).Beckman (5) markets a cationic electrode (39137, formerly designated 78137) that has a reported selectivity H+ > Ag+ > K*, NH4+ > Na' > Li+ >> Mgz+, Ca2+. This electrode has

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“…Note on the selectivities of cation-sensitive glass electrodes. Some results have been reported on the selectivities of cation-sensitive glass electrodes in non-aqueous solvents (50,51,67,68), but no systematic investigation has been carried out. When the glass electrode can respond in a Nernstian way to the activities of univalent cations in different solvents, the solvent effect to the selectivity constants of the electrode is considered to be determined mainly by the changes of solvation energies of the cations.…”

Section: Ph-sensitive Glass Electrodesmentioning

confidence: 99%