Theoretical calculations of thermodynamic functions of solvation of ions

Millen, W. A.; Watts, D. W.

doi:10.1021/ja01000a011

Cited by 37 publications

(12 citation statements)

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“…The dipole moment of a molecule in the liquid differs from that measured in the vapor phase (Millen and Watts, 1967) due to the induction of an additional moment by the dipole field of its neighbors. Thus, in the interlayer environment of the cation and the amide, the effective dipole moment of the amide may be greater than that determined in the vapor phase (Table 1).…”

Section: Resultsmentioning

confidence: 89%

“…Millen and Watts (1967) have discussed the relative permittivity of the solvation layers of an ion as a function of distance from the ion and suggest that the region of dielectric saturation is less for a monovalent ion than a divalent ion and as indicated above, Norrish (1954) has attributed differences in the swelling of montmorillonite in water to this cause. An alternative statement is that the relative permittivity in the interlayer spaces for Na-montmorillonite approaches more closely that of the bulk liquid water than Ca-or Mg-montmorillonite.…”

Section: Resultsmentioning

confidence: 98%

“…Multivalent cations cause greater dielectric saturation of the medium than monovalent cations (Millen and Watts, 1967); as a result of the lower relative permittivity the attractive potential is increased which is the cause of the reduced swelling (Norrish, 1954;Quirk, 1968). This therefore prevents extensive crystalline swelling despite the fact that the value of the swelling index for Mg-montmorillonite (8.9 • 103) is greater than Na-montmorillonite (7.6 • 103) when the value of E is taken as 78.…”

Section: Resultsmentioning

confidence: 99%

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Swelling of Montmorillonite in Polar Organic Liquids

Olejnik

1974

Clays and clay miner.

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Abstract--The crystalline and osmotic swelling of N~, Cs-, Mg-and Ca-montmorillonite has been measured in dimethyl sulphoxide and in formamide, N-methyl formamide, dimethyl formamide, N-methyl acetamide and dimethyl acetamide. These liquids have similar dipole moments but their relative permittivities vary appreciably from values less than water to values greater than water.Na montmorillonite exhibits osmotic swelling (diffuse double layer development -d(001) ~ 19 A) in formamide and N-methyl formamide and Cs gives osmotic swelling behavior in formamide. Cs-montmorillonite in the crystalline swelling region give spacings greater than those found for water with all liquids. Mg-and Ca-montmorillonite did not give spacings greater than 19 A in any of the liquids studied.The swelling behavior of montmorillonite is affected by relative permittivity but for liquids with a similar relative permittivity methyl substitution in the molecule may prevent the development of diffuse double layers on the particle surfaces. INTRODUCTIONThe swelling of montmorillonites in water has received considerable attention (e.g. Norrish and Quirk, 1954;Norrish, 1954;Warkentin and Schofield, 1962; Norfish and Raussel-Colom, 1963; Posner and Quirk, 1964a,b;Quirk, 1968)with the result that the swelling behavior of montmorillonites in relation to factors such as exchangeable cation, hydrostatic pressure and electrolyte concentration, is relatively well described. There still exists, however, some uncertainty in the detailed interpretation of the swelling behavior (Quirk, 1968) particularly in relation to the exchangeable cation and its polarizing power in affecting the properties of water in the neighborhood of the cation and the surface.The literature reveals that montmorillonites show limited expansion [d(001) < 19 A,] with a wide variety of polar organic compounds; swelling in relation to the properties of organic compounds has previously been examined by Barshad (1952) and Greene-Kelly (1955a,b) and, although some very polar organic liquids have been used, for instance nitrobenzene (Yariv, Russell and Farmer, 1966), basal spacings greater than 15.2/k have not been reported except for glycerol and ethylene glycol. Most of the earlier work deals with the bonding and mechanism of adsorption of organic compounds in montmorillonite or simply the spacing of the interlayer complexes.

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Section: Resultsmentioning

confidence: 89%

Section: Resultsmentioning

confidence: 98%

Section: Resultsmentioning

confidence: 99%

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Swelling of Montmorillonite in Polar Organic Liquids

Olejnik

1974

Clays and clay miner.

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“…Bernal and Fowler (1933) treated the interaction energy of ions and the molecules of the salvation sheath as ion-dipole interactions. They also considered the loss of energy involved in rearranging the solvent molecules around the ion; a consideration similar to that of Millen and Watts (1967), who calculated the energy required to create a hole in the solvent matrix large enough to accommodate the ion.…”

Section: +4 T----mentioning

confidence: 99%