RI 4408 Thermochemical study of the olivines and orthopyroxenes (ba15a029-4a3f-44b7-9d8b-0199ec4551f5)

"This paper contains some new thermodynamic data for silicates in the series Mg2SiO4-Fe2siO4 and MgSiO3-FeSiO3 and gives the results of a thermodynamic attack on the problems of stability end parageneses.. Although some data are lacking satisfactory agreement with mineralogical and petrological observations is indicated.The use of thermodynamic methods in mineralogy and petrology has been rather limited, because accurate thermal data, especially for the more complicated and more important rock-forming minerals, have been too scanty to permit any systematic application to problems in those fields. It is, nevertheless, a fascinating task to investigate to what extent the mode of occurrence and the stability relations of the minerals and mineral parageneses, as revealed by petrological and mineralogical observations, agree with predictions of thermodynamics. At the present stage of development calorimetric data are needed for most of the abundant silicate minerals.Measurement of the heats of solution in hydrofluoric acid of minerals in the series Mg2SiO4-Fe2SiO4 and MgSiO3-FeSiO3 affords a ready means of obtaining their heats of formation from the oxides. Combination of such data with entropy and heat-capacity values gives a means of obtaining free energies of formation from the oxides, which, in turn, are connected di¬rectly with stability and paragenoses.The two silicates of magnesium, Mg2SiO4 and MgSi03, occur as rock-forming constituents as forsterite and clinoenstatite or enstatite. The orthosilicate (forsterite) forms a series of isomorphic mixtures with ferrous-orthosilicate (fayalite). The continuity of this series, suggested by petrological observations, has boon proved experimentally by Bowon and Shairer.4/ The present work shows that those minerals constitute a series of perfect solid solutions - that is, a series of solid solutions for which heats of formation from the individual pure silicates, Mg2Si04 and Fe2SiO4, aro negligibly small.The metasilicates of magnesium and iron also form an isomorphic series. However, this series differs from the forstorito-fayalite series in the fact that the most iron-rich mixtures, between about En10Fs90 and pure Fs, appear to be unstable with respect to the paragenesis iron-rich olivine plus quartz. The supposed instability of pure FeSiO3 as a crystalline compound, at least at high and at moderate temperatures, is remarkable, as no crystal struc¬tural reason for such instability is apparent. The present work indicates, also, that these minerals form a perfect series of solid solutions and throws additional light on the instability question.In the following, the samples used in this investigation will be described. For each of the natural olivines and orthopyroxenes, with the exception of sample L, a chemical analysis was made of the purified and actually used fraction. All the analytical work was carried cut by Oleg v. Knorring, and the specific gravity determinations, by moans of a pycnomctcr, by Oiva Joensuu, both of the University of Helsinki, Finland. The determinations of the optical properties were made by Mrs. Toini Mikkola, of the Geological Survey of Finland."