SOLVENT EFFECT ON THE RATE CONSTANT OF ROTETIONAL ISOMERISM IN SOLUTIONS
溶剂对溶液中旋转异构率常数的影响
基本信息
- 批准号:06453020
- 负责人:
- 金额:$ 3.65万
- 依托单位:
- 依托单位国家:日本
- 项目类别:Grant-in-Aid for General Scientific Research (B)
- 财政年份:1994
- 资助国家:日本
- 起止时间:1994 至 1995
- 项目状态:已结题
- 来源:
- 关键词:
项目摘要
THE PURPOSE OF THIS WORK IS TO ELUCIDATE THE RATE CONSTANT OF ROTATIONAL ISOMERISM IN SOLUTIONS BY ULTRASONIC AND RAMAN SPECTROSCOPIC METHODS.THE ULTRASONIC RELAXATION SPECTRA OF SEC-BUTYLBROMID IN N-HEXANE AND DIISOBUTYLPHTHALATE WERE MEASURED IN THE FREQUENCY RANGE FROM 5 MHZ TO 800MHZ.THE VISCOSITY DEPENDENCE OF THE RELAXATION FREQUENCY OF THE RATE CONSTANT WERE OBSERVED.THE CHANGES IN THE ENTHALPY (DELTAH) AND VOLUME (DELTAV) ACCOMPANYING THE ROTATIONAL ISOMERISM WERE ESTIMATED FROM THE TEMPERATURE AND PRESSURE DEPENDENCE OF THE RAMAN SPECTRA CORRESPONDING THE ROTATIONAL ISOMERS.THE VALUES OF DELTAH AND DELTA1V DECREASED WITH INCREASING THE VISCOSITY IN SOLUTIONS.ON THE OTHER HANDS,THE ACTIVATION ENTHALPY,WHICH IS ESTIMATED FROM THE TEMPERATURE DEPENDENCE OF THE ULTRASONIC FREQUENCY ARE AROUND 18 KJ/MOL.THE VISCOSITY DEPENDENCE OF THE RATE CONSTANT OF SEC-BUTYLBROMID IS NOT INTERPRETED IN TERMS OF THE KRAMERS THEORY.THE DEVIATION FROM THE THEORY WAS RECOGNIZED IN THE HIGH VISCOSITY REGION.THE RESULTS OBTAINED FROM THE ULTRASONIC AND RAMAN SPECTROSCOPY INDICATED THAT THE POTENTIAL CURVES OF THE ROTATIONAL ISOMERISM IS MODIFIED BY THE CHANGE IN THE VISCOSITY IN SOLUTION.THAT IS THE INTERACTION BETWEEN SOLUTE AND SOLVENTS.IT IS DESIRABLE TO DEVELOP THE NEW THEORY OF THE RATE CONSTANT,WHICH PREDICTS THE VISCOSITY DEPENDENCE.
本文用超声波和拉曼光谱法测定了仲丁基溴在正己烷和邻苯二甲酸二异丁酯中的超声波弛豫谱,观察了弛豫频率与粘度的关系,并测定了焓(Δ H)和体积(Δ V)的变化。从对应于旋转异构体的拉曼光谱的温度和压力依赖性估计了伴随旋转异构体的Δ H和Δ 1V值,Δ H和Δ 1V值随溶液粘度的增加而减小,另一方面,活化能,由超声波频率的温度依赖性估算出其值约为18 KJ/MOL。丁溴不能用Kramers理论来解释。在高粘度区,偏离了Kramers理论。超声波和拉曼光谱的结果表明,溶液粘度的变化,即溶质与溶剂之间的相互作用,改变了旋转异构体的势能曲线。修正新的速率常数理论是合理的。其预测粘度依赖性。
项目成果
期刊论文数量(58)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
Tatsuro,Matsuoka: "Velocity Measurement Using Optical Beam Deflection" Jpn.J.Appl.Phys.34. 2778-2780 (1995)
Tatsuro,Matsuoka:“利用光束偏转进行速度测量”Jpn.J.Appl.Phys.34。
- DOI:
- 发表时间:
- 期刊:
- 影响因子:0
- 作者:
- 通讯作者:
Shinobu Koda: "Investigation on the Viscosity Dependence of the Rate Constant of Rotational Isomerism of Dibromoethane and Dibromopropane in Solutions" J.Chem.Soc.,Faraday Transactions. 91. 445-449 (1995)
Shinobu Koda:“溶液中二溴乙烷和二溴丙烷旋转异构的速率常数对粘度依赖性的研究”J.Chem.Soc.,法拉第交易。
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- 影响因子:0
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Shinobu Koda: "Ultrasonic Investigation on the States of Water in Hydrogel" Polymer. 35. 5626-5630 (1994)
Shinobu Koda:“水凝胶中水状态的超声波研究”聚合物。
- DOI:
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- 影响因子:0
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Tatsuro Matsuoka: "Effect of Addition of Suefactant on the Miccelle-Monomoer Exchange Peocess" J.Mol.Liquids. 99. 337-340 (1995)
Tatsuro Matsuoka:“添加表面活性剂对胶束-单体交换过程的影响”J.Mol.Liquids。
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- 影响因子:0
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NOMURA Hiroyasu其他文献
NOMURA Hiroyasu的其他文献
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{{ truncateString('NOMURA Hiroyasu', 18)}}的其他基金
Spatial and temporal scale of cooperative motions in supercooled liquids
过冷液体中协同运动的空间和时间尺度
- 批准号:
09440199 - 财政年份:1997
- 资助金额:
$ 3.65万 - 项目类别:
Grant-in-Aid for Scientific Research (B)
相似海外基金
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Discovery Grants Program - Individual
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- 批准号:
1961-1995 - 财政年份:1995
- 资助金额:
$ 3.65万 - 项目类别:
Discovery Grants Program - Individual