Accurate calculation of thermodynamic properties of electrolyte solution is essential in the design and optimization of many processes in chemical industries. A new electrolyte equation of state is developed for aqueo...Accurate calculation of thermodynamic properties of electrolyte solution is essential in the design and optimization of many processes in chemical industries. A new electrolyte equation of state is developed for aqueous electrolyte solutions. The Carnahan-Starling repulsive model and an attractive term based on square-well potential are adopted to represent the short range interaction of ionic and molecular species in the new electrolyte EOS. The long range interaction of ionic species is expressed by a simplified version of Mean Spherical Approximation theory （MSA）. The new equation of state also contains a Born term for charging free energy of ions. Three adjustable parameters of new eEOS per each electrolyte solution are size parameter, square-well potential depth and square-well potential interaction range. The new eEOS is applied for correlation of mean activity coefficient and prediction of osmotic coefficient of various strong aqueous electrolyte solutions at 25℃ and 0.1 MPa. In addition, the extension of the new eEOS for correlation of mean activity coefficient and solution density of a few aqueous electrolytes at temperature range of 0 to 100℃ is carried out.展开更多
A molecular thermodynamic model of polyelectrolyte developed previously was extended to polyelectrolyte solutions with added salts.Thermodynamic properties,such as activity coefficients of polyelectrolytes or added sa...A molecular thermodynamic model of polyelectrolyte developed previously was extended to polyelectrolyte solutions with added salts.Thermodynamic properties,such as activity coefficients of polyelectrolytes or added salts and osmotic coefficients of solvent, of a number of aqueous mixtures of polyelectrolytes and salts are analyzed with the proposed model.Successful correlation is obtained in the range of moderate or higher polyion concentration.For the same sample,thermodynamic properties of polyelectrolytes with and without simple electrolytes can be predicted mutually using parameters from regression data.展开更多
This work dealt with the computation of the mean activity coefficients of rare-earth halide aqueous solutions at 25℃, by means of the Quasi Random Lattice（QRL） model. The osmotic coefficients were then calculated c...This work dealt with the computation of the mean activity coefficients of rare-earth halide aqueous solutions at 25℃, by means of the Quasi Random Lattice（QRL） model. The osmotic coefficients were then calculated consistently, through the integration of the Gibbs-Duhem equation. Using of QRL was mainly motivated by its dependence on one parameter, given in the form of an electrolyte-dependent concentration, which was also the highest concentration at which the model could be applied. For all the electrolyte solutions here considered, this parameter was experimentally known and ranged from 1.5 to 2.2 mol/kg, at 25 ℃.Accordingly, rare- earth halide concentrations from strong dilution up to 2 mol/kg about could be considered without need for best-fit treatment in order to compute their osmotic and mean activity coefficients. The experimental knowledge about the parameter was an advantageous feature of QRL compared to existing literature models. Following a trend already observed with low charge electrolytes,a satisfactory agreement was obtained with the experimental values for all the investigated rare-earth chlorides and bromides. For the sake of compactness, in this work the considered rare-earth halides were all belonging to the P63/m space group in their crystalline（anhydrous） form.展开更多
A new expression for the osmotic and activity coefficients in single electrolyte solution is developed by reforming the Pitzer's osmotic equation.As a result,the correlations between the oMX,the sum of the"ha...A new expression for the osmotic and activity coefficients in single electrolyte solution is developed by reforming the Pitzer's osmotic equation.As a result,the correlations between the oMX,the sum of the"hard core"radii of ionsβ^(0)_(MX)andβ^(1)X_(MX),and the second virial coefficients/jjJx and'n Pitzer's equations are obtained.Furthermore,an"ionic overlap"model and its relevant equation are suggested.The relationships between the thermodynamic properties of aqueous electrolytes and the characteristic of their ions(ionic radii and ionic hydration)are discussed quantitatively.展开更多
In this work, a new activity coefficient model was deduced for the correlation of solid–liquid equilibrium(SLE) in electrolyte solutions. The new excess Gibbs energy equation for SLE contains two parts: the single el...In this work, a new activity coefficient model was deduced for the correlation of solid–liquid equilibrium(SLE) in electrolyte solutions. The new excess Gibbs energy equation for SLE contains two parts: the single electrolyte item and the mixed electrolyte item. Then a new hypothesis for the reference state of activity coefficients was proposed in the work. Literature data for single electrolyte solution and mixed electrolyte solution systems,with temperature spanning from 273.15 to 373.15 K, were successfully correlated using the developed model.展开更多
文摘Accurate calculation of thermodynamic properties of electrolyte solution is essential in the design and optimization of many processes in chemical industries. A new electrolyte equation of state is developed for aqueous electrolyte solutions. The Carnahan-Starling repulsive model and an attractive term based on square-well potential are adopted to represent the short range interaction of ionic and molecular species in the new electrolyte EOS. The long range interaction of ionic species is expressed by a simplified version of Mean Spherical Approximation theory （MSA）. The new equation of state also contains a Born term for charging free energy of ions. Three adjustable parameters of new eEOS per each electrolyte solution are size parameter, square-well potential depth and square-well potential interaction range. The new eEOS is applied for correlation of mean activity coefficient and prediction of osmotic coefficient of various strong aqueous electrolyte solutions at 25℃ and 0.1 MPa. In addition, the extension of the new eEOS for correlation of mean activity coefficient and solution density of a few aqueous electrolytes at temperature range of 0 to 100℃ is carried out.
基金Supported by the National Natural Science Foundation of China (No. 29736170, 29876006).
文摘A molecular thermodynamic model of polyelectrolyte developed previously was extended to polyelectrolyte solutions with added salts.Thermodynamic properties,such as activity coefficients of polyelectrolytes or added salts and osmotic coefficients of solvent, of a number of aqueous mixtures of polyelectrolytes and salts are analyzed with the proposed model.Successful correlation is obtained in the range of moderate or higher polyion concentration.For the same sample,thermodynamic properties of polyelectrolytes with and without simple electrolytes can be predicted mutually using parameters from regression data.
文摘This work dealt with the computation of the mean activity coefficients of rare-earth halide aqueous solutions at 25℃, by means of the Quasi Random Lattice（QRL） model. The osmotic coefficients were then calculated consistently, through the integration of the Gibbs-Duhem equation. Using of QRL was mainly motivated by its dependence on one parameter, given in the form of an electrolyte-dependent concentration, which was also the highest concentration at which the model could be applied. For all the electrolyte solutions here considered, this parameter was experimentally known and ranged from 1.5 to 2.2 mol/kg, at 25 ℃.Accordingly, rare- earth halide concentrations from strong dilution up to 2 mol/kg about could be considered without need for best-fit treatment in order to compute their osmotic and mean activity coefficients. The experimental knowledge about the parameter was an advantageous feature of QRL compared to existing literature models. Following a trend already observed with low charge electrolytes,a satisfactory agreement was obtained with the experimental values for all the investigated rare-earth chlorides and bromides. For the sake of compactness, in this work the considered rare-earth halides were all belonging to the P63/m space group in their crystalline（anhydrous） form.
文摘A new expression for the osmotic and activity coefficients in single electrolyte solution is developed by reforming the Pitzer's osmotic equation.As a result,the correlations between the oMX,the sum of the"hard core"radii of ionsβ^(0)_(MX)andβ^(1)X_(MX),and the second virial coefficients/jjJx and'n Pitzer's equations are obtained.Furthermore,an"ionic overlap"model and its relevant equation are suggested.The relationships between the thermodynamic properties of aqueous electrolytes and the characteristic of their ions(ionic radii and ionic hydration)are discussed quantitatively.
基金Supported by the National Natural Science Foundation of China(21376231)
文摘In this work, a new activity coefficient model was deduced for the correlation of solid–liquid equilibrium(SLE) in electrolyte solutions. The new excess Gibbs energy equation for SLE contains two parts: the single electrolyte item and the mixed electrolyte item. Then a new hypothesis for the reference state of activity coefficients was proposed in the work. Literature data for single electrolyte solution and mixed electrolyte solution systems,with temperature spanning from 273.15 to 373.15 K, were successfully correlated using the developed model.
