Silver bromide water potential

The standard potential of the silver-silver bromide electrode has been determined from emf measurements of cells with hydrogen electrodes and silver-silver bromide electrodes in solutions of hydrogen bromide in mixtures of water and N-methylacetamide (NMA). The mole fractions of NMA in the mixed solvents were 0.06, 0.15, 0.25, and 0.50, and the dielectric constants varied from 87 to 110 at 25°C. The molality of HBr covered the range 0.01-0.1 mol kg 1. Data for the mixed solvents were obtained at nine temperatures from 5° to 45°C. The results were used to derive the standard emf of the cell as well as the mean ionic activity coefficients and standard thermodynamic constants for HBr. The information obtained sheds some light on the nature of ion-ion and ion-solvent interactions in this system of high dielectric constant. 

No comparison exists for the standard potentials in terf-butanol-water mixtures or in anhydrous tert-butanol. However, the trends in the data obtained here in terf-butanol are similar to the trends observed in this work in ethanol-water and in anhydrous ethanol. See Figures 1 and 2 in which the standard potentials E° for the silver-silver bromide elec-... 

All cell potentials reached equilibrium in 1 or 2 hr, except when the solvent was anhydrous terf-butanol, in which the electrodes reached equilibrium only in dilute soltuions of HBr and even then only in a sluggish manner. This sluggish behavior has been reported (27) for the silver-silver bromide electrode in anhydrous ethanol when the acid was concentrated. In the dilute hydrobromic acid solutions used here, this phenomena was not observed in anhydrous ethanol. It is estimated that the standard electrode potential of the silver-silver bromide electrode in anhydrous terf-butanol is accurate to only d=l mV. However, these data are reported to the same degree of precision found in the other tert-buta-nol-water solvents in order to facilitate comparisons of the emf s in the various dilutions of tert-butanol used. 

K. H. Khoo, J. Chem. and Eng. Data, 17, 82 (1972). Redetermination of standard potential of silver-silver bromide electrode in methanol-water mixtures at 25 C. 

D. Bax, C. L. de Ligny, M. Alfenear, and N. J. Mohr, Rec. Trav. Chim., 91, 604 (1972). The standard potentials of the silver-silver bromide and of the silver-silver iodide electrode in some organic solvents and their mixtures with water. 

Iodide. A 0.01 M solution of potassium iodide, prepared from the dry salt with boiled-out water, is suitable for practice in this determination. The experimental details are similar to those given for bromide, except that the indicator electrode consists of a silver rod immersed in the solution. The titration cell may be charged with 10.00 mL of the iodide solution, 30 mL of water, and 10 mL of the stock solution of perchloric acid + potassium nitrate. In the neighbourhood of the equivalence point it is necessary to allow at least 30-60 seconds to elapse before steady potentials are established. 

The platinum anode must be isolated by a diaphragm to eliminate potential interference from the hydrogen ions produced by anodic oxidation of water. As a convenient alternative, a silver wire can be substituted for the platinum anode, provided that chloride or bromide ions are added to the analyte solution. The anode reaction then becomes... 

Some typical important industrial applications of coulometry include the continuous monitoring of mercaptan concentration in the materials used in rubber manufacture. The sample continuously reacts with bromine, which is reduced to bromide. A third electrode measures the potential of B12 vs. Br and, based on the measurement, automatically regulates the coulometric generation of the bromine. Coulometry is used in commercial instruments for the continuous analysis and process control of the production of chlorinated hydrocarbons. The chlorinated hydrocarbons are passed through a hot furnace, which converts the organic chloride to HCl. The latter is dissolved in water and the Cl titrated with Ag" ". The Ag" " is generated by coulometry from a sUver electrode, Ag°. It is necessary for the sample flow rate to be constant at all times. Integration of the coulometric current needed to oxidize the silver to silver ion results in a measurement of the Cl concentration. 

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