Thermodynamics in HCl in water-methylcellosolve mixtures—I. standard potentials of the silver/silver-chloride electrode

Sadek, H.; Tadros, Th.F.; El-Harakany, A. A.

doi:10.1016/0013-4686(71)85006-5

Cited by 31 publications

(16 citation statements)

References 19 publications

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“…where -In (1 + 0.002 Mm) subscripts s and w indicate the mixed solvent and water respectively, k' = RTIF, M = molar or mean molar mass of water or of the mixed solvents respectively, a, is the ion-size parameter, AoBo and Bo are the familiar Debye-Hiickel constants (14,15), values of which for this solvent system were taken from a previous paper (15), and b is the empirical constant depending upon the nature of the solvent, temperature, and also the ion-size parameter used for computing f(m). As in earlier studies (15,17), since alteration of a, values does not impart any significant change in the extrapolated values of AEO beyond experimental error of 20.5 mV, a, = 0 has been used.…”

Section: Cell [A]mentioning

confidence: 99%

“…These values were used to compute an extrapolation function (, K, ') defined (8) ,, values referred to respective solvents as the standard states were taken from the paper of Sadek et al (14). The standard states are so chosen that at infinite dilution in a given solvent the molal activity coefficients of the ions, and also the mole fraction of the solvent xsoH, are unity.…”

Section: Cell [B]mentioning

confidence: 99%

“…eqs. [13] or [14] would provide a method for determininga; in these mixed solvents. Now, it is often observed that determination of the primary thermodynamic quantity viz.…”

Section: Introductionmentioning

confidence: 99%

“…However, as Smits et al's (13) AGtO(HCl) values based on glass and Ag-AgC1 electrodes are found to differ appreciably from those of Sadek et al (14) based on Hz and Ag-AgC1 electrodes, and as similar differences are quite usual for dipolar aprotic cosolvent systems (13) we have considered it useful to determine the autoionization constant (K,) of these solvents by use of Hz and Ag-AgC1 electrodes. Thus, in this paper we are reporting AGtO values of [K+-(OH-);,,] as well as [H+(OH-),,,I in aqueous mixtures of 10,30,50, and 70 wt% ME as obtained by determining respectively the standard emf (AEO) of the double cell A and the autoionization constants (K,) of these mixed solvents by use of cell B Experimental 2-Methoxy ethanol (Merck, Pure) was purified in a manner described earlier (14,15); water used for the preparation of the mixed solvents and the electrolyte solutions was distilled thrice and made free from C 0 , and 0, first by boiling and then by flushing pure H,. For the studies of cell A the concentrations of the stock solutions of KOH (Merck, G.R.)…”

Section: Introductionmentioning

confidence: 99%

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Determination of absolute transfer free energies of hydroxyl ion from water to aqueous 2-methoxy ethanol

Bhattacharya¹,

Das²,

Kundu³

1981

Can. J. Chem.

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Absolute standard free energies of transfer AGtO of OH-from water to aqueous mixtures of 2-methoxy ethanol (ME) have been evaluated at 298.15 K by combining the apparent transfer free energies of the lyate ion that were obtained from the standard emf's of the double cell:Hg-HgO/KOH(m), solvent/K(Hg)/KOH(m) waterlHg0-Hg and that from the autoionization constants of these mixed solvents determined by use of the cell comprising H2-and Ag-AgC1 electrodes. The required AGtO values of K+ and H+ were determined earlier using the well-known tetraphenyl arsonium tetraphenyl boride (TATB) reference electrolyte method. These values and their non-Born type contributions in particular, are found to be increasingly positive in water-rich compositions, indicating that the relative stabilization of OH-and the acidity of the mixed solvents decrease with increasing cosolvent composition. These, when compared with those in aqueous mixtures of ethylene glycol and 1,2-dimethoxy ethane, are found to lie intermediate between the latter solvent systems conforming to what is expected from the structural and electronic features of the cosolvents.

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Section: Cell [A]mentioning

confidence: 99%

Section: Cell [B]mentioning

confidence: 99%

“…eqs. [13] or [14] would provide a method for determininga; in these mixed solvents. Now, it is often observed that determination of the primary thermodynamic quantity viz.…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Determination of absolute transfer free energies of hydroxyl ion from water to aqueous 2-methoxy ethanol

Bhattacharya¹,

Das²,

Kundu³

1981

Can. J. Chem.

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“…The ratio of the Unauthenticated Download Date | 5/11/18 11:00 AM relative permittivity of water t o i t s density, (~~/ p~) a t the temperature T is obtained from the expression given in Table 2 . These data enable b t o be calculated from equations (29) and (30), hence the integral Q(b) numerically from equation ( 2 7 ) , and then the association constant K, from equations (25) and (26). Further input data are a s e t of correspondingvaluesof: m, the molality (mol.Ckg solvent}-') of the 1 : l electrolyte i n the c e l l , t o the ionsofwhich the electrodes are reversible; p , the density (kg.dm-3) of the c e l l solution; and E , themeasured emf (in V) of the cell.…”

Section: According T O Bjerrum's Theorymentioning

confidence: 99%

The extrapolation of EMF data to infinite dilution in non-aqueous and mixed solvents

Marcus¹,

Mussini²

1991

Pure and Applied Chemistry

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Potentiometric Study of Hydrogen Chloride in 2‐Methoxyethanol Water Mixtures

Merken

Thun

Verbeek

1977

Bulletin des Soc Chimique

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The standard emf of the cell Pt;H2/HCl(solvent)/AgCl,Ag III is reported for the mixtures 80, 90, 95 and 98 wt-X Z-methoxyethanol and respectively 20, 10, 5 and 2 wt-9. water. The correlation of the present and previous results enables to present a structure for solutions of hydrogen chloride in mixtures of Z-methoxyethanol and water. EXPERIMENTAL PROCEDUREThe 2-methoxyethanol was obtained commercially and purified ( I ) . The stock solution of hydrochloric acid, in the Z-methoxyethanol water mixtures was standardized gravimetrically as silver chloride. The cell solutions were prepared by weight and corrected for the air buoyancy force.The silver-silver chloride electrodes and the hydrogen electrodes were prepared according the recommendations of Bates (5). Between any two silver-silver chloride electrodes, the bias potential, in aqueous 0.005 m NaC1, was less then 0.02 mV. Four pairs of electrodes were provided for each concentration. Before each run the electrodes, after being rinsed with the solvent mixture, were stirred in the solutions for two hours. In each group the bias potential between the silver-silver chloride electrodes was less then 0.03 mV and three per solution were selected. The electrodes were placed in the cell (6) which was purged with hydrogen gas

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Thermodynamics in HCl in water-methylcellosolve mixtures—I. standard potentials of the silver/silver-chloride electrode

Cited by 31 publications

References 19 publications

Determination of absolute transfer free energies of hydroxyl ion from water to aqueous 2-methoxy ethanol

Determination of absolute transfer free energies of hydroxyl ion from water to aqueous 2-methoxy ethanol

The extrapolation of EMF data to infinite dilution in non-aqueous and mixed solvents

Potentiometric Study of Hydrogen Chloride in 2‐Methoxyethanol Water Mixtures

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