-------------------------------------------------------- begin_model | keyword indicating beginning of a solution model Fe-Mg-Mn-Biotite with compound formation, Powell and Holland '99 Am Min, extended for Mn-solution. NOTES: * This model will only function for the MnASH and FASH subsystems if MGO is also used as a component. * This model was tested with the maple script compete_bio.mws JADC 4/03 * Stoichiometric definition of the mnts_i endmember corrected, 2/04. JADC 1 2 3 M1 M2 T2 _________________________ Mutliplicity 1 2 2 _________________________ 1 MnBi Mn Mn AlSi Species: 2 Ann Fe Fe AlSi 3 Phl Mg Mg AlSi Dependent: 4 MnTs Al Mn AlAl Dependent: 5 Sdph Al Fe AlAl 6 East Al Mg AlAl ________________________ Ordered Cpd: 7 Obi Fe Mg AlSi | Comments can be placed before character data within a solution | model as long as they are preceded by the comment marker "|", | in general comments should not be placed before numerica data, | but they can be written following numeric data on the same line. Bio(HP) | solution name. 8 | model type: Margules with dependent endmembers and speciation. 2 | the number of independent subcompositions, reciprocal solution if > 1. 3 2 | 3 species on site 1, 2 species on site 2. this line (see also Sect 1.3.1 | and Sect 4 [READ 3] in vdoc.pdf) defines the geometric | shape of the composition space, in this case a right triangular prism. | the following lines list the endmembers that define the 6 vertices of | this prism. the geometry can be understood by noting that although | biotite as 3 subcompositions (refer to the occupancy table above), the | site populations on all 3 sites are determined if the population on any | 2 crystallographic sites. the independent "chemical" subcompositions need | not correspond to the actual crystallographic sites, but in this case | M2 and T2 can be identified as sites 1 and 2, respectively. Thus the | species that mix on site 1 are Mg-Fe-Mn, and the species that mix on | site 2 are AlSi and AlAl. If the endmember with species i on site 1 and | species j on site 2 is written as endmember ij, then the 6 endmembers will | be read in the order: 11, 21, 31, 12, 22, 32 | if instead the binary site had been specified as site 1 and the ternary | site as site 2, then the endmembers would be read in the order: 11, 21, | 12, 22, 13, 23. mnbi ann phl | endmember names (refer to the above comment, see also Sect 4 [Read 4] in mnts_i sdph_i east | vdoc.pdf), by specifying mnbi as the endmember 11 (i.e., the first | endmember) the model implies that Mn is species 1 on site 1 (M2), and | AlSi is species 1 on site 2 (T2, and, by default, AlAl must be species 2 | on site 2). In this model, there is a remaining degree | of freedom in that the second species on the first site may be chosen as | either Fe or Mg. This degree of freedom is removed by specifying ann as | endmember 21, implying Fe is species 2 on site 1 (M2, and, by default, Mg | must be species 3 on site 1). [Note that although sdph has Fe on M2 it could | not be specified as the second endmember because it has species 2 (AlAl) on | site 2.] The order in which the 4 remaining species are entered is determined | by these assignements, thus the third endmember (31) must have Mg on M2 and | AlSi on T2 (phl), the fourth endmember (12) must have Mn on M2 and AlAl on | T2 (mnts), etc. Users should be careful to order the endmembers so as to be | consistent with these considerations, because mistakes may not be detected | by vertex and can have dire consequences for computed solution properties. 1 | 1 ordered species: | model types 6 and 8 require data defining the | properties of an ordered "species". this species | is defined as a stoichiometric combination of | two independent endmembers and the enthalpy of | formation of the ordered species from the | these independent endmbers. the format for this | data is | name = num_1 * name_1 + num_2 * name_2 text = enthalpy | where name is the arbitrary name of the ordered | species, num_j is a number or fraction (i.e., two | numbers separated by a '/') and name_j is the | name of a valid endmember. text is arbitrary and | enthalpy is the enthalpy of formation of the ordered species. obi = 2/3 phl + 1/3 ann enthalpy_of_formation = -10.73d3 2 | 2 dependent endmembers | model types 7 and 8 (reciprocal solutions) use | internal endmembers that are defined as a | stoichiometric combination of the other endmembers. | the names of these endmembers are arbitrary, but | here dependent endmembers are highlighted by the | suffix "_i", this also serves to distinguish the | endmembers from real equivalents that may be | present in the thermodynamic data file. | the format of this data is | name = num_1 * name_1 + num_2 * name_2 | where num_j is a number or fraction (i.e., two | numbers separated by a '/') and name_j is the | name of a valid endmember. mnts_i = 1 east + 2/3 mnbi - 2/3 phl sdph_i = 1 east + 1 ann - 1 obi 1 0 0 1 0 0 | endmember flags: if 0 the endmember is considered to be part of the solution. | subdivision model for (ternary) site 1 (M2): 0. .2 .1 1 | range and resolution of X(Mn), 1 => asymmetric subdivision 0. 1. .1 0 | range and resolution of X(Fe), imod = 0 -> cartesian subdivision 0. 1. .1 0 | range and resolution of {1-X(Ts)}, imod = 0 -> cartesian subdivision | the foregoing lines define the pseudocompound compositions generated | on each "chemical" mixing site of the solution (Sect 4 [READ 6] vdoc.pdf). | for each site the compositional "range" of c-1 species (c is the number of | species on the site as defined in READ 3) is specified as well as a scheme | for interpreting the range. each range is defined by 3 numbers XMIN, XMAX, | and XINC, and the scheme is specified by an integer (IMD) written after the | c-1 ranges. The simplest scheme is cartesian, in which case IMD = 0 and the | the XMIN, XMAX, and XINC indicate the range of compositions (from XMIN to XMAX) | of the respective c-1 species and the compositional spacing (XINC) of the | pseudocompounds. As entered above, the subdivision scheme will generate | pseudocompounds with X(Mn) on site 1 from 0 to 0.20 mol at 0.01 mol increments | for each X(Mn) isopleth, compounds will be generated with X(Fe) from 0 to 1-X(Mn), | where "0" and "1" correspond to XMIN and XMAX in the range for the second species | on site 1, and X(Mg) = 1 - X(Fe) - X(Mn). | Alternative subdivision shemes detailed in vdoc.pdf, may be useful for specialized | applications, e.g., creating models with variable compositional resolution. | By restricting the ranges specified in a model it is possible to focus pseudocompounds | over a particular portion of a solutions composition space, such focusing can be | computationally advantageous when it is known a priori that only a limited range of | compositions can be stable, but it should be undertaken with caution because the | results are not always easy to anticipate. | The primary difficulty in restricting compositional ranges is that the user | can explicitly control the composition of only c-1 compositions since the | cth composition is determined by difference. Additionally the subdivision ranges | are applied sequentially, with compositions that violate mass balance (sum of | compositions > 1) eliminated as they occur. Thus, in general, users have the greatest | control on the composition of the first species on a site and no direct control | on the composition of the last species. Since in most cases it is desired to | restrict the composition of dilute species, endmembers should be specified | (READ 4) so that the dilute species is not the last species. begin_excess_function | format is W(e1 e1 e2 ...) num1 num2 num3 | where the excess parameter = num1 + num2*T + num3*P | and is multiplied by y(e1)*y(e1)*y(e2)... W(phl ann) 9000. 0. 0. W(phl east) 10000. 0. 0. W(phl obi) 3000. 0. 0. W(ann east) -1000. 0. 0. W(ann obi) 6000. 0. 0. W(obi east) 10000. 0. 0. end_excess_function 3 | Configurational entropy: 3 sites, M1, M2, T1. 4 1. | 4 species on M1, 1 site per formula unit. | If a mixing site involves n species, VERTEX | expects to find n-1 site fraction definitions | in terms of the endmember fractions. These | definitions have the general format: | text = num + num1 * name1 + num2 * name2 | where num is a number or fraction (i.e., two | numbers separated by a '/') and name is the | name of a valid endmember. | WARNING! fractions can only be used in the site | fraction definitions, do not use fractions to specify | site multiplicities in the above line. z(m1,fe) = 1 ann + 1 obi z(m1,mg) = 1 phl z(m1,mn) = 1 mnbi 3 2. | 3 species on M2, 2 sites per formula unit. z(m2,fe) = 1 ann z(m2,mn) = 1 mnbi 2 2. | 2 species on T1, 2 site per formula unit. z(t1,si) = 0.5 phl +0.5 ann +0.5 obi +0.5 mnbi end_of_model -------------------------------------------------------- begin_model Ti-Biotite model after White, Powell & Holland (JMG, 2007) Model entered by Lucie Tajcamanova, May 11, 2007. DQF corrections to annite added, Mark Caddick, Nov, 2007. NOTE: this model requires make defintions for fbi and tbi in the thermodynamic data file. 1 2 3 4 M1 M2 T1 H ____________________________ Mutliplicity 1 2 2 2 ____________________________ Dependent: 1 ffbi Fe3+ Fe AlAl OH 2 fbi Fe3+ Mg AlAl OH Dependent: 3 ftbi Ti Fe AlSi O 4 tbi1 Ti Mg AlSi O Dependent: 5 Sdph Al Fe AlAl OH 6 East Al Mg AlAl OH Species: 7 Ann Fe Fe AlSi OH 8 Phl Mg Mg AlSi OH __________________________ Ordered: 9 Obi Fe Mg AlSi OH TiBio(WPH) | solution name. 8 | model type: Margules with dependent endmembers and speciation. 2 | the number of independent subcompositions, reciprocal solution if > 1. 2 4 | 2 species on site 1, 4 species on site 2. | M2 and M1 can be identified as sites 1 and 2, respectively. the | species that mix on site 1 are Mg-Fe and the species that mix on | site 2 are M2+, Al, Ti. Fe3+. The identity of M2+ on site 2 is determined by | the identity of the M2+ cation on site 1 ffbi_i fbi ftbi_i tbi1 sdph_i east | endmember names ann phl 1 | ordered species: obi = 2/3 phl + 1/3 ann enthalpy_of_formation = -10.73d3 3 | 3 dependent endmembers sdph_i = 1 east + 1 ann - 1 obi ffbi_i = 1 fbi + 1 ann - 1 obi ftbi_i = 1 tbi1 + 1 ann - 1 obi 0 0 0 0 0 0 0 0 0 | endmember flags: if 0 the endmember is considered to be part of the solution. | subdivision model for (binary) site 1 (M2): 0. 1. .1 0 | range and resolution of X(Fe) | subdivision model for (quinary) site 2 (M1) 0. 0.2 .1 1 | range and resolution of X(Fe3+,M1) 0. 0.2 .1 1 | range and resolution of X(Ti,M1) 0. 1. .1 0 | range and resolution of X(Al,M1) begin_excess_function | current preferred thermocalc values, Caddick, Nov '07 W(phl ann) 9000. 0. 0. W(phl east) 10000. 0. 0. W(phl obi) 3000. 0. 0. W(ann east) -1000. 0. 0. W(ann obi) 6000. 0. 0. W(ann fbi) 8000. 0 0 W(ann tbi1) 10000. 0 0 W(obi east) 10000. 0. 0. | values from White et al paper and earlier Perple_X verions. | W(phl ann) 12000. 0. 0. | W(phl east) 10000. 0. 0. | W(phl obi) 4000. 0. 0. | W(phl fbi) 0. 0. 0. | W(phl tbi1) 0. 0. 0. | W(ann east) 3000. 0. 0. | W(ann obi) 8000. 0. 0. | W(ann fbi) 8000. 0 0 | W(ann tbi1) 10000. 0 0 | W(obi east) 7000. 0. 0. end_excess_function 4 | Configurational entropy: 4 sites, M1, M2, T1 H. 5 1. | 5 species on M1, 1 site per formula unit. z(m1,fe) = 1 ann + 1 obi z(m1,mg) = 1 phl z(m1,Fe3+) = 1 fbi z(m1,Ti) = 1 tbi1 2 2. | 2 species on M2, 2 sites per formula unit. z(m2,fe) = 1 ann 2 2. | 2 species on T1, 2 site per formula unit. z(t1,al) = 1/2 + 1/2 east + 1/2 fbi 2 2. | 2 species on H, 2 site per formula unit. z(h,o) = 1 tbi1 begin_dqf_corrections dqf(ann) -3000 0 0 end_dqf_corrections end_of_model -------------------------------------------------------- begin_model | keyword indicating beginning of a solution model Ti-Fe-Mg-Mn-Biotite with compound formation, Powell and Holland '99 Am Min, extended for Mn-solution. NOTES: * This model will only function for the MnASH and FASH subsystems if MGO is also used as a component. * Stoichiometric definition of the mnts_i endmember corrected, 2/04. JADC 1 2 3 M1 M2 T2 _________________________ Mutliplicity 1 2 2 _________________________ Dependent: 1 mtbi Ti MnV AlSi Dependent: 2 ftbi Ti FeV AlSi 3 tbi Ti MgV AlSi 4 MnTs Al Mn AlAl Dependent: 5 Sdph Al Fe AlAl Dependent: 6 East Al Mg AlAl 7 MnBi Mn Mn AlSi Species: 8 Ann Fe Fe AlSi 9 Phl Mg Mg AlSi ________________________ Ordered Cpd: 10 Obi Fe Mg AlSi | Comments can be placed before character data within a solution | model as long as they are preceded by the comment marker "|", | in general comments should not be placed before numerica data, | but they can be written following numeric data on the same line. TiBio(HP) | solution name. 8 | model type: Margules with dependent endmembers and speciation. 2 | the number of independent subcompositions, reciprocal solution if > 1. 3 3 | 3 species on site 1, 2 species on site 2. this line (see also Sect 1.3.1 | and Sect 4 [READ 3] in vdoc.pdf) defines the geometric | shape of the composition space, in this case a 4 dimensional prism. | the following lines list the endmembers that define the 9 vertices of | this prism. the geometry can be understood by noting that although | biotite as 3 subcompositions (refer to the occupancy table above), the | site populations on all 3 sites are determined if the population on any | 2 crystallographic sites. the independent "chemical" subcompositions need | not correspond to the actual crystallographic sites, but in this case | M2 and M1 can be identified as sites 1 and 2, respectively. Thus the | species that mix on site 1 are Mg-Fe-Mn, and the species that mix on | site 2 are M2+, Al, Ti. The identity of M2+ on site 2 is determined by | the identity of the M2+ cation on site 1, and the vacancy population on | site 1 is determined by the Ti concentration on site 2. If the endmember | with species i on site 1 and species j on site 2 is written as endmember ij, | then the 9 endmembers will be read in the order: 11, 21, 31, 12, 22, 32, | 13, 23, 33. mtbi_i ftbi_i tbi mnts_i sdph_i east | endmember names (refer to the above comment, see also Sect 4 [Read 4] in mnbi ann phl | vdoc.pdf). 1 | ordered species: | model types 6 and 8 require data defining the | properties of an ordered "species". this species | is defined as a stoichiometric combination of | two independent endmembers and the enthalpy of | formation of the ordered species from the | these independent endmbers. the format for this | data is | name = num_1 * name_1 + num_2 * name_2 text = enthalpy | where name is the arbitrary name of the ordered | species, num_j is a number or fraction (i.e., two | numbers separated by a '/') and name_j is the | name of a valid endmember. text is arbitrary and | enthalpy is the enthalpy of formation of the ordered species. obi = 2/3 phl + 1/3 ann enthalpy_of_formation = -10.73d3 4 | 4 dependent endmembers | model types 7 and 8 (reciprocal solutions) use | internal endmembers that are defined as a | stoichiometric combination of the other endmembers. | the names of these endmembers are arbitrary, but | here dependent endmembers are highlighted by the | suffix "_i", this also serves to distinguish the | endmembers from real equivalents that may be | present in the thermodynamic data file. | the format of this data is | name = num_1 * name_1 + num_2 * name_2 | where num_j is a number or fraction (i.e., two | numbers separated by a '/') and name_j is the | name of a valid endmember. | for theoretical reasons that are too complicated to | explain here (see Powell & Holland 2001), if an ordered | species (e.g., obi) is included in a reciprocal solution | then any dependent endmembers that can be defined in terms | of this dependent endmember must be so defined. | i.e., here sdph_i must be defined in terms of obi, but | the mnts_i endmember can only be written in terms of | mnbi and phl. mnts_i = 1 east + 2/3 mnbi - 2/3 phl sdph_i = 1 east + 1 ann - 1 obi mtbi_i = 1 tbi + 1/3 mnbi - 1/3 phl ftbi_i = 1 tbi + 1/2 ann - 1/2 obi 0 0 0 0 0 0 0 0 0 | endmember flags: if 0 the endmember is considered to be part of the solution. | subdivision model for (ternary) site 1 (M2): 0. .2 .1 1 | range and resolution of X(Mn) 0. 1. .1 0 | range and resolution of X(Fe) | subdivision model for (ternary) site 2 (M1) 0. 1. .1 1 | range and resolution of X(Ti,M1) 0. 1. .1 0 | range and resolution of X(Al,M1) | the foregoing lines define the pseudocompound compositions generated | on each "chemical" mixing site of the solution (Sect 4 [READ 6] vdoc.pdf). | for each site the compositional "range" of c-1 species (c is the number of | species on the site as defined in READ 3) is specified as well as a scheme | for interpreting the range. each range is defined by 3 numbers XMIN, XMAX, | and XINC, and the scheme is specified by an integer (IMD) written after the | c-1 ranges. The simplest scheme is cartesian, in which case IMD = 0 and the | the XMIN, XMAX, and XINC indicate the range of compositions (from XMIN to XMAX) | of the respective c-1 species and the compositional spacing (XINC) of the | pseudocompounds. As entered above, the subdivision scheme will generate | pseudocompounds with X(Mn) on site 1 from 0 to 0.20 mol at 0.01 mol increments | for each X(Mn) isopleth, compounds will be generated with X(Fe) from 0 to 1-X(Mn), | where "0" and "1" correspond to XMIN and XMAX in the range for the second species | on site 1, and X(Mg) = 1 - X(Fe) - X(Mn). | Alternative subdivision shemes detailed in vdoc.pdf, may be useful for specialized | applications, e.g., creating models with variable compositional resolution. | By restricting the ranges specified in a model it is possible to focus pseudocompounds | over a particular portion of a solutions composition space, such focusing can be | computationally advantageous when it is known a priori that only a limited range of | compositions can be stable, but it should be undertaken with caution because the | results are not always easy to anticipate. | The primary difficulty in restricting compositional ranges is that the user | can explicitly control the composition of only c-1 compositions since the | cth composition is determined by difference. Additionally the subdivision ranges | are applied sequentially, with compositions that violate mass balance (sum of | compositions > 1) eliminated as they occur. Thus, in general, users have the greatest | control on the composition of the first species on a site and no direct control | on the composition of the last species. Since in most cases it is desired to | restrict the composition of dilute species, endmembers should be specified | (READ 4) so that the dilute species is not the last species. begin_excess_function | format is W(e1 e1 e2 ...) num1 num2 num3 | where the excess parameter = num1 + num2*T + num3*P | and is multiplied by y(e1)*y(e1)*y(e2)... W(phl ann) 9000. 0. 0. W(phl east) 10000. 0. 0. W(phl obi) 3000. 0. 0. W(phl tbi) -10000. 0. 0. W(ann east) -1000. 0. 0. W(ann obi) 6000. 0. 0. W(ann tbi) 12000. 0 0 W(obi east) 10000. 0. 0. end_excess_function 3 | Configurational entropy: 3 sites, M1, M2, T1. 5 1. | 4 species on M1, 1 site per formula unit. | If a mixing site involves n species, VERTEX | expects to find n-1 site fraction definitions | in terms of the endmember fractions. These | definitions have the general format: | text = num + num1 * name1 + num2 * name2 | where num is a number or fraction (i.e., two | numbers separated by a '/') and name is the | name of a valid endmember. | WARNING! fractions can only be used in the site | fraction definitions, do not use fractions to specify | site multiplicities in the above line. z(m1,fe) = 1 ann + 1 obi z(m1,mg) = 1 phl z(m1,mn) = 1 mnbi z(m1,al) = 1 east 4 2. | 4 species on M2, 2 sites per formula unit. z(m2,fe) = 1 ann z(m2,mn) = 1 mnbi z(m2,vac) = 1/2 tbi 2 2. | 2 species on T1, 2 site per formula unit. z(t1,al) = 1/2 + 1/2 east end_of_model | end of model keyword -------------------------------------------------------- begin_model This is the Sack & Ghiorso (1989 CMP 102:41-68) noncovergent ordering model for Fe-Mg opx. The model has been reformulated as a compound formation model for Perple_X. JADC 7/03 Sites M1 M2 ______________ Mutliplicity 1 1 ______________ 1 en Mg Mg Species: 2 fs Fe Fe ______________ Ordered Cpd: 3 opx Mg Fe E(SG) 6 model type margules with compound formation 2 | 2 endmembers en fs 1 | ordered species definition opx = 1/2 en + 1/2 fs enthalpy_of_formation = -16d3 0 0 endmember flags 0. 1. 0.1 0 | range and resolution of X(mg), imod = 0 -> cartesian subdivision begin_excess_function w(en fs) 26000. 0. 0. w(en opx) 16000. 0. 0. w(fs opx) 16000. 0. 0. end_excess_function 2 2 site entropy model (m1, m2) 2 1. 2 species on m2, mutiplicity = 1 z(m1,mg) = 1 en + 1 opx 2 1. 2 species on m1, mult. = 1 z(m2,mg) = 1 en end_of_model --------------------------------------------------------