Thermodynamic properties of andradite and application to skarn with coexisting andradite and hedenbergite

The enthalpy of formation of andradite (Ca₃Fe₂Si₃O₁₂) has been estimated as-5,769.700 (±5) kJ/mol from a consideration of the calorimetric data on entropy (316.4 J/mol K) and of the experimental phaseequilibrium data on the reactions: 1 $$\begin{gathered} 9/2 CaFeSi_2 O_6 + O_2 = 3/2 Ca_3 Fe_2 Si_3 O_{12} + 1/2 Fe_3 O_4 + 9/2 SiO_2 (a) \hfill \\ Hedenbergite andradite magnetite quartz \hfill \\ \end{gathered} $$ 1 $$\begin{gathered} 4 CaFeSi_2 O_6 + 2 CaSiO_3 + O_2 = 2 Ca_3 Fe_2 Si_3 O_{12} + 4 SiO_2 (b) \hfill \\ Hedenbergite wollastonite andradite quartz \hfill \\ \end{gathered} $$ 1 $$\begin{gathered} 18 CaSiO_3 + 4 Fe_3 O_4 + O_2 = 6Ca_3 Fe_2 Si_3 O_{12} (c) \hfill \\ Wollastonite magnetite andradite \hfill \\ \end{gathered} $$ 1 $$\begin{gathered} Ca_3 Fe_2 Si_3 O_{12} = 3 CaSiO_3 + Fe_2 O_3 . (d) \hfill \\ Andradite pseudowollastonite hematite \hfill \\ \end{gathered} $$ and $$log f_{O_2 } = E + A + B/T + D(P - 1)/T + C log f_{O_2 } .$$ Oxygen-barometric scales are presented as follows: $$\begin{gathered} E = 12.51; D = 0.078; \hfill \\ A = 3 log X_{Ad} - 4.5 log X_{Hd} ; C = 0; \hfill \\ B = - 27,576 - 1,007(1 - X_{Ad} )^2 - 1,476(1 - X_{Hd} )^2 . \hfill \\ \end{gathered} $$ For the assemblage andradite (Ad)-hedenbergite (Hd)-magnetite-quartz: $$\begin{gathered} E = 13.98; D = 0.0081; \hfill \\ A = 4 log(X_{Ad} / X_{Hd} ); C = 0; \hfill \\ B = - 29,161 - 1,342.8(1 - X_{Ad} )^2 - 1,312(1 - X_{Hd} )^2 . \hfill \\ \end{gathered} $$ For the assemblage andradite-hedenbergite-wollastonite-quartz: 1 $$\begin{gathered} E = 13.98;{\text{ }}D = 0.0081; \hfill \\ A = 4\log (X_{Ad} /X_{Hd} );{\text{ C = 0;}} \hfill \\ B = - 29,161 - 1,342.8(1 - X_{Ad} )^2 - 1,312(1 - X_{Hd} )^2 . \hfill \\ \end{gathered} $$ For the assemblage andradite-hedenbergite-calcitequartz: 1 $$\begin{gathered} E = - 1.69;{\text{ }}D = - 0.199; \hfill \\ A = 4\log (X_{Ad} /X_{Hd} );{\text{ C = 2;}} \hfill \\ B = - 20,441 - 1,342.8(1 - X_{Ad} )^2 - 1,312(1 - X_{Hd} )^2 . \hfill \\ \end{gathered} $$ For the assemblage andradite-hedenbergite-wollastonite-calcite: 1 $$\begin{gathered} E = - 17.36;{\text{ }}D = - 0.403; \hfill \\ A = 4\log (X_{Ad} /X_{Hd} );{\text{ C = 4;}} \hfill \\ B = - 11,720 - 1,342.8(1 - X_{Ad} )^2 - 1,312(1 - X_{Hd} )^2 \hfill \\ \end{gathered} $$ The oxygen fugacity of formation of those skarns where andradite and hedenbergite assemblage is typical can be calculated by using the above equations. The oxygen fugacity of formation of this kind of skarn ranges between carbon dioxide/graphite and hematite/magnetite buffers. It increases from the inside zones to the outside zones, and appears to decrease with the ore-types in the order Cu, Pb?Zn, Fe, Mo, W(Sn) ore deposits.