Smectites are a group of minerals traditionally analyzed by thermal methods due to their exceptionally large adsorbed-water contents and the presence of OH groups, which makes them unique among all common soil- and rock-forming minerals. The dehydration reaction of smectite is a low-temperature endothermic effect that ends typically below 200°C. Although the removal of bulk interlayer water requires activation energy (Ea) of just above 30 kJ/mol, the removal of the last few H2O molecules attached strongly to interlayer cations requires Ea > 100 kJ/mol. Dehydroxylation is the loss of structural OH groups that proceeds as evolution of H2O molecules out of the smectite structure and occurs in the 300–900°C range. In trioctahedral species, dehydroxylation is combined with recrystallization and proceeds usually at > 700°C. In dioctahedral species, the temperature of dehydroxylation is controlled by the type of octahedral vacancy, having trans-vacant and cis-vacant distinguished by the boundary at ~ 600°C, and by the octahedral cation–OH bond strength, following the order Mg > Al > Fe. The Ea of dehydroxylation correlates linearly with the temperature of maximum dehydroxylation; from > 170 kJ/mol for Cs+-exchanged beidellite and nontronite, through ~ 300 kJ/mol in Mg-rich montmorillonite, to > 500 kJ/mol in trioctahedral saponite. Dehydration and dehydroxylation of smectites can be accompanied by a number of other phenomena, such as dehydrogenation or defluorination. At high temperatures, smectite amorphization and recrystallization occurs. Unless amorphized and/or recrystallized, smectites can undergo rehydration and rehydroxylation, which are opposite reactions to dehydration and dehydroxylation, respectively. This review discusses the details of the above-mentioned thermal reactions of smectites, focusing on thermogravimetric methods, evolved gas analysis, and structural alterations. Factors affecting the accuracy and precision of thermal analysis of smectite are discussed along with examples of best laboratory practices. The paper also provides the most recent description and critical evaluation of smectite reaction kinetics.

The molecular aggregation of organic dyes onto clay mineral particles is a very complex phenomenon including dye adsorption, the migration of dye molecules, rearrangement of initially formed aggregates, etc. Some details of this complex process are not yet fully understood. The objective of the present study was to understand the influence of dye surface concentration on the dynamic processes in dye molecular aggregation. A stopped-flow rapid mixing device was used for accurate measurements of the molecular aggregation of the cationic dye rhodamine 123 (R123) in montmorillonite (MntK) colloidal dispersions. The influence of dye surface concentration, which was changed by altering the ratio of the amount of R123 to the mass of MntK (nR123/mMntK), was examined in detail. Chemometric analysis was used to reconstruct the spectral matrix to obtain linearly uncorrelated spectral profiles of the major components and their concentrations at the respective reaction times. The conversion of isolated R123 cations into oblique J-aggregates (head-to-tail molecular assemblies) was observed over time and the existence of a J-dimers intermediate was hypothesized. The reaction kinetics followed a biphasic exponential function. An unexpected effect of dye surface concentration on R123 aggregation was observed: the initial formation of the molecular aggregates increased significantly with dye surface concentration, but an inverse trend was observed after longer reaction times. While dye aggregates were formed slowly at low dye loadings, systems with high R123/MntK ratios (nR123/mMntK) reached spectral stability after the first few seconds of the reaction. After longer reaction times, the greatest degree of dye aggregation was achieved in the dispersion of the lowest dye loading. Such a phenomenon is described for the first time. The results presented here are important for understanding the complex processes occurring in systems based on organic cations and clay minerals, and should be considered in the development of functional hybrid materials of dyes and nanoparticles with a layered structure.

Differences in equilibration rates among crystals of different sizes may be used to deduce paleofluid changes over time if the crystal-growth mechanism is known. To explore isotopic equilibration rates as a function of illite growth, we studied B-isotope changes during illitization of smectite. Montmorillonite (<2.0 µm SWy-1, K saturated) was reacted with aqueous boric acid (1000 ppm B) at 300°C, 100 MPa in sealed Au capsules (1:1 fluid:mineral ratio). The initial fluid was 0‰ (NBS 951 standard) but after R1 ordering occurred (65 days of reaction) the fluid was changed to −7‰ in order to examine the rate of isotopic re-equilibration. Samples were taken intermittently throughout the experiment. Each aliquot was NH4 exchanged and size separated into fine (<0.2 µm), medium (0.2–2.0 µm) and coarse (>2.0 µm) fractions. The isotopic composition of B in the tetrahedral sheet was then measured for comparison with the predicted equilibrium values.

The fine fraction showed equilibrium isotope ratios within 10 days, indicating that small, newly nucleated crystals precipitate in equilibrium with the fluid under supersaturated, closed conditions. These fine-fraction minerals did not re-equilibrate when the fluid was changed. The medium fraction gradually equilibrated with the initial fluid as illite grew to values >50%, but did not re-equilibrate with the later fluid. The coarse fraction was slow to begin recrystallization, perhaps due to dissolution kinetics of large crystals or the presence of detrital contaminants. However, it showed the fastest rate of isotopic change with crystal growth after R1 ordering. We conclude that at 300°C, the initial B–O bonds formed in illite are stable, and isotopic re-equilibration only occurs on new crystal growth. Therefore, different isotope ratios are preserved in different crystal size fractions due to different rates of crystal growth. Large crystals may reflect equilibrium with recent fluid while smaller crystals may retain isotope compositions reflecting equilibrium with earlier fluids.

An apparatus is described for the measurement of the rates of fast precipitation reactions. It consists of a T-tube, where reactants are added to the arms of the T, mixed rapidly at the junction, and the rates of disappearance of reactants or appearance of products are measured along the stem of the T. The geometry of the system results in a steady state being established in the apparatus, enabling detailed analysis of reaction progress. The apparatus has been used to investigate the kinetics and mechanism of iron sulphide precipitation reactions. It has enabled measurements to be made with relatively high precision and good accuracy of the first 130 ms of reaction time.

In a diffusion-controlled process of nucleation and growth, adjacent porphyroblasts compete with one another for nutrients. When the effects of this competition are evaluated quantitatively for garnet porphyroblasts in pelitic rocks from the Picuris Range of New Mexico (U.S.A.), significant correlations arise between crystal sizes and the volumes of the domains from which the crystals drew their nutrients. These correlations strengthen the conclusion drawn from earlier work on spatial dispositions, zoning patterns, and crystal size distributions that the kinetics of intergranular diffusion governed the crystallisation of these porphyroblasts.

Computer simulations indicate that competition for nutrients during diffusion-controlled growth may have small but detectable effects on crystal size frequency distributions. Diffusional competition therefore introduces relatively minor inaccuracies into attempts to extract quantitative information on crystallisation processes from size distributions using models for the growth of isolated porphyroblasts. In contrast, the effects of diffusional competition on patterns of compositional zoning may be substantial, especially for porphyroblasts in rocks for which chemical inhomogeneity of the precursor leads to strongly clustered spatial dispositions. In such rocks, clustering may alter the patterns of compositional zoning in ways that obscure evidence for diffusion-controlled growth.

Two applications of parametric Rietveld refinement employing a newly developed robust computer program are presented. The first application focuses on the parametric kinetic analysis of the reactions involving phase transitions of various polymorphic forms of copper phthalocyanine pigments. The second application concerns the parameterization of crystallite size with respect to experimental temperature. XRPD data for nanocrystalline titanium dioxide measured in dependence on temperature are used in this case study. Both the applications were realized with the help of the developed program in combination with the launch mode of topas® software.

Melting experiments with plagioclases were performed in the systems Ab-An, Ab-An-H2O, Qz-Ab-An-H2O, and Qz-Or-Ab-An-H2O-CO2. The experimental products were analysed by electron microprobe, and the kinetics of the reactions were studied qualitatively.

Melting of the plagioclase in the system Ab-An (P = 1 atm, T = 1420°C) is very fast in the first minutes but becomes slower with increasing run duration and is incomplete even after 1000 hours. The Ab/An fractionation between melt and residual plagioclase is similar to that described by Bowen (1913).

Melting kinetics of plagioclase in the system Ab-An-H2O ( = 5 kbar, T = 1000°C) is controlled by the diffusion of water into the plagioclase structure. Melting is especially fast parallel to the a-axis. The experimental products show separation of melts and crystals.

In the tonalite system Qz-Ab-An-H2O, equilibrium melting could be observed down to 830°C ( = 2 kbar) but not a lower temperatures. The kinetics of the reaction is enhanced by deficiency or excess of alumina in the aluminosilicate melt surrounding the plagioclase crystals. The fractionation of Ab and An between melt and plagioclase crystals is more pronounced in the presence of quartz than in the Ab-An-H2O system. The ratio An/An + Ab is approximately 0·35 in the melt and 0·85 in the coexisting plagioclase T = 880°C).

In the haplogranodiorite system Qz-Or-Ab-An-H2O–CO2, melting reactions were performed at P = 0·5 kbar, T = 880°C, and of approximately 0·5. It is assumed that near equilibrium compositions of melt and coexisting residual plagioclase could be obtained in long duration runs (run time = 60 days). The distribution of Ab and An between melt and minerals is similar to that observed in the tonalite system. The partial melt coexisting with an An-rich plagioclase and Or-rich K-feldspar is relatively poor in An.

Large stochastic systems of marked particles are considered. These ‘populations' grow according to pairwise mutually catalytic reactions and in addition particles may exchange their type (mark) by a sampling procedure. We are interested in the explosive behavior of the model and its high density properties (law of large numbers).