Search

In this work, we investigate the degradation process of 1-chlorobutane, initiated by OH radicals, under atmospheric conditions (air pressure of 750 Torr and 296 K) from both experimental and theoretical approaches. In the first one, a relative kinetic method was used to obtain the rate coefficient for this reaction, while the products were identified for the first time (1-chloro-2-butanone, 1-chloro-2-butanol, 4-chloro-2-butanone, 3-hydroxy-butanaldehyde, and 3-chloro-2-butanol) using mass spectrometry, allowing suggesting a reaction mechanism. The theoretical calculations, for the reactive process, were computed using the BHandHLYP/6-311++G(d,p) level of theory, and the energies for all of the stationary points were refined at the CCSD(T) level. Five conformers for 1-chlorobutane and 33 reactive channels with OH radicals were found, which were considered to calculate the thermal rate coefficient (as the sum of the site-specific rate coefficients using canonical transition state theory). The theoretical rate coefficient (1.8 × 10-12 cm3 molecule-1 s-1) is in good agreement with the experimental value (2.22 ± 0.50) × 10-12 cm3 molecule-1 s-1 determined in this work. Finally, environmental impact indexes were calculated and a discussion on the atmospheric implications due to the emissions of this compound into the troposphere was given. Fil: Jara Toro, Rafael Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Barrera, Javier Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Aranguren Abrate, Juan Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Taccone, Raúl A.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Pino, Gustavo Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina

This chapter provides viscosity of the binary liquid mixture of 1-chlorobutane and 1-ethoxybutane at various temperature and concentrations.

This chapter provides viscosity of the binary liquid mixture of 1-chlorobutane and 2-methoxy-2-methylpropane at various temperature and concentrations.

Surface tensions of the ternary mixtures containing an isomer of butanol (1-butanol, 2-butanol, 2-methyl-1-propanol, or 2-methyl-2-propanol) + n-hexane + 1-chlorobutane have been measured at atmospheric pressure and 298.15 K. From these experimental data, surface tension deviations were calculated and fitted by the Cibulka’s equation. Experimental results have been compared to the predictions obtained by a group contribution method; furthermore, using this method, the excess surface molar compositions of n-hexane in the ternary mixtures have been also estimated.

Various ionic liquids have been examined along with some traditional phase-transfer catalysts, such as Aliquat reagents, in a standard liquid−liquid phase-transfer catalysis (LLPTC) reaction. A standard O-alkylation LLPTC reaction was chosen because of its relatively high yields and low incident of reaction side products. As expected, quaternary tetraalkyl ammonium catalysts all resulted in high conversion to product. Aliquat HTA-1, a high temperature phase-transfer catalyst normally used in nonaqueous reactions, resulted in yields only slightly higher than the noncatalyzed reaction. Substituted pyrrolidinium salts had relatively good catalytic activity, while substituted pyridinium and imidazolium catalysts showed either very little or no catalytic activity. Catalysts with fixed cationic charges resulted in high conversion for the etherification reactions; however, compounds with an aromatic π-bonding system were not suitable as phase-transfer catalysts.

Isothermal vapor-liquid equilibrium for the ternary mixtures 2-methyl-1-propanol + n-hexane + 1-chlorobutane and 2-methyl-2-propanol + n-hexane + 1-chlorobutane and for the binary mixtures 2-methyl1-propanol + n-hexane and 2-methyl-2-propanol + n-hexane have been studied at T ) 298.15 K. The experimental data were checked for thermodynamic consistency using the method of van Ness. The isothermal vapor-liquid equilibrium data of the ternary mixtures together with the corresponding constituent binary mixtures were correlated with the Wilson equation. The G E values obtained have been compared with those of the ternary mixtures 1-butanol or 2- butanol + n-hexane + 1-chlorobutane previously investigated. The study of vapor-liquid equilibrium (VLE) of multicomponent liquid mixtures in isothermal conditions provides experimental data of great interest in thermodynamics and chemical engineering and contributes decisively for the development of accurate methods to predict and correlate phase equilibrium. However, relatively few investigations on isothermal VLE of ternary mixtures can be found in the literature. In the past years, our laboratory has been involved in the study of several thermodynamic and transport properties of the ternary mixtures containing an isomer of butanol + n-hexane + 1-chlorobutane, 1-7 and we also have recently reported isothermal VLE data for the ternary systems 1-butanol or 2-butanol + n-hexane + 1-chlorobutane at 298.15 K. 8 To complete this systematic study, we report here vapor-liquid equilibrium data obtained at 298.15 K for the ternary systems 2-methyl-1-propanol or 2-methyl-2-propanol + n-hexane + 1-chlorobutane and for the binary mixtures 2-methyl-1-propanol or 2-methyl-2-propanol + n-hexane. Thermodynamic consistency of the experimental data has been checked by the method of van Ness. 9 We have also correlated activity coefficients of the components and excess Gibbs function of the mixtures using the Wilson equation. 10

The vapour pressures of binary (cyclohexanone + 1-chlorobutane, + 1,1,1-trichloroethane) mixtures were measured at the temperatures of (298.15, 308.15, and 318.15) K. The vapour pressures vs . liquid phase composition data have been used to calculate the excess molar Gibbs free energies G E of the investigated systems, using Barker’s method. Redlich–Kister, Wilson, UNIQUAC, and NRTL equations, taking into account the vapour phase imperfection in terms of the 2-nd virial coefficient, have represented the G E values. No significant difference between G E values obtained with these equations has been observed.

Vapor−liquid equilibrium has been measured at 333.15 K for the following binary mixtures: acetonitrile (3) + 1-chlorobutane (1), ethanol (2) + 1-chlorobutane (1), and ethanol (2) + acetonitrile (3) at 333.15 K. Values of the maximum of GE ranging from 700 J·mol−1 to 1150 J·mol−1 were found for the three systems. Consistency with data already published at different temperatures has been demonstrated as well as with experimental excess enthalpy for the ethanol + acetonitrile mixture. The results have been used to test the ability of a lattice-fluid theory to fit the GE and to predict the HE and VE excess functions. Although reasonable fits were found for the systems containing ethanol, worse results were found for 1-chlorobutane + acetonitrile. In general, the theoretical predictions of HE and VE are rather poor when the binary energy parameter of the theory is fitted to GE.

Refractive indices for the ternary mixtures formed by each one of the isomers of butanol (1-butanol, 2-butanol, 2-methyl-1-propanol and 2-methyl-2-propanol), with n-hexane and 1-chlorobutane, have been measured at 298.15 K. From these data the refractive index deviations were calculated and fitted by Cibulka’s equation, and the refractive index deviations were related to the corresponding excess volumes of the mixtures. Furthermore, several mixing rules were used to predict both refractive indices and excess volumes of the ternary mixtures from their densities or refractive indices.

Densities and viscosities of the ternary mixtures 2-methyl-1-propanol (or 2-methyl-2-propanol) + n-hexane + 1-chlorobutane have been measured at atmospheric pressure and 298.15 K. Excess molar volumes and viscosity deviations for the ternary mixtures were calculated from experimental data and fitted by the Cibulka equation. These properties have been analyzed taking into account the molecular interactions.

Densities of pure 1-chlorobutane, pure n-hexane, and their mixtures have been measured with an accuracy of ± 0.2 kg·m−3, over a temperature range of (283.15 to 333.15) K and a pressure range of (0.1 to 35) MPa using a vibrating tube densimeter. The experimental densities have been correlated by the Tait equation with the temperature-dependent parameters for pure components and by the van Laar-type equation with the temperature- and pressure-dependent parameters for the solution. The excess volumes have been calculated on the basis of experimental data, and the pressure and temperature influence on this property have been discussed.

Mo 2 C@a-C core-shell powders were prepared by reacting Mo powders with gaseous 1-chlorobutane or hexachlorobenzene at 1173 K. The chlorinated reactants acted as the source of carbon for the carburization of Mo and the source of chlorine, which assists the etching of Mo to reduced particle sizes.

Densities and viscosities of 1-chlorobutane + 1-butanol, + 2-methyl-1-propanol, + 2-butanol, or + 2-methyl-2-propanol were measured at several temperatures between 288.15 K and 318.15 K. At each temperature, the experimental viscosity data were correlated by means of the McAllister biparametric equation. By using our previous thermodynamic measurements (VLE, HE), we have tested the Wei and Rowley nonparametric model at T = 298.15 K, obtaining average absolute deviations that are comparable to those calculated for the biparametric model.

Solubilities of n-octadecane, n-nonadecane, n-eicosane, and n-tetracosane in dipropyl ether, dibutyl ether, 1-chlorobutane, and 1-chlorooctane have been measured by the synthetic method as functions of temperature from near 0 °C to the melting point of the alkane. All systems exhibit small deviations from ideal solubility, positive at lower solute compositions and, for some systems, slightly negative at higher solute compositions.

Vapour pressures of (1-chlorobutane + 1-octanol or 1-decanol) at several temperatures between T =278.15 K and T =323.15 K were measured by a static method. The reduction of the vapour pressures to obtain activity coefficients and excess molar Gibbs free energies was carried out by fitting the vapour pressure data to the Wilson equation according to Barker’s method. A description of the experimental behaviour according to the ERAS-model is presented.

Densities, ρ , and viscosities, η , for ternary liquid mixtures of tetrahydrofuran (1) + 1-chlorobutane (2) + 1-butanol (3) have been measured as a function of composition at temperatures of 283.15, 298.15 and 313.15 K and atmospheric pressure over the full range of composition. From theses results excess molar volume, V E , viscosity deviations, Δ η , from mole fraction average, and excess free energies of activation of viscous flow, Δ G ∗E , have been calculated. Excess molar volume, viscosity deviations and excess free energies of activation of viscous flow were fitted to Cibulka, Singh and Nagata equations. The results are discussed in terms of the molecular interaction between the components of the mixtures. Excess molar volumes and deviations of the viscosities for this ternary system were predicted from binary contributions using geometrical solution models, Tsao–Smith, Jacob–Fitzner, Kholer, Rastogi and Radojkovic. Additionally, experimental results are compared with those obtained by applying group-contribution method proposed by Wu.

Viscosities of the ternary mixture (2-butanol + hexane + 1-chlorobutane) at 298.15 K and 313.15 K have been measured at atmospheric pressure. Viscosity deviations for the ternary system were fitted to Cibulka's equation. To correlate experimental data of the ternary system, extended Nissan−Grunberg and McAllister equations have been used and their parameters have been calculated. The “viscosity−thermodynamic” model (UNIMOD) has been applied first to correlate experimental data for the binary mixtures and then to predict the viscosity for the ternary system. The group-contribution thermodynamic viscosity model (GC−UNIMOD) and the group contribution method proposed by Wu have been applied to predict the viscosity for the binary and ternary systems.

Experimental densities (ρ) and speeds of sound (u) were obtained for the ternary system (2-butanol + 1-chlorobutane + tetrahydrofuran) at three temperatures: 283.15, 298.15 and 313.15 K. Excess molar volumes (V E ) and isentropic compressibility deviations (Δκ S ) have been calculated from experimental data. A discussion of the thermodynamic behavior of the ternary system in terms of molecular interactions and structural and packing effects is presented.

The (p,Vm,T) behaviour of (octane + 1-chlorobutane) was measured at the temperatures (298.15, 308.15, 318.15, and 328.15) K and over the pressure range (0.1 to 40 MPa) with an accuracy in density of ±1·10 −4 g · cm −3 . An apparatus for (p,Vm,T) measurements of liquids and liquid mixtures whose main part is a high-pressure vibrating-tube densimeter working in a static mode was used for the measurements. Excess molar volumes were calculated from the data and fitted to the Redlich-Kister equation.

TiC nanoparticles (average diameter 10–150 nm) were prepared by reacting bulk Ti powders (average diameter 20 μm) with gaseous 1-chlorobutane at a relatively low temperature (1073–1273 K). 1-Chlorobutane provided the carbon atom in the TiC and the chlorine atom that assisted the shrinking of the size of the original Ti powders. The apparently simple procedure is a complex heterogeneous process combining etching, deposition, and carburization reactions.

The (p,Vm,T) behaviour of (heptane + 1-chlorobutane) was measured at the temperatures (298.15, 308.15, 318.15, and 328.15) K and in the pressure range 0.1 to 40 MPa with an accuracy in density of ±1·10 −4 g cm −3 . An apparatus for the (p,Vm,T) measurement of liquids and liquid mixtures whose main part is a high-pressure vibrating-tube densimeter working in a static mode was used for the measurement. Excess molar volumes were calculated from the data and fitted to the Redlich–Kister equation.

The densities and speeds of sound of the ternary mixture (2-butanol+n-hexane+1-chlorobutane) have been measured at T=298.15 and 313.15 K for the binary mixture (2-butanol+1-chlorobutane) at T=313.15 K. The excess molar volumes, and excess isentropic compressibilities were calculated and fitted to Cibulka’s equation. The Flory’s theory and the extended real associated solution (ERAS) model have been applied at T=298.15 K to predict the excess molar volume of the ternary mixture. The isentropic compressibilities have been compared with calculated values from the collision factor theory (CFT) and free length theory (FLT).

Experimental densities (ρ) and speeds of sound (u) were obtained for the ternary system (1-butanol+1-chlorobutane+tetrahydrofuran) at three temperatures: 283.15, 298.15, and 313.15 K. Excess molar volumes (V E ) and isentropic compressibility deviations (Δκ S ) have been calculated from experimental data. A discussion of the thermodynamic behavior of the ternary system with temperature variation is presented.

Experimental solubilities are reported for anthracene dissolved in six binary alcohol + 1-chlorobutane solvent mixtures at 25°C. The alcohol cosolvents studied were 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol and 3-methyl-1-butanol. Results of these measurements are used to test a mathematical representation based upon the combined Nearly Ideal Binary Solvent (NIBS)/Redlich-Kister equation. For the six systems studied, the Combined NIBS/Redlich-Kister equation was found to mathematically describe the experimental data, with overall average absolute deviations between measured and calculated values being approximately\pm 0.4%.

Vapour pressures of (1-chlorobutane + 1-butanol, or 2-methyl-2-propanol) at several temperatures between T = 278.15 and T = 323.15 K were measured by a static method. Reduction of the vapour pressures to obtain activity coefficients and excess molar Gibbs energies was carried out by fitting the vapour pressure data to the Redlich–Kister equation according to Barker’s method. For (1-chlorobutane + 2-methyl-2-propanol) azeotropic mixtures with a minimum boiling temperature were observed over the whole temperature range.

The interaction of 1-chlorobutane with nanocrystalline MgO at 200−350 °C has been found to result in both stoichiometric and catalytic dehydrochlorination of 1-chlorobutane to isomers of butene and...

Densities ρ and speeds of sound u for { x 1 C 4 H 10 O + x 2 C 6 H 14 + (1 − x 1 − x 2 ) C 4 H 9 C l } at T = 298.15 K and T = 313.15 K, and the constituent binary mixtures { x C 6 H 14 + (1 − x )C 4 H 9 Cl} at T = 298.15 K and { x C 4 H 10 O + (1 − x )C 6 H 14 } , { x C 4 H 10 O + (1 − x )C 4 H 9 Cl} , and { x C 6 H 14 + (1 − x )C 4 H 9 Cl} at T = 313.15 K have been measured. The isentropic compressibilities κ S , the excess isentropic compressibilities κ S E , and the speeds of sound deviations Δ u have been calculated for both the binary and the ternary systems, from the experimental data. The isentropic compressibilities have been compared with calculated values from the free length theory (FLT) and collision factor theory (CFT).

Excess molar volumes and excess viscosities of the propan-2-ol + tetrahydrofuran+ 1-chlorobutane system have been determined at 25°C from measurements ofdensities and viscosities. Various expressions are proposed in the literature tocalculate these excess properties from binary data. The empirical correlation ofCibulka is shown to be the best in this system for excess volume, viscosity, andenergy of activation for viscous flow. An application to excess molar volumeshas been made by using Flory's theory. For viscosities, we applied the equations ofGrunberg and Nissan, Katti and Chaudhri, Bloomfield and Dewan, and Wu—andfinally the GC-UNIMOD model.

Densities and excess molar volumes, VE, of heptane-1-chloropropane, heptane- 1-chlorobutane, heptane-1-chloropentane, and heptane-1-chlorohexane systems are reported at 298.15 K and atmospheric pressure over the whole composition range. Value of VE was found to be slightly negative at lower mole fractions and slightly positive at higher mole fractions in case of the heptane-1-chlorohexane system. For all the other systems, VE was positive. The VE results were correlated using the fourth-order Redlich-Kister equation, the maximum likelihood procedure being applied for evaluating the adjustable parameters.

Viscosities of the ternary mixture (1-butanol+n-hexane+1-chlorobutane) and the binary mixture (n-hexane+1-chlorobutane) have been measured at 298.15 K and 313.15 K. Viscosity deviations and excess Gibbs energy of activation of viscous flow for the binary and ternary systems were fitted to Redlich–Kister's and Cibulka's equations. The `viscosity–thermodynamic' model (UNIMOD) has been used to correlate experimental data for the binary mixtures and to predict the viscosities for the ternary system. The Group-Contribution Thermodynamic–Viscosity model (GC-UNIMOD), and the group contribution method proposed by Wu have been used to predict the viscosity of the binary and ternary systems.

Densities and viscosities were measured for the three binary mixtures formed by propan-2-ol, 1-chlorobutane, and acetonitrile at (293.15, 303.15, 313.15, and 323.15) K. Excess volumes and viscosity deviations from the mole fraction average were derived. The kinematic viscosities were compared with McAllister's model.

Densities of the liquid mixtures (n-hexane+1-chlorobutane) and (1-butanol+n-hexane+1-chlorobutane) have been measured by the vibrating tube technique at 298.15 K and 313.15 K. With these densities, excess molar volumes were calculated. An extended version of the so-called ERAS model has been used for describing VE of the complete ternary system at 298.15 K. Qualitatively the ERAS-model gives an adequate representation of this system, being similar the shapes of both the experimental and the predicted curves.

Vapor−liquid equilibria were measured at 101.3 kPa for three binary mixtures and one ternary mixture of 2-propanol, 1-chlorobutane, and acetonitrile. Thermodynamic consistency of data for the three binary mixtures was tested using the Herington method. The Soave−Redlich−Kwong equation of state was used to calculate the vapor-phase fugacity coefficients. The experimental vapor−liquid equilibrium data were reduced, and binary parameters for four activity coefficient models, such as van Laar, Wilson, NRTL, and UNIQUAC, were fitted. The four models with their best-fitted parameters were used to predict the ternary vapor−liquid equilibria. A comparison of model performances was made by using the criterion of absolute average deviations in boiling point and in vapor-phase composition.

Excess molar volumes at 298.15 K and atmospheric pressure were measured for {x1 CH3CO2(CH2)3CH3 + x2 C10H22 + (1 − x1 − x2) Cl(CH2)3CH3} and the corresponding binary mixtures, with an Anton Paar densimeter. All the experimental values were compared with the results obtained by different prediction methods.

The ternary system 1-chlorobutane (theta solvent)/2-butanol (nonsolvent)/poly(methyl methacrylate) was investigated by use of the theoretical Flory-Huggins-Pouchly model. The determination of the interaction parameters through the second virial coefficient according to the equation proposed by Pouchly was analyzed.