Derivative analysis of Raman spectra of liquid water in the OH (D) stretching region

Second derivative analysis of Raman spectra of H₂O, D₂O and HOD in liquid phase at room temperature for parallel and perpendicular polarized modes in the OH and OD stretching regions is reported. Five components obtained at approximately 3215, 3375, 3455, 3535 and 3640 cm⁻¹ for the second derivative plots of Raman spectra of liquid water are explained as due to the presence of three types of associated water species with (i) both OH bonds involved in moderately strong hydrogen bonds (SS), (ii) both OH bonds involved in weak hydrogen bonds (WW), and (iii) one OH bond involved in strong and one in weak hydrogen bonds (SW) respectively. The derivative plots obtained for Raman spectra of D₂O and HOD also contain features expected to be present on the basis of this model.     

Thermodynamics of micellization of tetradecyltrimethylammonium bromide in ethylene glycol–water binary mixtures

The aggregation behaviour of tetradecyltrimethylammonium bromide in ethylene glycol–water mixtures across a range of temperatures has been investigated by electrical conductivity measurements. The critical micelle concentration (cmc) and the degree of counterion dissociation of micelles were obtained at each temperature from plots of differential conductivity, (κ/c) _{T , P} , versus the square root of the total concentration of the surfactant. This procedure not only enables us to determine the cmc values more precisely than the conventional method, based on plots of conductivity against total concentration of surfactant, but also allows straightforward determination of the limiting molar conductance and the molar conductance of micellar species. The equilibrium model of micelle formation was applied to obtain the thermodynamics parameters of micellization. Only small differences have been observed in the standard molar Gibbs free energies of micellization over the temperature range investigated. The enthalpy of micellization was found to be negative in all cases, and it showed a strong dependence on temperature in the ethylene glycol poor solvent system. An enthalpy–entropy compensation effect was observed for all the systems, but whereas the micellization of the surfactant in the solvent system with 20 wt% ethylene glycol seems to occur under the same structural conditions as in pure water, in ethylene glycol rich mixtures the results suggest that the lower aggregation of the surfactant is due to the minor cohesive energy of the solvent system in relation to water. Received: 13 December 1998 Accepted in revised form: 25 February 1999     

Volumetric studies on binary mixtures of surfactants N,N′-bis(dimethyldodecyl)-1,2-ethanediammonium dibromide and 1-dodecyl-3-methylimidazolium bromide in aqueous solutions

The micellization of the binary mixed surfactants comprising of the Gemini surfactant N,N′-bis(dimethyldodecyl)-1,2-ethanediammonium dibromide and 1-dodecyl-3-methylimidazolium bromide has been studied by measurements of density. The apparent molar volumes were calculated for various surfactant concentrations and used to determine the critical micelle concentrations of the mixed surfactants at various compositions. An attractive effect was suggested by negative deviations of the experimental CMC values from the ideal ones. The Margules equation was applied to evaluate the micelle compositions, the activity coefficients of both components, and the excess molar Gibbs free energies of the mixed micelles. The stability of mixed micelles was shown to be enhanced as compared to those formed by single surfactants from the negative values of the excess Gibbs free energy. The comparison of the results obtained from the volumetric and ITC measurements indicated a reasonable good accordance with each other and confirmed the reliability of both methods for investigation on the properties of the mixed micelles.     

The NH stretching region of some imides and thioimides

The multiplet structure of νNH and νND bands of solid phtalimide, monothiophtalimide, dithiophtalimide, isatin, saccharin and of their deuterated analogues has been explained as being a result of Fermi resonance of the fundamentals of νNH and νND with combinations and/or overtones. The submaxima of 3080 and 2970 cm⁻¹ of saccharin as well as pronounced doublet of 2465 and 2345 cm⁻¹ of d-phtalimide move to lower frequency in the low temperature ir spectra, while the “windows” remain fixed at 3045 and 2380 cm⁻¹, respectively. These examples could be a striking demonstration of Evans type Fermi resonance.     

Thermodynamic and sintering studies in the CoWC system

Sintering studies of WC-11%Co samples have been performed in a dilatometer. The temperature dependence of the shrinkage and the shrinkage rate during heating and isothermal treatment has been determined using computer evaluation. The relative magnitude of the densification in the solid and liquid states, respectively, has been determined and correlated to the CoWC phase diagram. Furthermore, some structural changes occurring under decarburizing conditions have been explained. Mechanisms for solid and liquid state sintering are presented.     

Solvation thermodynamics of benzene,nitrobenzene, and aniline in water–acetonitrile mixtures

The enthalpies of dissolution of benzene, nitrobenzene, and aniline in water–acetonitrile mixtures are determined via calorimetry. The concentration dependences of the standard enthalpies of solvation of solutes are calculated. It is found that the concentration dependences of the standard enthalpies of solvation pass through maxima. The height of the observed maxima is shown to depend largely on the nature of the substituent. In the presence of a hydrophilic amino group capable of forming strong hydrogen bonds with water molecules, the value of a maximum falls; in the presence of a nitro group, it rises. The enthalpy parameters of pair interaction between molecules of water and benzene and its derivatives are calculated.     

Vibrational spectroscopy of D—Glucose: the CH stretching region

We recorded the infrared and Raman spectra of α- and β-D-Glucose and five deuterated derivatives, in the solid. A rule is proposed for the interpretation of the behaviour of the principal force constants of the CH bonds in the various positions, taking into account the interaction of each CH with the vicinal oxygen atom.     

Solid and liquid phase equilibria and solid-hydrate formation in binary mixtures of water with amines

Solid and liquid phase diagrams have been constructed for {water+triethylamine,or+N,N-dimethylformamide(DMF) or+N,N-dimethlacetamide (DMA)} Solid-hydrates form with the empirical formulae N(C2H5)3 3H2O,DMF 3H2O,DMF 2H2O,DMA 3H2O and (DMA)2 3H2O.All are congruently melting except the first which melts incongruently.The solid-hydrate formation is attributed to hydrogen bond.The results are compared with the references     

Vibrational spectra in the CH stretching region for potassium n-hexanoate and its specifically deuterated derivatives

Infrared and Raman spectra in the solid state for potassium n-hexanoate, CH₃(CH₂)₄CO₂K, and its six kinds of specifically deuterated derivatives have been measured in the CH stretching region. Complete vibrational assignments of the CH stretching vibrations have been made. Characteristic vibrational bands for the specifically deuterated position of the carbon atom have been discussed.     

Physicochemical properties of binary solutions of propylene carbonate–acetonitrile in the range of 253.15–313.15 K

The density, dynamic viscosity, and dielectric constant of propylene carbonate solutions with acetonitrile are measured over the composition of a mixed solvent at temperatures of 253.15, 273.15, 293.15, and 313.15 K. The molar volume, molar viscosity, and molar capacity of a mixture of propylene carbonate–acetonitrile and an excess amount of it are calculated. The effect the temperature and composition of the mixture have on the excess molar properties is discussed. A linear correlation is observed between the values of the molar fluidity, capacity, polarization, and molar volume of the studied system.     

Laser Raman spectroscopic study of water in gelatin–surfactant solutions and gels

A Raman spectroscopic study was carried out on water in gelatin at 4% w/v in gel (25 °C) and sol (40–60 °C) states at various concentrations (0.5, 1, 5, 10 and 15 mM) of anionic surfactant, sodium dodecyl sulfate (SDS). The in-phase collective stretching mode vibration of hydrogen-bonded -OH oscillators, centered around 3250 cm⁻¹ in a tetrahedral network of water molecules, was observed to be significantly affected by temperature and the presence of SDS. According to our observation this may be due to the thinning of the hydration water around the gelatin molecules due to strong thermal agitation. The peak center of the collective bands of water decreased linearly with SDS concentration in the gel state which implied that with the increase in concentration of SDS, the -OH oscillators gradually lost their attachment to gelatin chains and were replaced by SDS molecules. Ultimately this resulted in a thinning of the hydration layer around the gelatin and the oscillation frequency of -OH oscillators moved towards 3250 cm⁻¹ at 1 mM SDS concentration resulting in increased coupling of -OH oscillators to form the tetrahedral network at the critical micelle concentration (cmc) of SDS. The variation in the peak amplitudes and the systematic reversal of their trend about the cmc axis was surprising. At 40 °C the amplitude of the peak at 3250 cm⁻¹ increased drastically due to a possible coil expansion by about 7–8% which accommodated more interstitial water into the pseudonetwork leading to an increase in the number of nearest neighbors and for about 6% increase in the C value. However, at the cmc the peak amplitude was observed to be independent of temperature. Continuous shifting of the peak center and full width at half-maxima towards lower values was observed with increasing SDS concentrations in the gel state. Received: 28 September 1998 Accepted in revised form: 8 March 1999     

Solvent effects on the kinetics of solvolysis of trans-dichlorobis (N-methylethylenediamine)cobalt(III) ion in water–propan-2-ol and water–acetonitrile mixtures

First order solvolysis rates of the trans-dichlorobis (N-methylethylenediamine) cobalt(III) ion have been measured over a wide range of solvent compositions and temperatures in water–propan-2-ol and water–acetonitrile mixtures. The rate of solvolysis is faster in the former mixtures rather than the latter. Plots of log(rate constant) versus the reciprocal of the dielectric constant of the co-solvent, and also versus the Grunwald–Winstein Y-values are non-linear for both co-solvents; this non-linearity is derived from a large differential effect of solvent structure between the initial and transition states. However, extrema in the variation of enthalpy H and entropy S of activation correlate well with the extrema in physical properties of the mixtures which are related to changes in solvent structure. Linear plots of H versus S were obtained and the isokinetic temperature indicates that the reaction is entropy controlled. The application of a free-energy cycle shows that changes in solvent structure affect the pentacoordinated cobalt(III) ion in the transition state more than the hexacoordinated cobalt(III) ion in the initial state. In addition, the stabilizing influence of changes in solvent structure is greater in propan-2-ol–water mixtures than in acetonitrile–water mixtures, and the difference becomes greater as the mole fraction, x2 of the organic co-solvent increases.     

Estimation of the normal boiling points of water and 1,2-dimethoxyethane through the viscosity–temperature dependence in the corresponding binary mixtures

Excess quantities calculated from literature values of experimental density and viscosity in 1,2-dimethoxyethane + water binary systems (from 303.15 to 323.15 K) can lead us to test different correlation equations as well as their corresponding derivative properties. Inspection of the Arrhenius activation energy (Ea) and the enthalpy of activation of viscous flow (ΔH*) shows very close values; here, we can define partial molar activation energies Ea₁ and Ea₂ for 1,2-dimethoxyethane and water, respectively, along with their individual contribution separately. Correlation between the two Arrhenius parameters of viscosity in all compositions shows existence of main distinct interaction behaviours delimited by particular mole fractions in 1,2-dimethoxyethane. Moreover, we add that correlation between Arrhenius parameters reveals interesting Arrhenius temperature which is closely related to the vapourisation temperature in the liquid vapour equilibrium, and the limiting corresponding partial molar properties can permit us to estimate the boiling points of the pure components.     

Kinetic model of ethylene oxidation by p-benzoquinone in solutions of cationic palladium(ii) complexes in a binary acetonitrile—water solvent

Russian Chemical Bulletin - A kinetic model was developed for the reaction of ethylene oxidation to acetaldehyde by p-benzoquinone (Q) at 30 ℃ catalyzed by the cationic palladium(II)...     

The frequency of the HOH bending fundamental in solids and liquids

A survey has been made of HOH bending frequencies in water-containing solids and liquids, using data from the literature and from the author's laboratory. After the effects of hydrogen bonding and dynamic coupling have been allowed for, HOH bending frequencies are found to be lowered by cation—water interactions. This frequency lowering increases statistically with increasing cation charge and with decreasing cation size.     

Raman spectroscopic study of the uranyl sulphate mineral zippeite: low wavenumber and U–O stretching regions

The uranyl sulphate mineral zippeite was studied by Raman spectroscopy. The phase purity of the sample was initially checked by X-ray powder diffraction and its chemical composition was defined by electron microprobe (wavelength dispersive spectroscopy, WDS) analysis. The Raman spectroscopy research focused on the low wavenumber and uranyl stretching vibration regions. Vibration bands down to 50 cm^–1 were tentatively assigned. The U–O bond lengths were calculated based on empirical relations. Inferred values are consistent with those obtained from the crystal structure analysis of synthetic zippeite. Number of bands was interpreted on the basis of factor group analysis.