Processes > Surface Complexation

How to solve ''Reaction for species has not been defined''?

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Jin Lai:
Hello, I am Jin Lai.
I study in chemical engineering.

Below is my code, please help me to correct it and let it run.
__________________________________________________________________________________________________
Title   complex   formation
solution   hcl   mol/l
units   mg/l
ph   -0.24
temp   110
Ce546.943asCe+4
Pd8.7079asPd+2
Pt11.0292asPt+2
Rh2.2813asRh+3
Cl72916asCl-
Al4302.2asAl+3
Fe55.04asFe+2
Ni6.74asNi+2
Mg509.92asMg+2
Zn5.722asZn+2
Ti18.242asTi(oh)4


solution_master_species
Cl      Cl-   0   Cl   35.453
Pd      Pd+2   -2   Pd   106.42
Pt      Pt+2   -2   Pt   195.08
Rh      Rh+2   0   Rh   102.906
Rh(2)      Rh+2   0   Rh   102.906
Rh(3)      Rh+3   -2   Rh   102.906
H      H+   -1   H   1.008
H(0)      H2   0   H   1.008
H(1)      H+   -1   H   1.008
Ce      Ce+3   0   Ce   140.12
Ce(2)      Ce+2   0   Ce   140.12
Ce(3)      Ce+3   0   Ce   140.12
Ce(4)      Ce+4   0   Ce   140.12
Al      Al+3   0   Al   26.982
Fe      Fe+2   0   Fe   55.847
Fe(2)      Fe+2   0   Fe   55.847
Fe(3)      Fe+3   -2   Fe   55.847
Ni      Ni+2   0   Ni   58.693
Mg      Mg+2   0   Mg   24.305
Zn      Zn+2   0   Zn   65.39
Ti      Ti(OH)4   0   Ti   47.87

solution_species
1.000H+   =   H+
log_k   0.000
Pd+2 =  Pd+2
log_k 0
1.0000 Pd++ + 1.0000 Cl-  =  PdCl+
log_k    6.0993
2.0000 Cl- + 1.0000 Pd++  =  PdCl2
log_k           +10.7327
3.0000 Cl- + 1.0000 Pd++  =  PdCl3-
log_k           +13.0937
4.0000 Cl- + 1.0000 Pd++  =  PdCl4--
log_k           +15.1615
1.0000 Pd++ + 1.0000 H2O  =  PdO +2.0000 H+
log_k           -2.19
1.0000 Pd++ + 1.0000 H2O  =  PdOH+ +1.0000 H+
log_k   -1.0905
1.000Pt+2   =   Pt+2
log_k   0.000
1.000Cl- + 1.000Pt+2 = PtCl+
log_k   8.692
2.000Cl- + 1.000Pt+2  = PtCl2
log_k   15.515
3.000Cl- + 1.000Pt+2  = PtCl3-
log_k   18.526
4.000Cl- + 1.000Pt+2  = PtCl4-2
log_k   20.057
Pt + 0.500O2 + 2.000H+ = 1.000Pt+2 + 1.000H2O
log_k   -2.157
Pt+2 + OH- = Pt(OH)+
log_k   24.91
Pt+2 + 2OH- = Pt(OH)2
log_k   28.81
1.000Rh+2   =   Rh+2
log_k   0.000
Rh+3   =   Rh+3
log_k   0.0
0.250O2 + 1.000H+ + 1.000Rh+2  = Rh+3 + 0.500H2O
log_k   3.356
1.000Cl- + 1.000Rh+2  = RhCl+
log_k   -0.207
1.000Cl- + 1.000Rh+3  = RhCl+2
log_k   2.022
2.000Cl- + 1.000Rh+3  = RhCl2+
log_k   3.303
2.000Cl- + 1.000Rh+2  = RhCl2
log_k   -0.772
3.000Cl- + 1.000Rh+3  = RhCl3
log_k   3.338
3.000Cl- + 1.000Rh+2  = RhCl3-
log_k   -2.093
4.000Cl- + 1.000Rh+3  = RhCl4-
log_k   3.300
4.000Cl- + 1.000Rh+2  = RhCl4-2
log_k   -3.297
1.000Rh+3 + 1.000H2O  = RhO+ + 2.000H+
log_k   -5.402
1.000Rh+2 + 1.000H2O  = RhO + 2.000H+
log_k   -15.950
1.000Rh+2 + 1.000H2O  = RhOH+ + 1.000H+
log_k   -7.835
1.000Rh+3 + 1.000H2O  = RhOH+2 + 1.000H+
log_k   -2.499
Rh + 0.500O2 + 2.000H+ = 1.000Rh+2 + 1.000H2O
log_k   22.694
Rh+3 + 2H2O = Rh(OH)2+ + 2H+
log_k   -6.5
Rh+3 + 3H2O = Rh(OH)3 + 3H+
log_k   -10.5
Rh+3 4H2O = Rh(OH)4- + 4H+
log_k   -17.7
Rh+3 + 5H2O = Rh(OH)5-2 + 5H+
log_k   -26.9
Rh+3 + 6H2O = Rh(OH)6-3 + 6H+
log_k   -37.2
1.000Ce+3     = Ce+3
log_k   0.000
1.000Ce+3 + 0.500H2O  = Ce+2 + 0.250O2 + 1.000H+
log_k   -85.049
0.250O2 + 1.000Ce+3 + 1.000H+  = Ce+4 + 0.500H2O
log_k   -8.042
1.000Ce+3 + 1.000Cl-  = CeCl+2
log_k   0.321
1.000Ce+3 + 2.000Cl-  = CeCl2+
log_k   0.056
1.000Ce+3 + 3.000Cl-  = CeCl3
log_k   -0.356
1.000Ce+3 + 4.000Cl-  = CeCl4-
log_k   -0.695
1.000Al+3     = Al+3
log_k   0.000
1.000Fe+2     = Fe+2
log_k   0.000
0.250O2 + 1.000Fe+2 + 1.000H+  = Fe+3 + 0.500H2O
log_k   8.490
1.000Fe+3 + 4.000H2O  = Fe(OH)4- + 4.000H+
log_k   -21.604
2.000Fe+3 + 2.000H2O  = Fe2(OH)2+4 + 2.000H+
log_k   -2.922
1.000Cl- + 1.000Fe+2  = FeCl+
log_k   -0.160
1.000Cl- + 1.000Fe+3  = FeCl+2
log_k   1.520
2.000Cl- + 1.000Fe+3  = FeCl2+
log_k   0.700
2.000Cl- + 1.000Fe+2  = FeCl2
log_k   -1.740
1.000Fe+2 + 1.000H2O  = FeO + 2.000H+
log_k   -20.601
1.000Fe+3 + 1.000H2O  = FeO+ + 2.000H+
log_k   -5.483
1.000Fe+2 + 1.000H2O  = FeOH+ + 1.000H+
log_k   -9.501
1.000Fe+3 + 1.000H2O  = FeOH+2 + 1.000H+
log_k   -2.191
1.000Fe+3 + 2.000H2O  = HFeO2 + 3.000H+
log_k   -14.302
1.000Fe+2 + 2.000H2O  = HFeO2- + 3.000H+
log_k   -31.932
1.000Ni+2     = Ni+2
log_k   0.000
1.000Ni+2 + 2.000H2O  = HNiO2- + 3.000H+
log_k   -31.502
1.000Cl- + 1.000Ni+2  = NiCl+
log_k   0.151
1.000Ni+2 + 1.000H2O  = NiO + 2.000H+
log_k   -19.501
1.000Ni+2 + 1.000H2O  = NiOH+ + 1.000H+
log_k   -9.501
1.000Mg+2     = Mg+2
log_k   0.000
4.000Mg+2 + 4.000H2O  = Mg4(OH)4+4 + 4.000H+
log_k   -39.754
4.000Mg+2 + 4.000H2O  = Mg4(OH)4+4 + 4.000H+
log_k   -39.754
1.000Cl- + 1.000Mg+2  = MgCl+
log_k   0.350
1.000Mg+2 + 1.000H2O  = MgOH+ + 1.000H+
log_k   -11.681
1.000Zn+2     = Zn+2
log_k   0.000
1.000Zn+2 + 2.000H2O  = HZnO2- + 3.000H+
log_k   -28.140
1.000Cl- + 1.000Zn+2  = ZnCl+
log_k   0.394
2.000Cl- + 1.000Zn+2  = ZnCl2
log_k   0.470
3.000Cl- + 1.000Zn+2  = ZnCl3-
log_k   0.537
4.000Cl- + 1.000Zn+2  = ZnCl4-2
log_k   -0.384
1.000Zn+2 + 1.000H2O  = ZnO + 2.000H+
log_k   -19.173
1.000Zn+2 + 2.000H2O  = ZnO2-2 + 4.000H+
log_k   -40.518
1.000Zn+2 + 1.000H2O  = ZnOH+ + 1.000H+
log_k   -8.674
1.000Ti(OH)4     = Ti(OH)4
log_k   0.000


phases
fix_H+
H+   =   H+
log_k   0


equilibrium_phases
fix_H+   0.24


end

_________________________________________________________________________________________________

The output just tell me that,

ERROR: Elements in species have not been tabulated, Pt.
ERROR: Reaction for species has not been defined, Pt.
ERROR: Elements in species have not been tabulated, Rh.
ERROR: Reaction for species has not been defined, Rh.
ERROR: Calculations terminating due to input errors.


How can I solve '"Elements in species have not been tabulated" and "Reaction for species has not been defined"?
Any advice is really appreciated. I will try to correct and study harder.

I wish you a nice day!
Jin Lai.

dlparkhurst:
You have defined reactions in SOLUTION_SPECIES with "Pt" and "Rh" on the left-hand side of the equation. They must be defined once as the first species on the right-handed side of an equation. Consider whether these are aqueous species or are solids, which should be defined in PHASES.

Jin Lai:
I appreciate your help.

But I am confused why the other element like Pd or Fe don't need to define the first species on the right-handed side of an equation and no need to consider whether they are aqueous species or solids in phase.

And how do I define the Pt and Rh of the first species on the right-handed side of an equation and consider whether they are aqueous species or solids in phase? Is it also by the database?


I am very sorry that this is my first time writing the coding. Therefore, I am pretty unfamiliar with the limit of the code. Now I am trying to know the limit on the manual.

Thank you reply to me.
I wish you a nice day!
Jin Lai.

Jin Lai:
 
Dear Sir/Madam,
I tried following your suggestion to consider whether the species are aqueous or solid in PHASES, but still, I have an error in element Rh.
Do I still need to consider something I forget?

I appreciate your kind help.
The following is the coding that I correct.
_______________________________________________________________________________________________________

  Input file: C:\Users\Jin\Desktop\HCl complex formation.pqi
  Output file: C:\Users\Jin\Desktop\HCl complex formation.pqo
Database file: C:\Program Files (x86)\USGS\Phreeqc Interactive 3.7.3-15968\database\llnl.dat

------------------
Reading data base.
------------------

   LLNL_AQUEOUS_MODEL_PARAMETERS
   NAMED_EXPRESSIONS
   SOLUTION_MASTER_SPECIES
   SOLUTION_SPECIES
   PHASES
   EXCHANGE_MASTER_SPECIES
   EXCHANGE_SPECIES
   SURFACE_MASTER_SPECIES
   SURFACE_SPECIES
   RATES
   END
------------------------------------
Reading input data for simulation 1.
------------------------------------

   DATABASE C:\Program Files (x86)\USGS\Phreeqc Interactive 3.7.3-15968\database\llnl.dat
   Title   complex   formation
   solution   hcl   mol/l
   units   mg/L
   ph   -0.24
   temp   110
   Ce546.943asCe+4
   Pd8.7079asPd+2
   Pt11.0292asPt+2
   Rh2.2813asRh+3
   Cl72916asCl-
   Al4302.2asAl+3
   Fe55.04asFe+2
   Ni6.74asNi+2
   Mg509.92asMg+2
   Zn5.722asZn+2
   Ti18.242asTi(oh)4
   solution_master_species
   Cl      Cl-   0   Cl   35.453
   Pd      Pd+2   -2   Pd   106.42
   Pt      Pt+2   -2   Pt   195.08
   Rh      Rh+2   0   Rh   102.906
   Rh(2)      Rh+2   0   Rh   102.906
   Rh(3)      Rh+3   -2   Rh   102.906
   H      H+   -1   H   1.008
   H(0)      H2   0   H   1.008
   H(1)      H+   -1   H   1.008
   Ce      Ce+3   0   Ce   140.12
   Ce(2)      Ce+2   0   Ce   140.12
   Ce(3)      Ce+3   0   Ce   140.12
   Ce(4)      Ce+4   0   Ce   140.12
   Al      Al+3   0   Al   26.982
   Fe      Fe+2   0   Fe   55.847
   Fe(2)      Fe+2   0   Fe   55.847
   Fe(3)      Fe+3   -2   Fe   55.847
   Ni      Ni+2   0   Ni   58.693
   Mg      Mg+2   0   Mg   24.305
   Zn      Zn+2   0   Zn   65.39
   Ti      Ti(OH)4   0   Ti   47.87
   solution_species
   1.000H+   =   H+
   log_k   0.000
   Pd+2 =  Pd+2
   log_k 0
   1.0000 Pd++ + 1.0000 Cl-  =  PdCl+
   log_k    6.0993
   2.0000 Cl- + 1.0000 Pd++  =  PdCl2
   log_k           +10.7327
   3.0000 Cl- + 1.0000 Pd++  =  PdCl3-
   log_k           +13.0937
   4.0000 Cl- + 1.0000 Pd++  =  PdCl4--
   log_k           +15.1615
   1.0000 Pd++ + 1.0000 H2O  =  PdO +2.0000 H+
   log_k           -2.19
   1.0000 Pd++ + 1.0000 H2O  =  PdOH+ +1.0000 H+
   log_k   -1.0905
   Pt=Pt
   1.000Pt+2   =   Pt+2
   log_k   0.000
   1.000Cl- + 1.000Pt+2 = PtCl+
   log_k   8.692
   2.000Cl- + 1.000Pt+2  = PtCl2
   log_k   15.515
   3.000Cl- + 1.000Pt+2  = PtCl3-
   log_k   18.526
   4.000Cl- + 1.000Pt+2  = PtCl4-2
   log_k   20.057
   Pt + 0.500O2 + 2.000H+ = 1.000Pt+2 + 1.000H2O
   log_k   -2.157
   Pt+2 + OH- = Pt(OH)+
   log_k   24.91
   Pt+2 + 2OH- = Pt(OH)2
   log_k   28.81
   1.000Rh+2   =   Rh+2
   log_k   0.000
   Rh+3   =   Rh+3
   log_k   0.0
   0.250O2 + 1.000H+ + 1.000Rh+2  = Rh+3 + 0.500H2O
   log_k   3.356
   1.000Cl- + 1.000Rh+2  = RhCl+
   log_k   -0.207
   1.000Cl- + 1.000Rh+3  = RhCl+2
   log_k   2.022
   2.000Cl- + 1.000Rh+3  = RhCl2+
   log_k   3.303
   2.000Cl- + 1.000Rh+2  = RhCl2
   log_k   -0.772
   3.000Cl- + 1.000Rh+3  = RhCl3
   log_k   3.338
   3.000Cl- + 1.000Rh+2  = RhCl3-
   log_k   -2.093
   4.000Cl- + 1.000Rh+3  = RhCl4-
   log_k   3.300
   4.000Cl- + 1.000Rh+2  = RhCl4-2
   log_k   -3.297
   1.000Rh+3 + 1.000H2O  = RhO+ + 2.000H+
   log_k   -5.402
   1.000Rh+2 + 1.000H2O  = RhO + 2.000H+
   log_k   -15.950
   1.000Rh+2 + 1.000H2O  = RhOH+ + 1.000H+
   log_k   -7.835
   1.000Rh+3 + 1.000H2O  = RhOH+2 + 1.000H+
   log_k   -2.499
   Rh + 0.500O2 + 2.000H+ = 1.000Rh+2 + 1.000H2O
   log_k   22.694
   Rh+3 + 2H2O = Rh(OH)2+ + 2H+
   log_k   -6.5
   Rh+3 + 3H2O = Rh(OH)3 + 3H+
   log_k   -10.5
   Rh+3 4H2O = Rh(OH)4- + 4H+
   log_k   -17.7
   Rh+3 + 5H2O = Rh(OH)5-2 + 5H+
   log_k   -26.9
   Rh+3 + 6H2O = Rh(OH)6-3 + 6H+
   log_k   -37.2
   1.000Ce+3     = Ce+3
   log_k   0.000
   1.000Ce+3 + 0.500H2O  = Ce+2 + 0.250O2 + 1.000H+
   log_k   -85.049
   0.250O2 + 1.000Ce+3 + 1.000H+  = Ce+4 + 0.500H2O
   log_k   -8.042
   1.000Ce+3 + 1.000Cl-  = CeCl+2
   log_k   0.321
   1.000Ce+3 + 2.000Cl-  = CeCl2+
   log_k   0.056
   1.000Ce+3 + 3.000Cl-  = CeCl3
   log_k   -0.356
   1.000Ce+3 + 4.000Cl-  = CeCl4-
   log_k   -0.695
   1.000Al+3     = Al+3
   log_k   0.000
   1.000Fe+2     = Fe+2
   log_k   0.000
   0.250O2 + 1.000Fe+2 + 1.000H+  = Fe+3 + 0.500H2O
   log_k   8.490
   1.000Fe+3 + 4.000H2O  = Fe(OH)4- + 4.000H+
   log_k   -21.604
   2.000Fe+3 + 2.000H2O  = Fe2(OH)2+4 + 2.000H+
   log_k   -2.922
   1.000Cl- + 1.000Fe+2  = FeCl+
   log_k   -0.160
   1.000Cl- + 1.000Fe+3  = FeCl+2
   log_k   1.520
   2.000Cl- + 1.000Fe+3  = FeCl2+
   log_k   0.700
   2.000Cl- + 1.000Fe+2  = FeCl2
   log_k   -1.740
   1.000Fe+2 + 1.000H2O  = FeO + 2.000H+
   log_k   -20.601
   1.000Fe+3 + 1.000H2O  = FeO+ + 2.000H+
   log_k   -5.483
   1.000Fe+2 + 1.000H2O  = FeOH+ + 1.000H+
   log_k   -9.501
   1.000Fe+3 + 1.000H2O  = FeOH+2 + 1.000H+
   log_k   -2.191
   1.000Fe+3 + 2.000H2O  = HFeO2 + 3.000H+
   log_k   -14.302
   1.000Fe+2 + 2.000H2O  = HFeO2- + 3.000H+
   log_k   -31.932
   1.000Ni+2     = Ni+2
   log_k   0.000
   1.000Ni+2 + 2.000H2O  = HNiO2- + 3.000H+
   log_k   -31.502
   1.000Cl- + 1.000Ni+2  = NiCl+
   log_k   0.151
   1.000Ni+2 + 1.000H2O  = NiO + 2.000H+
   log_k   -19.501
   1.000Ni+2 + 1.000H2O  = NiOH+ + 1.000H+
   log_k   -9.501
   1.000Mg+2     = Mg+2
   log_k   0.000
   4.000Mg+2 + 4.000H2O  = Mg4(OH)4+4 + 4.000H+
   log_k   -39.754
   4.000Mg+2 + 4.000H2O  = Mg4(OH)4+4 + 4.000H+
   log_k   -39.754
   1.000Cl- + 1.000Mg+2  = MgCl+
   log_k   0.350
   1.000Mg+2 + 1.000H2O  = MgOH+ + 1.000H+
   log_k   -11.681
   1.000Zn+2     = Zn+2
   log_k   0.000
   1.000Zn+2 + 2.000H2O  = HZnO2- + 3.000H+
   log_k   -28.140
   1.000Cl- + 1.000Zn+2  = ZnCl+
   log_k   0.394
   2.000Cl- + 1.000Zn+2  = ZnCl2
   log_k   0.470
   3.000Cl- + 1.000Zn+2  = ZnCl3-
   log_k   0.537
   4.000Cl- + 1.000Zn+2  = ZnCl4-2
   log_k   -0.384
   1.000Zn+2 + 1.000H2O  = ZnO + 2.000H+
   log_k   -19.173
   1.000Zn+2 + 2.000H2O  = ZnO2-2 + 4.000H+
   log_k   -40.518
   1.000Zn+2 + 1.000H2O  = ZnOH+ + 1.000H+
   log_k   -8.674
   1.000Ti(OH)4     = Ti(OH)4
   log_k   0.000
   PHASES
   fix_H+
   H+   =   H+
   log_k   0
   Rh(element)
   Rh + 0.500O2 + 2.000H+ = 1.000Rh+2 + 1.000H2O
   log_k   22.694
   delta_h   -169.367   #kJ/mol   #98sas/sho
   analytical_expression   -4.2198365E+2   -6.5807108E-2   3.1965536E+4   1.5071669E+2   -1.409249E+6
   Rh2O(s)
   Rh2O + 0.6666675O2 + 4.66667H+ = 1.33333Rh+2 + 0.66667Rh+3 + 2.333335H2O
   log_k   32.170
   delta_h   -297.073   #kJ/mol   #Internal   calculation
   analytical_expression   -9.2880217E+2   -1.4590429E-1   6.5217476E+4   3.3096914E+2   -2.9537693E+6
   Rh2O3(s)
   Rh2O3 + 6.000H+ = 2.000Rh+3 + 3.000H2O
   log_k   12.342
   delta_h -213.359   #kJ/mol   #Internal   calculation
   analytical_expression -1.0500191E+3   -1.6722402E-1   6.5471364E+4   3.7474604E+2   -3.0808349E+6
   Pt(element)
   Pt + 0.500O2 + 2.000H+ = 1.000Pt+2 + 1.000H2O
   log_k   -2.157
   delta_h   -24.919   #kJ/mol   #By   convention
   PtS2
   PtS2 + 0.750H2O = 1.000Pt+2 + 1.500HS- + 0.250S2O3-2
   log_k   -74.387
   delta_h   392.207   #kJ/mol   #Internal   calculation
   equilibrium_phases
   fix_H+   0.24
   Rh(element)   0   0
   Rh2O(s)   0   0
   Rh2O3(s)   0   0
   Pt(element)   0   0
   PtS2   0   0
   end
-----
TITLE
-----

   complex   formation

ERROR: Elements in species have not been tabulated, Rh.
ERROR: Reaction for species has not been defined, Rh.
ERROR: Calculations terminating due to input errors.
-------------------------------
End of Run after 0.311 Seconds.
-------------------------------

dlparkhurst:
The first species on the right-hand-side of the equation is the species that is being defined in the SOLUTION_SPECIES data block. You have two definitions for the aqueous species Rh+2:

 
--- Code: ---   1.000Rh+2   =   Rh+2
   log_k   0.000
...
   Rh + 0.500O2 + 2.000H+ = 1.000Rh+2 + 1.000H2O
   log_k   22.694

--- End code ---

The first one is a correct definition for the master species Rh+2; the master species for element Rh is defined in the SOLUTION_MASTER_SPECIES data block. The second definition is not correct. Only aqueous species are defined in SOLUTION_SPECIES. If you intend to define Rh as an aqueous species, then the reaction needs to be reversed to have Rh as the first species on the right-hand-side, and the log_k would be -22.694.

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