A new stainless steel apparatus for measuring azeotropic points of binary as well as multicomponent systems at elevated pressures has been developed. The azeotropic temperatures and compositions of six binary systems composed of cyclohexane, 2-propanol, ethyl acetate, and butanone were determined at elevated pressures, correlated by empirical equations with pressure, and predicted by the UNIFAC group contribution method. The calculations demonstrate that the correlated data are in good agreement with experimental values.

The azeotropic data of the cyclohexane+2-propanol+ethyl acetate+butanone quaternary system were measured by using a stainless steel azeotrope apparatus developed by the authors at elevated pressures of 101.3, 302.0, 502.0, 702.0, and 902.0 kPa and predicted by using the Wilson and NRTL activity coefficient models with the paired energy parameters obtained from binary azeotropic data of the six corresponding systems. The calculated results demonstrate that the predicted data are in good agreement with the experimental, and the Wilson and NRTL equations are of comparable accuracy in the prediction of azeotropes for this miscible quaternary system at elevated pressures.

The adsorption equilibria of ternary and quaternary mixtures of short linear alkanes, involving methane, ethane, propane, and n-butane, were simulated by using the configurational-bias Monte Carlo technique in grand canonical ensemble in MFI zeolite. The simulation results are in good agreement with the experimental data. The adsorption isotherms in MFI zeolite show that the longer chain component is preferentially adsorbed at low pressures. Its adsorption increases and then decreases as the pressure increases. But the shorter chain component is adsorbed at higher pressures and its adsorption increases as the pressure increases. The selectivity of ISV and MFI is much higher than that of MOR. The selectivity increases rapidly as the mole fraction of methane in the gas phase increases, but the change of selectivity of MOR is not obvious in an methane-ethane-propane mixture. The adsorbed amount in mixtures is in the order of ISV>MFI>MOR.

The self-diffusion coefficients were calculated by molecular dynamics simulations and the effects of pore width, temperature, and fluid density on diffusion behavior of simple fluid argon and polar fluid water confined in micropores were analyzed and studied.Amathematical model describing diffusion behavior of fluids confined in micropores was proposed from the theories of molecular dynamics and molecular kinematics, and validated on the basis of the simulation results at various conditions. The model indicates that the diffusion coefficient is proportional to the square root of the pore width and to the temperature divided by the density squared. It is applicable to either liquid or gas states and only two parameters are required.

Deuterium oxide solutions of schizophyllan, a triple-helical polysaccharide, undergoing an order-disorder transition centered at 17℃, were studied by optical rotation (OR) and heat capacity (Cp) to elucidate the molecular mechanism of the transition and water structure in the solution and frozen states. The ordered structure at low temperature consisted of the side chains and water in the vicinity forming an ordered hydrogen-bonded network surrounding the helix core and was disordered at higher temperature. In the solution state appeared clearly defined transition curves in both the OR and Cp data. The results for three samples of different molecular weights were analyzed theoretically, treating this transition as a typical linear cooperative transition from the ordered to disordered states and explained quantitatively if the molecular weight polydispersity of the ample was considered. The excess heat capacity Cp EX defined as the Cp minus the contributions from schizophyllan and D2O was estimated. In the frozen state it increased with raising temperature above 150 K until the mixture melted. This was compared with the dielectric increment observed in this temperature range and ascribed to unfreezable water. From the heat capacity and dielectric data, unfreezable water is mobile but more ordered than free water. In the solution state, the excess heat capacity originates from the interactions of D2O molecules as bound water and structured water, and so forth. Thus the schizophyllan triple helix molds water into various structures of differing orders in solution and in the solid state.