pyEQL 1.4.0rc9__cp312-cp312-macosx_11_0_arm64.whl

pyEQL/activity_correction.py

@@ -0,0 +1,879 @@
+"""
+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: 2013-2024 by Ryan S. Kingsbury
+:license: LGPL, see LICENSE for more details.
+
+"""
+
+import logging
+import math
+
+import numpy as np
+from pint import Quantity
+
+from pyEQL import ureg
+from pyEQL.utils import create_water_substance
+
+logger = logging.getLogger(f"pyEQL.{__name__}")
+
+
+def _debye_parameter_B(temperature: str = "25 degC") -> Quantity:
+    r"""
+    Return the constant B used in the extended Debye-Huckel equation.
+
+    Args:
+        temperature: The temperature of the solution at which to calculate the constant.
+            Defaults to '25 degC'.
+
+    Returns:
+        The parameter B for use in extended Debye-Huckel equation (base e). For base 10,
+        divide the resulting value by 2.303. Note that B is often given in base 10 terms
+        in older textbooks and reference material (0.3281 at 25 degC).
+
+    Notes:
+        The parameter B is equal to:
+
+        .. math::
+
+            B = \bigg( \frac{2 N_A \rho_w e^2}{\epsilon_o \epsilon_r k T} \bigg) ^ {\frac{1}{2}}
+
+    References:
+        Bockris and Reddy. /Modern Electrochemistry/, vol 1. Plenum/Rosetta, 1977, p.210.
+
+        Archer, Donald G. and Wang, Peiming. "The Dielectric Constant of Water \
+        and Debye-Huckel Limiting Law Slopes." /J. Phys. Chem. Ref. Data/ 19(2), 1990.
+
+        https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemistry_Textbook_Maps/Physical_Chemistry_(LibreTexts)/25%3A_Solutions_II_-_Nonvolatile_Solutes/25.06%3A_The_Debye-Huckel_Theory
+
+        https://en.wikipedia.org/wiki/Debye%E2%80%93H%C3%BCckel_equation
+    """
+    T = ureg.Quantity(temperature)
+    water_substance = create_water_substance(
+        T,
+        ureg.Quantity(1, "atm"),
+    )
+
+    param_B = (
+        2
+        * ureg.N_A
+        * ureg.Quantity(water_substance.rho, "g/L")
+        * ureg.elementary_charge**2
+        / (ureg.epsilon_0 * water_substance.epsilon * ureg.boltzmann_constant * T)
+    ) ** 0.5
+    return param_B.to_base_units()
+
+
+def _debye_parameter_activity(temperature: str = "25 degC") -> "Quantity":
+    r"""
+    Return the constant A for use in the Debye-Huckel limiting law (base e).
+
+    Args:
+        temperature: The temperature of the solution at which to calculate the constant.
+            Defaults to '25 degC'.
+
+    Returns:
+        The parameter A for use in the Debye-Huckel limiting law (base e). For base 10,
+        divide the resulting value by 2.303. Note that A is often given in base 10 terms
+        in older textbooks and reference material (0.509 at 25 degC).
+
+    Notes:
+        The parameter A is equal to:
+
+        ..  math::
+
+            A^{\gamma} = \frac{e^3 \big( 2 \pi N_A \rho \big)^{0.5}}{(4 \pi \epsilon_o \epsilon_r k T)^{1.5}}
+
+        Note that this equation returns the parameter value that can be used to calculate
+        the natural logarithm of the activity coefficient. For base 10, divide the
+        value returned by 2.303.
+
+    References:
+        Archer, Donald G. and Wang, Peiming. "The Dielectric Constant of Water \
+        and Debye-Huckel Limiting Law Slopes." /J. Phys. Chem. Ref. Data/ 19(2), 1990.
+
+        https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemistry_Textbook_Maps/Physical_Chemistry_(LibreTexts)/25%3A_Solutions_II_-_Nonvolatile_Solutes/25.06%3A_The_Debye-Huckel_Theory
+
+        https://en.wikipedia.org/wiki/Debye%E2%80%93H%C3%BCckel_equation
+
+    See Also:
+        :func:`_debye_parameter_osmotic`
+
+    """
+    T = ureg.Quantity(temperature)
+    water_substance = create_water_substance(
+        T,
+        ureg.Quantity(1, "atm"),
+    )
+
+    debyeparam = (
+        ureg.elementary_charge**3
+        * (2 * np.pi * ureg.N_A * ureg.Quantity(water_substance.rho, "g/L")) ** 0.5
+        / (4 * np.pi * ureg.epsilon_0 * water_substance.epsilon * ureg.boltzmann_constant * T) ** 1.5
+    )
+
+    logger.debug(rf"Computed Debye-Huckel Limiting Law Constant A^{{\gamma}} = {debyeparam} at {temperature}")
+    return debyeparam.to("kg ** 0.5 / mol ** 0.5")
+
+
+def _debye_parameter_osmotic(temperature="25 degC"):
+    r"""
+    Return the constant A_phi for use in calculating the osmotic coefficient according to Debye-Huckel theory.
+
+    Args:
+        temperature: String representing the temperature of the solution. Defaults to '25 degC' if not specified.
+
+    Notes:
+        Not to be confused with the Debye-Huckel constant used for activity coefficients in the limiting law.
+        Takes the value 0.392 at 25 C.
+        This constant is calculated according to: [kim]_ [arch]_
+
+        .. math:: A^{\phi} = {1 \over 3} A^{\gamma}
+
+    References:
+        .. [kim] Kim, Hee-Talk and Frederick, William Jr, 1988. "Evaluation of Pitzer Ion Interaction Parameters of
+           Aqueous Electrolytes at 25 C. 1. Single Salt Parameters," *J. Chemical Engineering Data* 33, pp.177-184.
+
+        .. [arch] Archer, Donald G. and Wang, Peiming. "The Dielectric Constant of Water \
+           and Debye-Huckel Limiting Law Slopes." /J. Phys. Chem. Ref. Data/ 19(2), 1990.
+
+    Examples:
+        >>> _debye_parameter_osmotic() #doctest: +ELLIPSIS
+        0.3916...
+
+    See Also:
+        :func:`_debye_parameter_activity`
+
+    """
+    output = 1 / 3 * _debye_parameter_activity(temperature)
+    logger.debug(f"Computed Debye-Huckel Limiting slope for osmotic coefficient A^phi = {output} at {temperature}")
+    return output.to("kg ** 0.5 /mol ** 0.5")
+
+
+def _debye_parameter_volume(temperature="25 degC"):
+    r"""
+    Return the constant A_V, the Debye-Huckel limiting slope for apparent
+    molar volume.
+
+    Args:
+        temperature: String representing the temperature of the solution. Defaults to '25 degC' if not specified.
+
+    Notes:
+        Takes the value 1.8305 cm ** 3 * kg ** 0.5 /  mol ** 1.5 at 25 C.
+        This constant is calculated according to: [adw90]_
+
+        .. math:: A_V = -2 A_{\phi} R T \big[ \frac{3}{\epsilon} \frac{\partial \epsilon}{\partial p} \
+         - \frac{1}{\rho}\frac{\partial \rho}{\partial p} \big]
+
+        Notes: at this time, the term in brackets (containing the partial derivatives) is approximate.
+        These approximations give the correct value of the slope at 25 degC and
+        produce estimates with less than 10% error between 0 and 60 degC.
+
+        The derivative of epsilon with respect to pressure is assumed constant (for atmospheric pressure)
+        at -0.01275 1/MPa. Note that the negative sign does not make sense in light
+        of real data, but is required to give the correct result.
+
+        The second term is equivalent to the inverse of the bulk modulus of water, which
+        is taken to be 2.2 GPa. [permot]_
+
+    References:
+        .. [adw90] Archer, Donald G. and Wang, Peiming. "The Dielectric Constant of Water and Debye-Huckel Limiting
+            Law Slopes." J. Phys. Chem. Ref. Data/ 19(2), 1990.
+
+        .. [permot] http://hyperphysics.phy-astr.gsu.edu/hbase/permot3.html
+
+    See Also:
+        :func:`_debye_parameter_osmotic`
+
+    """
+    T = ureg.Quantity(temperature)
+    water_substance = create_water_substance(
+        T,
+        ureg.Quantity(1, "atm"),
+    )
+
+    # TODO - add partial derivatives to calculation
+    epsilon = water_substance.epsilon
+    dedp = ureg.Quantity(-0.01275, "1/MPa")
+    result = (
+        -2 * _debye_parameter_osmotic(temperature) * ureg.R * T * (3 / epsilon * dedp - 1 / ureg.Quantity(2.2, "GPa"))
+    )
+    # result = ureg.Quantity('1.898 cm ** 3 * kg ** 0.5 /  mol ** 1.5')
+
+    if T.to("degC").magnitude != 25:
+        logger.warning("Debye-Huckel limiting slope for volume is approximate when T is not equal to 25 degC")
+
+    logger.debug(f"Computed Debye-Huckel Limiting Slope for volume A^V = {result} at {temperature}")
+
+    return result.to("cm ** 3 * kg ** 0.5 /  mol ** 1.5")
+
+
+def get_activity_coefficient_debyehuckel(ionic_strength, z=1, temperature="25 degC"):
+    r"""
+    Return the activity coefficient of solute in the parent solution according to the Debye-Huckel limiting law.
+
+    Args:
+        z (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.
+
+    Notes:
+        Activity coefficient is calculated according to:
+
+        .. math:: \ln \gamma = A^{\gamma} z_i^2 \sqrt I
+
+        Valid only for I < 0.005
+
+    See Also:
+        :func:`_debye_parameter_activity`
+        :func:`get_activity_coefficient_davies`
+        :func:`get_activity_coefficient_guntelberg`
+
+    References:
+        Stumm, Werner and Morgan, James J. Aquatic Chemistry, 3rd ed,
+               pp 103. Wiley Interscience, 1996.
+    """
+    # check if this method is valid for the given ionic strength
+    if not ionic_strength.magnitude <= 0.005:
+        logger.warning("Ionic strength exceeds valid range of the Debye-Huckel limiting law")
+
+    log_f = -_debye_parameter_activity(temperature) * z**2 * ionic_strength**0.5
+
+    return np.exp(log_f) * ureg.Quantity(1, "dimensionless")
+
+
+def get_activity_coefficient_guntelberg(ionic_strength, z=1, temperature="25 degC"):
+    r"""
+    Return the activity coefficient of solute in the parent solution according to the Guntelberg approximation.
+
+    Args:
+        z (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.
+
+    Notes:
+        Activity coefficient is calculated according to:
+
+        .. math:: \ln \gamma = A^{\gamma} z_i^2 {\sqrt I \over (1 + \sqrt I)}
+
+        Valid for I < 0.1
+
+    See Also:
+        :func:`_debye_parameter_activity`
+        :func:`get_activity_coefficient_davies`
+        :func:`get_activity_coefficient_debyehuckel`
+
+    References:
+        Stumm, Werner and Morgan, James J. Aquatic Chemistry, 3rd ed,
+               pp 103. Wiley Interscience, 1996.
+    """
+    # check if this method is valid for the given ionic strength
+    if not ionic_strength.magnitude <= 0.1:
+        logger.warning("Ionic strength exceeds valid range of the Guntelberg approximation")
+
+    log_f = -_debye_parameter_activity(temperature) * z**2 * ionic_strength**0.5 / (1 + ionic_strength.magnitude**0.5)
+
+    return np.exp(log_f) * ureg.Quantity(1, "dimensionless")
+
+
+def get_activity_coefficient_davies(ionic_strength, z=1, temperature="25 degC"):
+    r"""
+    Return the activity coefficient of solute in the parent solution according to the Davies equation.
+
+    Args:
+        ionic_strength (Quantity): The ionic strength of the parent solution, mol/kg.
+        z (int, optional): The charge on the solute, including sign. Defaults to +1 if not specified.
+        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.
+
+    Notes:
+        Activity coefficient is calculated according to:
+
+        .. math:: \ln \gamma = A^{\gamma} z_i^2 ({\sqrt I \over (1 + \sqrt I)} + 0.2 I)
+
+        Valid for 0.1 < I < 0.5
+
+    See Also:
+        :func:`_debye_parameter_activity`
+        :func:`get_activity_coefficient_debyehuckel`
+        :func:`get_activity_coefficient_guntelberg`
+
+    References:
+        Stumm, Werner and Morgan, James J. Aquatic Chemistry, 3rd ed,
+               pp 103. Wiley Interscience, 1996.
+    """
+    # check if this method is valid for the given ionic strength
+    if not ionic_strength.magnitude <= 0.5 and ionic_strength.magnitude >= 0.1:
+        logger.warning("Ionic strength exceeds valid range of the Davies equation")
+
+    # the units in this empirical equation don't work out, so we must use magnitudes
+    log_f = (
+        -_debye_parameter_activity(temperature).magnitude
+        * z**2
+        * (ionic_strength.magnitude**0.5 / (1 + ionic_strength.magnitude**0.5) - 0.2 * ionic_strength.magnitude)
+    )
+
+    return np.exp(log_f) * ureg.Quantity(1, "dimensionless")
+
+
+def 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,
+):
+    """
+    Return the activity coefficient of solute in the parent solution according to the Pitzer model.
+
+    Args:
+        ionic_strength: The ionic strength of the parent solution, mol/kg
+        molality: The molal concentration of the parent salt, mol/kg
+        alpha1, alpha2: Coefficients for the Pitzer model. This function assigns the coefficients
+            proper units of kg ** 0.5 / mol ** 0.5 after they are entered.
+        beta0, beta1, beta2, C_phi:  Coefficients for the Pitzer model. These ion-interaction parameters are
+            specific to each salt system.
+        z_cation, z_anion: The charge on the cation and anion, respectively
+        nu_cation, nu_anion: The stoichiometric coefficient of the cation and anion in the salt
+        temperature: String representing the temperature of the solution. Defaults to '25 degC' if not specified.
+        b: 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*ureg.Quantity('mol/kg'),0.5*ureg.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*ureg.Quantity('mol/kg'),5.6153*ureg.Quantity('mol/kg'),3,0.5,0.0369993,0.354664,0.0997513,-0.00171868,1,-1,1,1,b=1.2)
+        0.76331...
+
+        Notes: 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*ureg.Quantity('mol/kg'),10*ureg.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*ureg.Quantity('mol/kg'),5*ureg.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*ureg.Quantity('mol/kg'),18*ureg.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:
+        :func:`_debye_parameter_activity`
+        :func:`_pitzer_B_MX`
+        :func:`_pitzer_B_phi`
+        :func:`_pitzer_log_gamma`
+    """
+    # assign proper units to alpha1, alpha2, and b
+    alpha1 = ureg.Quantity(alpha1, "kg ** 0.5 / mol ** 0.5")
+    alpha2 = ureg.Quantity(alpha2, "kg ** 0.5 / mol ** 0.5")
+    b = ureg.Quantity(b, "kg ** 0.5 / mol ** 0.5")
+    C_phi = ureg.Quantity(C_phi, "kg ** 2 /mol ** 2")
+
+    # assign units appropriate for the activity parameters
+    BMX = ureg.Quantity(_pitzer_B_MX(ionic_strength, alpha1, alpha2, beta0, beta1, beta2), "kg/mol")
+    Bphi = ureg.Quantity(_pitzer_B_phi(ionic_strength, alpha1, alpha2, beta0, beta1, beta2), "kg/mol")
+
+    loggamma = _pitzer_log_gamma(
+        ionic_strength,
+        molality,
+        BMX,
+        Bphi,
+        C_phi,
+        z_cation,
+        z_anion,
+        nu_cation,
+        nu_anion,
+        temperature,
+        b,
+    )
+
+    return np.exp(loggamma) * ureg.Quantity(1, "dimensionless")
+
+
+def 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,
+):
+    """
+    Return the apparent molar volume of solute in the parent solution according to the Pitzer model.
+
+    Args:
+        ionic_strength (Quantity): The ionic strength of the parent solution, mol/kg.
+        molality (Quantity): The molal concentration of the parent salt, mol/kg.
+        alpha1, 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, beta1, beta2, 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, z_anion (int): The formal charge on the cation and anion, respectively.
+        nu_cation, 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:
+        Notes: 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*ureg.Quantity('mol/kg'),0.25*ureg.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*ureg.Quantity('mol/kg'),1.0*ureg.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*ureg.Quantity('mol/kg'),10.0*ureg.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*ureg.Quantity('mol/kg'),20.0*ureg.Quantity('mol/kg'),2,0,0.000001742,0.0002926,0,0.000000424,46.9,1,-1,1,1,b=1.2)
+        51.145...
+
+        Notes: 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*ureg.Quantity('mol/kg'),0.8*ureg.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:
+        :func:`_debye_parameter_volume`
+        :func:`_pitzer_B_MX`
+    """
+    # TODO - find a cleaner way to make sure coefficients are assigned the proper units
+    # if they aren't, the calculation gives very wrong results
+    alpha1 = ureg.Quantity(alpha1, "kg ** 0.5 / mol ** 0.5")
+    alpha2 = ureg.Quantity(alpha2, "kg ** 0.5 / mol ** 0.5")
+    b = ureg.Quantity(b, "kg ** 0.5 / mol ** 0.5")
+    C_phi = ureg.Quantity(C_phi, "kg ** 2 /mol ** 2 / dabar")
+    V_o = ureg.Quantity(V_o, "cm ** 3 / mol")
+
+    # assign units appropriate for the volume parameter
+    BMX = ureg.Quantity(_pitzer_B_MX(ionic_strength, alpha1, alpha2, beta0, beta1, beta2), "kg /mol/dabar")
+
+    second_term = (
+        (nu_cation + nu_anion)
+        * abs(z_cation * z_anion)
+        * (_debye_parameter_volume(temperature) / 2 / b)
+        * np.log(1 + b * ionic_strength**0.5)
+    )
+
+    third_term = (
+        nu_cation
+        * nu_anion
+        * ureg.R
+        * ureg.Quantity(temperature)
+        * (2 * molality * BMX + molality**2 * C_phi * (nu_cation * nu_anion) ** 0.5)
+    )
+
+    volume = V_o + second_term + third_term
+
+    return volume.to("cm ** 3 / mol")
+
+
+def _pitzer_f1(x):
+    r"""
+    The function of ionic strength used to calculate \beta_MX in the Pitzer ion interaction model.
+
+    .. math:: f(x) = 2 [ 1- (1+x) \exp(-x)] / x ^ 2
+
+    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.
+    """
+    # return 0 if the input is 0
+    if x == 0:
+        return 0
+    return 2 * (1 - (1 + x) * np.exp(-x)) / x**2
+
+
+def _pitzer_f2(x):
+    r"""
+    The function of ionic strength used to calculate \beta_\gamma in the Pitzer ion interaction model.
+
+    .. math:: f(x) = -\frac{2}{x ^ 2} [ 1 - (\frac{1+x+ x^2}{2}) \exp(-x)]
+
+    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.
+    """
+    # return 0 if the input is 0
+    if x == 0:
+        return 0
+    return -2 * (1 - (1 + x + x**2 / 2) * np.exp(-x)) / x**2
+
+
+def _pitzer_B_MX(ionic_strength, alpha1, alpha2, beta0, beta1, beta2):
+    r"""
+    Return the B_MX coefficient for the Pitzer ion interaction model.
+
+    .. math:: B_MX = \beta_0 + \beta_1 f1(\alpha_1 I ^ {0.5}) + \beta_2 f2(\alpha_2 I ^ {0.5})
+
+    Args:
+        ionic_strength: The ionic strength of the parent solution, mol/kg
+        alpha1, alpha2: Coefficients for the Pitzer model, kg ** 0.5 / mol ** 0.5
+        beta0, beta1, beta2: Coefficients for the Pitzer model. These ion-interaction parameters are
+            specific to each salt system.
+
+    Returns:
+        The B_MX parameter for the Pitzer ion interaction model.
+
+    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.
+
+    See Also:
+        :func:`_pitzer_f1`
+
+    """
+    coeff = beta0 + beta1 * _pitzer_f1(alpha1 * ionic_strength**0.5) + beta2 * _pitzer_f1(alpha2 * ionic_strength**0.5)
+    return coeff.magnitude
+
+
+# def _pitzer_B_gamma(ionic_strength,alpha1,alpha2,beta1,beta2):
+#    '''
+#    Return the B^\gamma coefficient for the Pitzer ion interaction model.
+#
+#    .. math:: B_\gamma = [ \beta_1 f2(\alpha_1 I ^ 0.5) + beta_2 f2(\alpha_2 I^0.5) ] / I
+#
+#    Parameters
+#    ----------
+#    ionic_strength: number
+#                    The ionic strength of the parent solution, mol/kg
+#    alpha1, alpha2: number
+#                    Coefficients for the Pitzer model, kg ** 0.5 / mol ** 0.5.
+#    beta1, beta2: number
+#                    Coefficients for the Pitzer model. These ion-interaction parameters are
+#                    specific to each salt system.
+#
+#    Returns
+#    -------
+#    float
+#            The B^gamma parameter for the Pitzer ion interaction model.
+#
+#    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.
+#
+#    See Also
+#    --------
+#    _pitzer_f2
+#
+#    '''
+#    coeff = (beta1 * _pitzer_f2(alpha1 * ionic_strength ** 0.5) + beta2 * _pitzer_f2(alpha2 * ionic_strength ** 0.5)) / ionic_strength
+#    return coeff * ureg.Quantity('kg/mol')
+
+
+def _pitzer_B_phi(ionic_strength, alpha1, alpha2, beta0, beta1, beta2):
+    r"""
+    Returns the B^\Phi coefficient for the Pitzer ion interaction model.
+
+    This function calculates the B^\Phi coefficient using the formula:
+
+    .. math:: B^\Phi = \beta_0 + \beta1 \exp(-\alpha_1 I ^{0.5}) + \beta_2 \exp(-\alpha_2 I ^ {0.5})
+
+    or
+
+    .. math:: B^\Phi = B^\gamma - B_{MX}
+
+    Args:
+        ionic_strength: The ionic strength of the parent solution, mol/kg.
+        alpha1, alpha2: Coefficients for the Pitzer model, kg ** 0.5 / mol ** 0.5.
+        beta0, beta1, beta2: Coefficients for the Pitzer model. These ion-interaction parameters are
+            specific to each salt system.
+
+    Returns:
+        float: The B^Phi parameter for the Pitzer ion interaction model.
+
+    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.
+
+        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
+    """
+
+    # TODO - for some reason this specific method requires the use of math.exp rather than np.exp. Using np.exp raises
+    # a dimensionalityerror.
+    return beta0 + beta1 * math.exp(-alpha1 * ionic_strength**0.5) + beta2 * math.exp(-alpha2 * ionic_strength**0.5)
+
+
+# def _pitzer_C_MX(C_phi,z_cation,z_anion):
+#    '''
+#    Return the C^\Phi coefficient for the Pitzer ion interaction model.
+#
+#    .. math:: C_MX = C^\Phi / 2 \sqrt( \abs(z_+ z_-))
+#
+#    Parameters
+#    ----------
+#    C_phi: number
+#                    The C_phi parameter for the Pitzer ion interaction model.
+#    z_cation, z_anion: int
+#                    The formal charge on the cation and anion, respectively
+#
+#    Returns
+#    -------
+#    float
+#            The C_MX parameter for the Pitzer ion interaction model.
+#
+#    References
+#    ----------
+#    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
+#    '''
+#
+#    coeff = C_phi / ( 2 * abs(z_cation * z_anion) ** 0.5 )
+#    return coeff * ureg.Quantity('kg ** 2 /mol ** 2')
+
+
+def _pitzer_log_gamma(
+    ionic_strength,
+    molality,
+    B_MX,
+    B_phi,
+    C_phi,
+    z_cation,
+    z_anion,
+    nu_cation,
+    nu_anion,
+    temperature="25 degC",
+    b=ureg.Quantity(1.2, "kg**0.5/mol**0.5"),
+):
+    r"""
+    Returns the natural logarithm of the binary activity coefficient calculated by the Pitzer
+    ion interaction model.
+
+    .. math::
+
+        \ln \gamma_{MX} = -|z_+ z_-| A^{Phi} ( \frac{I ^ {0.5}}{(1 + b I ^ {0.5})} + \frac{2}{b} \ln{(1 + b I ^ {0.5})} )+ \frac{m (2 \nu_+ \nu_-)}{(\nu_+ + \nu_-)} (B_{MX} + B_{MX}^\Phi) + \frac{m^2(3 (\nu_+ \nu_-)^{1.5}}{(\nu_+ + \nu_-))} C_{MX}^\Phi
+
+    Args:
+        ionic_strength (Quantity): The ionic strength of the parent solution, mol/kg.
+        molality (Quantity): The concentration of the salt, mol/kg.
+        B_MX, B_phi, C_phi (Quantity): Calculated parameters for the Pitzer ion interaction model.
+        z_cation, z_anion (int): The formal charge on the cation and anion, respectively.
+        nu_cation, 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 kg ** 0.5 / mol ** 0.5 and considered independent of temperature and pressure.
+
+    Returns:
+        float: The natural logarithm of the binary activity coefficient calculated by the Pitzer ion interaction model.
+
+    References:
+        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
+    """
+    first_term = (
+        -1
+        * abs(z_cation * z_anion)
+        * _debye_parameter_osmotic(temperature)
+        * (ionic_strength**0.5 / (1 + b * ionic_strength**0.5) + 2 / b * np.log(1 + b * ionic_strength**0.5))
+    )
+    second_term = 2 * molality * nu_cation * nu_anion / (nu_cation + nu_anion) * (B_MX + B_phi)
+    third_term = 3 * molality**2 * (nu_cation * nu_anion) ** 1.5 / (nu_cation + nu_anion) * C_phi
+
+    return first_term + second_term + third_term
+
+
+def 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,
+):
+    """
+    Return the osmotic coefficient of water in an electrolyte solution according to the Pitzer model.
+
+    Args:
+        ionic_strength (Quantity): The ionic strength of the parent solution, mol/kg.
+        molality (Quantity): The molal concentration of the parent salt, mol/kg.
+        alpha1, 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, beta1, beta2, C_phi: Coefficients for the Pitzer model. These ion-interaction parameters are specific to each salt system.
+        z_cation, z_anion (int): The formal charge on the cation and anion, respectively.
+        nu_cation, 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*ureg.Quantity('mol/kg'),10.175*ureg.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*ureg.Quantity('mol/kg'),5.6153*ureg.Quantity('mol/kg'),3,0.5,0.0369993,0.354664,0.0997513,-0.00171868,1,-1,1,1,b=1.2)
+        1.0850 ...
+
+        Notes: 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*ureg.Quantity('mol/kg'),10*ureg.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*ureg.Quantity('mol/kg'),5*ureg.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*ureg.Quantity('mol/kg'),18*ureg.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:
+        :func:`_debye_parameter_activity`
+        :func:`_pitzer_B_MX`
+        :func:`_pitzer_B_phi`
+        :func:`_pitzer_log_gamma`
+    """
+    # assign proper units to alpha1, alpha2, and b
+    alpha1 = ureg.Quantity(alpha1, "kg ** 0.5 / mol ** 0.5")
+    alpha2 = ureg.Quantity(alpha2, "kg ** 0.5 / mol ** 0.5")
+    b = ureg.Quantity(b, "kg ** 0.5 / mol ** 0.5")
+    C_phi = ureg.Quantity(C_phi, "kg ** 2 /mol ** 2")
+    B_phi = ureg.Quantity(_pitzer_B_phi(ionic_strength, alpha1, alpha2, beta0, beta1, beta2), "kg/mol")
+
+    first_term = 1 - _debye_parameter_osmotic(temperature) * abs(z_cation * z_anion) * ionic_strength**0.5 / (
+        1 + b * ionic_strength**0.5
+    )
+    second_term = molality * 2 * nu_cation * nu_anion / (nu_cation + nu_anion) * B_phi
+    third_term = molality**2 * (2 * (nu_cation * nu_anion) ** 1.5 / (nu_cation + nu_anion)) * C_phi
+
+    return first_term + second_term + third_term