A minimum-modified Debye-Hückel(DH)theory for electrolytes with size asymmetry is developed.Com-pared with the conventional DH theory,the minimum-modified DH theory only introduces an extra surface charge density...A minimum-modified Debye-Hückel(DH)theory for electrolytes with size asymmetry is developed.Com-pared with the conventional DH theory,the minimum-modified DH theory only introduces an extra surface charge density to capture the electrostatic effect of the size asymmetry of the electrolytes and hence facilitates a boundary element method for electrostatic potential calculation.This theory can distinguish the electrostat-ic energies and excess chemical potentials of ions with the same sizes but opposite charges,and is applied to a binary primitive electrolyte solution with moderate electrostatic coupling.Compared with the hyper-netted chain theory,the validity of this modified DH theory demonstrates significant improvement over the conventional DH theory.展开更多
Peter Debye and Erich Hückel had developed a theory for the ionic activity coefficients in dilute solutions of strong electrolytes some 95 years ago [1]. Their limiting law still stands and is confirmed as close ...Peter Debye and Erich Hückel had developed a theory for the ionic activity coefficients in dilute solutions of strong electrolytes some 95 years ago [1]. Their limiting law still stands and is confirmed as close to reality in many experiments. In a previous article [2], it is shown that these limiting activity coefficients arise because the electrical contribution in the electrochemical potential of ionic species is overestimated traditionally with a factor 2. The smaller value removes inconsistencies in the models and complies better with the basic electrostatic principles. In this article further evidence is given in support of this alternative description. As consequence the dilute activity coefficients become unity, e.g. are removed, which means that the electrochemical potential of ions in dilute solutions is expressed directly in concentration, instead of activity, which simplifies modelling in such dilute solutions.展开更多
Debye-screening effects on the electron-impact excitation(EIE)processes for the dipole-allowed transition 1 s_(2)^(1)S→1 s2 p^(1)P in He-like Al^(11+)and Fe^(24+)ions are investigated using the fully relativistic dis...Debye-screening effects on the electron-impact excitation(EIE)processes for the dipole-allowed transition 1 s_(2)^(1)S→1 s2 p^(1)P in He-like Al^(11+)and Fe^(24+)ions are investigated using the fully relativistic distorted-wave methods with the Debye-Huckel(DH)model potential.Debye-screening effects on the continuum-bound(CB)interaction and target ion are discussed,both of which result in reduction of EIE cross sections.This reduction due to screening on the CB interaction is dominant.The non-spherical and spherical DH potentials are adopted for considering the screening effect on the CB interaction.It is found that the spherical DH potential could significantly overestimate the influence of plasma screening on EIE cross sections for multielectron He-like ions.展开更多
Complexation of two ligands, iminodiacetic acid and ethylenediamine-N,N′-diacetic acid, with molybdenum（Ⅵ） was studied in aqueous solutions. Molybdenum（Ⅵ） forms a mononuclear complex with the aforementioned lig...Complexation of two ligands, iminodiacetic acid and ethylenediamine-N,N′-diacetic acid, with molybdenum（Ⅵ） was studied in aqueous solutions. Molybdenum（Ⅵ） forms a mononuclear complex with the aforementioned ligands of the type MoO3L^2-. All measurements have been carried out at 25 ℃ and different ionic strengths ranging from 0.1 to 1.0 mol·L^-1 of NaClO4, with the pH justified to 6.0. Equilibrium concentration products and stoichiometry of the complexes have been determined from a combination of potentiometric and UV spectroscopic measurements. Comparison of the ionic strength effect on these complex formation reactions has been made using a Debye-Hückel type equation and Bronsted-Guggenheim-Scatchard specific ion interaction theory （SIT）. Debye-Hückel theory predicted the first order effects on simple electrolyte solutions. Interactions between the reacting species and the ionic medium were taken into account in the SIT model. All of the calculations have been done by the computer program Excel 2000.展开更多
The dynamic monitoring technology of inorganic ions using ion selective electrodes has some problems such as low precision,vulnerability to other ions,short service life,and high price.Due to the difficulty of dynamic...The dynamic monitoring technology of inorganic ions using ion selective electrodes has some problems such as low precision,vulnerability to other ions,short service life,and high price.Due to the difficulty of dynamic control based on ionic concentration of nutrient solution,EC and pH values of nutrient solution are often used as feedback control indexes in hydroponic system.In this study,estimation algorisms of EC and ionic EC contribution percentage based on ionic activity were proposed to understand the quantitative relationship between ionic concentration and EC.With a view to predicting the EC accurately by mean ionic activities of specific salts in nutrient solution based on a specific formula,ionic concentration could also be calculated by the actual measurement of EC combined with ionic EC contribution percentage.With Japanese horticultural experimental nutrient formula and Yamasaki tomato nutrient formula,significant linear correlations between estimated EC and measured EC were found with determination coefficients over 0.99.Ionic EC contribution percentage was not affected by different relative concentrations of nutrient solutions.However,ionic EC contribution percentage changed significantly when adding specific salts with different concentrations,and different changes were found in each anions and cations of specific salt added.When the same K+concentration was added in different forms of KNO_(3),K_(2_SO_(4),KCl,and KH_(2)PO_(4),the changes of ionic EC contribution percentage of K^(+)were similar,but those of other anions in potassium salts varied greatly.The relative errors of estimated EC of nutrient solutions based on ionic activities were only 1.3%in horticultural experimental nutrient solution and 1.8%in Yamasaki tomato nutrient solution with different relative concentrations compared to measured EC.The relative errors of estimated EC of nutrient solutions with specific salt added were only 0.1%-0.5%compared to measured EC in two nutrient solution.Therefore,the dynamic feedback control of ionic concentration of nutrient solution could be realized by using EC measurement combined with ionic EC contribution percentage to improve the ionic quantitative control in nutrient solution.The EC control of nutrient solution in automatic irrigation system might be upgraded to ionic concentration control by using algorisms above of ionic EC contribution percentage and EC estimation to meet dynamic demands of hydroponic crops for ionic concentration in different growth stages.展开更多
基金supported by the National Natural Science Foundation of China(No.21863001)a startup package from Guizhou Education University(to Tiejun Xiao)+1 种基金the Natural Science Foundation of de-partment of education of Guizhou province(No.QJKY[2015]483)a startup package from Guizhou Education University(to Yun Zhou).
文摘A minimum-modified Debye-Hückel(DH)theory for electrolytes with size asymmetry is developed.Com-pared with the conventional DH theory,the minimum-modified DH theory only introduces an extra surface charge density to capture the electrostatic effect of the size asymmetry of the electrolytes and hence facilitates a boundary element method for electrostatic potential calculation.This theory can distinguish the electrostat-ic energies and excess chemical potentials of ions with the same sizes but opposite charges,and is applied to a binary primitive electrolyte solution with moderate electrostatic coupling.Compared with the hyper-netted chain theory,the validity of this modified DH theory demonstrates significant improvement over the conventional DH theory.
文摘Peter Debye and Erich Hückel had developed a theory for the ionic activity coefficients in dilute solutions of strong electrolytes some 95 years ago [1]. Their limiting law still stands and is confirmed as close to reality in many experiments. In a previous article [2], it is shown that these limiting activity coefficients arise because the electrical contribution in the electrochemical potential of ionic species is overestimated traditionally with a factor 2. The smaller value removes inconsistencies in the models and complies better with the basic electrostatic principles. In this article further evidence is given in support of this alternative description. As consequence the dilute activity coefficients become unity, e.g. are removed, which means that the electrochemical potential of ions in dilute solutions is expressed directly in concentration, instead of activity, which simplifies modelling in such dilute solutions.
基金Project supported by the Science Challenge Project(Grant No.TZ2016001)the National Key Research and Development Program of China(Grants Nos.2017YFA0403200 and 2017YFA0402300)+1 种基金the Funds for Innovative Fundamental Research Group Project of Gansu Province,China(Grant No.20JR5RA541)the National Natural Science Foundation of China(Grants Nos.11774037 and 12064041)。
文摘Debye-screening effects on the electron-impact excitation(EIE)processes for the dipole-allowed transition 1 s_(2)^(1)S→1 s2 p^(1)P in He-like Al^(11+)and Fe^(24+)ions are investigated using the fully relativistic distorted-wave methods with the Debye-Huckel(DH)model potential.Debye-screening effects on the continuum-bound(CB)interaction and target ion are discussed,both of which result in reduction of EIE cross sections.This reduction due to screening on the CB interaction is dominant.The non-spherical and spherical DH potentials are adopted for considering the screening effect on the CB interaction.It is found that the spherical DH potential could significantly overestimate the influence of plasma screening on EIE cross sections for multielectron He-like ions.
文摘Complexation of two ligands, iminodiacetic acid and ethylenediamine-N,N′-diacetic acid, with molybdenum（Ⅵ） was studied in aqueous solutions. Molybdenum（Ⅵ） forms a mononuclear complex with the aforementioned ligands of the type MoO3L^2-. All measurements have been carried out at 25 ℃ and different ionic strengths ranging from 0.1 to 1.0 mol·L^-1 of NaClO4, with the pH justified to 6.0. Equilibrium concentration products and stoichiometry of the complexes have been determined from a combination of potentiometric and UV spectroscopic measurements. Comparison of the ionic strength effect on these complex formation reactions has been made using a Debye-Hückel type equation and Bronsted-Guggenheim-Scatchard specific ion interaction theory （SIT）. Debye-Hückel theory predicted the first order effects on simple electrolyte solutions. Interactions between the reacting species and the ionic medium were taken into account in the SIT model. All of the calculations have been done by the computer program Excel 2000.
基金This work was supported by National Key Research and Development Program of China(Grant No.2017YFD0201503).
文摘The dynamic monitoring technology of inorganic ions using ion selective electrodes has some problems such as low precision,vulnerability to other ions,short service life,and high price.Due to the difficulty of dynamic control based on ionic concentration of nutrient solution,EC and pH values of nutrient solution are often used as feedback control indexes in hydroponic system.In this study,estimation algorisms of EC and ionic EC contribution percentage based on ionic activity were proposed to understand the quantitative relationship between ionic concentration and EC.With a view to predicting the EC accurately by mean ionic activities of specific salts in nutrient solution based on a specific formula,ionic concentration could also be calculated by the actual measurement of EC combined with ionic EC contribution percentage.With Japanese horticultural experimental nutrient formula and Yamasaki tomato nutrient formula,significant linear correlations between estimated EC and measured EC were found with determination coefficients over 0.99.Ionic EC contribution percentage was not affected by different relative concentrations of nutrient solutions.However,ionic EC contribution percentage changed significantly when adding specific salts with different concentrations,and different changes were found in each anions and cations of specific salt added.When the same K+concentration was added in different forms of KNO_(3),K_(2_SO_(4),KCl,and KH_(2)PO_(4),the changes of ionic EC contribution percentage of K^(+)were similar,but those of other anions in potassium salts varied greatly.The relative errors of estimated EC of nutrient solutions based on ionic activities were only 1.3%in horticultural experimental nutrient solution and 1.8%in Yamasaki tomato nutrient solution with different relative concentrations compared to measured EC.The relative errors of estimated EC of nutrient solutions with specific salt added were only 0.1%-0.5%compared to measured EC in two nutrient solution.Therefore,the dynamic feedback control of ionic concentration of nutrient solution could be realized by using EC measurement combined with ionic EC contribution percentage to improve the ionic quantitative control in nutrient solution.The EC control of nutrient solution in automatic irrigation system might be upgraded to ionic concentration control by using algorisms above of ionic EC contribution percentage and EC estimation to meet dynamic demands of hydroponic crops for ionic concentration in different growth stages.
