Pressure and temperature dependence of the relaxation of the electrical double layer in hydrated magnesite rock (leukolite)

Anthony N. Papathanassiou , Elias Sakellis
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Abstract

The introduction of water into the pore space of naturally occurring magnesite (leukolite) induces an intense relaxation mechanism, which is related to the electric double layer (EDL) formed on opposing sides of the solid – mater interface. The relaxation of the EDL is studied by using Broadband Dielectric Spectroscopy at different conditions of combined temperature and hydrostatic pressure. The temperature evolution of the characteristic relaxation frequency, reveals two successive temperature regions: in the low temperature one, protonic conductivity over the network of water molecules in on the solid surface, couples to the ionic transport of charged defects occurring in the solid. At higher temperatures, near – zero activation energies are found: the phenomenon is discussed theoretically and attributed to decoupling and an exchange of protons with lattice site magnesium cations, the formation of a proton enriched sub-surface layer of magnesite and subsequent release of cations to the liquid. The values of the activation volume and their independence on temperature, support the aforementioned interpretation.

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水合菱镁岩(白石)电双层弛豫的压力和温度依赖性
当水进入天然菱镁矿(白石)的孔隙空间时,产生了强烈的弛豫机制,这与在固-物界面两侧形成的双电层(EDL)有关。利用宽带介电光谱研究了不同复合温度和静水压力条件下EDL的弛豫特性。特征弛豫频率的温度演化揭示了两个连续的温度区:在低温区,固体表面的水分子网络上的质子电导率与固体中带电缺陷的离子输运耦合。在较高的温度下,发现了接近零的活化能:从理论上讨论了这一现象,并将其归因于解耦和质子与晶格位镁离子的交换,菱镁矿的富质子亚表面层的形成以及随后阳离子释放到液体中。活化体积的值及其与温度的独立性支持上述解释。
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