pyEQL 1.4.0rc9__cp311-cp311-macosx_10_9_x86_64.whl

pyEQL/phreeqc/ext/iphreeqc-3.8.6-17100/src/phreeqcpp/gases.cpp

@@ -0,0 +1,748 @@
+#include "Phreeqc.h"
+#include "GasPhase.h"
+
+#if defined(PHREEQCI_GUI)
+#ifdef _DEBUG
+#define new DEBUG_NEW
+#undef THIS_FILE
+static char THIS_FILE[] = __FILE__;
+#endif
+#endif
+
+/* ---------------------------------------------------------------------- */
+int Phreeqc::
+setup_fixed_volume_gas(void)
+/* ---------------------------------------------------------------------- */
+{
+/*
+ *   Fill in data for gas phase unknown (sum of partial pressures)
+ *   in unknown structure
+ */
+	if (use.Get_gas_phase_ptr() == NULL)
+		return (OK);
+	cxxGasPhase *gas_phase_ptr = use.Get_gas_phase_ptr();
+/*
+ *   One for each gas component
+ */
+	gas_unknowns.clear();
+	gas_unknown = NULL;
+	gas_phase_ptr->Set_total_moles(0);
+	for (size_t i = 0; i < gas_phase_ptr->Get_gas_comps().size(); i++)
+	{
+		const cxxGasComp *comp_ptr = &(gas_phase_ptr->Get_gas_comps()[i]);
+		int j;
+		class phase *phase_ptr = phase_bsearch(comp_ptr->Get_phase_name().c_str(), &j, FALSE);
+		x[count_unknowns]->type = GAS_MOLES;
+		x[count_unknowns]->description = phase_ptr->name;
+		x[count_unknowns]->phase = phase_ptr;
+		x[count_unknowns]->moles = comp_ptr->Get_moles();
+		if (x[count_unknowns]->moles <= 0)
+		{
+			x[count_unknowns]->moles = MIN_TOTAL;
+		}
+		x[count_unknowns]->ln_moles = log(x[count_unknowns]->moles);
+		gas_unknowns.push_back(x[count_unknowns]);
+		gas_phase_ptr->Set_total_moles(gas_phase_ptr->Get_total_moles() + x[count_unknowns]->moles);
+		x[count_unknowns]->phase->moles_x = x[count_unknowns]->moles;
+		count_unknowns++;
+	}
+	if (gas_unknowns.size() > 0)
+	{
+		gas_unknown = gas_unknowns[0];
+	}
+
+	return (OK);
+}
+
+/* ---------------------------------------------------------------------- */
+int Phreeqc::
+build_fixed_volume_gas(void)
+/* ---------------------------------------------------------------------- */
+{
+/*
+ *   Put coefficients into lists to sum iaps to test for equilibrium
+ *   Put coefficients into lists to build jacobian for 
+ *      sum of partial pressures equation and
+ *      mass balance equations for elements contained in gases
+ */
+	size_t row, col;
+	class master *master_ptr;
+	class rxn_token *rxn_ptr;
+	class unknown *unknown_ptr;
+	LDBLE coef, coef_elt;
+
+	if (gas_unknown == NULL)
+		return (OK);
+	cxxGasPhase *gas_phase_ptr = use.Get_gas_phase_ptr();
+	for (size_t i = 0; i < gas_phase_ptr->Get_gas_comps().size(); i++)
+	{
+		const cxxGasComp *comp_ptr = &(gas_phase_ptr->Get_gas_comps()[i]);
+		int j;
+		class phase *phase_ptr = phase_bsearch(comp_ptr->Get_phase_name().c_str(), &j, FALSE);
+/*
+ *   Determine elements in gas component
+ */
+		count_elts = 0;
+		paren_count = 0;
+		if (phase_ptr->rxn_x.token.size() == 0)
+			continue;
+		add_elt_list(phase_ptr->next_elt, 1.0);
+#define COMBINE
+#ifdef COMBINE
+		change_hydrogen_in_elt_list(0);
+#endif
+/*
+ *   Build mass balance sums for each element in gas
+ */
+		if (debug_prep == TRUE)
+		{
+			output_msg(sformatf( "\n\tMass balance summations %s.\n",
+					   phase_ptr->name));
+		}
+
+		/* All elements in gas */
+		for (j = 0; j < (int) count_elts; j++)
+		{
+			unknown_ptr = NULL;
+			if (strcmp(elt_list[j].elt->name, "H") == 0)
+			{
+				unknown_ptr = mass_hydrogen_unknown;
+			}
+			else if (strcmp(elt_list[j].elt->name, "O") == 0)
+			{
+				unknown_ptr = mass_oxygen_unknown;
+			}
+			else
+			{
+				if (elt_list[j].elt->primary->in == TRUE)
+				{
+					unknown_ptr = elt_list[j].elt->primary->unknown;
+				}
+				else if (elt_list[j].elt->primary->s->secondary != NULL)
+				{
+					unknown_ptr =
+						elt_list[j].elt->primary->s->secondary->unknown;
+				}
+			}
+			if (unknown_ptr != NULL)
+			{
+				coef = elt_list[j].coef;
+				store_mb(&(gas_unknowns[i]->moles), &(unknown_ptr->f), coef);
+				if (debug_prep == TRUE)
+				{
+					output_msg(sformatf( "\t\t%-24s%10.3f\n",
+							   unknown_ptr->description, (double) coef));
+				}
+			}
+		}
+		if (gas_phase_ptr->Get_type() == cxxGasPhase::GP_PRESSURE)
+		{
+			/* Total pressure of gases */
+			store_mb(&(phase_ptr->p_soln_x), &(gas_unknown->f),
+					 1.0);
+		}
+/*
+ *   Build jacobian sums for mass balance equations
+ */
+		if (debug_prep == TRUE)
+		{
+			output_msg(sformatf( "\n\tJacobian summations %s.\n\n",
+					   phase_ptr->name));
+		}
+		for (j = 0; j < (int) count_elts; j++)
+		{
+			unknown_ptr = NULL;
+			if (strcmp(elt_list[j].elt->name, "H") == 0)
+			{
+				unknown_ptr = mass_hydrogen_unknown;
+			}
+			else if (strcmp(elt_list[j].elt->name, "O") == 0)
+			{
+				unknown_ptr = mass_oxygen_unknown;
+			}
+			else
+			{
+				if (elt_list[j].elt->primary->in == TRUE)
+				{
+					unknown_ptr = elt_list[j].elt->primary->unknown;
+				}
+				else if (elt_list[j].elt->primary->s->secondary != NULL)
+				{
+					unknown_ptr =
+						elt_list[j].elt->primary->s->secondary->unknown;
+				}
+			}
+			if (unknown_ptr == NULL)
+			{
+				continue;
+			}
+			if (debug_prep == TRUE)
+			{
+				output_msg(sformatf( "\n\t%s.\n",
+						   unknown_ptr->description));
+			}
+			row = unknown_ptr->number * (count_unknowns + 1);
+			coef_elt = elt_list[j].coef;
+			for (rxn_ptr = &phase_ptr->rxn_x.token[0] + 1;
+				 rxn_ptr->s != NULL; rxn_ptr++)
+			{
+
+				if (rxn_ptr->s->secondary != NULL
+					&& rxn_ptr->s->secondary->in == TRUE)
+				{
+					master_ptr = rxn_ptr->s->secondary;
+				}
+				else if (rxn_ptr->s->primary != NULL && rxn_ptr->s->primary->in == TRUE)
+				{
+					master_ptr = rxn_ptr->s->primary;
+				}
+				else
+				{
+					master_ptr = master_bsearch_primary(rxn_ptr->s->name);
+					master_ptr->s->la = -999.0;
+				}
+				if (debug_prep == TRUE)
+				{
+					output_msg(sformatf( "\t\t%s\n",
+							   master_ptr->s->name));
+				}
+				if (master_ptr->unknown == NULL)
+				{
+					continue;
+				}
+				if (master_ptr->in == FALSE)
+				{
+					error_string = sformatf(
+							"Element, %s, in phase, %s, is not in model.",
+							master_ptr->elt->name, phase_ptr->name);
+					error_msg(error_string, CONTINUE);
+					input_error++;
+				}
+				col = master_ptr->unknown->number;
+				coef = coef_elt * rxn_ptr->coef;
+				if (debug_prep == TRUE)
+				{
+					output_msg(sformatf( "\t\t%-24s%10.3f\t%d\t%d",
+							   master_ptr->s->name, (double) coef,
+							   row / (count_unknowns + 1), col));
+				}
+				store_jacob(&(gas_unknowns[i]->moles),
+					&(my_array[(size_t)row + (size_t)col]), coef);
+			}
+			if (gas_phase_ptr->Get_type() == cxxGasPhase::GP_PRESSURE)
+			{
+				/* derivative wrt total moles of gas */
+				if (debug_prep == TRUE)
+				{
+					output_msg(sformatf( "\t\t%-24s%10.3f\t%d\t%d",
+							   "gas moles", (double) elt_list[j].coef,
+							   row / (count_unknowns + 1),
+							   gas_unknown->number));
+				}
+				store_jacob(&(phase_ptr->fraction_x),
+					&(my_array[(size_t)row + (size_t)gas_unknown->number]), coef_elt);
+			}
+		}
+/*
+ *   Build jacobian sums for sum of partial pressures equation
+ */
+		if (gas_phase_ptr->Get_type() != cxxGasPhase::GP_PRESSURE)
+			continue;
+		if (debug_prep == TRUE)
+		{
+			output_msg(sformatf( "\n\tPartial pressure eqn %s.\n\n",
+					   phase_ptr->name));
+		}
+		unknown_ptr = gas_unknown;
+		row = unknown_ptr->number * (count_unknowns + 1);
+		for (rxn_ptr = &phase_ptr->rxn_x.token[0] + 1; rxn_ptr->s != NULL; rxn_ptr++)
+		{
+			if (rxn_ptr->s != s_eminus && rxn_ptr->s->in == FALSE)
+			{
+				error_string = sformatf(
+					"Element in species, %s, in phase, %s, is not in model.",
+					rxn_ptr->s->name, phase_ptr->name);
+				warning_msg(error_string);
+			}
+			else
+			{
+				if (rxn_ptr->s->secondary != NULL
+					&& rxn_ptr->s->secondary->in == TRUE)
+				{
+					master_ptr = rxn_ptr->s->secondary;
+				}
+				else if (rxn_ptr->s->primary != NULL && rxn_ptr->s->primary->in == TRUE)
+				{
+					master_ptr = rxn_ptr->s->primary;
+				}
+				else
+				{
+					master_ptr = master_bsearch_primary(rxn_ptr->s->name);
+					if (master_ptr && master_ptr->s)
+					{
+						master_ptr->s->la = -999.0;
+					}
+				}
+
+				if (master_ptr == NULL)
+				{
+					error_string = sformatf(
+						"Master species for %s, in phase, %s, is not in model.",
+						rxn_ptr->s->name, phase_ptr->name);
+					error_msg(error_string, CONTINUE);
+					input_error++;
+				}
+				else
+				{
+					if (debug_prep == TRUE)
+					{
+						output_msg(sformatf( "\t\t%s\n", master_ptr->s->name));
+					}
+					if (master_ptr->unknown == NULL)
+					{
+						assert(false);
+						continue;
+					}
+					if (master_ptr->in == FALSE)
+					{
+						error_string = sformatf(
+							"Element, %s, in phase, %s, is not in model.",
+							master_ptr->elt->name, phase_ptr->name);
+						warning_msg(error_string);
+					}
+					col = master_ptr->unknown->number;
+					coef = rxn_ptr->coef;
+					if (debug_prep == TRUE)
+					{
+						output_msg(sformatf( "\t\t%-24s%10.3f\t%d\t%d",
+							master_ptr->s->name, (double) coef,
+							row / (count_unknowns + 1), col));
+					}
+					store_jacob(&(phase_ptr->p_soln_x), &(my_array[(size_t)row + (size_t)col]), coef);
+				}
+			}
+		}
+	}
+	return (OK);
+}
+/* ---------------------------------------------------------------------- */
+LDBLE Phreeqc::
+calc_PR(void)
+/* ---------------------------------------------------------------------- */
+/*  Calculate fugacity and fugacity coefficient for gas pressures if critical T and P
+    are defined.
+  1) Solve molar volume V_m or total pressure P from Peng-Robinson's EOS:
+  P = R * T / (V_m - b) - a * aa / (V_m^2 + 2 * b * V_m - b^2)
+     a = 0.457235 * (R * T_c)^2 / P_c
+     b = 0.077796 * R * T_c / P_c
+     aa = (1 + kk * (1 - T_r^0.5))^2
+     kk = 0.37464 + 1.54226 * omega - 0.26992 * omega^2
+     T_r = T / T_c
+  multicomponent gas phase:
+     use: b_sum = Sum(x_i * b), x_i is mole-fraction
+          a_aa_sum = Sum_i( Sum_j(x_i * x_j * (a_i * aa_i * a_j * aa_j)^0.5) )
+  2) Find the fugacity coefficient phi for gas i:
+  log(phi_i) = B_ratio * (z - 1) - log(z - B) + A / (2.8284 * B) * (B_ratio - 2 / a_aa_sum * a_aa_sum2) *\
+           log((z + 2.4142 * B) / (z - 0.4142 * B))
+     B_ratio = b_i / b_sum
+     A = a_aa_sum * P / R_TK^2
+     B = b_sum * P / R_TK
+     a_aa_sum2 = Sum_j(x_j * (a_aa_i * a_aa_j)^0.5
+  3) correct the solubility of gas i with:
+  pr_si_f = log10(phi_i) -  Delta_V_i * (P - 1) / (2.303 * R * TK);
+*/
+{
+	LDBLE T_c, P_c;
+	LDBLE A, B, B_r, /*b2,*/ kk, oo, a_aa, T_r;
+	LDBLE m_sum, /*b_sum, a_aa_sum,*/ a_aa_sum2;
+	LDBLE phi;
+	LDBLE /*R_TK,*/ R = R_LITER_ATM; /* L atm / (K mol) */
+	LDBLE r3[4], r3_12, rp, rp3, rq, rz, ri, ri1, one_3 = 0.33333333333333333;
+	LDBLE disct, vinit, v1, ddp, dp_dv, dp_dv2;
+	int it;
+	class phase *phase_ptr;
+	LDBLE V_m = 0, P = 0;
+
+	LDBLE TK = tk_x;
+	bool halved;
+	R_TK = R * TK;
+	m_sum = b_sum = a_aa_sum = 0.0;
+	size_t i;
+
+	if (gas_unknowns.size() == 0)
+	{
+		error_msg("No gas unknowns.", STOP);
+	}
+	cxxGasPhase * gas_phase_ptr = use.Get_gas_phase_ptr();
+	
+	for (i = 0; i < gas_unknowns.size(); i++)
+	{
+		m_sum += gas_unknowns[i]->moles;
+		phase_ptr = gas_unknowns[i]->phase;
+		if (phase_ptr->t_c == 0.0 || phase_ptr->p_c == 0.0)
+			error_msg("Cannot calculate a mixture of ideal and Peng_Robinson gases,\n       please define Tc and Pc for the active gases in PHASES.", STOP);
+			//continue;
+		if (!phase_ptr->pr_a)
+		{
+			T_c = phase_ptr->t_c;
+			P_c = phase_ptr->p_c;
+			phase_ptr->pr_a = 0.457235 * R * R * T_c * T_c / P_c;
+			phase_ptr->pr_b = 0.077796 * R * T_c / P_c;
+			T_r = TK / T_c;
+			oo = phase_ptr->omega;
+			kk = 0.37464 + oo * (1.54226 - 0.26992 * oo);
+			phase_ptr->pr_alpha = pow(1 + kk * (1 - sqrt(T_r)), 2);
+			phase_ptr->pr_tk = TK;
+			phase_ptr->pr_in = true;
+		}
+		if (phase_ptr->pr_tk != TK)
+		{
+			T_r = TK / phase_ptr->t_c;
+			oo = phase_ptr->omega;
+			kk = 0.37464 + oo * (1.54226 - 0.26992 * oo);
+			phase_ptr->pr_alpha = pow(1 + kk * (1 - sqrt(T_r)), 2);
+			phase_ptr->pr_tk = TK;
+			phase_ptr->pr_in = true;
+		}
+	}
+	if (m_sum == 0)
+			return (OK);
+	gas_phase_ptr->Set_v_m(gas_phase_ptr->Get_volume() / m_sum);
+	for (i = 0; i < gas_unknowns.size(); i++)
+	{
+		phase_ptr = gas_unknowns[i]->phase;
+		phase_ptr->fraction_x = gas_unknowns[i]->moles / m_sum;							// phase_ptr->fraction_x updated
+	}
+
+	for (i = 0; i < gas_unknowns.size(); i++)
+	{
+		a_aa_sum2 = 0.0;
+		phase_ptr = gas_unknowns[i]->phase;
+		//if (phase_ptr->t_c == 0.0 || phase_ptr->p_c == 0.0)
+		//	continue;
+		b_sum += phase_ptr->fraction_x * phase_ptr->pr_b;
+		size_t i1;
+		class phase *phase_ptr1;
+		for (i1 = 0; i1 <  gas_unknowns.size(); i1++)
+		{
+			phase_ptr1 = gas_unknowns[i1]->phase;
+			//if (phase_ptr1->t_c == 0.0 || phase_ptr1->p_c == 0.0)
+			//	continue;
+			if (phase_ptr1->fraction_x == 0)
+				continue;
+			a_aa = sqrt(phase_ptr->pr_a * phase_ptr->pr_alpha *
+				        phase_ptr1->pr_a * phase_ptr1->pr_alpha);
+			a_aa *= calc_gas_binary_parameter(phase_ptr->name, phase_ptr1->name);
+			//if (!strcmp(phase_ptr->name, "H2O(g)"))
+			//{
+			//	if (!strcmp(phase_ptr1->name, "CO2(g)"))
+			//		a_aa *= 0.81; // Soreide and Whitson, 1992, FPE 77, 217
+			//	else if (!strcmp(phase_ptr1->name, "H2S(g)") || !strcmp(phase_ptr1->name, "H2Sg(g)"))
+			//		a_aa *= 0.81;
+			//	else if (!strcmp(phase_ptr1->name, "CH4(g)") || !strcmp(phase_ptr1->name, "Mtg(g)") || !strcmp(phase_ptr1->name, "Methane(g)"))
+			//		a_aa *= 0.51;
+			//	else if (!strcmp(phase_ptr1->name, "N2(g)") || !strcmp(phase_ptr1->name, "Ntg(g)"))
+			//		a_aa *= 0.51;
+			//	else if (!strcmp(phase_ptr1->name, "Ethane(g)"))
+			//		a_aa *= 0.51;
+			//	else if (!strcmp(phase_ptr1->name, "Propane(g)"))
+			//		a_aa *= 0.45;
+			//}
+			//if (!strcmp(phase_ptr1->name, "H2O(g)"))
+			//{
+			//	if (!strcmp(phase_ptr->name, "CO2(g)"))
+			//		a_aa *= 0.81;
+			//	else if (!strcmp(phase_ptr->name, "H2S(g)") || !strcmp(phase_ptr->name, "H2Sg(g)"))
+			//		a_aa *= 0.81;
+			//	else if (!strcmp(phase_ptr->name, "CH4(g)") || !strcmp(phase_ptr->name, "Mtg(g)") || !strcmp(phase_ptr->name, "Methane(g)"))
+			//		a_aa *= 0.51;
+			//	else if (!strcmp(phase_ptr->name, "N2(g)") || !strcmp(phase_ptr->name, "Ntg(g)"))
+			//		a_aa *= 0.51;
+			//	else if (!strcmp(phase_ptr->name, "Ethane(g)"))
+			//		a_aa *= 0.51;
+			//	else if (!strcmp(phase_ptr->name, "Propane(g)"))
+			//		a_aa *= 0.45;
+			//}
+			a_aa_sum += phase_ptr->fraction_x * phase_ptr1->fraction_x * a_aa;
+			a_aa_sum2 += phase_ptr1->fraction_x * a_aa;
+		}
+		phase_ptr->pr_aa_sum2 = a_aa_sum2;
+	}
+	b2 = b_sum * b_sum;
+
+	if (gas_phase_ptr->Get_type() == cxxGasPhase::GP_VOLUME)
+	{
+		V_m = gas_phase_ptr->Get_volume() / m_sum;
+		P = 0.0;
+		while (P <= 0)
+		{
+			P = R_TK / (V_m - b_sum) - a_aa_sum / (V_m * (V_m + 2 * b_sum) - b2);
+			if (P <= 0.0)
+			{
+				V_m *= 2.0;
+			//a_aa_sum /= 2.0;
+			}
+		}
+		if (iterations > 0 && P < 150 && V_m < 1.01)
+		{
+			// check for 3-roots...
+			r3[1] = b_sum - R_TK / P;
+			r3[2] = -3.0 * b2 + (a_aa_sum - R_TK * 2.0 * b_sum) / P;
+			r3[3] = b2 * b_sum + (R_TK * b2 - b_sum * a_aa_sum) / P;
+			// the discriminant of the cubic eqn...
+			disct = 18. * r3[1] * r3[2] * r3[3] -
+				4. * pow(r3[1], 3) * r3[3] + 
+				r3[1] * r3[1] * r3[2] * r3[2] -
+				4. * pow(r3[2], 3) - 
+				27. * r3[3] * r3[3];
+			if (disct > 0)
+			{
+				// 3-roots, find the largest P...
+				it = 0;
+				halved = false;
+				ddp = 1e-9;
+				v1 = vinit = 0.729;
+				dp_dv = f_Vm(v1, this);
+				while (fabs(dp_dv) > 1e-11 && it < 40)
+				{
+					it +=1;
+					dp_dv2 = f_Vm(v1 - ddp, this);
+					v1 -= (dp_dv * ddp / (dp_dv - dp_dv2));
+					if (!halved && (v1 > vinit || v1 < 0.03))
+					{
+						if (vinit > 0.329)
+							vinit -= 0.1;
+						else
+							vinit -=0.05;
+						if (vinit < 0.03)
+						{
+							vinit = halve(f_Vm, 0.03, 1.0, 1e-3);
+							if (f_Vm(vinit - 2e-3, this) < 0)
+								vinit = halve(f_Vm, vinit + 2e-3, 1.0, 1e-3);
+							halved = true;
+						}
+						v1 = vinit;
+					}
+					dp_dv = f_Vm(v1, this);
+					if (fabs(dp_dv) < 1e-11)
+					{
+						if (f_Vm(v1 - 1e-4, this) < 0)
+						{
+							v1 = halve(f_Vm, v1 + 1e-4, 1.0, 1e-3);
+							dp_dv = f_Vm(v1, this);
+						}
+					}
+				}
+				if (it == 40)
+				{
+// accept a (possible) whobble in the curve...
+//					error_msg("No convergence when calculating P in Peng-Robinson.", STOP);
+				}
+				if (V_m < v1 && it < 40)
+					P = R_TK / (v1 - b_sum) - a_aa_sum / (v1 * (v1 + 2 * b_sum) - b2);
+			}
+		}
+		if (P <= 0) // iterations = -1
+			P = 1.;
+		gas_phase_ptr->Set_total_p(P);												// phase_ptr->total_p updated
+		gas_phase_ptr->Set_v_m(V_m);
+	}
+	else
+	{
+		assert(false);
+		P = gas_phase_ptr->Get_total_p();
+		r3[1] = b_sum - R_TK / P;
+		r3_12 = r3[1] * r3[1];
+		r3[2] = -3.0 * b2 + (a_aa_sum - R_TK * 2.0 * b_sum) / P;
+		r3[3] = b2 * b_sum + (R_TK * b2 - b_sum * a_aa_sum) / P;
+		// solve t^3 + rp*t + rq = 0.
+		// molar volume V_m = t - r3[1] / 3... 
+		rp = r3[2] - r3_12 / 3;
+		rp3 = rp * rp * rp;
+		rq = (2.0 * r3_12 * r3[1] - 9.0 * r3[1] * r3[2]) / 27 + r3[3];
+		rz = rq * rq / 4 + rp3 / 27;
+		if (rz >= 0) // Cardono's method...
+		{
+			ri = sqrt(rz);
+			if (ri + rq / 2 <= 0)
+			{
+				V_m = pow(ri - rq / 2, one_3) + pow(- ri - rq / 2, one_3) - r3[1] / 3;
+			}
+			else
+			{
+				ri = - pow(ri + rq / 2, one_3);
+				V_m = ri - rp / (3.0 * ri) - r3[1] / 3;
+			}
+		}
+		else // use complex plane...
+		{
+			ri = sqrt(- rp3 / 27); // rp < 0
+			ri1 = acos(- rq / 2 / ri);
+			V_m = 2.0 * pow(ri, one_3) * cos(ri1 / 3) - r3[1] / 3;
+		}
+		gas_phase_ptr->Set_v_m(V_m);												 // phase_ptr->fraction_x updated
+	}
+ // calculate the fugacity coefficients...
+	for (i = 0; i < gas_unknowns.size(); i++)
+	{
+		phase_ptr = gas_unknowns[i]->phase;
+		if (phase_ptr->fraction_x == 0.0)
+		{
+			phase_ptr->pr_p = 0;
+			phase_ptr->pr_phi = 1;
+			phase_ptr->pr_si_f = 0.0;
+			//phase_ptr->logk[vm0] = 0.0; // ***
+			continue;
+		}	
+		phase_ptr->pr_p = phase_ptr->fraction_x * P;
+
+		//if (phase_ptr->t_c == 0.0 || phase_ptr->p_c == 0.0)
+		//{
+		//	phase_ptr->pr_phi = 1;
+		//	continue;
+		//}
+		rz = P * V_m / R_TK;
+		A = a_aa_sum * P / (R_TK * R_TK);
+		B = b_sum * P / R_TK;
+		B_r = phase_ptr->pr_b / b_sum;
+		if (rz > B)
+		{
+			phi = B_r * (rz - 1) - log(rz - B) + A / (2.828427 * B) * (B_r - 2.0 * phase_ptr->pr_aa_sum2 / a_aa_sum) *
+				  log((rz + 2.41421356 * B) / (rz - 0.41421356 * B));
+			phi = (phi > 4.44 ? 4.44 : (phi < -4.6 ? -4.6 : phi));
+		}
+		else
+			phi = -4.6; // fugacity coefficient = 0.01
+		phase_ptr->pr_phi = exp(phi);
+		phase_ptr->pr_si_f = phi / LOG_10;										// pr_si_f updated
+		// ****
+		//phase_ptr->logk[vm0] = V_m * 1e3 * phase_ptr->fraction_x;
+		phase_ptr->pr_in = true;
+	}
+	return (V_m);
+}
+
+/* ---------------------------------------------------------------------- */
+int Phreeqc::
+calc_fixed_volume_gas_pressures(void)
+/* ---------------------------------------------------------------------- */
+{
+	//int n_g = 0;
+	LDBLE lp;
+	class rxn_token *rxn_ptr;
+	class phase *phase_ptr;
+	bool PR = false, pr_done = false;
+	size_t i;
+/*
+ *   moles and partial pressures for gases
+ */
+	if (use.Get_gas_phase_ptr() == NULL)
+		return (OK);
+	cxxGasPhase *gas_phase_ptr = use.Get_gas_phase_ptr();
+	gas_phase_ptr->Set_total_moles(0);
+
+	for (i = 0; i < gas_unknowns.size(); i++)
+	{
+		phase_ptr = gas_unknowns[i]->phase;
+		if (phase_ptr->in == TRUE)
+		{
+			if (!PR && phase_ptr->t_c > 0 && phase_ptr->p_c > 0)
+				PR = true;
+			//n_g++;
+		}
+		gas_phase_ptr->Set_total_moles(gas_phase_ptr->Get_total_moles() + gas_unknowns[i]->moles);
+	}
+	if (PR && gas_phase_ptr->Get_total_moles() > 0)
+	{
+		calc_PR();
+		pr_done = true;
+		gas_phase_ptr->Set_total_moles(0);
+	} else
+	{
+		gas_phase_ptr->Set_total_p(0);
+		gas_phase_ptr->Set_total_moles(0);
+	}
+	for (i = 0; i < gas_unknowns.size(); i++)
+	{
+		phase_ptr = gas_unknowns[i]->phase;
+		if (phase_ptr->in == TRUE)
+		{
+			lp = -phase_ptr->lk;
+			//lp = -k_calc(phase_ptr->rxn_x.logk, tk_x, use.Get_gas_phase_ptr()->total_p * PASCAL_PER_ATM);
+			for (rxn_ptr = &phase_ptr->rxn_x.token[0] + 1; rxn_ptr->s != NULL;
+				 rxn_ptr++)
+			{
+				lp += rxn_ptr->s->la * rxn_ptr->coef;
+			}
+			phase_ptr->p_soln_x = exp(LOG_10 * (lp - phase_ptr->pr_si_f));
+
+			if (pr_done)
+			{
+				lp = phase_ptr->p_soln_x / gas_phase_ptr->Get_total_p() *
+					gas_phase_ptr->Get_volume() / gas_phase_ptr->Get_v_m();
+				phase_ptr->moles_x = lp;
+			}
+			else
+			{
+				phase_ptr->moles_x = phase_ptr->p_soln_x * gas_phase_ptr->Get_volume() / (R_LITER_ATM * tk_x);
+				gas_phase_ptr->Set_total_p(gas_phase_ptr->Get_total_p() + phase_ptr->p_soln_x);
+			}
+			gas_phase_ptr->Set_total_moles(gas_phase_ptr->Get_total_moles() + phase_ptr->moles_x);
+		}
+		else
+		{
+			phase_ptr->moles_x = 0;
+			phase_ptr->fraction_x = 0;
+		}
+	}
+
+	return (OK);
+}
+/* ---------------------------------------------------------------------- */
+double Phreeqc::
+calc_gas_binary_parameter(std::string name1, std::string name2) const
+/* ---------------------------------------------------------------------- */
+{
+	double f = 1.0;
+	std::pair<std::string, std::string> p(name1, name2);
+	std::map<std::pair<std::string, std::string>, double>::const_iterator gas_pair_it;
+	gas_pair_it = gas_binary_parameters.find(p);
+	if (gas_pair_it != gas_binary_parameters.end())
+	{
+		f = (1.0 - gas_pair_it->second);
+	}
+	else
+	{
+		if (!strcmp(name1.c_str(), "H2O(g)"))
+		{
+			if (!strcmp(name2.c_str(), "CO2(g)"))
+				f = 0.81; // Soreide and Whitson, 1992, FPE 77, 217
+			else if (!strcmp(name2.c_str(), "H2S(g)") || !strcmp(name2.c_str(), "H2Sg(g)"))
+				f = 0.81;
+			else if (!strcmp(name2.c_str(), "CH4(g)") || !strcmp(name2.c_str(), "Mtg(g)") || !strcmp(name2.c_str(), "Methane(g)"))
+				f = 0.51;
+			else if (!strcmp(name2.c_str(), "N2(g)") || !strcmp(name2.c_str(), "Ntg(g)"))
+				f = 0.51;
+			else if (!strcmp(name2.c_str(), "Ethane(g)"))
+				f = 0.51;
+			else if (!strcmp(name2.c_str(), "Propane(g)"))
+				f = 0.45;
+		}
+		if (!strcmp(name2.c_str(), "H2O(g)"))
+		{
+			if (!strcmp(name1.c_str(), "CO2(g)"))
+				f = 0.81;
+			else if (!strcmp(name1.c_str(), "H2S(g)") || !strcmp(name1.c_str(), "H2Sg(g)"))
+				f = 0.81;
+			else if (!strcmp(name1.c_str(), "CH4(g)") || !strcmp(name1.c_str(), "Mtg(g)") || !strcmp(name1.c_str(), "Methane(g)"))
+				f = 0.51;
+			else if (!strcmp(name1.c_str(), "N2(g)") || !strcmp(name1.c_str(), "Ntg(g)"))
+				f = 0.51;
+			else if (!strcmp(name1.c_str(), "Ethane(g)"))
+				f = 0.51;
+			else if (!strcmp(name1.c_str(), "Propane(g)"))
+				f = 0.45;
+		}
+	}
+	return f;
+}