from win32com.client import Dispatch import matplotlib.pyplot as plt import numpy as np from scipy.optimize import fmin import pandas as pd #Granodiorite in Type III, Ra surface complexation and precipitation def isotherm(input_param, test=True): iphreeqc = Dispatch("IPhreeqcCOM.Object") iphreeqc.LoadDatabase("PHREEQC_Davies_e-_ThermoChimie_v12a.dat") ################################################################### # INPUT parameters X1_coeff=input_param[0] X2_coeff=input_param[1] Ksp=input_param[2] S_conc=np.array([2.030e-3, 2.030e-3, 2.030e-3, 2.030e-3, 2.030e-3]) Ra_conc=np.array([4.689E-09,4.296E-09,4.158E-09,4.298E-09,3.751E-09]) Ba_conc=np.array([1.132E-03,1.123E-04,1.211E-05,1.772E-06,6.569E-07]) # Ksp=-10.25 result1=[[0 for col in range(1)] for row in range(5)] # only row numbers should be defined correctly result2=[[0 for col in range(1)] for row in range(5)] # only row numbers should be defined correctly for i in range(0,len(S_conc)): str_ini_part1=""" SURFACE_MASTER_SPECIES S_w S_wOH SURFACE_SPECIES S_wOH = S_wOH log_k 0 H+ + S_wOH = S_wOH2+ log_k 5.0491446 S_wOH = S_wO- + H+ log_k -8.78103445 S_wOH + Ba+2 = S_wOBa+ + H+ log_k """ str_ini_part1_1=str(X1_coeff) str_ini_part1_2=""" S_wOH + Ra+2 = S_wORa+ + H+ log_k """ str_ini_part1_3=str(X2_coeff) str_ini_part1_4=""" PHASES Barite Ba(SO4) = +1.000Ba+2 +1.000SO4-2 log_k -9.97 Ra(SO4)(s) Ra(SO4) = +1.000Ra+2 +1.000SO4-2 log_k """ str_ini_part2=str(Ksp) str_ini_part3=""" Fix_H+ H+ = H+ log_k 0 END """ str_ini_part4=""" SOLUTION 1 temp 25 pH 7.5 pe 4 redox pe units mol/L density 1 K 3.581e-4 Cs 5.267e-9 Mg 2.181e-3 Ca 3.668e-2 Sr 1.940e-4 C(4) 3.606e-4 S(-2) 9.356e-7 Cl 1.451e-1 charge Na 7.351e-2 S(6) """ str_ini_part5=str(S_conc[i]) str_ini_part6=""" Ra """ str_ini_part7=str(Ra_conc[i]) str_ini_part8=""" Ba """ str_ini_part9=str(Ba_conc[i]) str_ini_part10=""" -water 0.01 # kg SOLID_SOLUTIONS 1 BaRaSO4 -comp Ra(SO4)(s) 0 -comp Barite 0 SAVE SOLUTION 1 SELECTED_OUTPUT -reset false USER_PUNCH -Heading 10 PUNCH SUM_S_S("BaRaSO4", "Ba") 20 PUNCH SUM_S_S("BaRaSO4", "Ra") 30 PUNCH TOTMOLE("Ba") # Totol moles only in solution 40 PUNCH TOTMOLE("Ra") # Totol moles only in solution 60 PUNCH SYS("Ba") # moles in all system 70 PUNCH SYS("Ra") # moles in all system END USE SOLUTION 1 SURFACE 1 -sites DENSITY S_wOH 5.6 0.106 0.5 SELECTED_OUTPUT -reset false USER_PUNCH -Heading 10 PUNCH SUM_S_S("BaRaSO4", "Ba") 20 PUNCH SUM_S_S("BaRaSO4", "Ra") 30 PUNCH TOTMOLE("Ba") # Totol moles only in solution 40 PUNCH TOTMOLE("Ra") # Totol moles only in solution 60 PUNCH SYS("Ba") # moles in all system 70 PUNCH SYS("Ra") # moles in all system END """ input_str=str_ini_part1+str_ini_part1_1+str_ini_part1_2+str_ini_part1_3+str_ini_part1_4+str_ini_part2+str_ini_part3+str_ini_part4+str_ini_part5+str_ini_part6+str_ini_part7+str_ini_part8+str_ini_part9+str_ini_part10 #print(input_str) iphreeqc.RunString(input_str) run_result=iphreeqc.GetSelectedOutputArray() print(run_result) if i==0: result1[i]=[entry for entry in run_result][2:3] else: result1[i]=[entry for entry in run_result][2:3] if i==0: result2[i]=[entry for entry in run_result][3:] else: result2[i]=[entry for entry in run_result][3:] # print(result) result_all1=sum(result1, []) result_all1=np.array(result_all1) # print(result_all1) result_all2=sum(result2, []) result_all2=np.array(result_all2) # print(result_all2) result_Ba_SS=result_all1[:,0] result_Ra_SS=result_all1[:,1] result_Ba_aqueous=result_all2[:,2] result_Ra_aqueous=result_all2[:,3] result_Ba_all=result_all1[:,4] result_Ra_all=result_all1[:,5] #qe_model=result_Ra_SS*226*1000/0.5 qe_model=(result_Ra_all-result_Ra_aqueous)*226*1000/0.5 qe_exp=np.array([2.14E-05,1.90E-05,1.78E-05,1.75E-05,1.40E-05]) if test: print(result_all1) print(result_all2) plt.figure() plt.plot(Ba_conc, qe_model, "o") plt.plot(Ba_conc, qe_exp, "s") plt.xscale("log") print(qe_model) square_error=((qe_model-qe_exp)*1000)**2 sum_square_error=np.sum(square_error) return sum_square_error start_para=np.array([5,-1.5, -10.25]) para_optimized1=fmin(isotherm, start_para) print(para_optimized1) #para_optimized1=np.array([6.66044254, -1.08479668, -9.15468886]) isotherm(para_optimized1, test=True)