The solid complex of lithium perchlorate with 4 tert butylbenzo 15 crown 5（4 t BB15C5） has been prepared in iodobenzene. The composition of the solid was determined as Li（4 t BB15C5）ClO 4 and its melting point was...The solid complex of lithium perchlorate with 4 tert butylbenzo 15 crown 5（4 t BB15C5） has been prepared in iodobenzene. The composition of the solid was determined as Li（4 t BB15C5）ClO 4 and its melting point was 119121 ℃. The far IR shift of the complex is obvious. The far IR absorption band of the complex containing 100% 6Li can be found by extrapolation, resolving the difficulty in obtaining a sample of 100% 6Li up to now. A relative reduced partition function ratio, [（ s/s′）f ] org , being 1.045 is calculated. Since the [ （s/s′）f ] aq of lithium perchlorate in solid state had been obtained as 1.025 and may act as that in aqueous phase, the phase equilibrium separation factor α may be obtained as 1.019 by the quotient of 1.045/1.025 for the extractive system of （4 t BB15C5） C 6H 5I/LiClO 4 H 2O. The value of α is just equal to the value of intrinsic separation factor （1+ ε p） described previously. [WT5HZ]展开更多
Two reduced sequences of(s/s′)f (relative reduced partition function ratio) found in the present paper are LiSCN·B15C5>LiCCl3COO·B15C5 > LiClO4·B15C5 and LiClO4·4-mB15C5>LiClO4·B15C5...Two reduced sequences of(s/s′)f (relative reduced partition function ratio) found in the present paper are LiSCN·B15C5>LiCCl3COO·B15C5 > LiClO4·B15C5 and LiClO4·4-mB15C5>LiClO4·B15C5>LiClO4·Ph15C5,respectively.These solid lithium complexes with crown ethers were separated from tetrahydrofuran for the first sequence and from 3-methyl-1-butanol for the second one,respectively.Acording to the analysis of the data obtained,an independent character of the three factors(solvents,anion of lithium salts,and the sidegroup of 15C5 series),playing a part in contribution to(s/s′)f,have been brought to light preliminarily.展开更多
测定了乙醇、异丙醇和正丁醇与环己烷,甲苯混合溶液的红外光谱,且从溶质、溶剂相互作用的角度对其进行了讨论,在分析现有的红外位移理论处理公式的基础上,从溶剂的极性参数 Et 表征醇烃分子间的特殊相互作用,对几种醇在十多种溶剂中的...测定了乙醇、异丙醇和正丁醇与环己烷,甲苯混合溶液的红外光谱,且从溶质、溶剂相互作用的角度对其进行了讨论,在分析现有的红外位移理论处理公式的基础上,从溶剂的极性参数 Et 表征醇烃分子间的特殊相互作用,对几种醇在十多种溶剂中的红外位移进行了关联,得到了较为满意的结果.展开更多
An all-atom dimethyl sulfoxide （DMSO） and water model have been used for molecular dynamics simulation. The NMR and IR spectra are also performed to study the structures and interactions in the DMSO-water system. An...An all-atom dimethyl sulfoxide （DMSO） and water model have been used for molecular dynamics simulation. The NMR and IR spectra are also performed to study the structures and interactions in the DMSO-water system. And there are traditional strong hydrogen bonds and weak C-H- ~ ~ O contacts existing in the mixtures according to the analysis of the radial distribution functions. The insight structures in the DMSO-water mixtures can be classified into different regions by the analysis of the hydrogen-bonding network. Interestingly, the molar fraction of DMSO 0.35 is found to be a special concentration by the network. It is the transitional region which is from the water rich region to the DMSO rich region. The stable aggregates of （DMSO）m＇S=O…… HW-OW-（H20）n might play a key role in this region. Moreover, the simulation is compared with the chemical shifts in NMR and wavenumbers in IR with concentration dependence. And the statistical results of the average number hydrogen bonds in the MD simulations are in agreement with the experiment data in NMR and IR spectra.展开更多
文摘The solid complex of lithium perchlorate with 4 tert butylbenzo 15 crown 5（4 t BB15C5） has been prepared in iodobenzene. The composition of the solid was determined as Li（4 t BB15C5）ClO 4 and its melting point was 119121 ℃. The far IR shift of the complex is obvious. The far IR absorption band of the complex containing 100% 6Li can be found by extrapolation, resolving the difficulty in obtaining a sample of 100% 6Li up to now. A relative reduced partition function ratio, [（ s/s′）f ] org , being 1.045 is calculated. Since the [ （s/s′）f ] aq of lithium perchlorate in solid state had been obtained as 1.025 and may act as that in aqueous phase, the phase equilibrium separation factor α may be obtained as 1.019 by the quotient of 1.045/1.025 for the extractive system of （4 t BB15C5） C 6H 5I/LiClO 4 H 2O. The value of α is just equal to the value of intrinsic separation factor （1+ ε p） described previously. [WT5HZ]
文摘Two reduced sequences of(s/s′)f (relative reduced partition function ratio) found in the present paper are LiSCN·B15C5>LiCCl3COO·B15C5 > LiClO4·B15C5 and LiClO4·4-mB15C5>LiClO4·B15C5>LiClO4·Ph15C5,respectively.These solid lithium complexes with crown ethers were separated from tetrahydrofuran for the first sequence and from 3-methyl-1-butanol for the second one,respectively.Acording to the analysis of the data obtained,an independent character of the three factors(solvents,anion of lithium salts,and the sidegroup of 15C5 series),playing a part in contribution to(s/s′)f,have been brought to light preliminarily.
文摘An all-atom dimethyl sulfoxide （DMSO） and water model have been used for molecular dynamics simulation. The NMR and IR spectra are also performed to study the structures and interactions in the DMSO-water system. And there are traditional strong hydrogen bonds and weak C-H- ~ ~ O contacts existing in the mixtures according to the analysis of the radial distribution functions. The insight structures in the DMSO-water mixtures can be classified into different regions by the analysis of the hydrogen-bonding network. Interestingly, the molar fraction of DMSO 0.35 is found to be a special concentration by the network. It is the transitional region which is from the water rich region to the DMSO rich region. The stable aggregates of （DMSO）m＇S=O…… HW-OW-（H20）n might play a key role in this region. Moreover, the simulation is compared with the chemical shifts in NMR and wavenumbers in IR with concentration dependence. And the statistical results of the average number hydrogen bonds in the MD simulations are in agreement with the experiment data in NMR and IR spectra.
