There are reports in the literature on the discovery of novel materials that were observed to shrink upon heating. Treatment of these materials in the same manner as the materials with positive coefficient of thermal ...There are reports in the literature on the discovery of novel materials that were observed to shrink upon heating. Treatment of these materials in the same manner as the materials with positive coefficient of thermal expansion can lead to the misinterpretation of the laws of thermodynamics. This is because volume expansivity is usually defined at constant pressure. Negative values for volume expansivity can be shown using Maxwell’s reciprocity relations to lead to negative values for absolute temperature for ideal gas. For real systems, using Helmholz free energy analysis at equilibrium an expression for the volume expansivity was derived. It can be seen that this expression would be always positive for real physical changes, either heating or cooling. Isentropic volume expansivity is proposed as better suited for analysis of materials with negative thermal expansion, NTE and composites used in space such as Hubble telescope and Chandra telescope with zero coefficient of thermal expansion. This kind of a switch from isobaric to isentropic has precedence in the history of development of speed of sound.展开更多
This study examines the issues in development of pharmacokinetic single compartment model for systems that obey free radical copolymerization kinetics. Copolymer composition as a function of reactivity ratios of comon...This study examines the issues in development of pharmacokinetic single compartment model for systems that obey free radical copolymerization kinetics. Copolymer composition as a function of reactivity ratios of comonomers for well mixed case was derived. For some cases, such as DEF-AN, diethyl fumarate and acrylonitrile system multiplicity in composition were found. The analysis is extended to n monomers. State space model expressions are used and the QSSA assumption is stated in state space equation form. Conditions when damped oscillations can be expected are noted. In addition to multiplicity in product composition, an account of reactivity ratios and other instances of multi- plicity were found during the pharmacodynamics of the free radical polymerization reactions. A careful study of initiated case, thermal case, 1 CSTR and 2 CSTRS was undertaken and results were presented. Numerical integration techniques were employed on the desktop computer. Steady state and transient state conversion for initiated case and thermal case for 1 CSTR and 2 CSTRs were calculated and plotted in Figures 7-9 and 12. No multiplicity was found in the thermal case for 1 CSTR in the dynamics of transient monomer conversion. Multiplicity was found in the initiated case for 1 CSTR in the dynamics of transient conversion of monomer. The multiplicity was found in the second CSTR for the case of 2 CSTRs in series. No multiplicity was found in the case of initiator decay.展开更多
文摘There are reports in the literature on the discovery of novel materials that were observed to shrink upon heating. Treatment of these materials in the same manner as the materials with positive coefficient of thermal expansion can lead to the misinterpretation of the laws of thermodynamics. This is because volume expansivity is usually defined at constant pressure. Negative values for volume expansivity can be shown using Maxwell’s reciprocity relations to lead to negative values for absolute temperature for ideal gas. For real systems, using Helmholz free energy analysis at equilibrium an expression for the volume expansivity was derived. It can be seen that this expression would be always positive for real physical changes, either heating or cooling. Isentropic volume expansivity is proposed as better suited for analysis of materials with negative thermal expansion, NTE and composites used in space such as Hubble telescope and Chandra telescope with zero coefficient of thermal expansion. This kind of a switch from isobaric to isentropic has precedence in the history of development of speed of sound.
文摘This study examines the issues in development of pharmacokinetic single compartment model for systems that obey free radical copolymerization kinetics. Copolymer composition as a function of reactivity ratios of comonomers for well mixed case was derived. For some cases, such as DEF-AN, diethyl fumarate and acrylonitrile system multiplicity in composition were found. The analysis is extended to n monomers. State space model expressions are used and the QSSA assumption is stated in state space equation form. Conditions when damped oscillations can be expected are noted. In addition to multiplicity in product composition, an account of reactivity ratios and other instances of multi- plicity were found during the pharmacodynamics of the free radical polymerization reactions. A careful study of initiated case, thermal case, 1 CSTR and 2 CSTRS was undertaken and results were presented. Numerical integration techniques were employed on the desktop computer. Steady state and transient state conversion for initiated case and thermal case for 1 CSTR and 2 CSTRs were calculated and plotted in Figures 7-9 and 12. No multiplicity was found in the thermal case for 1 CSTR in the dynamics of transient monomer conversion. Multiplicity was found in the initiated case for 1 CSTR in the dynamics of transient conversion of monomer. The multiplicity was found in the second CSTR for the case of 2 CSTRs in series. No multiplicity was found in the case of initiator decay.
