pychnosz 1.1.12__cp310-cp310-macosx_15_0_x86_64.whl

pychnosz/models/hkf.py

@@ -0,0 +1,523 @@
+"""
+HKF (Helgeson-Kirkham-Flowers) equation of state implementation.
+
+This module implements the revised HKF equations for calculating thermodynamic
+properties of aqueous species, based on the tested functions from HKF_cgl.py.
+
+References:
+- Shock, E.L. et al. (1992). Calculation of the thermodynamic properties of 
+  aqueous species at high pressures and temperatures. J. Chem. Soc. Faraday Trans.
+- Johnson, J.W. et al. (1992). SUPCRT92: A software package for calculating the 
+  standard molal thermodynamic properties. Computers & Geosciences.
+- R CHNOSZ hkf.R implementation
+"""
+
+import pandas as pd
+import numpy as np
+import math
+import copy
+import warnings
+from .water import water
+
+def convert_cm3bar(value):
+    return value*4.184 * 10
+
+def gfun(rhohat, Tc, P, alpha, daldT, beta):
+    ## g and f functions for describing effective electrostatic radii of ions
+    ## split from hkf() 20120123 jmd
+    ## based on equations in
+    ## Shock EL, Oelkers EH, Johnson JW, Sverjensky DA, Helgeson HC, 1992
+    ## Calculation of the Thermodynamic Properties of Aqueous Species at High Pressures
+    ## and Temperatures: Effective Electrostatic Radii, Dissociation Constants and
+    ## Standard Partial Molal Properties to 1000 degrees C and 5 kbar
+    ## J. Chem. Soc. Faraday Trans., 88(6), 803-826  doi:10.1039/FT9928800803
+    # rhohat - density of water in g/cm3
+    # Tc - temperature in degrees Celsius
+    # P - pressure in bars
+
+    # Vectorized version - handle both scalars and arrays
+    rhohat = np.atleast_1d(rhohat)
+    Tc = np.atleast_1d(Tc)
+    P = np.atleast_1d(P)
+    alpha = np.atleast_1d(alpha)
+    daldT = np.atleast_1d(daldT)
+    beta = np.atleast_1d(beta)
+
+    # Broadcast to same shape
+    shape = np.broadcast_shapes(rhohat.shape, Tc.shape, P.shape, alpha.shape, daldT.shape, beta.shape)
+    rhohat = np.broadcast_to(rhohat, shape)
+    Tc = np.broadcast_to(Tc, shape)
+    P = np.broadcast_to(P, shape)
+    alpha = np.broadcast_to(alpha, shape)
+    daldT = np.broadcast_to(daldT, shape)
+    beta = np.broadcast_to(beta, shape)
+
+    # Initialize output arrays
+    g = np.zeros(shape)
+    dgdT = np.zeros(shape)
+    d2gdT2 = np.zeros(shape)
+    dgdP = np.zeros(shape)
+
+    # only rhohat less than 1 will give results other than zero
+    mask = rhohat < 1
+    if not np.any(mask):
+        return {"g": g, "dgdT": dgdT, "d2gdT2": d2gdT2, "dgdP": dgdP}
+
+    # eta in Eq. 1
+    eta = 1.66027E5
+    # Table 3
+    ag1 = -2.037662
+    ag2 = 5.747000E-3
+    ag3 = -6.557892E-6
+    bg1 = 6.107361
+    bg2 = -1.074377E-2
+    bg3 = 1.268348E-5
+
+    # Work only with masked values
+    Tc_m = Tc[mask]
+    P_m = P[mask]
+    rhohat_m = rhohat[mask]
+    alpha_m = alpha[mask]
+    daldT_m = daldT[mask]
+    beta_m = beta[mask]
+
+    # Eq. 25
+    ag = ag1 + ag2 * Tc_m + ag3 * Tc_m ** 2
+    # Eq. 26
+    bg = bg1 + bg2 * Tc_m + bg3 * Tc_m ** 2
+    # Eq. 24
+    g_m = ag * (1 - rhohat_m) ** bg
+
+    # Table 4
+    af1 = 0.3666666E2
+    af2 = -0.1504956E-9
+    af3 = 0.5017997E-13
+
+    # Eq. 33
+    f = ( ((Tc_m - 155) / 300) ** 4.8 + af1 * ((Tc_m - 155) / 300) ** 16 ) * \
+        ( af2 * (1000 - P_m) ** 3 + af3 * (1000 - P_m) ** 4 )
+
+    # limits of the f function (region II of Fig. 6)
+    ifg = (Tc_m > 155) & (P_m < 1000) & (Tc_m < 355)
+
+    # Eq. 32 - apply f correction where ifg is True
+    # Check for complex values
+    f_is_real = ~np.iscomplex(f)
+    apply_f = ifg & f_is_real
+    g_m = np.where(apply_f, g_m - f.real, g_m)
+
+    # at P > 6000 bar (in DEW calculations), g is zero 20170926
+    g_m = np.where(P_m > 6000, 0, g_m)
+
+    ## now we have g at P, T
+    # put the results in their right place (where rhohat < 1)
+    g[mask] = g_m
+    
+    ## the rest is to get its partial derivatives with pressure and temperature
+    ## after Johnson et al., 1992
+    # alpha - coefficient of isobaric expansivity (K^-1)
+    # daldT - temperature derivative of coefficient of isobaric expansivity (K^-2)
+    # beta - coefficient of isothermal compressibility (bar^-1)
+
+    # Eqn. 76
+    d2fdT2 = (0.0608/300*((Tc_m-155)/300)**2.8 + af1/375*((Tc_m-155)/300)**14) * (af2*(1000-P_m)**3 + af3*(1000-P_m)**4)
+    # Eqn. 75
+    dfdT = (0.016*((Tc_m-155)/300)**3.8 + 16*af1/300*((Tc_m-155)/300)**15) * \
+        (af2*(1000-P_m)**3 + af3*(1000-P_m)**4)
+    # Eqn. 74
+    dfdP = -(((Tc_m-155)/300)**4.8 + af1*((Tc_m-155)/300)**16) * \
+        (3*af2*(1000-P_m)**2 + 4*af3*(1000-P_m)**3)
+    d2bdT2 = 2 * bg3  # Eqn. 73
+    d2adT2 = 2 * ag3  # Eqn. 72
+    dbdT = bg2 + 2*bg3*Tc_m  # Eqn. 71
+    dadT = ag2 + 2*ag3*Tc_m  # Eqn. 70
+
+    # Convert complex to NaN
+    d2fdT2 = np.where(np.iscomplex(d2fdT2), np.nan, np.real(d2fdT2))
+    dfdT = np.where(np.iscomplex(dfdT), np.nan, np.real(dfdT))
+    dfdP = np.where(np.iscomplex(dfdP), np.nan, np.real(dfdP))
+
+    # Initialize derivative arrays for masked region
+    dgdT_m = np.zeros_like(g_m)
+    d2gdT2_m = np.zeros_like(g_m)
+    dgdP_m = np.zeros_like(g_m)
+
+    # Calculate derivatives where alpha and daldT are not NaN
+    alpha_valid = ~np.isnan(alpha_m) & ~np.isnan(daldT_m)
+    if np.any(alpha_valid):
+        # Work with valid subset
+        av_idx = alpha_valid
+        bg_av = bg[av_idx]
+        rhohat_av = rhohat_m[av_idx]
+        alpha_av = alpha_m[av_idx]
+        daldT_av = daldT_m[av_idx]
+        g_av = g_m[av_idx]
+        ag_av = ag[av_idx]
+        Tc_av = Tc_m[av_idx]
+        dbdT_av = dbdT[av_idx]
+        dadT_av = dadT[av_idx]
+
+        # Handle log of (1-rhohat) safely
+        with np.errstate(divide='ignore', invalid='ignore'):
+            log_term = np.log(1 - rhohat_av)
+            log_term = np.where(np.isfinite(log_term), log_term, 0)
+
+        # Eqn. 69
+        dgadT = bg_av*rhohat_av*alpha_av*(1-rhohat_av)**(bg_av-1) + log_term*g_av/ag_av*dbdT_av
+        D = rhohat_av
+
+        # transcribed from SUPCRT92/reac92.f
+        dDdT = -D * alpha_av
+        dDdTT = -D * (daldT_av - alpha_av**2)
+        Db = (1-D)**bg_av
+        dDbdT = -bg_av*(1-D)**(bg_av-1)*dDdT + log_term*Db*dbdT_av
+        dDbdTT = -(bg_av*(1-D)**(bg_av-1)*dDdTT + (1-D)**(bg_av-1)*dDdT*dbdT_av + \
+            bg_av*dDdT*(-(bg_av-1)*(1-D)**(bg_av-2)*dDdT + log_term*(1-D)**(bg_av-1)*dbdT_av)) + \
+            log_term*(1-D)**bg_av*d2bdT2 - (1-D)**bg_av*dbdT_av*dDdT/(1-D) + log_term*dbdT_av*dDbdT
+        d2gdT2_calc = ag_av*dDbdTT + 2*dDbdT*dadT_av + Db*d2adT2
+
+        # Apply f correction where ifg is True
+        ifg_av = ifg[av_idx]
+        d2fdT2_av = d2fdT2[av_idx]
+        dfdT_av = dfdT[av_idx]
+        d2gdT2_calc = np.where(ifg_av, d2gdT2_calc - d2fdT2_av, d2gdT2_calc)
+
+        dgdT_calc = g_av/ag_av*dadT_av + ag_av*dgadT  # Eqn. 67
+        dgdT_calc = np.where(ifg_av, dgdT_calc - dfdT_av, dgdT_calc)
+
+        dgdT_m[av_idx] = dgdT_calc
+        d2gdT2_m[av_idx] = d2gdT2_calc
+
+    # Calculate dgdP where beta is not NaN
+    beta_valid = ~np.isnan(beta_m)
+    if np.any(beta_valid):
+        bv_idx = beta_valid
+        bg_bv = bg[bv_idx]
+        rhohat_bv = rhohat_m[bv_idx]
+        beta_bv = beta_m[bv_idx]
+        g_bv = g_m[bv_idx]
+
+        dgdP_calc = -bg_bv*rhohat_bv*beta_bv*g_bv*(1-rhohat_bv)**-1  # Eqn. 66
+        ifg_bv = ifg[bv_idx]
+        dfdP_bv = dfdP[bv_idx]
+        dgdP_calc = np.where(ifg_bv, dgdP_calc - dfdP_bv, dgdP_calc)
+        dgdP_m[bv_idx] = dgdP_calc
+
+    # Put results back into full arrays
+    dgdT[mask] = dgdT_m
+    d2gdT2[mask] = d2gdT2_m
+    dgdP[mask] = dgdP_m
+
+    return {"g": g, "dgdT": dgdT, "d2gdT2": d2gdT2, "dgdP": dgdP}
+
+def hkf(property=None, parameters=None, T=298.15, P=1,
+    contrib = ["n", "s", "o"], H2O_props=["rho"], water_model="SUPCRT92"):
+    # calculate G, H, S, Cp, V, kT, and/or E using
+    # the revised HKF equations of state
+    # H2O_props - H2O properties needed for subcrt() output
+    # constants
+    Tr = 298.15 # K
+    Pr = 1      # bar
+    Theta = 228 # K
+    Psi = 2600  # bar
+
+    # Convert T and P to arrays for vectorized operations
+    T = np.atleast_1d(T)
+    P = np.atleast_1d(P)
+
+    # DEBUG
+    if False:
+        print(f"\nDEBUG HKF input:")
+        print(f"  T (K): {T}")
+        print(f"  P (bar): {P}")
+
+    # make T and P equal length
+    if P.size < T.size:
+        P = np.full_like(T, P[0] if P.size == 1 else P)
+    if T.size < P.size:
+        T = np.full_like(P, T[0] if T.size == 1 else T)
+
+    n_conditions = T.size
+    
+    # GB conversion note: handle error messages later
+#     # nonsolvation, solvation, and origination contribution
+#     notcontrib <- ! contrib %in% c("n", "s", "o")
+#     if(TRUE %in% notcontrib) stop(paste("contrib must be in c('n', 's', 'o); got", c2s(contrib[notcontrib])))
+    
+    # get water properties
+    # rho - for subcrt() output and g function
+    # Born functions and epsilon - for HKF calculations
+    H2O_props += ["QBorn", "XBorn", "YBorn", "epsilon"]
+
+    if water_model == "SUPCRT92":
+      # using H2O92D.f from SUPCRT92: alpha, daldT, beta - for partial derivatives of omega (g function)
+      H2O_props += ["alpha", "daldT", "beta"]
+    
+    elif water_model == "IAPWS95":
+      # using IAPWS-95: NBorn, UBorn - for compressibility, expansibility
+      H2O_props += ["alpha", "daldT", "beta", "NBorn", "UBorn"]
+    
+    elif water_model == "DEW":
+      # using DEW model: get beta to calculate dgdP
+      H2O_props += ["alpha", "daldT", "beta"]
+
+    # DEBUG: Print T and P being passed to water
+    if False:
+        print(f"DEBUG HKF calling water():")
+        print(f"  T type: {type(T)}, T: {T}")
+        print(f"  P type: {type(P)}, P: {P}")
+        print(f"  H2O_props: {H2O_props}")
+
+    H2O_PrTr = water(H2O_props, T=Tr, P=Pr)
+    H2O_PT = water(H2O_props, T=T, P=P)
+
+    # DEBUG: Print what water returned
+    if False:
+        print(f"DEBUG HKF water() returned:")
+        print(f"  H2O_PT type: {type(H2O_PT)}")
+        if isinstance(H2O_PT, dict):
+            print(f"  H2O_PT keys: {H2O_PT.keys()}")
+            print(f"  epsilon: {H2O_PT.get('epsilon', 'NOT FOUND')}")
+
+    # Handle dict output from water function
+    def get_water_prop(water_dict, prop):
+        """Helper function to get water property from dict or DataFrame"""
+        if isinstance(water_dict, dict):
+            return water_dict[prop]
+        else:
+            return water_dict.loc["1", prop]
+
+    # Get epsilon values and handle potential zeros
+    epsilon_PT = get_water_prop(H2O_PT, "epsilon")
+    epsilon_PrTr = get_water_prop(H2O_PrTr, "epsilon")
+
+    # Check for zero or very small epsilon values and warn
+    if np.any(epsilon_PT == 0) or np.any(np.abs(epsilon_PT) < 1e-10):
+        warnings.warn(f"HKF: epsilon at P,T is zero or very small: {epsilon_PT}. H2O_PT keys: {H2O_PT.keys() if isinstance(H2O_PT, dict) else 'not dict'}")
+
+    with np.errstate(divide='ignore', invalid='ignore'):
+        ZBorn = -1 / epsilon_PT
+        ZBorn_PrTr = -1 / epsilon_PrTr
+    
+    # a class to store the result
+    out_dict = {} # dictionary to store output
+    
+    for k in parameters.index:
+        
+        if parameters["state"][k] != "aq":
+            out_dict[k] = {p:float('NaN') for p in property}
+        else:
+            sp = parameters["name"][k]
+
+            # loop over each species
+            PAR = copy.copy(parameters.loc[k, :])
+
+            PAR["a1.a"] = copy.copy(PAR["a1.a"]*10**-1)
+            PAR["a2.b"] = copy.copy(PAR["a2.b"]*10**2)
+            PAR["a4.d"] = copy.copy(PAR["a4.d"]*10**4)
+            PAR["c2.f"] = copy.copy(PAR["c2.f"]*10**4)
+            PAR["omega.lambda"] = copy.copy(PAR["omega.lambda"]*10**5)
+
+            # substitute Cp and V for missing EoS parameters
+            # here we assume that the parameters are in the same position as in thermo()$OBIGT
+            # we don't need this if we're just looking at solvation properties (Cp_s_var, V_s_var)
+
+            # GB conversion note: this block checks various things about EOS parameters.
+            # for now, just set hasEOS to True
+            hasEOS = True # delete this once the following block is converted to python
+    #         if "n" in contrib:
+    #             # put the heat capacity in for c1 if both c1 and c2 are missing
+    #             if all(is.na(PAR[, 18:19])):
+    #                 PAR[, 18] = PAR["Cp"]
+    #             # put the volume in for a1 if a1, a2, a3 and a4 are missing
+    #             if all(is.na(PAR[, 14:17])):
+    #                 PAR[, 14] = convert(PAR["V"], "calories")
+    #             # test for availability of the EoS parameters
+    #             hasEOS = any(!is.na(PAR[, 14:21]))
+    #             # if at least one of the EoS parameters is available, zero out any NA's in the rest
+    #             if hasEOS:
+    #                 PAR[, 14:21][, is.na(PAR[, 14:21])] = 0
+
+            # compute values of omega(P,T) from those of omega(Pr,Tr)
+            # using g function etc. (Shock et al., 1992 and others)
+            omega = PAR["omega.lambda"]  # omega_PrTr
+            # its derivatives are zero unless the g function kicks in
+            dwdP = np.zeros(n_conditions)
+            dwdT = np.zeros(n_conditions)
+            d2wdT2 = np.zeros(n_conditions)
+            Z = PAR["z.T"]
+
+            omega_PT = np.full(n_conditions, PAR["omega.lambda"])
+            if Z != 0 and Z != "NA" and PAR["name"] != "H+":
+                # compute derivatives of omega: g and f functions (Shock et al., 1992; Johnson et al., 1992)
+                rhohat = get_water_prop(H2O_PT, "rho")/1000  # just converting kg/m3 to g/cm3
+
+                # temporarily filter out Python's warnings about dividing by zero, which is possible
+                # with the equations in the gfunction
+                # Possible complex output is acounted for in gfun().
+                with warnings.catch_warnings():
+                    warnings.simplefilter('ignore')
+                    g = gfun(rhohat, T-273.15, P, get_water_prop(H2O_PT, "alpha"), get_water_prop(H2O_PT, "daldT"), get_water_prop(H2O_PT, "beta"))
+
+                # after SUPCRT92/reac92.f
+                eta = 1.66027E5
+                reref = (Z**2) / (omega/eta + Z/(3.082 + 0))
+                re = reref + abs(Z) * g["g"]
+                omega_PT = eta * (Z**2/re - Z/(3.082 + g["g"]))
+                Z3 = abs(Z**3)/re**2 - Z/(3.082 + g["g"])**2
+                Z4 = abs(Z**4)/re**3 - Z/(3.082 + g["g"])**3
+                dwdP = (-eta * Z3 * g["dgdP"])
+                dwdT = (-eta * Z3 * g["dgdT"])
+                d2wdT2 = (2 * eta * Z4 * g["dgdT"]**2 - eta * Z3 * g["d2gdT2"])
+
+            # loop over each property
+            w = float('NaN')
+            for i,PROP in enumerate(property) :
+
+                # over nonsolvation, solvation, or origination contributions - vectorized
+                hkf_p = np.zeros(n_conditions)
+
+                for icontrib in contrib :
+                    # various contributions to the properties
+                    if icontrib == "n":
+                        # nonsolvation ghs equations
+                        if PROP == "H":
+                            p_c = PAR["c1.e"]*(T-Tr) - PAR["c2.f"]*(1/(T-Theta)-1/(Tr-Theta))
+                            p_a = PAR["a1.a"]*(P-Pr) + PAR["a2.b"]*np.log((Psi+P)/(Psi+Pr)) + \
+                              ((2*T-Theta)/(T-Theta)**2)*(PAR["a3.c"]*(P-Pr)+PAR["a4.d"]*np.log((Psi+P)/(Psi+Pr)))
+                            p = p_c + p_a
+                        elif PROP == "S":
+                            p_c = PAR["c1.e"]*np.log(T/Tr) - \
+                              (PAR["c2.f"]/Theta)*( 1/(T-Theta)-1/(Tr-Theta) + \
+                              np.log( (Tr*(T-Theta))/(T*(Tr-Theta)) )/Theta )
+                            p_a = (T-Theta)**(-2)*(PAR["a3.c"]*(P-Pr)+PAR["a4.d"]*np.log((Psi+P)/(Psi+Pr)))
+                            p = p_c + p_a
+                        elif PROP == "G":
+                            p_c = -PAR["c1.e"]*(T*np.log(T/Tr)-T+Tr) - \
+                              PAR["c2.f"]*( (1/(T-Theta)-1/(Tr-Theta))*((Theta-T)/Theta) - \
+                              (T/Theta**2)*np.log((Tr*(T-Theta))/(T*(Tr-Theta))) )
+                            p_a = PAR["a1.a"]*(P-Pr) + PAR["a2.b"]*np.log((Psi+P)/(Psi+Pr)) + \
+                              (PAR["a3.c"]*(P-Pr) + PAR["a4.d"]*np.log((Psi+P)/(Psi+Pr)))/(T-Theta)
+                            p = p_c + p_a
+                            # at Tr,Pr, if the origination contribution is not NA, ensure the solvation contribution is 0, not NA
+                            if not np.isnan(PAR["G"]):
+                                p = np.where((T==Tr) & (P==Pr), 0, p)
+                        # nonsolvation cp v kt e equations
+                        elif PROP == "Cp":
+                            p = PAR["c1.e"] + PAR["c2.f"] * ( T - Theta ) ** (-2)
+                        elif PROP == "V":
+                            p = convert_cm3bar(PAR["a1.a"]) + \
+                              convert_cm3bar(PAR["a2.b"]) / (Psi + P) + \
+                              (convert_cm3bar(PAR["a3.c"]) + convert_cm3bar(PAR["a4.d"]) / (Psi + P)) / (T - Theta)
+#                         elif PROP == "kT":
+#                             p = (convert(PAR["a2.b"], "cm3bar") + \
+#                               convert(PAR["a4.d"], "cm3bar") / (T - Theta)) * (Psi + P) ** (-2)
+#                         elif PROP == "E":
+#                             p = convert( - (PAR["a3.c"] + PAR["a4.d"] / convert((Psi + P), "calories")) * \
+#                               (T - Theta) ** (-2), "cm3bar")
+                        else:
+                            print("BAD")
+
+                    if icontrib == "s":
+                        # solvation ghs equations
+                        if PROP == "G":
+                            p = -omega_PT*(ZBorn+1) + omega*(ZBorn_PrTr+1) + omega*get_water_prop(H2O_PrTr, "YBorn")*(T-Tr)
+                            # at Tr,Pr, if the origination contribution is not NA, ensure the solvation contribution is 0, not NA
+                            if(np.isnan(PAR["G"])):
+                                p = np.where((T==Tr) & (P==Pr), 0, p)
+                        if PROP == "H":
+                            p = -omega_PT*(ZBorn+1) + omega_PT*T*get_water_prop(H2O_PT, "YBorn") + T*(ZBorn+1)*dwdT + \
+                                   omega*(ZBorn_PrTr+1) - omega*Tr*get_water_prop(H2O_PrTr, "YBorn")
+                        if PROP == "S":
+                            p = omega_PT*get_water_prop(H2O_PT, "YBorn") + (ZBorn+1)*dwdT - omega*get_water_prop(H2O_PrTr, "YBorn")
+                        # solvation cp v kt e equations
+                        if PROP == "Cp":
+                            p = omega_PT*T*get_water_prop(H2O_PT, "XBorn") + 2*T*get_water_prop(H2O_PT, "YBorn")*dwdT + T*(ZBorn+1)*d2wdT2
+                        if PROP == "V":
+                            term1 = -convert_cm3bar(omega_PT) * get_water_prop(H2O_PT, "QBorn")
+                            term2 = convert_cm3bar(dwdP) * (-ZBorn - 1)
+                            p = term1 + term2
+
+                            # DEBUG
+                            if False:
+                                print(f"\nDEBUG solvation V terms:")
+                                print(f"  omega_PT: {omega_PT}")
+                                print(f"  QBorn: {get_water_prop(H2O_PT, 'QBorn')}")
+                                print(f"  dwdP: {dwdP}")
+                                print(f"  ZBorn: {ZBorn}")
+                                print(f"  term1 (-ω*QBorn): {term1}")
+                                print(f"  term2 (dwdP*(-Z-1)): {term2}")
+                                print(f"  total p: {p}")
+                        # TODO: the partial derivatives of omega are not included here here for kt and e
+                        # (to do it, see p. 820 of SOJ+92 ... but kt requires d2wdP2 which we don"t have yet)
+                        if PROP == "kT":
+                            p = convert_cm3bar(omega) * get_water_prop(H2O_PT, "NBorn")
+                        if PROP == "E":
+                            p = -convert_cm3bar(omega) * get_water_prop(H2O_PT, "UBorn")
+
+                    if icontrib == "o":
+                        # origination ghs equations
+                        if PROP == "G":
+                            p = PAR["G"] - PAR["S"] * (T-Tr)
+                            # don"t inherit NA from PAR$S at Tr
+                            p = np.where(T == Tr, PAR["G"], p)
+                        elif PROP == "H":
+                            p = np.full(n_conditions, PAR["H"])
+                        elif PROP == "S":
+                            p = np.full(n_conditions, PAR["S"])
+                        # origination eos equations (Cp, V, kT, E): senseless
+                        else:
+                            p = np.zeros(n_conditions)
+
+                    # accumulate the contribution
+                    hkf_p = hkf_p + p
+
+                    # DEBUG
+                    if False and PROP == "V":
+                        print(f"\nDEBUG HKF V calculation (species {k}, contrib={icontrib}):")
+                        print(f"  T: {T}")
+                        print(f"  P: {P}")
+                        print(f"  contribution p: {p}")
+                        print(f"  accumulated hkf_p: {hkf_p}")
+
+                # species have to be numbered (k) instead of named because of name repeats in db (e.g., cr polymorphs)
+                if i > 0:
+                    out_dict[k][PROP] = hkf_p
+                else:
+                    out_dict[k] = {PROP:hkf_p}
+
+                # DEBUG
+                if False and PROP == "V":
+                    print(f"\nDEBUG HKF final V for species {k}: {hkf_p}")
+
+    return(out_dict, H2O_PT)
+
+
+def calculate_born_functions(T: np.ndarray, P) -> dict:
+    """Calculate Born functions needed for HKF solvation calculations."""
+    
+    # Get water properties needed for Born functions
+    water_props = water(["epsilon", "rho"], T=T, P=P)
+    
+    # Basic Born functions (simplified - full implementation would include all derivatives)
+    epsilon = water_props['epsilon']
+    rho = water_props['rho']
+    
+    # Dielectric constant derivatives (simplified approximations)
+    deps_dT = -np.gradient(epsilon) / np.gradient(T) if len(T) > 1 else np.zeros_like(T)
+    deps_dP = np.zeros_like(T)  # Would need pressure derivative
+    
+    # Born functions (simplified)
+    QBorn = 1.0 / epsilon
+    XBorn = deps_dT / epsilon**2
+    YBorn = np.gradient(XBorn) / np.gradient(T) if len(T) > 1 else np.zeros_like(T)
+    NBorn = deps_dP / epsilon**2
+    UBorn = np.zeros_like(T)  # Second derivative term
+    
+    return {
+        'QBorn': QBorn,
+        'XBorn': XBorn, 
+        'YBorn': YBorn,
+        'NBorn': NBorn,
+        'UBorn': UBorn
+    }