Acid and non-acid forms of kaolinite clays were found by potentiometric and conductometric titrations to possess a weak acid species, the concentration of which was increased by acidic preparation conditions and by the presence of soil organic matter bound to the clay. A stronger acid species was also found in untreated and in organic-free, HCl-treated samples (washed free of excess acid). The end points for organic-free and/or ion-exchanged samples were used to predict the end points for untreated samples. A surface-chemical model involving MOH2+, MOH, and MO− species (where M = Al and/or Fe) was fitted to the titration data and to the cation-exchange capacities. MOH2+ is the stronger acid and MOH the weaker acid; exchange of Na+ counterions by H+ converts MO−Na+ sites to MOH sites. Humic acid was probably complexed or chelated to some hydroxylated Al/Fe sites through COOH and phenolic OH groups. The COOH groups contributed supplementary stronger acid species which were not exchangeable, whereas the OH groups contributed supplementary weaker acid species and also increased the CEC relative to that for organic-free samples.

The conductivites of the Na and H ion-exchanged forms of kaolinitic clay rejects from sand-washing operations, both purified and as found naturally as a complex with soil organic matter, were examined. The two Na-clays showed linear conductivity-concentration characteristics, each having two regions with different slopes intersecting at ∼3.3% by weight of clay, which probably reflect a structural change from sol to gel. In the gel region, only the Na-counterions conducted, the reduction in conductivity with concentration being due to a smaller proportion of these ions in the Gouy layer and/or a decrease in their mobilities. In the sol, an additional, concentration-dependent conductivity arose from the electrophoretic motion of clusters of clay particles which gradually broke down on dilution. The two acid clays showed curved conductivity-concentration characteristics consistent with a weak acid dissociation equilibrium; the pKa values of 6.37 to 6.56 are close to those determined independently from titration with alkali. A stronger acid species detected in the titrations was not seen in the conductivity. The MOH2+/MOH/MO− model of the clay-surface species and one set of the predicted concentrations of each species (see preceding paper) are consistent with the observed conductivities. The MOH2+ species probably bridged the edges and faces of clay particles so that the H atoms were identical, but became different when alkali was added.

The effects of Na-citrate-dithionite (NaCD), ammonium oxalate in the dark (NH4Ox-D), and photolytic reaction under ultraviolet radiation (NH4Ox-P) on the mineralogy of <2-µm fractions of selected soils from Virginia were investigated. The NH4Ox-D treatment removed the smallest amounts of Al (<0.22%) and Fe (<0.50%) from all soils, indicating low levels of noncrystalline material in these materials. From the six soils examined, NH4Ox-P treatment extracted 5–62% more Fe and 12–300% more Al than the NaCD treatment. The NH4Ox-D and NaCD treatments revealed no X-ray diffraction detectable alterations to mineral phases present in <2-µm fractions of these soils. The NH4Ox-P treatment, on the other hand, produced considerable degradation of hydroxy-interlayered vermiculites in these soils, as evidenced by a shift of the 14-Å X-ray diffraction maxima to lower spacings with heat treatment of the sample. The NH4Ox-P treatment removed variable amounts of hydroxy-Al material from the interlayers of 2:1 layer silicates, depending on their stability and degree of development.

The crystal structure of natural boehmite, AlOOH, from Tveidalen, Langesundsfjorden, Norway, with a = 3.693(1), b = 12.221(2) and c = 2.865(1) Å, was refined from single crystal X-ray diffraction data (MoKα maximum 2θ = 120°) to an Rw value of 0.032 in space groups Amam and A21am. In both cases the proton was found to occupy positions of the type (x, 0.038, 0), where x = 0.104 and 0.396, about 0.75 Å from the donor oxygen atom. This arrangement corresponds to the presence of chains of asymmetric hydrogen bonds with random polarity parallel to the a axis, and indicates that the effective space group is Amam. No significant electron density was observed either at the center (0, 0, 0) or at the position (1/4, y, 0), corresponding to symmetric and bifurcated hydrogen bonds, respectively, between the layers of octahedra.

Calculations of the total energy of a representative portion of the boehmite structure as a function of hydroxyl orientation, using semiempirical molecular orbitals of the Hückel type, are in agreement with the observed electron density distribution and suggest a preference for (1) sp3, rather than sp2, hybridization of the donor oxygen atom orbitals, and (2) asymmetric, rather than symmetric hydrogen bonds. Disorder of the hydrogen atom positions within individual hydrogen bond chains is shown to be much less likely than disorder between adjacent fully coherent chains.

Noncrystalline aluminosilicate gels with Al2O3/(Al2O3 + SiO2) weight ratios from 0.3 to 0.5 were reacted in 0.1 N KOH at temperatures varying from 125° to 175°C. The pH of the solutions dropped sharply with increasing gel:solution ratios, indicating that the coordination number of Al in the products changed from IV to VI. The degree of hydrolysis appeared to be higher with KOH than with NaOH. X-ray powder diffraction and infrared spectroscopy showed that disordered kaolinite was the only crystalline product formed. Thermal data and surface area measurements indicated that the kaolinite was formed by a condensation process.