The kinetics of silica-water reactions

Rimstidt, J. Donald; Barnes, H. L.

doi:10.1016/0016-7037(80)90220-3

Cited by 1,125 publications

(751 citation statements)

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“…Experimentally determined activation energies for the amide bond lie in the range between 76 kJ mol À1 and 105 kJ mol À1 , [35][36][37][38][39] the corresponding values for the siloxane bond are between 67 kJ mol À1 and 96 kJ mol À1 . 35,[40][41][42] Theoretical values are 63-113 kJ mol À1 for the amide [43][44][45][46][47][48][49] and 71-142 kJ mol À1 for the siloxane bond. [50][51][52][53][54] Bershtein et al, who have studied the mechanically activated hydrolysis of C(O)-N and Si-O bonds in bulk material in moisture, have found activation energies between 84 kJ mol À1 and 105 kJ mol À1 for C(O)-N and 80 kJ mol À1 -96 kJ mol À1 for Si-O.…”

Section: Resultsmentioning

confidence: 99%

Mechanically activated rupture of single covalent bonds: evidence of force induced bond hydrolysis

Schmidt

Kersch

Beyer

et al. 2011

Phys. Chem. Chem. Phys.

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We have used temperature-dependent single molecule force spectroscopy to stretch covalently anchored carboxymethylated amylose (CMA) polymers attached to an amino-functionalized AFM cantilever. Using an Arrhenius kinetics model based on a Morse potential as a one-dimensional representation of covalent bonds, we have extracted kinetic and structural parameters of the bond rupture process. With 35.5 kJ mol À1 , we found a significantly smaller dissociation energy and with 9.0 Â 10 2 s À1 to 3.6 Â 10 3 s À1 also smaller Arrhenius pre-factors than expected for homolytic bond scission. One possible explanation for the severely reduced dissociation energy and Arrhenius pre-factors is the mechanically activated hydrolysis of covalent bonds. Both the carboxylic acid amide and the siloxane bond in the amino-silane surface linker are in principle prone to bond hydrolysis. Scattering, slope and curvature of the scattered data plots indicate that in fact two competing rupture mechanisms are observed.

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Section: Resultsmentioning

confidence: 99%

Mechanically activated rupture of single covalent bonds: evidence of force induced bond hydrolysis

Schmidt

Kersch

Beyer

et al. 2011

Phys. Chem. Chem. Phys.

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“…The temperature dependence of the (high strain) friction coefficient of muscovite under hydrous conditions is poorly known, though recent work by Mariani et al [2006] suggests little temperature effect. Previous work on pressure solution compaction in quartz sands has shown that pressure solution is probably dissolution rate controlled under upper to midcrustal conditions, so we have used the dissolution rate law reported by Rimstidt and Barnes [1980] to describe the rate limiting step of pressure solution. The geometrical parameters in our high-velocity model were taken in the middle range already mentioned in the application of our model to the experimental results (see also Table 1).…”

Section: Application To Naturementioning

confidence: 99%

“…In our calculation, we have assumed an aseismic creep rate of 10 À3 mm s À1 (or 30 mm yr À1 ) and a coseismic slip rate of 1 m s À1 , based on GPS measurements across the San Andreas Fault and previous estimates of coseismic slip rates [e.g., Becker et al, 2004;Scholz, 2002]. We have again used the dissolution rate law reported by Rimstidt and Barnes [1980] to describe the rate limiting step of pressure solution . As phyllosilicates have been reported both to increase [Bjørkum, 1996;Dewers and Ortoleva, 1991;Renard et al, 2001] and decrease IPS compaction rates , we also show model curves for increased (10 times) and decreased (10 times) dissolution rates (see Figure 11).…”

Section: Implications For Seismogenesismentioning

confidence: 99%

“…We assumed a coseismic slip rate of 1 m s À1 , an overburden density of 2750 kg m À3 , and a hydrostatic fluid pressure (l = 0.36). Three different dissolution rates were used, which are Rimstidt and Barnes' [1980] dissolution rate equation (black lines), 10 times this dissolution rate (dark gray lines), and 0.1 times (light gray line). We determined stress drops for a fault zone thickness of 1 mm and 10 m. Also shown are static stress drop estimates for various earthquakes.…”

Section: Further Implicationsmentioning

confidence: 99%

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A microphysical model for strong velocity weakening in phyllosilicate‐bearing fault gouges

2007

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[1] Previous rotary shear experiments, performed on a halite-muscovite fault gouge analogue system have shown that the presence of phyllosilicates, under conditions favoring the operation of cataclasis and pressure solution in the matrix phase, can have major effects on the frictional behavior of gouges. While 100% halite and 100% muscovite samples exhibit rate-independent frictional/brittle behavior, the strength of mixtures containing 10-30% muscovite is both normal stress and sliding velocitydependent. At high sliding velocities (>1 mm s À1 ), such mixtures show unusually marked velocity weakening, along with the development of a structureless, cataclastic microstructure. In the present paper, a micromechanical model is developed in an attempt to explain this behavior. The model assumes a granular flow process involving competition between intergranular dilatation and compaction by pressure solution. The predictions of the model agree favorably with the experimental results. Extension of the model to quartz-mica systems implies that the presence of phyllosilicates plus the operation of pressure solution can strongly promote (unstable) velocity-weakening behavior at rapid slip rates on natural faults, under midcrustal conditions. Static stress drop predictions based on the model agree reasonably well with estimates from seismic observations. Our results may help explain the discrepancy between laboratory-derived rate-and-state friction parameter values, obtained for dry, low-strain and/or single-phase rock systems, and the values for natural fault rocks inferred from seismological data.Citation: Niemeijer, A. R., and C. J. Spiers (2007), A microphysical model for strong velocity weakening in phyllosilicate-bearing fault gouges,

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“…Although many other experiments performed at lower pressures [Lasaga, 1984;Blunt and Stillings, 1995] measure quartz rates that are slower than feldspar reaction rates, Heald [ 1955] showed that under stress the solution rate of quartz may be greatly enhanced relative to feldspars. Another interesting point is that reaction rates that fit the permeability data are constant with temperature and stress, although they are expected to increase with temperature [Rimstidt and Barnes, 1980]. It is not clear why rates in the experimental system are not a strong function of temperature and stress, but Hickman and Evans [1995] showed that under pressure solution conditions temperature may have little effect on dissolution rates.…”

Section: Discussion Of Modeling Results To the Experimental System Inmentioning

confidence: 99%

Precipitation sealing and diagenesis: 2. Theoretical analysis

Aharonov¹,

Tenthorey²,

Scholz³

1998

J. Geophys. Res.

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Abstract. We propose a new model to describe precipitation-induced permeability reduction during chemical diagenesis of sandstones. The model has two parts: (1) geochemical model for determining the expected mass of precipitates and (2) physical model relating how a given mass of precipitates affects permeability. The model is used to study the experiments reported by Tenthorey et al. [this issue], where reactions involving dissolution of quartz and feldspar and precipitation of authigenic minerals were observed to cause drastic permeability reduction in feldspathic sandstone. We find that the geochemical evolution of the system dictates permeability evolution, and thus permeability dependence on temperature and stress is related to geochemical responses to these variables. The model predictions for the experimental system of Tenthorey et al. provide a very good fit to the experimental permeability curves over all times, stresses, and temperatures within the experimental range. Following the experiments and model, we suggest that precipitation of secondary mineral phases is an extremely efficient method for permeability reduction but one that depends critically on the system's approach to equilibrium. The reaction products of chemical diagenesis observed in rocks are the consequence of chemical reactions that occur in natural systems as they approach equilibrium, and we predict extensive and rapid permeability reduction as a result of such reactions.

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The kinetics of silica-water reactions

Cited by 1,125 publications

References 11 publications

Mechanically activated rupture of single covalent bonds: evidence of force induced bond hydrolysis

Mechanically activated rupture of single covalent bonds: evidence of force induced bond hydrolysis

A microphysical model for strong velocity weakening in phyllosilicate‐bearing fault gouges

Precipitation sealing and diagenesis: 2. Theoretical analysis

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