The Energies and Entropies of Activation of the Reaction between Bromoacetate and Thiosulfate Ions<sup>1</sup>

Mer, Victor K. La; Kamner, Mildred E.

doi:10.1021/ja01315a099

Cited by 23 publications

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“…If we combine Equations 17 and 3, neglect nonelectrostatic effects, and assume small concentrations to negate the effects of ionic strength (discussed above), we get k = (7iA + 7b2 _ £m2N k0 2ekB T \rA rB ru ) (18) Except at low values of the dielectric constant, Equation 18 is in good agreement with experiment, as shown by the reaction of bromoacetate and thiosulfate ions (26,27) in Figure 7.…”

Section: Ch3mentioning

confidence: 64%

Molecular Thermodynamics of Chemical Reactions

Eckert¹

1967

Ind. Eng. Chem.

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method is limited by the number of available UNIFAC parameters, although experimental determination of new parameters is proceeding rapidly. As more parameters become available, a more extensive evaluation of this m e t h d should be accomplis hed . Bronsted, J. M . , "Zur Theorie der Chemischen ReaktionsgeschGndigkeit," 2. Phys. Chem., 102, 169 (1922). Eckert, C. A,, "Molecular Thermodynamics of Chemical Reactions," Znd. Eng. Chern., 59(9), 20 (1967 Recent developments in heavy fossil-energy technology have renewed interest in hydrogen-heavy hydrocarbon vapor-liquid equilibria, especially at higher temperatures. In this work we present a correlation for Henry's constants for hydrogen in typical hydrocarbons and nonpolar solvents in the temperature range 248-700°K. NOTATION HENRY'S CONSTANTFor hydrogen (2) dissolved in a solvent (l), Henry's constant H is defined by:where x is the liquid-phase mole-fraction and f is the fugacity given by:where P is the total pressure and y is the vapor-phase mole fraction. The vapor-phase fugacity coefficient 4 can he calculated from an equation of state (Prausnitz, 1969).The well-known K factor is related t o Henry's constant by:0001-1541-XI-43N9-OH44-52.00. "The .4mrrican In\titute of Cheniic.il Enginwr*,where y,T is the (unsymmetric) liquid-phase activity coefficient.Since the solubility x2 is normally small and since hydrogen's gas-phase properties are normally well approximated by those of an ideal gas, the ratio y:/& is close to unity even at moderately high pressures, provided only that the temperature of the system is well below the solvent's critical. Figure 1 shows experimental Henry's constants for hydrogen in 14 solvents in the region 248-700°K. Note the scale at the right which refers to carbon disulfide and benzene. For hydrogen in this temperature range, Henry's constants uniformly fall with rising temperature. Over the temperature range indicated, Henry's constants vary by one order of magnitude, depending on temperature and solvent. SCALED-PARTICLE THEORYTo correlate H , we use the scaled-particle theory of Reiss et al. (1959Reiss et al. ( , 1960 as discussed by Pierrotti (1963Pierrotti ( , 1976. The partial Gibhs energy of dissolving a solute in a liquid consists of two parts: first, the work needed to create a cavity in the solvent to place a solute molecule and second, the energy of interaction between the dissolved solute and the surrounding solvent. (The entropy of interaction is neglected.)

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Section: Ch3mentioning

confidence: 64%

Molecular Thermodynamics of Chemical Reactions

Eckert¹

1967

Ind. Eng. Chem.

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“…(5.50) was replaced by (<51ç£)/(5Ã) ñ . The contribution to the energy of activation E n made by the ionic atmosphere has been derived [21] E n = a / 1 /^x (5.55) But d(\/T) Fn = ^Ë AE^ ( 5 > 5 6 ) 2D therefore 3ÍAE Á AE Â å 2 Ä£ ç = -AD Ã dlnD 31nFl i i+ j^f + 8^f\ (5 Both Eqs.…”

Section: Electrostatics and Energy Of Activation For Ion-ion Reactmentioning

confidence: 99%

Solvent Influence on Rates and Mechanisms

Amis

Hinton

1973

Solvent Effects on Chemical Phenomena

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“…The only systematic work in this direction seems to date back to 1935 (101). In the reaction between bromoacetate and thiosulfate, at an ionic strength of THE TEMPERATURE-DEPENDENCE OF E. 28 1 0.02 M , dEa/dT was found to be approximately -8.6 cal mole-l deg-1.…”

Section: [T -5 (3l -+)]mentioning

confidence: 99%

The Temperature‐Dependence of E _a

Perlmutter-Hayman

1976

Progress in Inorganic Chemistry

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The Energies and Entropies of Activation of the Reaction between Bromoacetate and Thiosulfate Ions¹

Cited by 23 publications

References 0 publications

Molecular Thermodynamics of Chemical Reactions

Molecular Thermodynamics of Chemical Reactions

Solvent Influence on Rates and Mechanisms

The Temperature‐Dependence of E _a

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The Energies and Entropies of Activation of the Reaction between Bromoacetate and Thiosulfate Ions1

Cited by 23 publications

References 0 publications

Molecular Thermodynamics of Chemical Reactions

Molecular Thermodynamics of Chemical Reactions

Solvent Influence on Rates and Mechanisms

The Temperature‐Dependence of E a

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The Energies and Entropies of Activation of the Reaction between Bromoacetate and Thiosulfate Ions¹

The Temperature‐Dependence of E _a