Liquid mixtures involving complex formation : Extensions of the ideal associated solution theory

Fenby, DV; Chand, Apramita; Inglese, A.; Grolier, J.-P.E.; Kehiaian, H.V.

doi:10.1071/ch9771401

Cited by 19 publications

(4 citation statements)

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“…The BSSE-corrected bond strength is 3.4-3.8 kcal mol -1 , the same as that predicted for the ACN-HOH complex. This runs contrary to chemical intuition, in that CHCl 3 is either known as a weak hydrogen bond donor or just simply taken to be a noncomplexing solvent; 10,79 its complexing ability is similar 80 to that of CCl 4 . Further, the predicted solvent shift for the hydrogen-bonded complex is ca.…”

Section: Rationalizing the Solvent Shift On The Basis Of The Solvent ...mentioning

confidence: 92%

The Solvation of Acetonitrile

1999

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Acetonitrile is an extremely important solvent and cosolvent. Despite this, we have no general picture of the nature of mixed liquids containing acetonitrile applicable across-solvent families. We consider the properties of acetonitrile dissolved in 33 solvents, focusing on interpretation of the environment-sensitive solvent shift, Δν, of its CN stretch frequency, ν2. The two major models (dispersive and specific solvation) which have been proposed to interpret Δν are based on diverse experiments with incompatible conclusions. We ascertain the robust features of these models and combine them into a new one in which solvent−solvent and solvent−solute forces compete to determine the structure of the solution and hence Δν. First, Δν is analyzed in terms of solvent repulsive and dielectric effects combined with specific solvation effects. To interpret this specific solvation, 95 MP2 or B3LYP calculations are performed to evaluate structures and CN frequency shifts for CH3CN complexed with one molecule of either water, methanol, ethanol, 2-propanol, tert-butyl alcohol, phenol, benzyl alcohol, acetic acid, trifluoroacetic acid, 2,2,2-trifluoroethanol, 1,1,1,3,3,3-hexafluoro-2-propanol, acetonitrile, chloroform, carbon tetrachloride, tetrahydrofuran, formamide, pyridine, or Cl-, as well as 45 parallel calculations for the solvent monomers or dimers. The results are then convolved using known structural properties of the various solutions and/or related neat liquids, leading to an interpretation of the observed solvent shifts. Also, we measure Δν for acetonitrile in aqueous solution using Fourier transform Raman spectroscopy and show that the results are consistent with, but require modification of, microheterogeneity theories for the structure of acetonitrile−water solutions. Although such theories are still in their infancy, we suggest that microheterogeneity could also account for most known properties of acetonitrile−alcohol solutions and, in fact, be a quite general phenomenon.

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Section: Rationalizing the Solvent Shift On The Basis Of The Solvent ...mentioning

confidence: 92%

The Solvation of Acetonitrile

1999

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“…1. attributed entirely to the chemical reactions. 11 We also compare our results to those given by this theory for selected systems. ).…”

Section: Introductionmentioning

confidence: 82%

“…(9)È(11), N is the number of data points of each system.DISQUAC represents fairly well the thermodynamic properties of larger deviations are observed for systems containing and cyclic diethers. For example, the theoretical HE CHCl 3 curves of the or ]1,4-dioxane mix-CHCl 3 ] 1,3-dioxolane, tures are more symmetrical than the experimental ones (Fig.…”

mentioning

confidence: 99%

Thermodynamics of mixtures with strongly negative deviations from Raoult's law Part 2. Application of the DISQUAC model to mixtures of CHCl3 or CH2Cl2 with oxaalkanes. Comparison with Dortmund UNIFAC results

González¹,

Fuenté²,

Cobos³

1999

Phys. Chem. Chem. Phys.

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“…Hepler et al 274 conclude that the associated-ideal model is satisfactory in accounting for trends in Gibbs functions and in first derivatives of G but less satisfactory in the case of second and higher derivatives, e.g., in accounting for trends in C,-properties (cf., ref. 275). Rather more success is for a dispersive and quasi-chemical treatment based on pseudo-lattice models (DISQUAC).…”

Section: Weak Electrolytesmentioning

confidence: 99%

Chapter 4. Isobaric heat capacities

Blandamer¹,

Burgess²,

Scott³

1985

Annu. Rep. Prog. Chem., Sect. C

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Isobaric Heat Capacities and the First Law of ThermodynamicsThis report has a thermodynamic theme in which we comment on the isobaric heat capacities of liquids and solutions in terms of their total isobaric heat capacities and the partial molar isobaric heat capacities of chemical substances making up these systems. Unless otherwise stated, all thermodynamic variables in this Report describe closed systems at constant temperature and pressure.When a single-phase (i.e., homogeneous) system receives heat Q from the surroundings, the ratio of Q to the rise in temperature is the heat capacity C. A small rise in temperature for a given Q means a system can store a large amount of thermal energy. The ability of systems to provide such a store has considerable technological, environmental, and physiological importance. If heat Q is absorbed by a system at constant pressure, the change in enthalpy AH equals Q. The isobaric heat capacity of a system Cp is an extensive variable defined' in Table 1.The dependent variable H is defined by the independent variables T, p, and 5 where d< is the extent of change.2 Hence the isobaric heat capacity is expressed as the sum of two contributions (Table 1). We identify in Table 1 Hepler's Equation, marking Loren Hepler's many contributions to this subject. In particular Hepler has shown3-' how the product is calculated for several systems of chemical interest.

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Liquid mixtures involving complex formation : Extensions of the ideal associated solution theory

Cited by 19 publications

References 0 publications

The Solvation of Acetonitrile

The Solvation of Acetonitrile

Thermodynamics of mixtures with strongly negative deviations from Raoult's law Part 2. Application of the DISQUAC model to mixtures of CHCl3 or CH2Cl2 with oxaalkanes. Comparison with Dortmund UNIFAC results

Chapter 4. Isobaric heat capacities

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