Experimental determination of Mn-Mg mixing properties in garnet,olivine and oxide

We have measured the mixing properties of Mn-Mg olivine and Mn-Mg garnet at 1300° C from a combination of interphase partitioning experiments involving these phases, Pt-Mn alloys and Mn-Mg oxide solid solutions. Activity coefficients of Mn dilute in Pt-Mn alloys at 1300° C/1 atm were measured by equilibrating the alloy with MnO at known f_O2. Assuming that the log f_O2 of the Mn-MnO equilibrium under these conditions is-17.80 (Robie et al. 1978), we obtain for _Mn: log_Mn = –5.25 + 3.67 X_Mn + 11.41X²_Mn Mixing properties of (Mn,Mg)O were determined by reversing the Mn contents of the alloys in equilibrium with oxide at known f_O2. Additional constraints were obtained by measuring the maximum extent of immiscibility in (Mn,Mg)O at 800 and 750° C. The data are adequately described by an asymmetric (Mn,Mg)O solution with the following upper and lower limits on nonideality: (a) W_Mn = 19.9kj/Mol; W_Mg = 13.7kj/Mol; (b) W_Mn = 19.9kj/Mol; W_Mg = 8.2kj/Mol; Olivine-oxide partitioning was tightly bracketed at 1300° C and oxide properties used to obtain activity-composition relations for Mn-Mg olivine. Despite strong M2 ordering of Mn in olivine, the macroscopic properties are adequately described by a symmetric model with: W^ol = 5.5 ± 2.5 kj/mol (1-site basis) Using these values for olivine, garnet-olivine partitioning at 27 kbar/1300° C leads to an Mn-Mg interaction parameter in garnet given by: W^gt = 1.5 ± 2.5kJ/mol (1-site basis) Garnet-olivine partitioning at 9 kbar/1000° C is consistent with the same extent of garnet nonideality and the apparent absence of excess volume on the pyrope-spessartine join indicates that any pressure-dependence of W^Gt must be small. If olivine and garnet properties are both treated as unknown and the garnet-olivine partitioning data alone used to derive W^Ol and W^Gt, by multiple linear regression, best-fit values of 6.16 and 1.44 kJ/mol. are obtained. These are in excellent agreement with the values derived from metal-oxide, oxide-olivine and olivine-garnet equilibria.