Excess volumes of isomeric butanols with di-n-butyl ether

The excess volumes of four isomeric butanols with di-n-butyl ether were determined at 30°C. The isomeric effect was distinctly observed in the excess volume profiles. 1-Butanol and 2-methyl-l-propanol systems exhibited negative excess volumes throughout the concentration range. The 2-butanol system had positive excess volumes up to 0.9 mol fraction of alcohol after which it became negative, while the 2-methyl-2-propanol system exhibited positive excess volumes throughout the concentration range. NCL Communication No. 4678     

Enthalpies of complex formation of dibutyl and tributyl amines with isomeric butanols

Enthalpies of complex formation (ΔH _c) of dibutyl and tributyl amines with the four isomeric butanols were determined at 30°C. The present data were compared with the previous data on isomeric butanols with monobutyl amine complexes. The ΔH _c in the case ofn-alcohol has been found to decrease by about 4·0±0·4 kJ/mole on replacement of each hydrogen atom of the NH₂ group. The branching of the butyl chain, also, decreases the strength of the complex due to steric hindrance. NCL Communication No. 3864.     

Enthalpies of mixing of acetonitrile with isomeric butanols: Enthalpies of hydrogen-bonded complexes

The enthalpies of mixing of four isomeric butanols with acetonitrile were determined at 30°C by a Calvet type microcalorimeter. All the four systems showed endothermic behaviour. The enthalpies of hydrogen bonded complex formation were determined by means of a thermochemical cycle. 1-butanol formed a stronger bonding (−13kJ/mole) than the other three isomers (−11.20kJ/mole). The strength of the H-bond of alcohol with C ≡ N is much less than that with C-N. NCL communication no. 4883     

Excess molar enthalpies of 1,3-dioxolane,or 1,4-dioxane with isomeric butanols

Using a flow-mixing calorimeter, excess molar enthalpies of 1,3-dioxolane, or 1,4-dioxane, with isomeric butanols were determined at the temperatures of 298.15 K and 313.15 K. All the studied systems show positive excess molar enthalpies. The results are compared with calculated values from the UNIFAC model.     

Effect of different butanols on the adsorption of sodium dodecylsulfate on alumina

The adsorption of sodium dodecylsulfate onto alumina from aqueous solutions (0.3 M NaCl) was determined in the presence of short-chain alcohols,i.e.,1-, 2-,iso-, andtert-butanol. All adsorption isotherms of the surfactant show the same trend upon the addition of the different short-chain alcohols. The isotherm reaches its saturation level at lower surfactant equilibrium concentrations than without alcohol, and the saturation adsorption density level decreases. The reason for these changes is attributed mostly to the lowering effect of butanols on the critical micelle concentration of sodium dodecylsulfate in the aqueous bulk phase, but also the competitive adsorption of the alcohols is considered.     

The pyrolytic identification of organic molecules: IV. The pyrolytic behavior of the isomeric butanols

A study of the pyrolytic behavior of the butanol isomers has been made in order to establish a basis for their identification from the thermolysis pattern of each butanol. The identity of the volatile products was established by gas chromatographic analysis. Each isomer was found to decompose via degradation reactions characteristic of the structural arrangement of each alcohol molecule for which mechanisms are proposed.     

Excess enthalpies for mixtures of cyclohexanone with isomeric propanols and butanols at 298.15 K

Excess enthalpies (H ^E ) for mixtures of cyclohexanone with propan-1-ol. propan-2-ol, butan-1-ol, butan-2-ol and 2-methyl propan-1-ol at 298.15 K have been measured over the entire composition range. All mixed endothermically with the maximum values ofH ^E occurring at equimole fraction. Comments about the molecular interactions contributing to the excess enthalpies of a cyclic ketone + an alcohol are made on the basis of these results.     

Viscosities of 1-chlorobutane and 1,4-dichlorobutane with isomeric butanols at 25 and 40°C

This paper reports viscosities and excess viscosities for binary systems of 1-chlorobutane and 1,4-dichlorobutane with isomeric butanols at 25 and 40°C. Results show negative deviations from ideal behavior. Viscosities and excess viscosities were correlated by means of the Grunberg-Nissan equation and the Redlich-Kister equation.     

The adiabatic compressibility of two-phase systems of salt mixture melts based on lithium fluoride

The adiabatic compressibility coefficients of stratifying liquid lithium fluoride mixtures with potassium, rubidium, and cesium bromides and iodides were determined by the acoustic method with invoking density data. The difference of the compressibilities of phases along the saturation line was found to depend on the ratio between component bond energies. A compressibility jump was observed experimentally in the passage through the critical point.     

Enthalpies of mixing of di- n -butyl ether with isomeric butanols: Enthalpies of hydrogen-bonded complexes

The enthalpies of mixing of four isomeric butanols with di-n-butyl ether were determined at 30°C by a Calvet type microcalorimeter. All the four systems showed endothermic behaviour. The enthalpies of complex formation were calculated by the thermochemical cycle. The strength of H-bonding decreases in the order l-butanol, l-methyl-1-propanol, 2-methyl-2-propanol, 2-butanol. The results are explained on the basis of a steric effect on interaction. NCL Communication No. 4430.     

Dissolved states of ionene polymers in water-acetone and their relation to the ionic partial molar adiabatic compressibility and volume

Solution properties of water-soluble synthetic polymer, 3,3-ionene and 6,6-ionene chloride and bromide disolved in water-acetone mixtures up to acetone content 50 wt% were investigated. Their partial molar volumes V ₂ ^o and partial molar adiabatic compressibilities K _s ^o were determined. Ionic additivity of V ₂ ^o with respect to the cation of backbone polymer chain and the counter-anion was confirmed quantitatively. The ionic additivity of V ₂ ^o is discussed along with the K _s ^o in their relation to the counterion binding of ionene polymers. Effects of ionic sites on the ionene are strong but they don't break the solvation layer.     

Volume and adiabatic compressibility of optically active and inactive tartaric acids and tartrates

The differences of partial molal volume and adiabatic compressibility at infinite dilution of optically active diastereoisomers in water are reported. The L and meso tartaric acids and their potassium salts are examined. The results are interpreted in terms of specificity of H bonding between the solvent H₂O and the stereoisomers in the charged and uncharged forms. The results are of interest in relation to biochemical specificities and stereospecific behavior of optical enantiomers.     

Stereochemical aspects of micellar properties of esterified glucoside surfactants in water: apparent molar volume, adiabatic compressibility, and aggregation number

 The apparent molar volume and the apparent molar adiabatic compressibility of the sugar-based surfactants methyl 6-O-octanoyl-α-d-glucopyranoside (α-MOnG), methyl 6-O-octanoyl-β-d-glucopyranoside (β-MOnG), and octyl β-d-glucoside were measured over a wide concentration range. Also, the aggregation number of their micelles was determined from the Debye plot using static light scattering data. It was found that the micellar aggregation number for α-MOnG is 179 at 35 °C, which is 1.5 times larger than that for β-MOnG, suggesting that the anomerism of the head group influences the packing of the monomers during micelle formation. Received: 30 September 1999 Accepted: 15 December 1999     

Dehydration of butanols on copper-containing zirconium orthophosphates

The catalytic properties of ternary zirconium phosphates Na_1-2x Cu_xZr₂(Po₄)₃ in the transformations of butanols were been studied. It was found that the structure of alcohol and the copper content (x = 0, 0.15, 0.25, 0.35) affect the rate and selectivity of dehydration. The activity and selectivity changed as the content of copper that substitutes for sodium ions increased. The general conversion of alcohol and selectivity in dehydration decreased in the series butanol-2 →-isobutanol → butanol-1, due probably to the change in the apparent activation energy of the reaction, depending on the stability of alcohol binding to the surface.     

Effect of water on the low temperature conductivity of polymer electrolytes

The proton conductivity of radiation-grafted ethylenetetrafluoroethylene-grafted-poly(styrene sulfonic) acid (ETFE-g-PSSA) and Nafion 117 membranes between 25 and -37 degrees C is reported. The freezing of water in the membranes, which strongly depends on the internal acid concentration, results in a 4-fold decrease in proton conductivity. The activation energies before and after the freezing of the membranes are approximately 0.15 and 0.4 eV, consistent with proton transport through liquid water and strongly bound water, respectively. Differential scanning calorimetry data show that up to 14 H(2)O molecules per H(+)/SO(3)(-) group remain unfrozen at subzero temperatures and are believed to be responsible for the low temperature conductivity that is observed. These results indicate that proton conductivity in membranes may be achieved via strongly bound and highly polarized water.     

Effect of temperature on the adsorption of water in porous carbons

We report experimental and simulation studies to investigate the effect of temperature on the adsorption isotherms for water in carbons. Adsorption isotherms are measured by a gravimetric technique in carbon-fiber monoliths at 378 and 423 K and studied by molecular simulation in ideal carbon pores in the temperature range 298-600 K. Experimental adsorption isotherms show a gradual water uptake, as the pressure increases, and narrow adsorption-desorption hysteresis loops. In contrast, simulated adsorption isotherms at room temperature are characterized by negligible uptake at low pressures, sudden and complete pore filling once a threshold pressure is reached, and wide adsorption-desorption hysteresis loops. As the temperature increases, the relative pressure at which pore filling occurs increases and the size of the hysteresis loop decreases. Experimental adsorption-desorption hysteresis loops are narrower than those from simulation. Discrepancies between simulation and experimental results are attributed to heterogeneities in chemical composition, pore connectivity, and nonuniform pore-size distribution, which are not accounted for in the simulation model. The hysteresis phase diagram for confined water is obtained by recording the pressure-density conditions that bound the simulated hysteresis loop at each temperature. We find that the hysteresis critical temperature, i.e., the lowest temperature at which no hysteresis is detected, can be hundreds of degrees lower than the vapor-liquid critical temperature for bulk model water. The properties of confined water are discussed with the aid of simulation snapshots and by analyzing the structure of the confined fluid.     

Apparent molar volumes and apparent molar heat capacities of aqueous solutions of isomeric butanols at temperatures from 278.15 K to 393.15 K and at the pressure 0.35 MPa

Apparent molar heat capacities C_{p, φ}and apparent molar volumesV_φ were determined for aqueous solutions of 1-butanol, 2-butanol (both R andS isomers), isobutanol (2-methyl-1-propanol), and t -butanol (2-methyl-2-propanol) at temperatures from 278.15 K to 393.15 K and at the pressure 0.35 MPa. The molalities investigated ranged from 0.02 mol · kg ^− 1to 0.5 mol · kg ^− 1. We used a vibrating-tube densimeter (DMA 512P, Anton Paar, Austria) to determine the densities and volumetric properties. Heat capacities were obtained using a twin fixed-cell, power-compensation, differential-output, temperature-scanning calorimeter (NanoDSC 6100, Calorimetry Sciences Corporation, Provo, UT, U.S.A.). The results were fit by regression to equations that describe the surfaces (V_φ, T, m) and (C_p,φ, T, m). Infinite dilution partial molar volumesV₂^o and heat capacities C_p,2^owere obtained over the range of temperatures by extrapolation of these surfaces to m =  0.     

Role of rotational temperature in adiabatic molecular alignment

One-dimensional alignment of molecules in the adiabatic limit, where the pulse duration greatly exceeds the molecular rotational periods, is studied experimentally. Four different asymmetric top molecules (iodobenzene, p-diiodobenzene, 3,4-dibromothiophene, and 4,4'-dibromobiphenyl), rotationally cooled through a high pressure supersonic pulsed valve, are aligned by a 9-ns-long pulse. Their orientations are measured through Coulomb explosion, induced by a 130-fs-long pulse, and by recording the direction of the recoiling ions. The paper focuses on the crucial role of the initial rotational temperature for the degree of alignment. In particular, we show that at molecular temperatures in the 1 K range very strong alignment is obtained already at intensities of a few times 10(11) W/cm2 for all four molecules. At the highest intensities (approximately 10(12) W/cm2) the molecules can tolerate without ionizing >or=0.92 in the case of iodobenzene. This is the strongest degree of alignment ever reported for any molecule.