pyEQL package¶
Submodules¶
pyEQL.activity_correction module¶
pyEQL activity correction library.
This file contains functions for computing molal-scale activity coefficients of ions and salts in aqueous solution.
Individual functions for activity coefficients are defined here so that they can be used independently of a pyEQL solution object. Normally, these functions are called from within the get_activity_coefficient method of the Solution class.
- copyright:
2013-2023 by Ryan S. Kingsbury
- license:
LGPL, see LICENSE for more details.
- pyEQL.activity_correction.get_activity_coefficient_davies(ionic_strength, formal_charge=1, temperature='25 degC')[source]¶
Return the activity coefficient of solute in the parent solution according to the Davies equation.
- Parameters:
formal_charge (int, optional) – The charge on the solute, including sign. Defaults to +1 if not specified.
ionic_strength (Quantity) – The ionic strength of the parent solution, mol/kg
temperature (str Quantity, optional) – String representing the temperature of the solution. Defaults to ‘25 degC’ if not specified.
- Returns:
Quantity – The mean molal (mol/kg) scale ionic activity coefficient of solute, dimensionless.
See Also
——–
_debye_parameter_activity
Notes
Activity coefficient is calculated according to:
\[\ln \gamma = A^{\gamma} z_i^2 ({\sqrt I \over (1 + \sqrt I)} + 0.2 I)\]Valid for 0.1 < I < 0.5
References
- Stumm, Werner and Morgan, James J. Aquatic Chemistry, 3rd ed,
pp 103. Wiley Interscience, 1996.
- pyEQL.activity_correction.get_activity_coefficient_debyehuckel(ionic_strength, formal_charge=1, temperature='25 degC')[source]¶
Return the activity coefficient of solute in the parent solution according to the Debye-Huckel limiting law.
- Parameters:
formal_charge (int, optional) – The charge on the solute, including sign. Defaults to +1 if not specified.
ionic_strength (Quantity) – The ionic strength of the parent solution, mol/kg
temperature (str Quantity, optional) – String representing the temperature of the solution. Defaults to ‘25 degC’ if not specified.
- Returns:
Quantity – The mean molal (mol/kg) scale ionic activity coefficient of solute, dimensionless.
See Also
——–
_debye_parameter_activity
Notes
Activity coefficient is calculated according to:
\[\ln \gamma = A^{\gamma} z_i^2 \sqrt I\]Valid only for I < 0.005
References
- Stumm, Werner and Morgan, James J. Aquatic Chemistry, 3rd ed,
pp 103. Wiley Interscience, 1996.
- pyEQL.activity_correction.get_activity_coefficient_guntelberg(ionic_strength, formal_charge=1, temperature='25 degC')[source]¶
Return the activity coefficient of solute in the parent solution according to the Guntelberg approximation.
- Parameters:
formal_charge (int, optional) – The charge on the solute, including sign. Defaults to +1 if not specified.
ionic_strength (Quantity) – The ionic strength of the parent solution, mol/kg
temperature (str Quantity, optional) – String representing the temperature of the solution. Defaults to ‘25 degC’ if not specified.
- Returns:
Quantity – The mean molal (mol/kg) scale ionic activity coefficient of solute, dimensionless.
See Also
——–
_debye_parameter_activity
Notes
Activity coefficient is calculated according to:
\[\ln \gamma = A^{\gamma} z_i^2 {\sqrt I \over (1 + \sqrt I)}\]Valid for I < 0.1
References
- Stumm, Werner and Morgan, James J. Aquatic Chemistry, 3rd ed,
pp 103. Wiley Interscience, 1996.
- pyEQL.activity_correction.get_activity_coefficient_pitzer(ionic_strength, molality, alpha1, alpha2, beta0, beta1, beta2, C_phi, z_cation, z_anion, nu_cation, nu_anion, temperature='25 degC', b=1.2)[source]¶
Return the activity coefficient of solute in the parent solution according to the Pitzer model.
- Parameters:
ionic_strength (Quantity) – The ionic strength of the parent solution, mol/kg
molality (Quantity) – The molal concentration of the parent salt, mol/kg
alpha1 (number) – Coefficients for the Pitzer model. This function assigns the coefficients proper units of kg ** 0.5 / mol ** 0.5 after they are entered.
alpha2 (number) – Coefficients for the Pitzer model. This function assigns the coefficients proper units of kg ** 0.5 / mol ** 0.5 after they are entered.
beta0 (number) – Coefficients for the Pitzer model. These ion-interaction parameters are specific to each salt system.
beta1 (number) – Coefficients for the Pitzer model. These ion-interaction parameters are specific to each salt system.
beta2 (number) – Coefficients for the Pitzer model. These ion-interaction parameters are specific to each salt system.
C_phi (number) – Coefficients for the Pitzer model. These ion-interaction parameters are specific to each salt system.
z_cation (int) – The formal charge on the cation and anion, respectively
z_anion (int) – The formal charge on the cation and anion, respectively
nu_cation (int) – The stoichiometric coefficient of the cation and anion in the salt
nu_anion (int) – The stoichiometric coefficient of the cation and anion in the salt
temperature (str Quantity) – String representing the temperature of the solution. Defaults to ‘25 degC’ if not specified.
b (number, optional) – Coefficient. Usually set equal to 1.2 and considered independent of temperature and pressure. If provided, this coefficient is assigned proper units of kg ** 0.5 / mol ** 0.5 after entry.
- Returns:
Quantity – The mean molal (mol/kg) scale ionic activity coefficient of solute, dimensionless
Examples
——–
>>> get_activity_coefficient_pitzer(0.5*unit.Quantity(‘mol/kg’),0.5*unit.Quantity(‘mol/kg’),1,0.5,-.0181191983,-.4625822071,.4682,.000246063,1,-1,1,1,b=1.2)
0.61915…
>>> get_activity_coefficient_pitzer(5.6153*unit.Quantity(‘mol/kg’),5.6153*unit.Quantity(‘mol/kg’),3,0.5,0.0369993,0.354664,0.0997513,-0.00171868,1,-1,1,1,b=1.2)
0.76331…
NOTE (the examples below are for comparison with experimental and modeling data presented in)
the May et al reference below.
10 mol/kg ammonium nitrate. Estimated result (from graph) = 0.2725
>>> get_activity_coefficient_pitzer(10*unit.Quantity(‘mol/kg’),10*unit.Quantity(‘mol/kg’),2,0,-0.01709,0.09198,0,0.000419,1,-1,1,1,b=1.2)
0.22595 …
5 mol/kg ammonium nitrate. Estimated result (from graph) = 0.3011
>>> get_activity_coefficient_pitzer(5*unit.Quantity(‘mol/kg’),5*unit.Quantity(‘mol/kg’),2,0,-0.01709,0.09198,0,0.000419,1,-1,1,1,b=1.2)
0.30249 …
18 mol/kg ammonium nitrate. Estimated result (from graph) = 0.1653
>>> get_activity_coefficient_pitzer(18*unit.Quantity(‘mol/kg’),18*unit.Quantity(‘mol/kg’),2,0,-0.01709,0.09198,0,0.000419,1,-1,1,1,b=1.2)
0.16241 …
References
Scharge, T., Munoz, A.G., and Moog, H.C. (2012). Activity Coefficients of Fission Products in Highly Salinary Solutions of Na+, K+, Mg2+, Ca2+, Cl-, and SO42- : Cs+. /Journal of Chemical& Engineering Data (57), p. 1637-1647.
Kim, H., & Jr, W. F. (1988). Evaluation of Pitzer ion interaction parameters of aqueous electrolytes at 25 degree C. 1. Single salt parameters. Journal of Chemical and Engineering Data, (2), 177-184.
May, P. M., Rowland, D., Hefter, G., & Königsberger, E. (2011). A Generic and Updatable Pitzer Characterization of Aqueous Binary Electrolyte Solutions at 1 bar and 25 °C. Journal of Chemical & Engineering Data, 56(12), 5066-5077. doi:10.1021/je2009329
Beyer, R., & Steiger, M. (2010). Vapor Pressure Measurements of NaHCOO + H 2 O and KHCOO + H 2 O from 278 to 308 K and Representation with an Ion Interaction (Pitzer) Model. Journal of Chemical & Engineering Data, 55(2), 830-838. doi:10.1021/je900487a
See Also:¶
_debye_parameter_activity _pitzer_B_MX _pitzer_B_gamma _pitzer_B_phi _pitzer_log_gamma
- pyEQL.activity_correction.get_apparent_volume_pitzer(ionic_strength, molality, alpha1, alpha2, beta0, beta1, beta2, C_phi, V_o, z_cation, z_anion, nu_cation, nu_anion, temperature='25 degC', b=1.2)[source]¶
Return the apparent molar volume of solute in the parent solution according to the Pitzer model.
- Parameters:
ionic_strength (Quantity) – The ionic strength of the parent solution, mol/kg
molality (Quantity) – The molal concentration of the parent salt, mol/kg
alpha1 (number) – Coefficients for the Pitzer model. This function assigns the coefficients proper units of kg ** 0.5 / mol ** 0.5 after they are entered.
alpha2 (number) – Coefficients for the Pitzer model. This function assigns the coefficients proper units of kg ** 0.5 / mol ** 0.5 after they are entered.
beta0 (number) – Pitzer coefficients for the apparent molar volume. These ion-interaction parameters are specific to each salt system.
beta1 (number) – Pitzer coefficients for the apparent molar volume. These ion-interaction parameters are specific to each salt system.
beta2 (number) – Pitzer coefficients for the apparent molar volume. These ion-interaction parameters are specific to each salt system.
C_phi (number) – Pitzer coefficients for the apparent molar volume. These ion-interaction parameters are specific to each salt system.
V_o (number) – The V^o Pitzer coefficient for the apparent molar volume.
z_cation (int) – The formal charge on the cation and anion, respectively
z_anion (int) – The formal charge on the cation and anion, respectively
nu_cation (int) – The stoichiometric coefficient of the cation and anion in the salt
nu_anion (int) – The stoichiometric coefficient of the cation and anion in the salt
temperature (str Quantity) – String representing the temperature of the solution. Defaults to ‘25 degC’ if not specified.
b (number, optional) – Coefficient. Usually set equal to 1.2 and considered independent of temperature and pressure. If provided, this coefficient is assigned proper units of kg ** 0.5 / mol ** 0.5 after entry.
- Returns:
Quantity – The apparent molar volume of the solute, cm ** 3 / mol
Examples
——–
NOTE (the example below is for comparison with experimental and modeling data presented in)
the Krumgalz et al reference below.
0.25 mol/kg CuSO4. Expected result (from graph) = 0.5 cm * 3 / mol*
>>> get_apparent_volume_pitzer(1.0*unit.Quantity(‘mol/kg’),0.25*unit.Quantity(‘mol/kg’),1.4,12,0.001499,-0.008124,0.2203,-0.0002589,-6,2,-2,1,1,b=1.2)
0.404…
1.0 mol/kg CuSO4. Expected result (from graph) = 4 cm * 3 / mol*
>>> get_apparent_volume_pitzer(4.0*unit.Quantity(‘mol/kg’),1.0*unit.Quantity(‘mol/kg’),1.4,12,0.001499,-0.008124,0.2203,-0.0002589,-6,2,-2,1,1,b=1.2)
4.424…
10.0 mol/kg ammonium nitrate. Expected result (from graph) = 50.3 cm * 3 / mol*
>>> get_apparent_volume_pitzer(10.0*unit.Quantity(‘mol/kg’),10.0*unit.Quantity(‘mol/kg’),2,0,0.000001742,0.0002926,0,0.000000424,46.9,1,-1,1,1,b=1.2)
50.286…
20.0 mol/kg ammonium nitrate. Expected result (from graph) = 51.2 cm * 3 / mol*
>>> get_apparent_volume_pitzer(20.0*unit.Quantity(‘mol/kg’),20.0*unit.Quantity(‘mol/kg’),2,0,0.000001742,0.0002926,0,0.000000424,46.9,1,-1,1,1,b=1.2)
51.145…
NOTE (the examples below are for comparison with experimental and modeling data presented in)
the Krumgalz et al reference below.
0.8 mol/kg NaF. Expected result = 0.03
>>> get_apparent_volume_pitzer(0.8*unit.Quantity(‘mol/kg’),0.8*unit.Quantity(‘mol/kg’),2,0,0.000024693,0.00003169,0,-0.000004068,-2.426,1,-1,1,1,b=1.2)
0.22595 …
References
May, P. M., Rowland, D., Hefter, G., & Königsberger, E. (2011). A Generic and Updatable Pitzer Characterization of Aqueous Binary Electrolyte Solutions at 1 bar and 25 °C. Journal of Chemical & Engineering Data, 56(12), 5066-5077. doi:10.1021/je2009329
Krumgalz, Boris S., Pogorelsky, Rita (1996). Volumetric Properties of Single Aqueous Electrolytes from Zero to Saturation Concentration at 298.15 K Represented by Pitzer’s Ion-Interaction Equations. Journal of Physical Chemical Reference Data, 25(2), 663-689.
See Also:¶
_debye_parameter_volume _pitzer_B_MX
- pyEQL.activity_correction.get_osmotic_coefficient_pitzer(ionic_strength, molality, alpha1, alpha2, beta0, beta1, beta2, C_phi, z_cation, z_anion, nu_cation, nu_anion, temperature='25 degC', b=1.2)[source]¶
Return the osmotic coefficient of water in an electrolyte solution according to the Pitzer model.
- Parameters:
ionic_strength (Quantity) – The ionic strength of the parent solution, mol/kg
molality (Quantity) – The molal concentration of the parent salt, mol/kg
alpha1 (number) – Coefficients for the Pitzer model. This function assigns the coefficients proper units of kg ** 0.5 / mol ** 0.5 after they are entered.
alpha2 (number) – Coefficients for the Pitzer model. This function assigns the coefficients proper units of kg ** 0.5 / mol ** 0.5 after they are entered.
beta0 – Coefficients for the Pitzer model. These ion-interaction parameters are specific to each salt system.
beta1 – Coefficients for the Pitzer model. These ion-interaction parameters are specific to each salt system.
beta2 – Coefficients for the Pitzer model. These ion-interaction parameters are specific to each salt system.
C_phi – Coefficients for the Pitzer model. These ion-interaction parameters are specific to each salt system.
z_cation (int) – The formal charge on the cation and anion, respectively
z_anion (int) – The formal charge on the cation and anion, respectively
nu_cation (int) – The stoichiometric coefficient of the cation and anion in the salt
nu_anion (int) – The stoichiometric coefficient of the cation and anion in the salt
temperature (str Quantity) – String representing the temperature of the solution. Defaults to ‘25 degC’ if not specified.
b (number, optional) – Coefficient. Usually set equal to 1.2 and considered independent of temperature and pressure. If provided, this coefficient is assigned proper units of kg ** 0.5 / mol ** 0.5 after entry.
- Returns:
Quantity – The osmotic coefficient of water, dimensionless
Examples
——–
Experimental value according to Beyer and Stieger reference is 1.3550
>>> get_osmotic_coefficient_pitzer(10.175*unit.Quantity(‘mol/kg’),10.175*unit.Quantity(‘mol/kg’),1,0.5,-.0181191983,-.4625822071,.4682,.000246063,1,-1,1,1,b=1.2)
1.3552 …
Experimental value according to Beyer and Stieger reference is 1.084
>>> get_osmotic_coefficient_pitzer(5.6153*unit.Quantity(‘mol/kg’),5.6153*unit.Quantity(‘mol/kg’),3,0.5,0.0369993,0.354664,0.0997513,-0.00171868,1,-1,1,1,b=1.2)
1.0850 …
NOTE (the examples below are for comparison with experimental and modeling data presented in)
the May et al reference below.
10 mol/kg ammonium nitrate. Estimated result (from graph) = 0.62
>>> get_osmotic_coefficient_pitzer(10*unit.Quantity(‘mol/kg’),10*unit.Quantity(‘mol/kg’),2,0,-0.01709,0.09198,0,0.000419,1,-1,1,1,b=1.2)
0.6143 …
5 mol/kg ammonium nitrate. Estimated result (from graph) = 0.7
>>> get_osmotic_coefficient_pitzer(5*unit.Quantity(‘mol/kg’),5*unit.Quantity(‘mol/kg’),2,0,-0.01709,0.09198,0,0.000419,1,-1,1,1,b=1.2)
0.6925 …
18 mol/kg ammonium nitrate. Estimated result (from graph) = 0.555
>>> get_osmotic_coefficient_pitzer(18*unit.Quantity(‘mol/kg’),18*unit.Quantity(‘mol/kg’),2,0,-0.01709,0.09198,0,0.000419,1,-1,1,1,b=1.2)
0.5556 …
References
Scharge, T., Munoz, A.G., and Moog, H.C. (2012). Activity Coefficients of Fission Products in Highly Salinary Solutions of Na+, K+, Mg2+, Ca2+, Cl-, and SO42- : Cs+. /Journal of Chemical& Engineering Data (57), p. 1637-1647.
Kim, H., & Jr, W. F. (1988). Evaluation of Pitzer ion interaction parameters of aqueous electrolytes at 25 degree C. 1. Single salt parameters. Journal of Chemical and Engineering Data, (2), 177-184.
May, P. M., Rowland, D., Hefter, G., & Königsberger, E. (2011). A Generic and Updatable Pitzer Characterization of Aqueous Binary Electrolyte Solutions at 1 bar and 25 °C. Journal of Chemical & Engineering Data, 56(12), 5066-5077. doi:10.1021/je2009329
Beyer, R., & Steiger, M. (2010). Vapor Pressure Measurements of NaHCOO + H 2 O and KHCOO + H 2 O from 278 to 308 K and Representation with an Ion Interaction (Pitzer) Model. Journal of Chemical & Engineering Data, 55(2), 830-838. doi:10.1021/je900487a
See Also:¶
_debye_parameter_activity _pitzer_B_MX _pitzer_B_gamma _pitzer_B_phi _pitzer_log_gamma
pyEQL.engines module¶
pyEQL engines for computing aqueous equilibria (e.g., speciation, redox, etc.).
- copyright:
2013-2023 by Ryan S. Kingsbury
- license:
LGPL, see LICENSE for more details.
- class pyEQL.engines.EOS[source]¶
Bases:
ABC
Abstract base class for pyEQL equation of state classes.
- abstract equilibrate(solution)[source]¶
Adjust the speciation and pH of a Solution object to achieve chemical equilibrium.
The Solution should be modified in-place, likely using add_moles / set_moles, etc.
- Parameters:
solution – pyEQL Solution object
- Returns
Nothing. The speciation of the Solution is modified in-place.
- Raises:
ValueError if the calculation cannot be completed, e.g. due to insufficient number of –
parameters or lack of convergence. –
- abstract get_activity_coefficient(solution, solute)[source]¶
Return the molal scale activity coefficient of solute, given a Solution object.
- Parameters:
solution – pyEQL Solution object
solute – str identifying the solute of interest
- Returns
Quantity: dimensionless quantity object
- Raises:
ValueError if the calculation cannot be completed, e.g. due to insufficient number of –
parameters. –
- abstract get_osmotic_coefficient(solution)[source]¶
Return the molal scale osmotic coefficient of a Solution.
- Parameters:
solution – pyEQL Solution object
- Returns
Quantity: dimensionless molal scale osmotic coefficient
- Raises:
ValueError if the calculation cannot be completed, e.g. due to insufficient number of –
parameters. –
- class pyEQL.engines.IdealEOS[source]¶
Bases:
EOS
Ideal solution equation of state engine.
- equilibrate(solution)[source]¶
Adjust the speciation of a Solution object to achieve chemical equilibrium.
- get_activity_coefficient(solution, solute)[source]¶
Return the molal scale activity coefficient of solute, given a Solution object.
- class pyEQL.engines.NativeEOS[source]¶
Bases:
EOS
pyEQL’s native EOS. Uses the Pitzer model when possible, falls back to other models (e.g. Debye-Huckel) based on ionic strength if sufficient parameters are not available.
- equilibrate(solution)[source]¶
Adjust the speciation of a Solution object to achieve chemical equilibrium.
- get_activity_coefficient(solution, solute)[source]¶
Whenever the appropriate parameters are available, the Pitzer model [may] is used. If no Pitzer parameters are available, then the appropriate equations are selected according to the following logic: [stumm].
I <= 0.0005: Debye-Huckel equation 0.005 < I <= 0.1: Guntelberg approximation 0.1 < I <= 0.5: Davies equation I > 0.5: Raises a warning and returns activity coefficient = 1
The ionic strength, activity coefficients, and activities are all calculated based on the molal (mol/kg) concentration scale. If a different scale is given as input, then the molal-scale activity coefficient \(\gamma_\pm\) is converted according to [rbs]
\[f_\pm = \gamma_\pm * (1 + M_w \sum_i \nu_i \m_i)\]\[y_\pm = m \rho_w / C \gamma_\pm\]where \(f_\pm\) is the rational activity coefficient, \(M_w\) is the molecular weight of water, the summation represents the total molality of all solute species, \(y_\pm\) is the molar activity coefficient, \(\rho_w\) is the density of pure water, \(m\) and \(C\) are the molal and molar concentrations of the chosen salt (not individual solute), respectively.
- Parameters:
solute – String representing the name of the solute of interest
scale – The concentration scale for the returned activity coefficient. Valid options are “molal”, “molar”, and “rational” (i.e., mole fraction). By default, the molal scale activity coefficient is returned.
verbose – If True, pyEQL will print a message indicating the parent salt that is being used for activity calculations. This option is useful when modeling multicomponent solutions. False by default.
- Returns
The mean ion activity coefficient of the solute in question on the selected scale.
See also
get_ionic_strength get_salt activity_correction.get_activity_coefficient_debyehuckel activity_correction.get_activity_coefficient_guntelberg activity_correction.get_activity_coefficient_davies activity_correction.get_activity_coefficient_pitzer
Notes
For multicomponent mixtures, pyEQL implements the “effective Pitzer model” presented by Mistry et al. [mistry]. In this model, the activity coefficient of a salt in a multicomponent mixture is calculated using an “effective molality,” which is the molality that would result in a single-salt mixture with the same total ionic strength as the multicomponent solution.
\[m_effective = 2 I \over (\nu_{+} z_{+}^2 + \nu{_}- z_{-} ^2)\]References
[may]May, P. M., Rowland, D., Hefter, G., & Königsberger, E. (2011). A Generic and Updatable Pitzer Characterization of Aqueous Binary Electrolyte Solutions at 1 bar and 25 °C. Journal of Chemical & Engineering Data, 56(12), 5066-5077. doi:10.1021/je2009329
[stumm]Stumm, Werner and Morgan, James J. Aquatic Chemistry, 3rd ed, pp 165. Wiley Interscience, 1996.
[rbs]Robinson, R. A.; Stokes, R. H. Electrolyte Solutions: Second Revised Edition; Butterworths: London, 1968, p.32.
[mistry]Mistry, K. H.; Hunter, H. a.; Lienhard V, J. H. Effect of composition and nonideal solution behavior on desalination calculations for mixed electrolyte solutions with comparison to seawater. Desalination 2013, 318, 34-47.
- get_osmotic_coefficient(solution)[source]¶
Return the molal scale osmotic coefficient of solute, given a Solution object.
Osmotic coefficient is calculated using the Pitzer model. [may] If appropriate parameters for the model are not available, then pyEQL raises a WARNING and returns an osmotic coefficient of 1.
If the ‘rational’ scale is given as input, then the molal-scale osmotic coefficient \(\phi\) is converted according to [rbs]
\[g = - \phi * M_{w} \sum_{i} \nu_{i} \m_{i}) / \ln x_{w}\]where \(g\) is the rational osmotic coefficient, \(M_{w}\) is the molecular weight of water, the summation represents the total molality of all solute species, and \(x_{w}\) is the mole fraction of water.
- Parameters:
scale –
"molal" (The concentration scale for the returned osmotic coefficient. Valid options are) –
:param : :param “rational”: :type “rational”: i.e., mole fraction :param coefficient is returned.:
- Returns
- Quantity:
The osmotic coefficient
See also
get_water_activity get_ionic_strength get_salt
Notes
For multicomponent mixtures, pyEQL adopts the “effective Pitzer model” presented by Mistry et al. [mstry]. In this approach, the osmotic coefficient of each individual salt is calculated using the normal Pitzer model based on its respective concentration. Then, an effective osmotic coefficient is calculated as the concentration-weighted average of the individual osmotic coefficients.
For example, in a mixture of 0.5 M NaCl and 0.5 M KBr, one would calculate the osmotic coefficient for each salt using a concentration of 0.5 M and an ionic strength of 1 M. Then, one would average the two resulting osmotic coefficients to obtain an effective osmotic coefficient for the mixture.
(Note: in the paper referenced below, the effective osmotic coefficient is determined by weighting using the “effective molality” rather than the true molality. Subsequent checking and correspondence with the author confirmed that the weight factor should be the true molality, and that is what is implemented in pyEQL.)
References
[may]May, P. M., Rowland, D., Hefter, G., & Königsberger, E. (2011). A Generic and Updatable Pitzer Characterization of Aqueous Binary Electrolyte Solutions at 1 bar and 25 °C. Journal of Chemical & Engineering Data, 56(12), 5066-5077. doi:10.1021/je2009329
[rbs]Robinson, R. A.; Stokes, R. H. Electrolyte Solutions: Second Revised Edition; Butterworths: London, 1968, p.32.
[mstry]Mistry, K. H.; Hunter, H. a.; Lienhard V, J. H. Effect of composition and nonideal solution behavior on desalination calculations for mixed electrolyte solutions with comparison to seawater. Desalination 2013, 318, 34-47.
Examples
>>> s1 = pyEQL.Solution([['Na+','0.2 mol/kg'],['Cl-','0.2 mol/kg']]) >>> s1.get_osmotic_coefficient() <Quantity(0.923715281, 'dimensionless')>
>>> s1 = pyEQL.Solution([['Mg+2','0.3 mol/kg'],['Cl-','0.6 mol/kg']],temperature='30 degC') >>> s1.get_osmotic_coefficient() <Quantity(0.891409618, 'dimensionless')>
pyEQL.equilibrium module¶
pyEQL methods for chemical equilibrium calculations (e.g. acid/base, reactions, redox, complexation, etc.).
NOTE: these methods are not currently used but are here for the future.
- copyright:
2013-2023 by Ryan S. Kingsbury
- license:
LGPL, see LICENSE for more details.
- pyEQL.equilibrium.adjust_temp_arrhenius(rate_constant, activation_energy, temperature, reference_temperature=<Quantity(25, 'degree_Celsius')>)[source]¶
(float,float,number, optional number) -> float.
Adjust a reaction equilibrium constant from one temperature to another.
- Parameters:
rate_constant (Quantity) – The parameter value (usually a rate constant) being adjusted
activation_energy (Quantity) – The activation energy of the process, in kJ/mol
temperature (Quantity) – the desired reaction temperature.
reference_temperature (Quantity, optional) – the temperature at which equilibrium_constant is valid Defaults to 25 degrees C if omitted.
- Returns:
Quantity – The adjusted reaction equilibrium constant
See Also
——–
kelvin
Notes
This function implements the Arrhenius equation to adjust measured rate constants to other temperatures. TODO - add better reference
\[\begin{split}ln(\\frac{K2}{K1} = \\frac{E_a}{R} ( \\frac{1}{T_{1}} - {\\frac{1}{T_2}} )\end{split}\]References
Examples:¶
>>> adjust_temp_arrhenius(7,900*unit.Quantity('kJ/mol'),37*unit.Quantity('degC'),97*unit.Quantity('degC')) 1.8867225...e-24
- pyEQL.equilibrium.adjust_temp_pitzer(c1, c2, c3, c4, c5, temp, temp_ref=<Quantity(298.15, 'kelvin')>)[source]¶
Calculate a parameter for the Pitzer model based on temperature-dependent coefficients c1,c2,c3,c4,and c5.
- Parameters:
c1 (float) – Temperature-dependent coefficients for the pitzer parameter of interest.
c2 (float) – Temperature-dependent coefficients for the pitzer parameter of interest.
c3 (float) – Temperature-dependent coefficients for the pitzer parameter of interest.
c4 (float) – Temperature-dependent coefficients for the pitzer parameter of interest.
c5 (float) – Temperature-dependent coefficients for the pitzer parameter of interest.
temp (Quantity) – The temperature at which the Pitzer parameter is to be calculated
temp_ref (Quantity, optional) – The reference temperature on which the parameters are based. 298.15 K if omitted.
documentation (As described in the PHREEQC) –
- pyEQL.equilibrium.adjust_temp_vanthoff(equilibrium_constant, enthalpy, temperature, reference_temperature=<Quantity(25, 'degree_Celsius')>)[source]¶
(float,float,number, optional number) -> float.
Adjust a reaction equilibrium constant from one temperature to another.
- Parameters:
equilibrium_constant (float) – The reaction equilibrium constant for the reaction
enthalpy (Quantity) – The enthalpy change (delta H) for the reaction in kJ/mol. Assumed independent of temperature (see Notes).
temperature (Quantity) – the desired reaction temperature in degrees Celsius
reference_temperature (Quantity, optional) – the temperature at which equilibrium_constant is valid. (25 degrees C if omitted).
- Returns:
adjusted reaction equilibrium constant
- Return type:
Notes
This function implements the Van’t Hoff equation to adjust measured equilibrium constants to other temperatures.
\[ln(K2 / K1) = {\delta H \over R} ( {1 \over T_1} - {1 \over T_2} )\]This implementation assumes that the enthalpy is independent of temperature over the range of interest.
References
- Stumm, Werner and Morgan, James J. Aquatic Chemistry, 3rd ed, pp 53.
Wiley Interscience, 1996.
Examples:¶
>>> adjust_temp_vanthoff(0.15,unit.Quantity('-197.6 kJ/mol'),unit.Quantity('42 degC'),unit.Quantity(' 25degC')) 0.00203566...
If the ‘ref_temperature’ parameter is omitted, a default of 25 C is used.
>>> adjust_temp_vanthoff(0.15,unit.Quantity('-197.6 kJ/mol'),unit.Quantity('42 degC')) 0.00203566...
- pyEQL.equilibrium.alpha(n, pH, pKa_list)[source]¶
- Returns the acid-base distribution coefficient (alpha) of an acid in the
n-deprotonated form at a given pH.
- Parameters:
n (int) – The number of protons that have been lost by the desired form of the acid. Also the subscript on the alpha value. E.g. for bicarbonate (HCO3-), n=1 because 1 proton has been lost from the fully-protonated carbonic acid (H2CO3) form.
pKa_list (list of floats or ints) – The pKa values (negative log of equilibrium constants) for the acid of interest. There must be a minimum of n pKa values in the list.
- Returns:
The fraction of total acid present in the specified form.
- Return type:
Notes
The acid-base cient is calculated as follows: [stm]
\[\alpha_n = \frac{term_n}{[H+]^n + k_{a1}[H+]^{n-1} + k_{a1}k_{a2}[H+]^{n-2} ... k_{a1}k_{a2}...k_{an} }\]Where :math: ‘ erm_n’ refers to the nth term in the denominator, starting from 0
References
[stm]Stumm, Werner and Morgan, James J. Aquatic Chemistry, 3rd ed, pp 127-130. Wiley Interscience, 1996.
Examples:¶
>>> alpha(1,8,[4.7]) 0.999...
The sum of all alpha values should equal 1
>>> alpha(0,8,[6.35,10.33]) 0.021... >>> alpha(1,8,[6.35,10.33]) 0.979... >>> alpha(2,8,[6.35,10.33]) 2.043...e-09
If pH is equal to one of the pKa values the function should return 0.5.
>>> alpha(1,6.35,[6.35,10.33]) 0.5
pyEQL.functions module¶
pyEQL functions that take Solution objects as inputs or return Solution objects.
- copyright:
2013-2023 by Ryan S. Kingsbury
- license:
LGPL, see LICENSE for more details.
- pyEQL.functions.autogenerate(solution='')[source]¶
This method provides a quick way to create Solution objects representing commonly-encountered solutions, such as seawater, rainwater, and wastewater.
- Parameters:
solution (str) – String representing the desired solution Valid entries are ‘seawater’, ‘rainwater’, ‘wastewater’,and ‘urine’
- Returns:
A pyEQL Solution object.
- Return type:
Notes
The following sections explain the different solution options:
‘’ - empty solution, equivalent to pyEQL.Solution()
‘rainwater’ - pure water in equilibrium with atmospheric CO2 at pH 6
‘seawater’ or ‘SW’- Standard Seawater. See Table 4 of the Reference for Composition [1]
‘wastewater’ or ‘WW’ - medium strength domestic wastewater. See Table 3-18 of [2]
‘urine’ - typical human urine. See Table 3-15 of [2]
‘normal saline’ or ‘NS’ - normal saline solution used in medicine [3]
‘Ringers lacatate’ or ‘RL’ - Ringer’s lactate solution used in medicine [4]
References:¶
- pyEQL.functions.donnan_eql(solution, fixed_charge)[source]¶
Return a solution object in equilibrium with fixed_charge.
- Parameters:
solution (Solution object) – The external solution to be brought into equilibrium with the fixed charges
fixed_charge (str quantity) – String representing the concentration of fixed charges, including sign. May be specified in mol/L or mol/kg units. e.g. ‘1 mol/kg’
- Returns:
A solution that has established Donnan equilibrium with the external (input) Solution
- Return type:
Notes
The general equation representing the equilibrium between an external electrolyte solution and an ion-exchange medium containing fixed charges is
\[\frac{a_{-}}{\bar a_{-}}^{\frac{1}{z_{-}} \frac{\bar a_{+}}{a_{+}}^{\frac{1}{z_{+}} = exp(\frac{\Delta \pi \bar V}{{RT z_{+} \nu_{+}}})\]Where subscripts \(+\) and \(-\) indicate the cation and anion, respectively, the overbar indicates the membrane phase, \(a\) represents activity, \(z\) represents charge, \(\nu\) represents the stoichiometric coefficient, \(V\) represents the partial molar volume of the salt, and \(\Delta \pi\) is the difference in osmotic pressure between the membrane and the solution phase.
In addition, electroneutrality must prevail within the membrane phase:
\[\bar C_{+} z_{+} + \bar X + \bar C_{-} z_{-} = 0\]Where \(C\) represents concentration and \(X\) is the fixed charge concentration in the membrane or ion exchange phase.
This function solves these two equations simultaneously to arrive at the concentrations of the cation and anion in the membrane phase. It returns a solution equal to the input solution except that the concentrations of the predominant cation and anion have been adjusted according to this equilibrium.
NOTE that this treatment is only capable of equilibrating a single salt. This salt is identified by the get_salt() method.
References
- Strathmann, Heiner, ed. Membrane Science and Technology vol. 9, 2004. Chapter 2, p. 51.
See Also:¶
get_salt()
- pyEQL.functions.entropy_mix(Solution1, Solution2)[source]¶
Return the ideal mixing entropy associated with mixing two solutions.
- Parameters:
Solution1 (Solution objects) – The two solutions to be mixed.
Solution2 (Solution objects) – The two solutions to be mixed.
- Returns:
The ideal mixing entropy associated with complete mixing of the Solutions, in Joules.
- Return type:
Quantity
Notes
The ideal entropy of mixing is calculated as follows
\[\begin{split}\\Delta_{mix} S = \\sum_i (n_c + n_d) R T \\ln x_b - \\sum_i n_c R T \\ln x_c - \\sum_i n_d R T \\ln x_d\end{split}\]Where \(n\) is the number of moles of substance, \(T\) is the temperature in kelvin, and subscripts \(b\), \(c\), and \(d\) refer to the concentrated, dilute, and blended Solutions, respectively.
Note that dissociated ions must be counted as separate components, so a simple salt dissolved in water is a three component solution (cation, anion, and water).
References
- Koga, Yoshikata, 2007. *Solution Thermodynamics and its Application to Aqueous Solutions:
A differential approach.* Elsevier, 2007, pp. 23-37.
- pyEQL.functions.gibbs_mix(Solution1, Solution2)[source]¶
Return the Gibbs energy change associated with mixing two solutions.
- Parameters:
Solution1 (Solution objects) – The two solutions to be mixed.
Solution2 (Solution objects) – The two solutions to be mixed.
- Returns:
The change in Gibbs energy associated with complete mixing of the Solutions, in Joules.
- Return type:
Quantity
Notes
The Gibbs energy of mixing is calculated as follows
\[\begin{split}\\Delta_{mix} G = \\sum_i (n_c + n_d) R T \\ln a_b - \\sum_i n_c R T \\ln a_c - \\sum_i n_d R T \\ln a_d\end{split}\]Where \(n\) is the number of moles of substance, \(T\) is the temperature in kelvin, and subscripts \(b\), \(c\), and \(d\) refer to the concentrated, dilute, and blended Solutions, respectively.
Note that dissociated ions must be counted as separate components, so a simple salt dissolved in water is a three component solution (cation, anion, and water).
References
- Koga, Yoshikata, 2007. *Solution Thermodynamics and its Application to Aqueous Solutions:
A differential approach.* Elsevier, 2007, pp. 23-37.
- pyEQL.functions.mix(Solution1, Solution2)[source]¶
Mix two solutions together.
Returns a new Solution object that results from the mixing of Solution1 and Solution2
- Parameters:
Solution1 (Solution objects) – The two solutions to be mixed.
Solution2 (Solution objects) – The two solutions to be mixed.
- Returns:
A Solution object representing the mixed solution.
- Return type:
pyEQL.logging_system module¶
Create a logging system using Python’s built-in module.
Each module within pyEQL has its own logger, with a StreamHandler attached to it that directs formatted messages to standard output. This is intended to facilitate the use of pyEQL as an interactive console program, at the expense of some flexibility when using it as a true library in another application.
The default logging levels are mapped to pyEQL events as follows:
- DEBUG - detailed messages about function execution including methods used, data sources,
temperature adjustments, etc.
INFO - Messages indicating calculation steps, function calls, etc. WARNING - assumptions or limitations of module output ERROR - Module could not complete a task due to invalid input or other problem CRITICAL - not used
- copyright:
2013-2023 by Ryan S. Kingsbury
- license:
LGPL, see LICENSE for more details.
pyEQL.salt_ion_match module¶
pyEQL salt matching library.
This file contains functions that allow a pyEQL Solution object composed of individual species (usually ions) to be mapped to a solution of one or more salts. This mapping is necessary because some parameters (such as activity coefficient data) can only be determined for salts (e.g. NaCl) and not individual species (e.g. Na+)
- copyright:
2013-2023 by Ryan S. Kingsbury
- license:
LGPL, see LICENSE for more details.
- class pyEQL.salt_ion_match.Salt(cation, anion)[source]¶
Bases:
object
Class to represent a salt.
- get_effective_molality(ionic_strength)[source]¶
Calculate the effective molality according to [mistry].
\[2 I \over (\nu_+ z_+^2 + \nu_- z_- ^2)\]- Parameters:
ionic_strength (Quantity) – The ionic strength of the parent solution, mol/kg
- Returns:
Quantity
- Return type:
the effective molality of the salt in the parent solution
References
[mistry]Mistry, K. H.; Hunter, H. a.; Lienhard V, J. H. Effect of composition and nonideal solution behavior on desalination calculations for mixed electrolyte solutions with comparison to seawater. Desalination 2013, 318, 34-47.
- pyEQL.salt_ion_match.generate_salt_list(sol, unit='mol/kg')[source]¶
Generate a list of salts that represents the ionic composition of a solution.
- Returns:
A dictionary of Salt objects, where Salt objects are the keys and the amounts are the values.
- Return type:
- pyEQL.salt_ion_match.identify_salt(sol)[source]¶
Analyze the components of a solution and identify the salt that most closely approximates it. (e.g., if a solution contains 0.5 mol/kg of Na+ and Cl-, plus traces of H+ and OH-, the matched salt is 0.5 mol/kg NaCl).
Create a Salt object for this salt.
- Return type:
A Salt object.
pyEQL.solute module¶
pyEQL Solute class.
This file contains functions and methods for managing properties of individual solutes. The Solute class contains methods for accessing ONLY those properties that DO NOT depend on solution composition. Solute properties such as activity coefficient or concentration that do depend on compsition are accessed via Solution class methods.
- copyright:
2013-2023 by Ryan S. Kingsbury
- license:
LGPL, see LICENSE for more details.
- class pyEQL.solute.Datum(value: str, reference: str | None = None, data_type: Literal['computed', 'experimental', 'fitted', 'unknown'] = 'unknown')[source]¶
Bases:
object
Document containing data for a single computed or experimental property.
- property magnitude¶
- property uncertainty¶
- property unit¶
- class pyEQL.solute.Solute(formula: str, charge: int, molecular_weight: str, elements: list, chemsys: str, pmg_ion: ~pymatgen.core.ion.Ion, formula_html: str, formula_latex: str, formula_hill: str, formula_pretty: str, oxi_state_guesses: tuple, n_atoms: int, n_elements: int, size: dict = <factory>, thermo: dict = <factory>, transport: dict = <factory>, model_parameters: dict = <factory>)[source]¶
Bases:
object
represent each chemical species as an object containing its formal charge, transport numbers, concentration, activity, etc.
- Parameters:
formula – str Chemical formula for the solute. Charged species must contain a + or - and (for polyvalent solutes) a number representing the net charge (e.g. ‘SO4-2’).
- classmethod from_formula(formula: str)[source]¶
Create an Ion document from a chemical formula. The formula is passed to pymatgen.core.Ion.from_formula() and used to populate the basic chemical informatics fields (e.g., formula, charge, molecular weight, elements, etc.) of the IonDoc.
- pmg_ion: Ion¶
pyEQL.solution module¶
pyEQL Solution Class.
- copyright:
2013-2023 by Ryan S. Kingsbury
- license:
LGPL, see LICENSE for more details.
- class pyEQL.solution.Solution(solutes: List[List[str]] | Dict[str, str] | None = None, volume: str | None = None, temperature: str = '298.15 K', pressure: str = '1 atm', pH: float = 7, pE: float = 8.5, solvent: str | list = 'H2O', engine: Literal['native', 'ideal'] = 'native', database: str | Path | Store | None = None)¶
Bases:
MSONable
Class representing the properties of a solution. Instances of this class contain information about the solutes, solvent, and bulk properties.
- add_amount(solute, amount)¶
Add the amount of ‘solute’ to the parent solution.
- Parameters:
solute (str) – String representing the name of the solute of interest
amount (str quantity) – String representing the concentration desired, e.g. ‘1 mol/kg’ If the units are given on a per-volume basis, the solution volume is not recalculated If the units are given on a mass, substance, per-mass, or per-substance basis, then the solution volume is recalculated based on the new composition
- Return type:
Nothing. The concentration of solute is modified.
- add_solute(formula, amount)¶
Primary method for adding substances to a pyEQL solution.
- Parameters:
formula (str) – Chemical formula for the solute. Charged species must contain a + or - and (for polyvalent solutes) a number representing the net charge (e.g. ‘SO4-2’).
amount (str) – The amount of substance in the specified unit system. The string should contain both a quantity and a pint-compatible representation of a unit. e.g. ‘5 mol/kg’ or ‘0.1 g/L’
- add_solvent(formula, amount)¶
Same as add_solute but omits the need to pass solvent mass to pint.
- property alkalinity¶
Return the alkalinity or acid neutralizing capacity of a solution.
- Returns:
The alkalinity of the solution in mg/L as CaCO3
- Return type:
Quantity
Notes
The alkalinity is calculated according to [stm]
\[Alk = \sum_{i} z_{i} C_{B} + \sum_{i} z_{i} C_{A}\]Where \(C_{B}\) and \(C_{A}\) are conservative cations and anions, respectively (i.e. ions that do not participate in acid-base reactions), and \(z_{i}\) is their signed charge. In this method, the set of conservative cations is all Group I and Group II cations, and the conservative anions are all the anions of strong acids.
References
[stm]Stumm, Werner and Morgan, James J. Aquatic Chemistry, 3rd ed, pp 165. Wiley Interscience, 1996.
- as_dict() dict ¶
Convert the Solution into a dict representation that can be serialized to .json or other format.
- property bjerrum_length: Quantity¶
Return the Bjerrum length of a solution.
Bjerrum length represents the distance at which electrostatic interactions between particles become comparable in magnitude to the thermal energy.:math:lambda_B is calculated as
\[\lambda_B = {e^2 \over (4 \pi \epsilon_r \epsilon_o k_B T)}\]where \(e\) is the fundamental charge, \(\epsilon_r\) and \(\epsilon_r\) are the relative permittivity and vacuum permittivity, \(k_B\) is the Boltzmann constant, and \(T\) is the temperature.
- Parameters:
None –
- Returns:
The Bjerrum length, in nanometers.
- Return type:
Quantity
References
https://en.wikipedia.org/wiki/Bjerrum_length
Examples
>>> s1 = pyEQL.Solution() >>> s1.bjerrum_length <Quantity(0.7152793009386953, 'nanometer')>
See also
- property charge_balance: float¶
Return the charge balance of the solution.
Return the charge balance of the solution. The charge balance represents the net electric charge on the solution and SHOULD equal zero at all times, but due to numerical errors will usually have a small nonzero value. It is calculated according to:
\[CB = \sum_i n_i z_i\]where \(n_i\) is the number of moles, and \(z_i\) is the charge on species i.
- Returns:
The charge balance of the solution, in equivalents (mol of charge).
- Return type:
- property conductivity¶
Compute the electrical conductivity of the solution.
- Parameters:
None –
- Returns:
The electrical conductivity of the solution in Siemens / meter.
- Return type:
Quantity
Notes
Conductivity is calculated by summing the molar conductivities of the respective solutes, but they are activity-corrected and adjusted using an empricial exponent. This approach is used in PHREEQC and Aqion models [aq] [hc]
\[EC = {F^2 \over R T} \sum_i D_i z_i ^ 2 \gamma_i ^ {\alpha} m_i\]Where:
\[\alpha = \begin{cases} {\frac{0.6}{\sqrt{| z_{i} | }}} & {I < 0.36 | z_{i} | } {\frac{\sqrt{I}}{| z_i |}} & otherwise \end{cases}\]Note: PHREEQC uses the molal rather than molar concentration according to http://wwwbrr.cr.usgs.gov/projects/GWC_coupled/phreeqc/phreeqc3-html/phreeqc3-43.htm
References
- copy()¶
Return a copy of the solution.
- property debye_length: Quantity¶
Return the Debye length of a solution.
Debye length is calculated as [wk3]
\[\kappa^{-1} = \sqrt({\epsilon_r \epsilon_o k_B T \over (2 N_A e^2 I)})\]where \(I\) is the ionic strength, \(\epsilon_r\) and \(\epsilon_r\) are the relative permittivity and vacuum permittivity, \(k_B\) is the Boltzmann constant, and \(T\) is the temperature, \(e\) is the elementary charge, and \(N_A\) is Avogadro’s number.
Returns The Debye length, in nanometers.
References .. [wk3] https://en.wikipedia.org/wiki/Debye_length#Debye_length_in_an_electrolyte
See also
- property density: Quantity¶
Return the density of the solution.
Density is calculated from the mass and volume each time this method is called.
- Returns:
Quantity
- Return type:
The density of the solution.
- property dielectric_constant: Quantity¶
Returns the dielectric constant of the solution.
- Parameters:
None –
- Returns:
Quantity
- Return type:
the dielectric constant of the solution, dimensionless.
Notes
Implements the following equation as given by Zuber et al.
\[\epsilon = \epsilon_{solvent} \over 1 + \sum_i \alpha_i x_i\]where \(\alpha_i\) is a coefficient specific to the solvent and ion, and \(x_i\) is the mole fraction of the ion in solution.
References
.A. Zuber, L. Cardozo-Filho, V.F. Cabral, R.F. Checoni, M. Castier, An empirical equation for the dielectric constant in aqueous and nonaqueous electrolyte mixtures, Fluid Phase Equilib. 376 (2014) 116-123. doi:10.1016/j.fluid.2014.05.037.
- classmethod from_dict(d: dict) Solution ¶
Instantiate a Solution from a dictionary generated by as_dict().
- get_activity(solute: str, scale: Literal['molal', 'molar', 'rational'] = 'molal', verbose: bool = False)¶
Return the thermodynamic activity of the solute in solution on the chosen concentration scale.
- Parameters:
solute – String representing the name of the solute of interest
scale – The concentration scale for the returned activity. Valid options are “molal”, “molar”, and “rational” (i.e., mole fraction). By default, the molal scale activity is returned.
verbose – If True, pyEQL will print a message indicating the parent salt that is being used for activity calculations. This option is useful when modeling multicomponent solutions. False by default.
- Returns
The thermodynamic activity of the solute in question (dimensionless)
Notes
The thermodynamic activity depends on the concentration scale used [rs] . By default, the ionic strength, activity coefficients, and activities are all calculated based on the molal (mol/kg) concentration scale.
References
[rs]Robinson, R. A.; Stokes, R. H. Electrolyte Solutions: Second Revised Edition; Butterworths: London, 1968, p.32.
- get_activity_coefficient(solute: str, scale: Literal['molal', 'molar', 'fugacity', 'rational'] = 'molal', verbose: bool = False)¶
Return the activity coefficient of a solute in solution.
The model used to calculte the activity coefficient is determined by the Solution’s equation of state engine.
- Parameters:
solute – The solute for which to retrieve the activity coefficient
scale – The activity coefficient concentration scale
verbose – If True, pyEQL will print a message indicating the parent salt that is being used for activity calculations. This option is useful when modeling multicomponent solutions. False by default.
- Returns
Quantity: the activity coefficient as a dimensionless pint Quantity
- get_alkalinity(**kwargs)¶
- get_amount(solute, units)¶
Return the amount of ‘solute’ in the parent solution.
The amount of a solute can be given in a variety of unit types. 1. substance per volume (e.g., ‘mol/L’) 2. substance per mass of solvent (e.g., ‘mol/kg’) 3. mass of substance (e.g., ‘kg’) 4. moles of substance (‘mol’) 5. mole fraction (‘fraction’) 6. percent by weight (%) 7. number of molecules (‘count’)
- Parameters:
- Return type:
The amount of the solute in question, in the specified units
- get_bjerrum_length(**kwargs)¶
- get_charge_balance(**kwargs)¶
- get_chemical_potential_energy(activity_correction=True)¶
Return the total chemical potential energy of a solution (not including pressure or electric effects).
- Parameters:
activity_correction (bool, optional) – If True, activities will be used to calculate the true chemical potential. If False, mole fraction will be used, resulting in a calculation of the ideal chemical potential.
- Returns:
The actual or ideal chemical potential energy of the solution, in Joules.
- Return type:
Quantity
Notes
The chemical potential energy (related to the Gibbs mixing energy) is calculated as follows: [koga]
\[E = R T \sum_i n_i \ln a_i\]or
\[E = R T \sum_i n_i \ln x_i\]Where \(n\) is the number of moles of substance, \(T\) is the temperature in kelvin, \(R\) the ideal gas constant, \(x\) the mole fraction, and \(a\) the activity of each component.
Note that dissociated ions must be counted as separate components, so a simple salt dissolved in water is a three component solution (cation, anion, and water).
References
[koga]Koga, Yoshikata, 2007. Solution Thermodynamics and its Application to Aqueous Solutions: A differential approach. Elsevier, 2007, pp. 23-37.
- get_conductivity(**kwargs)¶
- get_debye_length(**kwargs)¶
- get_density(**kwargs)¶
- get_dielectric_constant(**kwargs)¶
- get_hardness(**kwargs)¶
- get_ionic_strength(**kwargs)¶
- get_lattice_distance(solute)¶
Calculate the average distance between molecules.
Calculate the average distance between molecules of the given solute, assuming that the molecules are uniformly distributed throughout the solution.
- Parameters:
solute (str) – String representing the name of the solute of interest
- Returns:
Quantity
- Return type:
The average distance between solute molecules
Examples
>>> soln = Solution([['Na+','0.5 mol/kg'],['Cl-','0.5 mol/kg']]) >>> soln.get_lattice_distance('Na+') 1.492964.... nanometer
Notes
The lattice distance is related to the molar concentration as follows:
\[d = ( C_i N_A ) ^ {-{1 \over 3}}\]
- get_mass(**kwargs)¶
- get_mobility(solute)¶
Calculate the ionic mobility of the solute.
- Parameters:
solute (str) – String identifying the solute for which the mobility is to be calculated.
- Returns:
float
- Return type:
The ionic mobility. Zero if the solute is not charged.
Notes
This function uses the Einstein relation to convert a diffusion coefficient into an ionic mobility [smed]
\[\mu_i = {F |z_i| D_i \over RT}\]References
[smed]Smedley, Stuart I. The Interpretation of Ionic Conductivity in Liquids. Plenum Press, 1980.
- get_molar_conductivity(solute)¶
Calculate the molar (equivalent) conductivity for a solute.
- Parameters:
solute – String identifying the solute for which the molar conductivity is to be calculated.
- Returns
The molar or equivalent conductivity of the species in the solution. Zero if the solute is not charged.
Notes
Molar conductivity is calculated from the Nernst-Einstein relation [smed]
\[\kappa_i = {z_i^2 D_i F^2 \over RT}\]Note that the diffusion coefficient is strongly variable with temperature.
References
[smed]Smedley, Stuart. The Interpretation of Ionic Conductivity in Liquids, pp 1-9. Plenum Press, 1980.
- get_mole_fraction(**kwargs)¶
- get_moles_solvent() Quantity ¶
Return the moles of solvent present in the solution.
- Returns
The moles of solvent in the solution.
- get_osmolality(activity_correction=False)¶
Return the osmolality of the solution in Osm/kg.
- Parameters:
activity_correction (bool) – If TRUE, the osmotic coefficient is used to calculate the osmolarity. This correction is appropriate when trying to predict the osmolarity that would be measured from e.g. freezing point depression. Defaults to FALSE if omitted.
- get_osmolarity(activity_correction=False)¶
Return the osmolarity of the solution in Osm/L.
- Parameters:
activity_correction (bool) – If TRUE, the osmotic coefficient is used to calculate the osmolarity. This correction is appropriate when trying to predict the osmolarity that would be measured from e.g. freezing point depression. Defaults to FALSE if omitted.
- get_osmotic_coefficient(scale: Literal['molal', 'molar', 'rational'] = 'molal')¶
Return the osmotic coefficient of an aqueous solution.
The method used depends on the Solution object’s equation of state engine.
- get_osmotic_pressure(**kwargs)¶
- get_pressure(**kwargs)¶
- get_salt()¶
Determine the predominant salt in a solution of ions.
Many empirical equations for solution properties such as activity coefficient, partial molar volume, or viscosity are based on the concentration of single salts (e.g., NaCl). When multiple ions are present (e.g., a solution containing Na+, Cl-, and Mg+2), it is generally not possible to directly model these quantities. pyEQL works around this problem by treating such solutions as single salt solutions.
The get_salt() method examines the ionic composition of a solution and returns an object that identifies the single most predominant salt in the solution, defined by the cation and anion with the highest mole fraction. The Salt object contains information about the stoichiometry of the salt to enable its effective concentration to be calculated (e.g., 1 M MgCl2 yields 1 M Mg+2 and 2 M Cl-).
- Parameters:
None –
- Returns:
Salt object containing information about the parent salt.
- Return type:
See also
get_activity()
,get_activity_coefficient()
,get_water_activity()
,get_osmotic_coefficient()
,get_osmotic_pressure()
,get_viscosity_kinematic()
Examples
>>> s1 = Solution([['Na+','0.5 mol/kg'],['Cl-','0.5 mol/kg']]) >>> s1.get_salt() <pyEQL.salt_ion_match.Salt object at 0x7fe6d3542048> >>> s1.get_salt().formula 'NaCl' >>> s1.get_salt().nu_cation 1 >>> s1.get_salt().z_anion -1
>>> s2 = pyEQL.Solution([['Na+','0.1 mol/kg'],['Mg+2','0.2 mol/kg'],['Cl-','0.5 mol/kg']]) >>> s2.get_salt().formula 'MgCl2' >>> s2.get_salt().nu_anion 2 >>> s2.get_salt().z_cation 2
- get_salt_dict() dict ¶
Determine the predominant salt in a solution of ions.
Many empirical equations for solution properties such as activity coefficient, partial molar volume, or viscosity are based on the concentration of single salts (e.g., NaCl). When multiple ions are present (e.g., a solution containing Na+, Cl-, and Mg+2), it is generally not possible to directly model these quantities.
The get_salt_dict() method examines the ionic composition of a solution and simplifies it into a list of salts. The method returns a dictionary of Salt objects where the keys are the salt formulas (e.g., ‘NaCl’). The Salt object contains information about the stoichiometry of the salt to enable its effective concentration to be calculated (e.g., 1 M MgCl2 yields 1 M Mg+2 and 2 M Cl-).
- Parameters:
None –
- Returns:
dict – A dictionary of Salt objects, keyed to the salt formula
See Also
——–
- get_salt_list(**kwargs)¶
- get_solute(**kwargs)¶
- get_solvent(**kwargs)¶
- get_solvent_mass(**kwargs)¶
- get_temperature(**kwargs)¶
- get_total_amount(element, units)¶
Return the total amount of ‘element’ (across all solutes) in the solution.
- Parameters:
- Return type:
The total amount of the element in the solution, in the specified units
Notes
There is currently no way to distinguish between different oxidation states of the same element (e.g. TOTFe(II) vs. TOTFe(III)). This is planned for a future release.
See also
- get_total_moles_solute() Quantity ¶
Return the total moles of all solute in the solution.
- get_transport_number(solute, activity_correction=False)¶
Calculate the transport number of the solute in the solution.
- Parameters:
solute – String identifying the solute for which the transport number is to be calculated.
activity_correction – If True, the transport number will be corrected for activity following the same method used for solution conductivity. Defaults to False if omitted.
Returns – The transport number of solute
Notes –
Transport number is calculated according to :
\[t_i = {D_i z_i^2 C_i \over \sum D_i z_i^2 C_i}\]Where \(C_i\) is the concentration in mol/L, \(D_i\) is the diffusion coefficient, and \(z_i\) is the charge, and the summation extends over all species in the solution.
If activity_correction is True, the contribution of each ion to the transport number is corrected with an activity factor. See the documentation for Solution.conductivity for an explanation of this correction.
References – Geise, G. M.; Cassady, H. J.; Paul, D. R.; Logan, E.; Hickner, M. A. “Specific ion effects on membrane potential and the permselectivity of ion exchange membranes.”” Phys. Chem. Chem. Phys. 2014, 16, 21673-21681.
- get_viscosity_dynamic(**kwargs)¶
- get_viscosity_kinematic(**kwargs)¶
- get_viscosity_relative(**kwargs)¶
- get_volume(**kwargs)¶
- get_water_activity()¶
Return the water activity.
- Returns:
The thermodynamic activity of water in the solution.
- Return type:
Quantity
See also
Notes
Water activity is related to the osmotic coefficient in a solution containing i solutes by:
\[\ln a_{w} = - \Phi M_{w} \sum_{i} m_{i}\]Where \(M_{w}\) is the molar mass of water (0.018015 kg/mol) and \(m_{i}\) is the molal concentration of each species.
If appropriate Pitzer model parameters are not available, the water activity is assumed equal to the mole fraction of water.
References
Blandamer, Mike J., Engberts, Jan B. F. N., Gleeson, Peter T., Reis, Joao Carlos R., 2005. “Activity of water in aqueous systems: A frequently neglected property.” Chemical Society Review 34, 440-458.
Examples:¶
>>> s1 = pyEQL.Solution([['Na+','0.3 mol/kg'],['Cl-','0.3 mol/kg']]) >>> s1.get_water_activity() <Quantity(0.9900944932888518, 'dimensionless')>
- property hardness¶
Return the hardness of a solution.
Hardness is defined as the sum of the equivalent concentrations of multivalent cations as calcium carbonate.
NOTE: at present pyEQL cannot distinguish between mg/L as CaCO3 and mg/L units. Use with caution.
- Parameters:
None –
- Returns:
The hardness of the solution in mg/L as CaCO3
- Return type:
Quantity
- property ionic_strength: Quantity¶
Return the ionic strength of the solution.
Return the ionic strength of the solution, calculated as 1/2 * sum ( molality * charge ^2) over all the ions.
Molal (mol/kg) scale concentrations are used for compatibility with the activity correction formulas.
- Returns:
Quantity – The ionic strength of the parent solution, mol/kg.
See Also
——–
Notes
The ionic strength is calculated according to:
\[I = \sum_i m_i z_i^2\]Where \(m_i\) is the molal concentration and \(z_i\) is the charge on species i.
Examples:¶
>>> s1 = pyEQL.Solution([['Na+','0.2 mol/kg'],['Cl-','0.2 mol/kg']]) >>> s1.ionic_strength <Quantity(0.20000010029672785, 'mole / kilogram')>
>>> s1 = pyEQL.Solution([['Mg+2','0.3 mol/kg'],['Na+','0.1 mol/kg'],['Cl-','0.7 mol/kg']],temperature='30 degC') >>> s1.ionic_strength <Quantity(1.0000001004383303, 'mole / kilogram')>
- list_activities(decimals=4)¶
List the activity of each species in a solution.
- list_concentrations(unit='mol/kg', decimals=4, type='all')¶
List the concentration of each species in a solution.
- Parameters:
unit (str) – String representing the desired concentration unit.
decimals (int) – The number of decimal places to display. Defaults to 4.
type (str) – The type of component to be sorted. Defaults to ‘all’ for all solutes. Other valid arguments are ‘cations’ and ‘anions’ which return lists of cations and anions, respectively.
- Returns:
Dictionary containing a list of the species in solution paired with their amount in the specified units
- Return type:
- list_salts(unit='mol/kg', decimals=4)¶
- list_solutes()¶
List all the solutes in the solution.
- property mass: Quantity¶
Return the total mass of the solution.
The mass is calculated each time this method is called. :param None:
- Returns:
Quantity
- Return type:
the mass of the solution, in kg
- property osmotic_pressure¶
Return the osmotic pressure of the solution relative to pure water.
- Returns
The osmotic pressure of the solution relative to pure water in Pa
See also
get_water_activity get_osmotic_coefficient get_salt
Notes
Osmotic pressure is calculated based on the water activity [sata] [wk]
\[\Pi = \frac{RT}{V_{w}} \ln a_{w}\]Where \(\Pi\) is the osmotic pressure, \(V_{w}\) is the partial molar volume of water (18.2 cm**3/mol), and \(a_{w}\) is the water activity.
- References
- [sata]
Sata, Toshikatsu. Ion Exchange Membranes: Preparation, Characterization, and Modification. Royal Society of Chemistry, 2004, p. 10.
Examples
>>> s1=pyEQL.Solution() >>> s1.osmotic_pressure 0.0
>>> s1 = pyEQL.Solution([['Na+','0.2 mol/kg'],['Cl-','0.2 mol/kg']]) >>> soln.osmotic_pressure <Quantity(906516.7318131207, 'pascal')>
- p(solute, activity=True)¶
Return the negative log of the activity of solute.
Generally used for expressing concentration of hydrogen ions (pH)
- Parameters:
- Returns:
The negative log10 of the activity (or molar concentration if activity = False) of the solute.
- Return type:
Quantity
- property pH: Quantity¶
Return the pH of the solution.
- property pressure: Quantity¶
Return the hydrostatic pressure of the solution in atm.
- set_amount(solute, amount)¶
Set the amount of ‘solute’ in the parent solution.
- Parameters:
solute (str) – String representing the name of the solute of interest
amount (str Quantity) –
String representing the concentration desired, e.g. ‘1 mol/kg’ If the units are given on a per-volume basis, the solution volume is not recalculated and the molar concentrations of other components in the solution are not altered, while the molal concentrations are modified.
If the units are given on a mass, substance, per-mass, or per-substance basis, then the solution volume is recalculated based on the new composition and the molal concentrations of other components are not altered, while the molar concentrations are modified.
- Return type:
Nothing. The concentration of solute is modified.
- set_pressure(**kwargs)¶
- set_temperature(**kwargs)¶
- set_volume(**kwargs)¶
- property solvent_mass¶
Return the mass of the solvent.
This property is used whenever mol/kg (or similar) concentrations are requested by get_amount()
- Returns:
Quantity
- Return type:
the mass of the solvent, in kg
See also
- property temperature: Quantity¶
Return the temperature of the solution in Kelvin.
- property viscosity_dynamic: Quantity¶
Return the dynamic (absolute) viscosity of the solution.
Calculated from the kinematic viscosity
See Also:¶
viscosity_kinematic
- property viscosity_kinematic¶
Return the kinematic viscosity of the solution.
Notes
The calculation is based on a model derived from the Eyring equation and presented in
\[\ln \nu = \ln {\nu_w MW_w \over \sum_i x_i MW_i } + 15 x_+^2 + x_+^3 \delta G^*_{123} + 3 x_+ \delta G^*_{23} (1-0.05x_+)\]Where:
\[\delta G^*_{123} = a_o + a_1 (T)^{0.75}\]\[\delta G^*_{23} = b_o + b_1 (T)^{0.5}\]In which \(\nu\) is the kinematic viscosity, MW is the molecular weight, \(x_{+}\) is the mole fraction of cations, and \(T\) is the temperature in degrees C.
The a and b fitting parameters for a variety of common salts are included in the database.
References
Vásquez-Castillo, G.; Iglesias-Silva, G. a.; Hall, K. R. An extension of the McAllister model to correlate kinematic viscosity of electrolyte solutions. Fluid Phase Equilib. 2013, 358, 44-49.
See Also:¶
Module contents¶
pyEQL¶
pyEQL is a python package for calculating the properties of aqueous solutions and performing chemical thermodynamics computations.
- copyright:
2013-2023 by Ryan S. Kingsbury
- license:
LGPL, see LICENSE for more details.