Molecular orbital analysis on dissolution of smectite under strong alkaline condition with high Ca concentration

Matsue, Naoto*; Abidin, Z.*; Fujii, Naoki*; Oda, Chie; Honda, Akira

Nendo Kagaku, 52(2), p.62 - 70, 2014/00

https://doi.org/10.11362/jcssjnendokagaku.52.2_62

Bentonite is expected to be used along with cement as engineered barrier components of TRU waste geological disposal system. There is a concern that the bentonite dissolved or altered owing to the contact with strong alkaline and high Ca concentration water derived from the reaction of the cement and groundwater. The first-principles quantum chemical calculations using the cluster model of montmorillonite, the main component of bentonite, were performed, and it was indicated that octahedral Al has higher solubility than octahedral Mg under strong alkaline condition and unsaturated Si-O-Al bond connecting tetrahedral and octahedral sheets at the edge of 110 and 010 planes cleaves easily. The adsorption of OH on tetrahedral Si atom caused dissolution of adjacent Si and Al atoms in addition to the Si atom. While, the dissociation of Si-OH and Al-OH groups and the difference in exchangeable cation species were shown to be less likely to affect the dissolution behavior of montmorillonite.