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英温度和组成对硅酸盐玻璃结构和动力学的影响
Geochimico et Cosmochimica Acla Vol. 52, pp. 2659-2669 0016-7037/88/$3.00 + .M)
Copyright 0 1988 Pergamon Pressplc.Printed in U.S.A.
Effects of te~pe~ture on the spheres of silicate liquids: 29Si NMR results
MARK E. BRANDRISSand JONATHANF. STEBBINS
Department of Geology, Stanford University, Stanford, CA 94305, U.S.A.
(Received May 5, 1988; accepted in revisedform August 12, 1988)
Abstract-The effectof temperature on the structures of three silicate liquids has been studied by %i NMR spectmmopy
on glass samples prepared with differentglasstransition temperatures. The ~rn~sitio~ studied are (NarO). Si02).sa
and (CaO) *~(Na~O),,~(SiO~).,~and fCao)25(Mgo).,,(Si4).,. In the tirst two, the abundance of SiO, tetrahedra
with four bridging oxygens (Q’) increases significantly with tempemtum. This change-results from the disproportionation
reaction 2Q3 S Q2 + Q’ (Q is a Si04 tetrahedron with n bridging oxygens), with the observed increase in dispro-
portionation at higher temperatures implying increased randomization of the anionic structure. In the (Na20).34(Si02).66
composition, the temperature dependence of Q4 abundance enables us to estimate AH0 for this reaction to be
30 + 15 kJ per mole of Si. Although this reaction thus makes only a minor contribution to the configurational heat
capacity of each liquid, it probabl
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