Nonlinear dielectric effect of phenyl and methyl isothiocyanates in benzene and carbon tetrachloride

The nonlinear dielectric effect (NDE) of phenyl isothiocyanate and methyl isothiocyanate in benzene and carbon tetrachloride as solvents has been investigated. A different NDE dependence on the concentration for both investigated isothiocyanates and a significant solvent effect in the case of methyl isothiocyanate were observed.     

Nonlinear dielectric effect in benzonitrile and lauronitrile solutions

The nonlinear dielectric effect, NDE, and the calculated correlation factors R^p and R^s are reported for binary solutions of benzonitrile and lauronitrile in benzene and cyclohexane. Substantial differences found for solutions in these two solvents have been explained in terms of critical phenomena in cyclohexane solution.     

Nonlinear dielectric effect fortert-nitrobutane andtert-butylnitrile in hexane and benzene solutions

A nonlinear dielectric effect, and the calculated correlation factors R _p and R _s are reported for binary solutions of tert-nitrobutane and tert-butylnitrile in hexane and benzene. The results are discussed in terms of the three main mechanism: association of polar molecules, fluctuations in concentration and density, and intermolecular processes due to a strong electric field. The dipolar part of the cohesion energy is also accounted for.     

Frequency of OH in solutions of n-butanol in carbon tetrachloride: effect of dilution

It is noted that the 1 <-- 0 transition for nuOH shows a blue shift as the relative concentration of n-butanol in a CCl4-n-butanol is reduced. The magnitude of the shift decreases for the 2 <-- 0 transition and there is almost no shift for the 3 <-- 0 transition. These observations are consistent with the observed red shift [Y. Mizugai, F. Takimoto, M. Katayama, Chem. Phys. Lett. 76 (1980) 615] on dilution for the 5 <-- 0 transition in n-butanol. The observations have been interpreted on the basis of formation of O-H....Cl hydrogen bond.     

Gamma radiolysis of solutions of carbon tetrachloride in secondary alcohols

Oxidation of cyclohexanol free from peroxide by carbon tetrachloride under the influence of gamma radiation was carried out both for air saturated and deareated systems. Large values for the formation of HCl are obtained. A kinetic expression consistent with experimental observations has been derived.     

Infrared spectrum of benzene in bromine and carbon tetrachloride solutions

The benzene—bromine complex at room temperature has been re-studied by infrared with bromine in excess of benzene. Solutions of 0.225 M benzene in bromine—carbon tetrachloride mixtures were studied. Under this condition, the spectral changes of measurable benzene absorption bands were observed more clearly than previously. The out-of-plane vibrations of benzene were observed to shift to higher frequencies. The equilibrium constant was found to be 0.11 ? mole^?1. The accord with the equilibrium constant derived from benzene rich systems supports the concept of a specific interaction. A C_6V symmetry is favoured for the geometry of the complex.     

Nonlinear dielectric effect in a critical solution

This paper presents measurements of Δ/E² versus T for the critical solution nitroethane in cyclohexane. The Δ/E² for the temperature near the critical temperature T_c has a positive value and satisfies the following dependence: Δ/E² ∝ 1/(T ? T_c)^λ where λ = 0.34.     

Ebulliometric study of solutions of certain salts in benzene and carbon tetrachloride

The activity coefficients of the solvent (1n f ₁) have been determined by ebulliometry for solutions of certain salts in benzene and CCl₄. The results, together with data in the literature have been used to calculate the second and third virial coefficients of 1n f ₁ for a number of salt solutions in benzene, CCl₄, and dioxane. It is shown that the positive deviations from ideality in such solutions depend on the nature of the anion, the length of the amine radical, the temperature, and the nature of the solvent.     

GC-FTIR-MS analysis of volatile radiolysis products of nitrophenol solutions in carbon tetrachloride

Capillary gas chromatography — Fourier transform infrared spectroscopy combined with capillary gas chromatography — mass spectrometry is employed for the analysis of major volatile products in the -radiolysis of isomeric nitrophenol solutions in carbon tetrachloride. Isomeric di- and trichlorophenols, chloronitrophenols and dichloroisocyanatobenzenes in addition to those formed with m- and p-isomers, are among the important products formed in the solution of o-nitrophenol in carbon tetrachloride. Formation of dichloroisocyanatobenzene is explained by the interaction of dichlorocarbene with the nitro group followed by the ipso-substitution of OH and H atom by chlorine atom.This paper constitutes part of the Ph.D. thesis of M.K. Sahoo and was presented at the 10th conference on Chromatographic method and its significance for human health with international participation, Stará Lesná, High Tatras, Slovakia, Nov. 4–6, 1992.     

Dielectric relaxation of acetonitrile and propionitrile in benzene and carbon tetrachloride solutions

Dielectric permittivities and losses have been measured at wavelengths of 3 × 10⁴, 10.0, 3.23, 1.95, 1.25, and 0.40 cm at three temperatures 24, 40, and 60°C for benzene and carbon tetrachloride solutions of acetonitrile and propionitrile at a fixed concentration of 25 mole per cent. The far-infrared spectra in the range 10–150 cm⁻¹ of dilute solutions of both the nitriles have been investigated. A single relaxation time has been obtained for acetonitrile at each temperature whereas the dielectric data of propionitrile indicate the presence of multiple dispersion regions at microwave frequencies.     

Molecular self-assembling of chiral and racemic butan-2-ol in carbon tetrachloride solutions

The self-association of (R)-, (S)- and (RS)-butan-2-ol in their carbon tetrachloride solutions was studied through the mid-infrared (mid-IR) and near-infrared (NIR) spectroscopic observations. The mid-IR and NIR spectra for each chiral butan-2-ol were compared with those for the racemic (RS)-butan-2-ol. Although it has been reported that the hydrogen bonding among the chiral butan-2-ol molecules was stronger than that among the racemic ones, any distinguishable differences between the chiral and the racemic butan-2-ol in CCl₄ solution or even in their pure liquid state were not observed both in their mid-IR and NIR spectra. A superior analytical method, assuming a successive association process for the alcohol molecules, was applied to the analysis of the sharp band at 3630 cm⁻¹ (the OH-stretching vibration mode attributed to free OH-monomer) for the (R)-, (S)- or (RS)-butan-2-ol in CCl₄. The mean association number N for each alcohol increased with increasing in concentration until 0.12 mol dm⁻³ and then becomes constant (about four). On the other hand, Zanker's plotting method, assuming an equilibrium between monomers and only one kind of polymer species, was also applied to the analysis of the above spectroscopic results; the association number n evaluated from the Zanker's method fairly agreed with the N value in the concentration region of 0.12–0.60 mol dm⁻³.     

Photolysis of acetone in carbon tetrachloride

Conclusions The efficient photolysis of acetone proceeds upon the photoexcitation of the donor-acceptor complex of acetone and CCl₄ by light with 300 > < 330 nm with the formation of chloroketones and CHC1₃ as the major products. A mechanism was proposed for the photolysis of acetone in the presence of CCl₄.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2601–2603, November, 1987.     

Adsorption of alkenyl succinic anhydride from solutions in carbon tetrachloride on a fine magnetite surface

The adsorption of alkenyl succinic anhydride from a solution in carbon tetrachloride on a fine magnetite surface at a temperature of 298.15 K is studied using fine magnetite, which forms the basis of magnetic fluids, as the adsorbent. An adsorption isotherm is recorded and interpreted in terms of the theory of the volume filling of micropores (TVFM). Adsorption process parameters are calculated on the basis of the isotherm. It is shown that at low equilibrium concentrations, the experimental adsorption isotherm is linear in the TVFM equation coordinates.     

Vibrational relaxation carbon tetrachloride

By use of spontaneous Brillouin scattering, the vibrational relaxation of carbon tetrachloride was determined as a function of temperature. Comparison of experimental results with theoretical predictions leads to the conclusion that there is a simultaneous relaxation of three internal modes.     

Nonlinear dielectric effect near the critical point of binary mixtures

The nonlinear dielectric effect (NDE) was measured in two binary systems near the critical point. The effect of independent of specific dipole-dipole interactions in contrast with previous conceptions. Its singular part is proportional to (T ? T_c)^{?$\text{1}\text{2}$} in agreement with Snider's theory as applied to NDE.     

Infrared studies of fluoroalcohol-base complexes in the gas phase,carbon tetrachloride solutions and argon matrices

Hydrogen bonded complexes of fluoroalcohols with oxygen-containing bases like dimethyl ether and alkanols have been investigated in argon matrices, in CCl₄ solutions and in the gas phase. The increase of the proton donor capacities with succesive substitution of fluorine atoms into the alkyl group of alcohols is indicated by a strong increase of the shift Δν of the OH stretching frequency in the complexes. For alkanols as acceptors, an increase of Δν is observed along the series CH₃OH, CH₃CH₂OH, (CH₃)₂CHOH, and (CH₃)₃CHOH. The frequency shifts Δν increase as one passes from the gas phase to CCl₄ solutions and argon matrices.     

Spectrophotometric determination of carbon tetrachloride via ultrasonic oxidation of iodide accelerated by dissolved carbon tetrachloride

Ultrasonic oxidation of iodide was investigated in the presence of carbon tetrachloride (CCl₄). The ultrasonic oxidation of potassium iodide led to formation of iodine and then I₃⁻ in the presence of excess iodide, and the generated I₃⁻ shows strong UV absorption with a molar absorptivity of 2.31 × 10⁴ L mol⁻¹ cm⁻¹ at the maximum absorption wavelength of 351 nm. The ultrasonic oxidation of iodide was found to be significantly promoted by a small addition of CCl₄, and it was further found that the generation rate was increased with the amount of CCl₄ added. This can be used to analyze the level of CCl₄ dissolved in aqueous solutions. Under optimum conditions, the concentration of generated iodine (or its absorption at 351 nm) was found to correlated linearly with the concentration of CCl₄ in the range of 0.2-50 mg L⁻¹ (detection limit = 0.09 mg L⁻¹, R² = 0.999). As an alternative indirect spectrophotometric method of CCl₄ determination, the proposed method was successfully applied to determine the concentrations of CCl₄ in several practical samples, showing merits of being sensitive and simple of operation.