The Effect of Choleates on the Solubilization of Water in Water/AOT/Cyclohexane (W/O)-Microemulsions

Experimental investigations on the cosurfactant effect of alkali and tetraalkylammonium choleates in water/AOT/cyclohexane (W/O)-microemulsions were carried out. The results prompted considerations on a thermodynamic and molecular level. The molecular view emphasizes the significance of hydration interactions between cosurfactant and solubilized water.     

Further interference peaks in mass analysed ion kinetic energy spectra

It is shown that interference peaks in mass analysed ion kinetic energy spectra can also occur from ions decomposing in the accelerating region of the ion source.     

Cliffordalgebren und neue isoparametrische Hyperflächen

Ohne ZusammenfassungDie gemeinsame Arbeit der Autoren wurde durch Einladungen nach Bonn (SFB40) und Berlin (TUB) sehr gefördert     

The Distortion of Electrically Conducting,Thermodynamically Stable Microphases by an Electric Field

O'Konski's considerations regarding the distortion of spherical droplets by electric fields in binary two-phase systems has been extended to three-component water/surfactant/oil systems with so-called ultra-low interfacial tensions, i.e. spherically aqueous microphases. It is shown that the deformation is almost negligible for fields up to about 5 10⁵ Vm^?1 such as those applied in electro-optical Kerr-effect measurements with microemulsions if only perturbations of the mean orientation of the surfactants in the interface are considered.     

Destabilized carbenium ions. Secondary and tertiary α-acetylbenzyl cations and α-benzoylbenzyl cations

The secondary α-acetylbenzyl and α-benzoylbenzyl cations, as well as their tertiary analogues, have been generated in a mass spectrometer by electron impact induced fragmentation of the corresponding α-bromoketones. These ions belong to the interesting family of destabilized α-acylcarbenium ions. While primary α-acylcarbenium ions appear to be unstable, the secondary and tertiaiy ions exhibit the usual behaviour of stable entities in a potential energy well. This can be attributed to a ‘push-pull’ substitution at the carbenium ion centre by an electron-releasing phenyl group and an electron-withdrawing acyl substituent. The characteristic unimolecular reaction of the metastaible secondary and tertiary α-acylbenzyl cations is the elimination of CO by a rearrangement reaction involving a 1,2-shift of a methyl group and a phenyl group, respectively. The loss of CO is accompanied by a very large kinetic energy release, which gives rise to broad and dish-topped peaks for this process in the mass-analysed ion kinetic energy spectra of the corresponding ions. This behaviour is attributed to the rigid critical configuration of a corner-protonatei cyclopropanone derivative and a bridged phenonium ion derivative, respectively, for this reaction. For the tertiary α-acetyl-α-methylbenzyl cations, it has been shown by deuterium labelling and by comparison of collisional activation spectra that these ions equilibrate prior to decomposition with their ‘protomer’ derivatives formed by proton migration from the α-methyl substituent to the carbonyl group and to the benzene ring.     

Mechanisms of mass spectrometric fragmentations: X–Interaction between remote or-groups in decalin-1,5-diols and their dimethyl ethers

The mass spectra of the five stereoisomers of decalin-1,5-diol and its dimethyl ether have been investigated. The differences in the mass spectra of stereoisomers I to III with a trans- decalin ting system are small. The differences are much larger in the mass spectra of the two isomers IV and V of the cis-decalin series and the elimination of CH₂O, formed by interaction between the two methoxy groups, from the molecular ion is only observed in the mass spectrum of Vb.     

Dielectric Properties of Apolar Micelle Solutions Containing Solubilized Water

Varying amounts of water have been solubilized in a micelle solution of sodium di-2-pentyl–sulfoscuccinate in benzene and the complex permittivity has been observed in the range 200 KHz to 10 MHz. Part of a dielectric dispersion is seen, which extends to higher frequencies with a broad distribution of relaxation times. Due to association processes, the static dielectric increment is found to vary non-linearly with hydrated micelle concentration and with the amount of solubilized water, whereas a linear variation with micelle concentration is found if no water is added. These effects are explained on the assumption that part of the solubilized water increases the dipole moment of the micelle. Additionally, at higher water concentrations, a sudden increase in the conductivity of the solution is observed, which is taken to indicate a conformational change of the solubilized micelle.