The standard electromotive forces of the reversible cells consisted of the Corning monovalent general cation selective electrode (M + ISE) and chloride selective electrode (Cl ISE), namely Cl --ISE｜RbCl( m ),H 2O(1- ...The standard electromotive forces of the reversible cells consisted of the Corning monovalent general cation selective electrode (M + ISE) and chloride selective electrode (Cl ISE), namely Cl --ISE｜RbCl( m ),H 2O(1- x ),DMF( x )｜M +-ISE have been measured, and the standard free energies of transfer(Δ S t ) of RbCl from H 2O to mixtures of H 2O DMF have been calculated, the standard transfer entropies(Δ S t ) have been also calculated from temperature coefficients of Δ G t of RbCl at seven temperatures from 283.15 K to 318.15 K. The behavior of change of Δ S t of RbCl with experimental temperature and mole fraction ( x ) of DMF in the mixed solvents and its influence on the structure of the mixed solvents were discussed on the basis of solvation theory ofelectrolyte solution.展开更多
Standard Gibbs energies of transfer,△Gθt,of Tl(Ⅰ)from water to aqueous sucrose and aqueous glucose solutions(mass fractions of sucrose and glucose W=0,010,020,030,040 and 050)were determined by po...Standard Gibbs energies of transfer,△Gθt,of Tl(Ⅰ)from water to aqueous sucrose and aqueous glucose solutions(mass fractions of sucrose and glucose W=0,010,020,030,040 and 050)were determined by polarography at 298±1K.In aqueous sucrose and glucose solutions containing 50×10-2mol·L-1LiClO4,the reversible halfwave potential and the diffusion coefficients for Tl(Ⅰ)were determined,respectively.Values of △Gθt,obtained from the reversible halfwave potentials vs.the ferrocene electrode scale,are negative and these decrease with increasing concentration of sucrose and glucose,indicating increasing stability of Tl(Ⅰ)in sucrosewater and glucosewater solutions.The △Gθt values were split into electrostatic and chemical contributions.The decreased chemical contribution shows that the mixtures are more basic than pure water.The experimental results were discussed in terms of solutesolvent and solutesolute interactions in the ternary systems.展开更多
The standard transfer Gibbs energies (Δ trG° )of KBPh4 from reference solvent of water to water/ethanol, water/propanol, water/2- propanol,water/ethylene glycol, water/glycerol mixtures in different proportional...The standard transfer Gibbs energies (Δ trG° )of KBPh4 from reference solvent of water to water/ethanol, water/propanol, water/2- propanol,water/ethylene glycol, water/glycerol mixtures in different proportional ratio have been studied. The interactions of KBPh4 with the above mixed solvents were analyzed. The standard transfer Gibbs energy of cavity(Δ trG° cav) and the standard transfer Gibbs energy of interaction(Δ trG° int) from water to water/2- propanol mixtures at 298.15 K were calculated by the Scaled Particle Theory (SPT).展开更多
针对近红外光谱数据的维度高、特征之间存在严重的多重共线性的特点,提出了无迁移标准的通过校正分布差异的标定迁移方法(calibration transfer via correcting distributions difference,CT-CDD).CT-CDD首先建立主仪器的偏最小二乘模型...针对近红外光谱数据的维度高、特征之间存在严重的多重共线性的特点,提出了无迁移标准的通过校正分布差异的标定迁移方法(calibration transfer via correcting distributions difference,CT-CDD).CT-CDD首先建立主仪器的偏最小二乘模型,然后通过偏最小二乘模型提取主仪器和从仪器的潜变量,并且分别对主仪器和从仪器的潜变量进行聚类.该方法基于这样的假设:聚类后的主仪器和从仪器的每一部分特征光谱均服从单高斯分布.最后,找到2个仪器的最接近的子分布,通过校正均值和方差来校正数据分布的差异.实验结果表明CT-CDD通常更加鲁棒并且还可以实现最低的均方根预测误差.展开更多
The electrochemical behavior of Cu(II)Cu(Hg)system in aqueous sucrose solutions was studied by polarography and cyclic squarewave voltammetry.The reversible halfwave potential and the diffusion coefficients for ...The electrochemical behavior of Cu(II)Cu(Hg)system in aqueous sucrose solutions was studied by polarography and cyclic squarewave voltammetry.The reversible halfwave potential and the diffusion coefficients for Cu(II) were polarographically determined.The standard Gibbs energies of transfer of Cu(II) from water to sucrosewater solutions,ΔGt,were obtained from the reversible halfwave potentials.The measured values are negative with increasing concentration of sucrose,indicating increasing stability of Cu(II) in sucrosewater solutions.The ΔGt values were split into electrostatic and chemical contributions.The decreased chemical contribution shows that the mixtures are more basic than pure water.展开更多
文摘The standard electromotive forces of the reversible cells consisted of the Corning monovalent general cation selective electrode (M + ISE) and chloride selective electrode (Cl ISE), namely Cl --ISE｜RbCl( m ),H 2O(1- x ),DMF( x )｜M +-ISE have been measured, and the standard free energies of transfer(Δ S t ) of RbCl from H 2O to mixtures of H 2O DMF have been calculated, the standard transfer entropies(Δ S t ) have been also calculated from temperature coefficients of Δ G t of RbCl at seven temperatures from 283.15 K to 318.15 K. The behavior of change of Δ S t of RbCl with experimental temperature and mole fraction ( x ) of DMF in the mixed solvents and its influence on the structure of the mixed solvents were discussed on the basis of solvation theory ofelectrolyte solution.
文摘Standard Gibbs energies of transfer,△Gθt,of Tl(Ⅰ)from water to aqueous sucrose and aqueous glucose solutions(mass fractions of sucrose and glucose W=0,010,020,030,040 and 050)were determined by polarography at 298±1K.In aqueous sucrose and glucose solutions containing 50×10-2mol·L-1LiClO4,the reversible halfwave potential and the diffusion coefficients for Tl(Ⅰ)were determined,respectively.Values of △Gθt,obtained from the reversible halfwave potentials vs.the ferrocene electrode scale,are negative and these decrease with increasing concentration of sucrose and glucose,indicating increasing stability of Tl(Ⅰ)in sucrosewater and glucosewater solutions.The △Gθt values were split into electrostatic and chemical contributions.The decreased chemical contribution shows that the mixtures are more basic than pure water.The experimental results were discussed in terms of solutesolvent and solutesolute interactions in the ternary systems.
文摘The standard transfer Gibbs energies (Δ trG° )of KBPh4 from reference solvent of water to water/ethanol, water/propanol, water/2- propanol,water/ethylene glycol, water/glycerol mixtures in different proportional ratio have been studied. The interactions of KBPh4 with the above mixed solvents were analyzed. The standard transfer Gibbs energy of cavity(Δ trG° cav) and the standard transfer Gibbs energy of interaction(Δ trG° int) from water to water/2- propanol mixtures at 298.15 K were calculated by the Scaled Particle Theory (SPT).
文摘针对近红外光谱数据的维度高、特征之间存在严重的多重共线性的特点,提出了无迁移标准的通过校正分布差异的标定迁移方法(calibration transfer via correcting distributions difference,CT-CDD).CT-CDD首先建立主仪器的偏最小二乘模型,然后通过偏最小二乘模型提取主仪器和从仪器的潜变量,并且分别对主仪器和从仪器的潜变量进行聚类.该方法基于这样的假设:聚类后的主仪器和从仪器的每一部分特征光谱均服从单高斯分布.最后,找到2个仪器的最接近的子分布,通过校正均值和方差来校正数据分布的差异.实验结果表明CT-CDD通常更加鲁棒并且还可以实现最低的均方根预测误差.
文摘The electrochemical behavior of Cu(II)Cu(Hg)system in aqueous sucrose solutions was studied by polarography and cyclic squarewave voltammetry.The reversible halfwave potential and the diffusion coefficients for Cu(II) were polarographically determined.The standard Gibbs energies of transfer of Cu(II) from water to sucrosewater solutions,ΔGt,were obtained from the reversible halfwave potentials.The measured values are negative with increasing concentration of sucrose,indicating increasing stability of Cu(II) in sucrosewater solutions.The ΔGt values were split into electrostatic and chemical contributions.The decreased chemical contribution shows that the mixtures are more basic than pure water.
