Inverted high-temperature quartz

Abstract

Fifty-two samples of inverted high-temperature quartz from volcanic rocks were investigated by Guinier-Jago powder diffractometry and differential scanning calorimetry (DSC). Quartz megacrysts from Clear Lake and Cinder Cone, California show a variability of ≃2.5 ° K in their α-β transition temperature (T α-β). Quartz phenocrysts and quartz from crystalline rocks give a range of 0.5 ° K in T α-β. Neutron activation analysis of single crystals demonstrates that Al is the principal impurity (17–380 ppm). Its concentration is inversely correlated with T α-β. A very small variation was found in the a and c lattice parameters among the specimens of volcanic quartz studied. This variation does not correlate with Al content or transition temperature. Mean values at 22 ° C (a=4.1934±0.0004 A, c=5.4046±0.0006 A) are similar to those of quartz grown at low temperatures. Enthalpy of the α-β transition (ΔH α-β), obtained over 9.0 ° from DSC runs, is dependent upon sample grain size and for a crushed powder with zero hysteresis (T α-β on heating=T α-β on cooling) is 92.0 ±1.4 cal/mol. In contrast, a single piece of quartz requires ΔH α-β be 107.7±1.4 cal/mol and has a T α-β hysteresis of 1.1 ° K. Regression of published data provides equations for the variation of the molar volume (cc/mol) of quartz with v. These equations imply a ΔV α-β of 0.205±0.031 cc/- mol. Expressions are also provided for the temperature dependence of the thermal coefficient of expansion, α, the compressibility, β, and (∂/gb/∂T)p (which is identically -(∂α/∂P) T ). DSC heat capacity measurements over the range 400 to 900 ° K were fitted to extended Maier-Kelley type expressions to give: $$\begin{gathered} C_P = 10.31 + 9.116 \times 10^{ - 3} T - \frac{{1.812 \times 10^5 }}{{T^2 }} \hfill \\ - {\text{5}}{\text{.630}} \times 10^{ - 2} {\text{ }}\frac{T}{{(T - 848)}} - 0.3553\frac{T}{{(T - 848)^2 }} \hfill \\ - 0.9011\frac{T}{{\left( {T - 848} \right)^3 }} \hfill \\ (400{\text{ to 842}}^ \circ {\text{K), and}} \hfill \\ C_P = - 318.8 + 0.2532T \hfill \\ {\text{ + }}\frac{{8.687 \times 10^7 }}{{T^2 }} + 0.1603\frac{T}{{\left( {T - 848} \right)^4 }} \hfill \\ \end{gathered} $$ (851 to 900 ° K), which together with the values of ΔH α−β measured over the range 842–851° K give 7875.3 cal/mol for H900-H400. The behavior of α, β, and C p as a function of T emphasizes that structural changes which occur at the α−β transition do so over a broad temperature interval.