The applicability of the density rule of Pathwardhan and Kumer and the rule based on the linear isopiestic relation is studied by comparison with experimental density data in the literature. Predicted and measured val...The applicability of the density rule of Pathwardhan and Kumer and the rule based on the linear isopiestic relation is studied by comparison with experimental density data in the literature. Predicted and measured values for 18 electrolyte mixtures are compared. The two rules are good for mixtures with and without common ions, including those containing associating ions. The deviations of the rule based on the linear isopiestic relation are slightly higher for the mixtures involving very strong ion complexes, but the predictions are still quite satisfactory.The density rule of Pathwardhan and Kumer is more accurate for these mixtures. However, it is not applicable for mixtures containing non-electrolytes. The rule based on the linear isopiestic relation is extended to mixtures involving non-electrolytes. The predictions for the mixtures containing both electrolytes and non-electrolytes and the non-electrolyte mixtures are accurate. All these results indicate that this rule is a widely applicable approach.展开更多
Photochemical and thermal isomerization of various azobenzenes was systematically investigated to understand the correlation between the molecular structure and trans → cis isomerization characteristics of azobenzene...Photochemical and thermal isomerization of various azobenzenes was systematically investigated to understand the correlation between the molecular structure and trans → cis isomerization characteristics of azobenzenes. A blue shift in π-π absorption band of ortho-alkylated azobenzenes （1o and 2o） was observed together with a reduction in molar extinction coefficient （e） in comparison with both meta-alkylated azobenzenes （4m and 5m） and 7p lacking the meta and ortho substituents. For orthoalkylated azobenzene, photochemical trans-to-cis isomerization and thermal back cis-to-trans isomerization in solution oc- curred slowly when compared with 4m, 5m and 7p. The half-life time of the cis form of 20 was found to be 380 h, which is about 8-50 times longer than those of comparable 4m, 5m （43-13 h） and 7p （7 h）. Furthermore, comparison of the molecular structure and isomerization characteristics of azobenzene thiol （20 and 5m） self-assembled monolayers on flat gold surfaces indicates that the trans-to-cis photoconversion in monolayer systems is influenced by steric hindrance and strong intermoleculax interaction between azobenzene units.展开更多
基金Supported by the Science Foundation of University of Petroleum (No. ZX9903), the Open Science Foundation of the State Key Laboratory of Heavy Oil Processing (No. 200005), and the National Natural Science Foundation of China (No. 20006010).
文摘The applicability of the density rule of Pathwardhan and Kumer and the rule based on the linear isopiestic relation is studied by comparison with experimental density data in the literature. Predicted and measured values for 18 electrolyte mixtures are compared. The two rules are good for mixtures with and without common ions, including those containing associating ions. The deviations of the rule based on the linear isopiestic relation are slightly higher for the mixtures involving very strong ion complexes, but the predictions are still quite satisfactory.The density rule of Pathwardhan and Kumer is more accurate for these mixtures. However, it is not applicable for mixtures containing non-electrolytes. The rule based on the linear isopiestic relation is extended to mixtures involving non-electrolytes. The predictions for the mixtures containing both electrolytes and non-electrolytes and the non-electrolyte mixtures are accurate. All these results indicate that this rule is a widely applicable approach.
基金supported by the Global COE Program from the Ministry of Education,Culture,Sports,Science,and Technology of Japanese Government
文摘Photochemical and thermal isomerization of various azobenzenes was systematically investigated to understand the correlation between the molecular structure and trans → cis isomerization characteristics of azobenzenes. A blue shift in π-π absorption band of ortho-alkylated azobenzenes （1o and 2o） was observed together with a reduction in molar extinction coefficient （e） in comparison with both meta-alkylated azobenzenes （4m and 5m） and 7p lacking the meta and ortho substituents. For orthoalkylated azobenzene, photochemical trans-to-cis isomerization and thermal back cis-to-trans isomerization in solution oc- curred slowly when compared with 4m, 5m and 7p. The half-life time of the cis form of 20 was found to be 380 h, which is about 8-50 times longer than those of comparable 4m, 5m （43-13 h） and 7p （7 h）. Furthermore, comparison of the molecular structure and isomerization characteristics of azobenzene thiol （20 and 5m） self-assembled monolayers on flat gold surfaces indicates that the trans-to-cis photoconversion in monolayer systems is influenced by steric hindrance and strong intermoleculax interaction between azobenzene units.
