# Concrete minerals for use with 
# DATABASE c:\phreeqc\database\pitzer.dat
# Read this file in your input file with 
#        INCLUDE$ c:\phreeqc\database\concrete_pz.dat

PRINT; -reset false

SOLUTION_MASTER_SPECIES
Al		Al(OH)4-	0	Al	26.9815
H(0)		H2	0	H
O(0)		O2	0	O
SOLUTION_SPECIES
Al(OH)4- = Al(OH)4-; -dw 1.04e-9 # dw from Mackin & Aller, 1983, GCA 47, 959
2 H2O = O2 + 4 H+ + 4 e-; log_k  -86.08; delta_h  134.79 kcal; -dw  2.35e-9
2 H+ + 2 e- = H2; log_k  -3.15;  delta_h  -1.759 kcal; -dw  5.13e-9

PITZER # Using data from Weskolowski, 1992, GCA
#Park & Englezos 99 The model Pitzer coeff's are different from pitzer.dat, data are everywhere below the calc'd osmotic from Weskolowski.
-B0
  Al(OH)4-  K+   -0.0669  0 0  8.24e-3
  Al(OH)4-  Na+  -0.0289  0 0  1.18e-3
-B1
  Al(OH)4-  K+    0.668  0 0 -1.93e-2
  Al(OH)4-  Na+   0.461  0 0 -2.33e-3
-C0
  Al(OH)4-  K+    0.0499  0 0  -3.63e-3
  Al(OH)4-  Na+   0.0073  0 0  -1.56e-4
-THETA
  Al(OH)4-   Cl- -0.0233  0 0  -8.11e-4
  Al(OH)4-   OH-  0.0718  0 0  -7.29e-4
   # Al(OH)4-   SO4-2    -0.012
-PSI
  Al(OH)4-   Cl-   K+    0.0009  0 0   9.94e-4
  Al(OH)4-   Cl-   Na+   0.0048  0 0   1.32e-4
  Al(OH)4-   OH-   Na+  -0.0048  0 0   1.00e-4
  Al(OH)4-   OH-   K+    0  0 0  0
  Al(OH)4-   K+    Na+   0  0 0  0
END

# # AFm (short for monosulfoaluminate) is an anion-exchanger, with the general formula Ca4Al2(Y-2)(OH)12:6H2O.
# # Listed are the solubilities of end-members in the neutral form as Y-AFm, and with 5% surface charge as Y-AFmsura.
# #
# # Example of the combination of the charged AFmsura and charge-balancing EDL calculations:
# SURFACE_MASTER_SPECIES
# Sura Sura+
# SURFACE_SPECIES
# Sura+ = Sura+
# SOLUTION 1
# pH 7 charge
# REACTION 1
# Ca3O3Al2O3 1 gypsum 1; 0.113 # MW gfw("Ca3O3Al2O3CaSO4(H2O)2") = 442.4. 0.113 for w/s = 20
# SAVE solution 2
# END

# RATES
# Sum_all_AFmsura # Sums up with the single charge formula, Ca2Al...
# 10 tot_ss = 2 * equi("AFmsura")
# 20 SAVE (m - tot_ss) * time
# -end

# USE solution 2
# EQUILIBRIUM_PHASES 2
# AFmsura 0 0
# KINETICS 2
# Sum_all_AFmsura; -formula H2O 0; -m0 0; -time_step 30
# SURFACE 2
# Sura Sum_all_AFmsura kin 0.05 8.6e3; -donnan debye 2 ; -equil 1
# END

PHASES
O2(g)
  O2 = O2; -log_k  -2.8983
  -analytic -7.5001 7.8981e-3 0.0 0.0 2.0027e5
H2(g)
 H2 = H2; -log_k  -3.1050
 -analytic   -9.3114    4.6473e-3   -49.335    1.4341    1.2815e5

Portlandite # Reardon, 1990
  Ca(OH)2 = Ca+2 + 2 OH-
  -log_k -5.19; -Vm 33.1

Gibbsite
  Al(OH)3 + OH- = Al(OH)4-
  -log_k  -1.123;  -Vm  32.2
  -analyt  -7.234  1.068e-2  0  1.1829 # data from Wesolowski, 1992, GCA 56, 1065

# AFm with a single exchange site...
OH-AFm # Appelo, 2021
  Ca2AlOH(OH)6:6H2O = 2 Ca+2 + Al(OH)4- + 3 OH- + 6 H2O
  -log_k  -12.84; -Vm  185
OH-AFmsura
  Ca2Al(OH)0.95(OH)6:6H2O+0.05 = 2 Ca+2 + Al(OH)4- + OH- + 1.95 OH- + 6 H2O
  -log_k  -12.74; -Vm  185

Cl-AFm # Friedel's salt.  Appelo, 2021
  Ca2AlCl(OH)6:2H2O = 2 Ca+2 + Al(OH)4- + Cl- + 2 OH- + 2 H2O
  -log_k  -13.68; -Vm  136
Cl-AFmsura
  Ca2AlCl0.95(OH)6:2H2O+0.05 = 2 Ca+2 + Al(OH)4- + 0.95 Cl- + 2 OH- + 2 H2O
  -log_k  -13.59; -Vm  136

# AFm with a double exchange site...
SO4-AFm # Monosulfoaluminate. Appelo, 2021
  Ca4Al2(SO4)(OH)12:6H2O = 4 Ca+2 + 2 Al(OH)4- + SO4-2 + 4 OH- + 6 H2O
  -log_k  -29.15; -Vm  309
SO4-AFmsura
  Ca4Al2(SO4)0.95(OH)12:6H2O+0.1 = 4 Ca+2 + 2 Al(OH)4- + 0.95   SO4-2 + 4 OH- + 6 H2O
  -log_k  -28.88; -Vm  309

SO4-OH-AFm # Hemisulfoaluminate. Appelo, 2021
  Ca4Al2(SO4)0.5(OH)(OH)12:9H2O = 4 Ca+2 + 2 Al(OH)4- + 0.5 SO4-2 + 5 OH- + 9 H2O
  -log_k  -27.24; -Vm  340
SO4-OH-AFmsura
  Ca4Al2(SO4)0.475(OH)0.95(OH)12:9H2O+0.1 = 4 Ca+2 + 2 Al(OH)4- + 0.475 SO4-2 + 4.95 OH- + 9 H2O
  -log_k  -26.94; -Vm  340

CO3-AFm # Monocarboaluminate. Appelo, 2021
  Ca4Al2(CO3)(OH)12:5H2O = 4 Ca+2 + 2 Al(OH)4- + CO3-2 + 4 OH- + 5 H2O
  -log_k  -31.32; -Vm  261
CO3-AFmsura
  Ca4Al2(CO3)0.95(OH)12:5H2O+0.1 = 4 Ca+2 + 2 Al(OH)4- + 0.95  CO3-2 + 4 OH- + 5 H2O
  -log_k  -31.05; -Vm  261

CO3-OH-AFm # Hemicarboaluminate. Appelo, 2021
  Ca4Al2(CO3)0.5(OH)(OH)12:5.5H2O = 4 Ca+2 + 2 Al(OH)4- + 0.5 CO3-2 + 5 OH- + 5.5 H2O
  -log_k  -29.06; -Vm  284
CO3-OH-AFmsura
  Ca4Al2(CO3)0.475(OH)0.95(OH)12:5.5H2O+0.1 = 4 Ca+2 + 2 Al(OH)4- + 0.475 CO3-2 + 4.95 OH- + 5.5 H2O
  -log_k  -28.84; -Vm  284

SO4-Cl-AFm # Kuzel's salt. Appelo, 2021
  Ca4Al2(SO4)0.5Cl(OH)12:5H2O = 4 Ca+2 + 2 Al(OH)4- + 0.5 SO4-2 + Cl- + 4 OH- + 5 H2O
  -log_k  -28.52; -Vm  290
SO4-Cl-AFmsura
  Ca4Al2(SO4)0.475Cl0.95(OH)12:5H2O+0.1 = 4 Ca+2 + 2 Al(OH)4- + 0.475 SO4-2 + 0.95 Cl- + 4 OH- + 5 H2O
  -log_k  -28.41; -Vm  290

# No Fe(OH)4- in Pitzer...
# SO4-AFem # Lothenbach 2019
  # Ca4Fe2(SO4)(OH)12:6H2O = 4 Ca+2 + 2 Fe(OH)4- + SO4-2 + 4 OH- + 6 H2O
  # -log_k  -31.57;  -Vm  321
# CO3-AFem # Lothenbach 2019
  # Ca4Fe2(CO3)(OH)12:6H2O = 4 Ca+2 + 2 Fe(OH)4- + CO3-2 + 4 OH- + 6 H2O
  # -log_k  -34.59;  -Vm  292
# CO3-OH-AFem # Lothenbach 2019. ?? 3.5 H2O??
  # Ca4Fe2(CO3)0.5(OH)(OH)12:3.5H2O = 4 Ca+2 + 2 Fe(OH)4- + 0.5 CO3-2 + 5 OH- + 3.5 H2O
  # -log_k  -30.83;  -Vm  273

Ettringite # Matschei, 2007, fig. 27
  Ca6Al2(SO4)3(OH)12:26H2O = 6 Ca+2 + 2 Al(OH)4- + 3 SO4-2 + 4 OH- + 26 H2O
  -log_k  -44.8; -Vm  707
  -analyt  334.09  0  -26251  -117.57  # 5 - 75 C

CO3-ettringite # Matschei, 2007, tbl 13
  Ca6Al2(CO3)3(OH)12:26H2O = 6 Ca+2 + 2 Al(OH)4- + 3 CO3-2 + 4 OH- + 26 H2O;
  -log_k  -46.50; -Vm  652

C2AH8 # Matschei, fig. 19
  Ca2Al2(OH)10:3H2O = 2 Ca+2 + 2 Al(OH)4- + 2 OH- + 3 H2O
  -log_k  -13.55; -Vm  184 
  -analyt  -225.37  -0.12380  0  100.522 # 1 - 50 ºC

CAH10  # Matschei, fig. 19
  CaAl2(OH)8:6H2O = Ca+2 + 2 Al(OH)4- + 6 H2O
  -log_k  -7.60; -Vm  194
  -delta_h  43.2 # 1 - 20 ºC

Hydrogarnet_Al # Matschei, 2007, Table 5
  (CaO)3Al2O3(H2O)6 = 3 Ca+2 + 2 Al(OH)4- + 4 OH-
  -log_k -20.84; -Vm 150
 # -analyt  -20.64  -0.002  0  0.16 # 5 - 105 ºC
 # -delta_h 6.4 kJ # Geiger et al., 2012, AM 97, 1252-1255

Hydrogarnet_Si # Matschei, 2007, Table 6
  Ca3Al2Si0.8(OH)15.2 = 3 Ca+2 + 2 Al(OH)4- + 0.8 H4SiO4 + 4 OH-
  -log_k  -33.69; -Vm 143
  -analyt  -476.84  -0.2598  0  210.38 # 5 - 85 ºC

Jennite # CSH2.1. Lothenbach 2019
  Ca1.67SiO3.67:2.1H2O + 0.57 H2O = 1.67 Ca+2 + 2.34 OH- + H3SiO4-
  -log_k  -13.12; -Vm  78.4

Tobermorite-I # Lothenbach 2019
  CaSi1.2O3.4:1.6H2O + 0.6 H2O = Ca+2 + 0.8 OH- + 1.2 H3SiO4-
  -log_k -6.80; -Vm  70.4

Tobermorite-II # Lothenbach 2019
  Ca0.833SiO2.833:1.333H2O + 0.5 H2O = 0.833Ca+2 + 0.666 OH- + H3SiO4-
  -log_k -7.99; -Vm  58.7

PRINT; -reset true
# Refs
# Appelo 2021, Cem. Concr. Res. 140, https://doi.org/10.1016/j.cemconres.2020.106270
# Lothenbach, B. et al. 2019, Cem. Concr. Res. 115, 472-506.
# Matschei, T. et al., 2007, Cem. Concr. Res. 37, 1379-1410. 