ISSN:
1365-2389
Source:
Blackwell Publishing Journal Backfiles 1879-2005
Topics:
Geosciences
,
Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
Notes:
We prepared five samples of pure goethite and three samples of aluminous goethite with mole fractions of aluminium ranging from 0·05 to 0·20. One of the samples of pure goethite was repeatedly heated in an autoclave at 150°C. We studied the samples using transmission electron microscopy and XRD and we measured the surface area (BET), rate of dissolution of the samples in acid, the surface charge in four concentrations of sodium nitrate from pH 4–10, and the sorption of calcium and chloride from a dilute solution of calcium chloride. Surface areas ranged from 18 to 132 m2 g−1. The BET adsorption-desorption isotherms had hysteresis loops which increased as the surface area increased. These showed that there were pores present with diameters smaller than 2 nm and that the number of pores increased as the surface area increased. All samples of goethite showed typical X-ray diffraction patterns but with peak heights decreasing, and width increasing, as surface area increased. Mean coherence lengths, as determined by XRD line broadening, were smaller than those determined by transmission electron microscopy. This was because each crystal was composed of several domains, and the XRD data reflect the size of the domains. Heating one of the goethite samples in an autoclave caused most of the domains to coalesce and slightly decreased the surface area. As the surface area of the eight goethite samples increased, the mean coherence length in the direction of the a, b and c axes decreased. The better crystallized samples dissolved more slowly in acid and the dissolution curves were sigmoid because the acid was able to penetrate between the domains allowing access to a larger surface area and consequently accelerated dissolution. The points of zero charge increased with increasing surface area of the goethite. The charge carried by the goethite at pH values distant from the point of zero charge increased as the surface area increased. This may indicate movement of protons or hydroxyl ions into pores or other defects in the crystal. The effects of pH and of salt concentration on surface charge were closely described by the variable-charge/variable-potential model. This model also closely described adsorption of Ca2+ and Cl− from calcium chloride solutions requiring only the allocation of constants for these ions. The substitution of aluminium for iron did not affect the charge properties of goethite.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1111/j.1365-2389.1997.tb00188.x
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