The influence of hydrogen bonds on the physical and chemical properties of hydrogen bonding fluid system of AaDd type is investigated from two viewpoints by the principle of statistical mechanics. In detail, we proposed two new ways that can be used to obtain the equilibrium size distribution of the hydrogen bonding clusters, and derived the analytical expression of a relationship between the hydrogen bonding free energy and hydrogen bonding degree. For the nonlinear hydrogen bonding systems, it is shown that the sol-gel phase transition can take place under proper conditions, which is further proven to be a kind of geometrical phase transition rather than a thermodynamic one. Moreover, several problems associated with the geometrical phase transition and liquid-solid phase transition in nonlinear hydrogen bonding systems are discussed.
WANG Haijun1,2, HONG Xiaozhong3, GU Fang1 & BA Xinwu1 1. College of Chemistry and Environment Science, Hebei University, Baoding 071002, China
The equation of the state of the hydrogen bonding fluid system of AaDd type is studied by the principle of statistical mechanics. The influences of hydrogen bonds on the equation of state of the system are obtained based on the change in volume due to hydrogen bonds. Moreover,the number density fluc-tuations of both molecules and hydrogen bonds as well as their spatial correlation property are inves-tigated. Furthermore,an equation describing relation between the number density correlation function of "molecules-hydrogen bonds" and that of molecules and hydrogen bonds is derived. As application,taking the van der Waals hydrogen bonding fluid as an example,we considered the effect of hydrogen bonds on its relevant statistical properties.
WANG HaiJun1,2,GU Fang1,HONG XiaoZhong3 & BA XinWu1 1 College of Chemistry and Environment Science,Hebei University,Baoding 071002,China
The number of the hyperbranched polymers in the system is investigated for the polymerization process to give the asymptotic form of the concentration of the n-mer. The polydispersity exponent is calculated, which coincides with that of the classical result. Finally, the asymptotic forms of the number, the weight and the z-average degrees of the polymerization were evaluated analytically to obtain polydispersity index, which is close to 1 as the reaction is quantitatively completed.
Making use of the invariant property of the equilibrium size distribution of the hydrogen bonding clus- ters formed in hydrogen bonding system of AaDd type,the analytical expressions of the free energy in pregel and postgel regimes are obtained.Then the gel free energy and the scaling behavior of the number of hydrogen bonds in gel phase near the critical point are investigated to give the corre- sponding scaling exponents and scaling law.Meanwhile,some properties of intermolecular and in- tramolecular hydrogen bonds in the system,sol and gel phases are discussed.As a result,the explicit relationship between the number of intramolecular hydrogen bonds and hydrogen bonding degree is obtained.
