The Preparation of the Hydrogen Electrode and the Removal of a Common Source of Trouble in connection with its Use

Popoff, Stephen; Kunz, Allison; Snow, Rachel

doi:10.1021/j150289a009

Cited by 13 publications

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“…The hydrogen electrodes were prepared by a modification of the method of Popoff, Kunz, and Snow [16]. The platinum foils were plated lightly with gold and then electrolyzed for 90 seconds in a 3-percent solution of chloroplatinic acid.…”

Section: Preparation Of the Buffer Solutions And Electrodesmentioning

confidence: 99%

The second dissociation constant of p-phenolsulfonic acid and pH values of phenolsulfonate-chloride buffers from 0 degrees to 60 degrees C

Bates¹,

Siegel²,

Acree³

1943

J. RES. NATL. BUR. STAN.

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The thermodynamic dissociation constant of the phenol group of p-phenolsulfonic acid was calculated from electromotive-force measurements of hydrogensilver-chloride cells without liquid junction. Thirty-nine buffer mixtures of potassium p-phenolsulfonate, sodium hydroxide, and sodium chloride were studied in five series of experiment s from 0° to 60° C at intervals of 5 degrees. In three series, t he molal ratio of phenolsulfonate ion to phenolate-sulfonate ion was unity, and in two series the buffer ratio was 2 :3. For two series of experiments, one at each buffer ratio, the molality of sodium chloride was m aintained constant near 0.05 for all dilutions of t he buffer. In the other experiments, the molality of each component of t he solut ion varied bet ween 0.0037 and 0.1.The values of pK2' the negative of the common logarithm of the second dissociat ion constant, between 0° and 60° C are given by the equation012139T, where T is in degrees Kelvin.Equations were formulated to give the changes of free energy, heat content, entropy, and heat capacity that accompany t he dissociation, at infinite dilution, of a mole of phenolsulfonate ion at any temperature between 0° and 60° C. For the dissociation of the phenol group at 25° C, ~F o is 12,351 cal, ~Ho is 4,036 cal, ~So is -27.9 cal deg-1, and ~c o p is -33 cal deg-1•The pH value of each buffer-chloride mixture was calculated from the experimental data and the activity coefficients that were found to characterize each series of solutions. The pH values of other phenolsulfonate buffers which have m olal ratios, mdm2, of phenolsulfonate ion to bivalent phenolate-sulfonate ion between 2/3 and 1 can be computed for temperatures between 0° and 60° C with an accuracy of ± 0.002 unit from their compositions and from the dissociation constants and ionic parameters given in this paper. The equation used is pH =pK2 -log (mt/m2) -3A.JJ;f(1 +8B-V JL), where JL is the ionic strength . Buffer solutions of this type are suitable pH standards in the range 8.6 to 9.0. CONTENTS

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Section: Preparation Of the Buffer Solutions And Electrodesmentioning

confidence: 99%

The second dissociation constant of p-phenolsulfonic acid and pH values of phenolsulfonate-chloride buffers from 0 degrees to 60 degrees C

Bates¹,

Siegel²,

Acree³

1943

J. RES. NATL. BUR. STAN.

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“…Although it is well known that palladium adsorbs more hydrogen than platinum of iridium, it is not the amount of hydrogen that is adsorbed but the catalytic activity that determines the effectiveness of a hydrogen electrode. Popoff, Kunz, and Snow [29) found that electrodes given a preliminary plating of gold, as rpcommended by Lewis, Brighton, and Sebastian [30) bellause gold is impervious to hydrogen and therefore should come to equilibrium more quickly, showed no differences from electrodes not plated with gold. In order to determine whether the same characteristics prevail at other temperatures, similar measurements were made at 0°, 45°, and 60° C, using a new pair 'Of hydrogen and silver-silver-chloride electrodes and a pair aged for 1 week.…”

Section: >-mentioning

confidence: 93%

A comparison of platinum and palladium hydrogen-electrodes in aqueous solutions of acid potassium phthalate

Hamer¹,

Acree²

1944

J. RES. NATL. BUR. STAN.

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A study was made of the reproducibility of hyd rogen electrodes of various types and of silver-sHver-chloride electrodes of the thermal-electrolytic type in aqueous solutions of phthalates, in order to learn whether phthalates are reduced to hexahydrophthalic acid and the electromotive force thereby changed. If so, glass electrodes would have to be used to determine the pH valu es of solut ions of phthalates. This type of study is necessary for all reducible materials. E lectromotive-force measurements of the electrode combinations were made for various periods of t ime. The potentials of hydrogen electrodes prepared with platinum sponge under a variety of conditions constantly increased with time !:nd frequently were erratic, whereas those made with palladium sponge under different condit ions remained remarkably constant for periods of 35 hours. Even after 75 hours, the potentials increased only 0.3 mv-which corresponds to an increase of only 0.005 in pH. Palladium or platinum electrodes having the same type of coating but of different ages agreed in potential after 2 hours in phthalate solutions. The ra te and the magnitude of the increase in potential for the platinum electrodes after approximately 2 hours depend mainly upon the thickness of the metallic sponge. The characteristics of the palladium electrodes were practically independent of the thickness of the metallic sponge ; of the current density used in the electrolysis; of the concentration, composition, acidity, and conductance of the plating solution ; and of the concentration, composition, pH, and buffer capacity of the phthalate solutions in which the electrodes were used. The difference in the behavior of platinum and palladium hydrogen-elect rodes may be caused by their different catalytic activity.

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Studien über Knallgas‐Ketten

Tobler¹

1933

Zeitschrift für Elektrochemie und angewandte physikalische Chem

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The Preparation of the Hydrogen Electrode and the Removal of a Common Source of Trouble in connection with its Use

Cited by 13 publications

References 0 publications

The second dissociation constant of p-phenolsulfonic acid and pH values of phenolsulfonate-chloride buffers from 0 degrees to 60 degrees C

The second dissociation constant of p-phenolsulfonic acid and pH values of phenolsulfonate-chloride buffers from 0 degrees to 60 degrees C

A comparison of platinum and palladium hydrogen-electrodes in aqueous solutions of acid potassium phthalate

Studien über Knallgas‐Ketten

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