Spectrophotometric study of the dissociation of <i>p</i>-nitroanilinium ion in a binary aqueous-dipolar aprotic solvent system (H<sub>2</sub>O + acetonitrile) at 25 °C: effect of the solvent

De, A. L.; De, T. K.

doi:10.1139/v84-304

Cited by 3 publications

(2 citation statements)

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“…AG:(NO,PhNH:) is more negative than AG,"(Bu,N+), as expected for a larger hydrocarbon group in the 4-nitroanilinium cation. De et al293 30 have also derived values for AG,"(NO,PhNH:Cl-) in water-ethanonitrile and in water-ethane-1,2-diol mixtures in the same manner as described above for water-urea mixtures. The values for AG,"(NO,PhNHi) calculated using the appropriate values for AG,"(Cl-)l, 39 * are compared in fig.…”

Section: Comparison Of Ag"(i) In Water-urea Mixtures With Ag"(i) In M...mentioning

confidence: 99%

Ionic solvation in water–cosolvent mixtures. Part 11.—Free energies of transfer of single ions from water into water–urea mixtures

Groves¹,

Wells²

1985

J. Chem. Soc., Faraday Trans. 1

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The use of the spectrophotometric solvent sorting method for determining the free energy of transfer of the proton, AG,"(H+), from water into waterxosolvent mixtures has been extended to mixtures formed by adding structure breaking urea to water. Values for AG;(XZ-) are calculated from values for AG,"(H,X) using the experimentally determined values for AG,"(H+), and the derived values for AG:(XZ-) with x = 1.0 are used to calculate values for AG:(M+). Values for AG,"(XZ-) are positive and values for AG:(M+) are negative at mole fractions of urea x < 0.15, as found for mixtures of water with structure-forming cosolvents (excluding BPh,).However, in water-urea mixtures, the influence of structure-forming hydrocarbon ligands in controlling values for AG,"(i) is much reduced, compared with their influence when structureforming cosolvents are used: for example, AG:(BPh;) is positive with added urea and negative with other cosolvents. Moreover, values for AG,"(i) for i = Ph,As+ and BPh;, which are closely related in size and peripheral hydrocarbon structure, differ considerably in water-urea mixtures, showing the importance of the sign of the charge.

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Section: Comparison Of Ag"(i) In Water-urea Mixtures With Ag"(i) In M...mentioning

confidence: 99%

Ionic solvation in water–cosolvent mixtures. Part 11.—Free energies of transfer of single ions from water into water–urea mixtures

Groves¹,

Wells²

1985

J. Chem. Soc., Faraday Trans. 1

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“…To understand the solvent effect on the dissociation equilibria, dissociation constants of some monopositively charged acids, nitroanilinium ions were determined earlier (1,2) in some mixed solvents. This paper reports the dissociation constant of uncharged acid, 2,4,6-trinitrophenol, in aqueous mixtures of methanol and ethanol.…”

Section: Introductionmentioning

confidence: 99%

Studies of the dissociation of 2,4,6-trinitrophenol in aqueous mixtures of methanol and ethanol at 25 °C

De¹,

Atta²

1985

Can. J. Chem.

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have been determined at 25'C in aqueous mixtures containing 30,50,70, and 90% by weight of methanol and 30, 50,70,90, and 95% by weight of ethanol by spectrophotometric method. Solvent effect on the dissociation of the acid: 6(A Go) = 2 . 3 0 3 R T [~( X )~ -P(,K)~] shows an unusual behaviour, the value decreases and passes through a minimum and ultimately becomes positive as the proportion of organic component in the solvent is progressively increased. The results have been compared with those of other uncharged acids like acetic acid, benzoic acid available from literature. The difference of behaviour (minimum characteristic in F ( A G 9 curve) has been attributed to very strong dispersion interaction of trinitrophenolate anion with the organic component of the solvent. The overall behaviour of this acid indicates that solvent effect is an involved process being guided by electrostatic and dispersion interactions besides relative solvent basicities.A. L. DE et A. K. ATTA. Can. J. Chem. 63, 3 129 (1985). Faisent appel a des mkthodes spectroscopiques et optrant a 25"C, on a CtudiC les constantes thermodynamiques de dissociation (,K),, du trinitro-2,4,6 phenol dans des solutions aqueuses contenant 30, 50, 70 et 90% en poids de methanol et 30, 50, 70, 90 et 95% en poids d'tthanol. L'effet du solvant sur la dissociation de I'acide 6 ( A G 7 = 2 , 3 0 3 R T [~( . X )~ -P(,K)~] montre un comportement inhabituel, la valeur diminue, passe par un minimum et finalement devient positive lorsqu'on augmente progressivement la proportion de compose organique du solvant. On a compare les resultats avec ceux d'autres acides non charges tels l'acide acetique, I'acide benzoique, repertories dans la litterature. On a attribuk la difference de comportement (minimum caracteristique dans la courbe de 6(A Go) a une interaction de dispersion trks forte de I'anion trinitrophCnolate avec la partie organique du solvant. Le comportement global de cet acide indique que la participation de I'effet du solvant est gouvernie par des interactions de dispersion et Clectrostatiques en plus de la basicit6 relative du solvant.[Traduit par le journal] Introduction It is well known that the dissociation of acids is a complex phenomenon dictated by various types of interactions of the species involved in the ionization equilibrium. To understand the solvent effect on the dissociation equilibria, dissociation constants of some monopositively charged acids, nitroanilinium ions were determined earlier (1, 2) in some mixed solvents. This paper reports the dissociation constant of uncharged acid, 2,4,6-trinitrophenol, in aqueous mixtures of methanol and ethanol.

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Partition of solutes from the gas phase and from water to wet and dry di-n-butyl ether: a linear free energy relationship analysis

Abraham

Zissimos

Acree

2001

Phys. Chem. Chem. Phys.

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Spectrophotometric study of the dissociation of p-nitroanilinium ion in a binary aqueous-dipolar aprotic solvent system (H₂O + acetonitrile) at 25 °C: effect of the solvent

Cited by 3 publications

References 16 publications

Ionic solvation in water–cosolvent mixtures. Part 11.—Free energies of transfer of single ions from water into water–urea mixtures

Ionic solvation in water–cosolvent mixtures. Part 11.—Free energies of transfer of single ions from water into water–urea mixtures

Studies of the dissociation of 2,4,6-trinitrophenol in aqueous mixtures of methanol and ethanol at 25 °C

Partition of solutes from the gas phase and from water to wet and dry di-n-butyl ether: a linear free energy relationship analysis

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Spectrophotometric study of the dissociation of p-nitroanilinium ion in a binary aqueous-dipolar aprotic solvent system (H2O + acetonitrile) at 25 °C: effect of the solvent

Cited by 3 publications

References 16 publications

Ionic solvation in water–cosolvent mixtures. Part 11.—Free energies of transfer of single ions from water into water–urea mixtures

Ionic solvation in water–cosolvent mixtures. Part 11.—Free energies of transfer of single ions from water into water–urea mixtures

Studies of the dissociation of 2,4,6-trinitrophenol in aqueous mixtures of methanol and ethanol at 25 °C

Partition of solutes from the gas phase and from water to wet and dry di-n-butyl ether: a linear free energy relationship analysis

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Spectrophotometric study of the dissociation of p-nitroanilinium ion in a binary aqueous-dipolar aprotic solvent system (H₂O + acetonitrile) at 25 °C: effect of the solvent