Measurements and Correlation for Diffusion Coefficients for Large Molecules in Non-organic Solvents

无机溶剂中大分子扩散系数的测量和关联

基本信息

  • 批准号:
    15560658
  • 负责人:
  • 金额:
    $ 2.3万
  • 依托单位:
  • 依托单位国家:
    日本
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
  • 财政年份:
    2003
  • 资助国家:
    日本
  • 起止时间:
    2003 至 2005
  • 项目状态:
    已结题

项目摘要

Although the Taylor dispersion method has been widely employed to measure diffusion coefficients of organic compounds in various solvents such as supercritical fluids and aqueous solutions, it is not suitable for polar compounds due to severe tailing. We have developed the chromatographic impulse response (CIR) method with a polymer coated capillary column for measurements for polar solutes. The objective of this project is to measure and correlate diffusion coefficients of various large molecular and/or polar compounds under supercritical carbon dioxide.To apply the CIR method to measurements for higher molecular weight compounds, two technical improvement methods have been developed : correction of the secondary flow effect and noise elimination technique for response curves having extremely low absorbance intensity. A conversion formula to correct for the secondary flow effect was derived from the second central moment of the CIR method with a coiled capillary column at relatively h … More igh flow rates. Its practical expression was obtained analytically by the perturbation method up to λ^<10>, where λ is the ratio of the tube radius to the coil radius. The effective range of DeSc^<1/2> < 8-9.5 without correction widened to DeSc^<1/2> < 18-19 to determine the diffusion coefficient within 1% error. The curve-fitting method with the noise elimination treatment was quite effective for determining the D_<12> values accurately, and was valid at the lowest absorbance intensities, on the order of 10^<-4> absorbance unit of UV-Vis multi-detector, corresponding to the smallest quantity of the solute. Using the CIR method with the noise elimination technique and the correction of the secondary flow effect, diffusion coefficients of various compounds such as acids, esters, glycerides, and alcohols were measured in supercritical carbon dioxide. Two predictive correlations, equation of D_<12>/T with solvent viscosity, and the Schmidt number correlation, were found effective for the prediction. Less
虽然Taylor分散法已被广泛用于测量有机化合物在各种溶剂(如超临界流体和水溶液)中的扩散系数,但由于严重的尾化,该方法不适用于极性化合物。我们开发了一种用于极性溶质测量的聚合物涂层毛细管柱色谱脉冲响应(CIR)方法。本项目的目的是测量和关联各种大分子和/或极性化合物在超临界二氧化碳下的扩散系数。为了将CIR方法应用于高分子量化合物的测量,开发了两种技术改进方法:校正二次流效应和对极低吸光度响应曲线的噪声消除技术。在相对高流速条件下,利用螺旋毛细管柱CIR法的第二次中心矩,导出了校正二次流效应的换算公式。用微扰法解析得到了λ^<10>的实际表达式,其中λ为管半径与线圈半径之比。将未经校正的DeSc^<1/2> < 8-9.5的有效范围扩大到DeSc^<1/2> < 18-19,确定扩散系数误差在1%以内。采用消噪处理的曲线拟合方法对D_<12>值的准确测定非常有效,并且在最低的吸光度强度下有效,约为10^<-4>的UV-Vis多检测器吸光度单位,对应溶质的最小量。采用带消噪技术和校正二次流效应的CIR方法,测定了超临界二氧化碳中酸、酯、甘油酯、醇等化合物的扩散系数。D_<12>/T与溶剂黏度的预测关系式和Schmidt数关系式是有效的预测方法。少

项目成果

期刊论文数量(33)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
クロマトグラフィックインパルス応答法による超臨界流体中における有機化合物の相互拡散系数の測定
色谱脉冲响应法测量超临界流体中有机化合物的相互扩散系数
  • DOI:
  • 发表时间:
    2004
  • 期刊:
  • 影响因子:
    0
  • 作者:
    船造俊孝;孔昌一;影井清一郎
  • 通讯作者:
    影井清一郎
Binary diffusion coefficient, partition ratio and partial molar volumes at infinite dilution for β-carotene and a-tocopherol in supercritical carbon dioxide
超临界二氧化碳中β-胡萝卜素和α-生育酚无限稀释时的二元扩散系数、分配比和偏摩尔体积
Measurement of binary diffusion coefficient from impulse response curve having extremely low absorbance intensity under supercritical condition by noise elimination technique
利用噪声消除技术测量超临界条件下吸光度极低的脉冲响应曲线的二元扩散系数
  • DOI:
  • 发表时间:
    2004
  • 期刊:
  • 影响因子:
    0
  • 作者:
    T.Funazukuri;C.Y.Kong;S.Kagei
  • 通讯作者:
    S.Kagei
Binary diffusion coefficients, partition ratios and partial molar volumes at infinite dilution for β-carotene and a-tocopherol in supercritical carbon dioxide
超临界二氧化碳中 β-胡萝卜素和 α-生育酚无限稀释时的二元扩散系数、分配比和偏摩尔体积
Measurements of Binary Diffusion Coefficient and Partition Ratio at Infinite Dilution for Linoleic Acid and Arachidonic Acid in Supercritical Carbon Dioxide
  • DOI:
    10.1021/je020205i
  • 发表时间:
    2003-04
  • 期刊:
  • 影响因子:
    0
  • 作者:
    T. Funazukuri;C. Y. Kong;T. Kikuchi;S. Kagei
  • 通讯作者:
    T. Funazukuri;C. Y. Kong;T. Kikuchi;S. Kagei
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FUNAZUKURI Toshitaka其他文献

FUNAZUKURI Toshitaka的其他文献

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{{ truncateString('FUNAZUKURI Toshitaka', 18)}}的其他基金

Development of zero-emission process with ammonia
开发氨零排放工艺
  • 批准号:
    23651075
  • 财政年份:
    2011
  • 资助金额:
    $ 2.3万
  • 项目类别:
    Grant-in-Aid for Challenging Exploratory Research
Diffusion coefficients of elemental compounds in various atmospheres
元素化合物在各种气氛中的扩散系数
  • 批准号:
    22360325
  • 财政年份:
    2010
  • 资助金额:
    $ 2.3万
  • 项目类别:
    Grant-in-Aid for Scientific Research (B)
Measurement and correlation of diffusion coefficients in gas expanded liquids
气体膨胀液体中扩散系数的测量和相关性
  • 批准号:
    18560725
  • 财政年份:
    2006
  • 资助金额:
    $ 2.3万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
Mass transfer in supercritical fluids related to the solute-solvent interactions
超临界流体中与溶质-溶剂相互作用相关的传质
  • 批准号:
    08650888
  • 财政年份:
    1996
  • 资助金额:
    $ 2.3万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)

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