Architecture of the hydrophobic and hydrophilic layers as found from crystal structure analysis of N-benzyl-N,N-dimethylalkylammonium bromides.

The molecular and crystal structures of N-benzyl-N,N-dimethylalkylammonium bromides monohydrates with chain length n=8-10 have been determined. The crystals are isostructural with the N-benzyl-N,N-dimethyldodecylammonium bromide monohydrate. The structures consist of alternated hydrophobic and hydrophilic layers perpendicular to [001]. The attraction between N+ of the cation head-groups and Br- anions is achieved through weak C_H...Br interactions. The water molecules incorporated into ionic layers are donors for two O_H...Br hydrogen bonds and serve as the acceptors in two weak interactions of C_H...O type. The methylene chains, with the slightly curved general shape, have the extended all-trans conformation. The mutual packing of the chains in the hydrophobic layers is governed by weak C_H...pi interactions.

10-Methylacridinium ion as a fluorimetric probe measuring the activity of halide anions in aqueous solutions of cationic surfactants.

The quenching of fluorescence of 10-methylacridinium ion by inorganic anions in aerated aqueous solutions was studied at room temperature. In the case of cationic surfactants, with chloride and bromide anions as counterions, characteristic breaks on the Stern-Volmer plots could be observed at concentrations corresponding to the critical micelle concentration of the surfactants. It is shown that the ratio of the slopes of the two linear fragments of the plots, in the micellar and premicellar concentration ranges, gives an estimate of the value of the ionization degree, alpha, of the micelles. This approach is applicable also in aqueous-alcohol systems.

Benzyltripropylammonium bromide: a structure in polar space group P4(2)bc.

Crystals of the title compound, C(16)H(28)N(+).Br(-), were grown from solution in a mixture of acetone and propan-2-ol by slow evaporation. The structure was solved in the polar space group P4(2)bc with five moieties in the asymmetric unit, namely two benzyltripropylammonium cations in general positions, and two Br(-) anions in special Wyckoff positions (4a2. and 4b2.) and one in a general position. The structure consists of two kinds of molecular columns parallel to c, built of cations connected through C-H.pi hydrogen bonds and stabilized by weak C-H.Br interactions.

Adsorption isotherms of homologous alkyldimethylbenzylammonium bromides on sodium montmorillonite.

The adsorption of homologous alkyldimethylbenzylammonium bromides, [C(6)H(5)CH(2)N(CH(3))(2)R]Br, on sodium montmorillonite from aqueous NaCl solutions at room temperature has been studied. R stands for the methyl-, butyl-, hexyl-, octyl-, decyl-, and dodecyl-group, and the corresponding ammonium cations will be denoted as C1+, C4+, C6+, C8+, C10+, and C12+, respectively. C1+, the reference cation, attains the plateau region of adsorption at a level close to the cation exchange capacity (CEC) of the clay. The chain-length dependence on adsorptivity of the homologous cations exhibits an unexpected peculiarity. In the case of short-chain homologues of C1+ their adsorption onto sodium montmorillonite decreases in the order C1+>C4+>C6+. This behavior is due, presumably, to the growing steric hindrances at the surface of clay, which occur because of the limited area available for the bulky organic cations at the exchange sites. These limitations appear to be out-balanced in the case of higher homologues for which the increasingly growing hydrophobic effects lead to the expected sequence of adsorptivity of the cations, i.e., C1+

Thermodynamics of micellization of alkyldimethylbenzylammonium chlorides in aqueous solutions.

Specific conductivities of alkyldimethylbenzylammonium chlorides (alkyl=decyl-, dodecyl-, tetradecyl-, and hexadecyl-) in aqueous solutions were measured as a function of molality and temperature. Critical micelle molalities (cmc) and degrees of ionization of the micelles, beta, were estimated from the dependence of the specific conductivity on molality. It was found that temperature dependence of cmc is U-shaped with a minimum shifting toward higher temperatures with a decrease in the chain length of the alkyl group. The temperature dependence of ln xcmc (where xcmc is the cmc in mole fraction units) was fitted to the equation of Muller, which we modified by taking into account the temperature dependencies both of beta and of change in heat capacity upon micellization. From the fitting parameters, Gibbs free energies, enthalpies, and entropies of micellization as a function of temperature were estimated.