Iddingsite rimming olivine in a basanite from the Limberg, Germany, is composed of saponite and goethite. Transmission electron microscopy of ion-thinned, oriented crystals suggests a two-stage alteration process. At first, the olivine breaks into a mosaic of 50-Å diameter {110} bounded needle-shaped domains which change to a metastable hexagonal phase having a = 3.1 Å and c = 4.6 Å, probably of close-packed, metal-oxygen octahedra. This reaction opens solution channels in the olivine which are detectable from about 20-Å diameter and are parallel to the olivine y-axis. Laths of smectite, one or two layers thick, 20 Å wide, and as much as 100 Å long parallel to their y-axis nucleate from the metastable phase and begin to fill in the solution channels. The laths orient with smectite (001) parallel to olivine (100). As the channels widen, prismatic {110} goethite crystals form directly from the metastable hexagonal phase. This first stage thus provides heterogeneous nuclei of smectite and goethite, formed epitactically and perhaps topotactically from a metastable intermediary.

In a second stage,these nuclei enlarge by deposition from solution as water migrates readily through the solution channels. A reduction in total volume allows smectite veins to form, misoriented with respect to the olivine. The reaction conserves iron, requires the addition of aluminum and water, and releases magnesium and silicon. Electron microprobe analyses of the iddingsite indicate that the smectite is saponite.

The ability of a high surface-area gibbsite to adsorb Cu2+ was studied using a Cu2+ ion-selective electrode, electron spin resonance, infrared spectroscopy, and electron microscopy. The gibbsite chemi-sorbed small amounts of monomelic Cu2+ (<0.5 mmole/100 g) which was oriented with its z-axis perpendicular to the (001) plane of the mineral. The proposed chemisorption sites are at gibbsite crystal “steps” observed by electron microscopy. Although Cu2+ adsorption on gibbsite as a function of pH was largely reversible, exposure of the chemisorbed Cu2+ to NH3 did not result in desorption from the surface despite the displacement of several OH− or H2O ligands by NH3. The results indicate that at least one Cu-O-Al bond is formed in the process of chemisorption.

At pH > 5, the gibbsite appeared to promote the hydrolysis and polymerization of Cu2+, with further adsorption at the surfaces. Infrared spectroscopy revealed no effect of the adsorption on the (001) surface hydroxyl groups, although the anisotropic diffusion of protons in the gibbsite structure was verified from deuteration studies.

As part of a laboratory study of the hydrothermal alteration of kimberlite, a mass balance procedure has been developed for estimating the relative proportions of synthetic phyllosilicate phases— chlorite, vermiculite, smectite, kaolinite and serpentine—present in reaction products. The procedure is based on a combination of X-ray powder diffraction (XRD) measurements (for phase identification), atomic absorption determinations (for total Si, Al, Fe, and Mg) and published analyses of clay minerals (for stoichiometric deductions). It centers on the computer inversion of a 4 × 4 matrix form of four simultaneous equations representing the mass balance of Si, Al, Fe, and Mg in four chosen minerals and incorporates a systematic routine for selecting from all possible permutations of high and low estimates of the mineral chemical analyses acceptable sets of product stoichiometries and phase proportions consistent with the total metal analyses. To minimize uncertainties and computing time, the program takes account of elemental relationships and water mass balances associated with phyllosilicates. It also accommodates data relevant to poorly crystalline phases for which a range of theoretical type-analyses modeled on aluminum oxyhydroxides and 9–11-Å, 2:1 layered aluminosilicates are employed.

The procedure produces reliable trends in phase proportions consistent with the intensities of characteristic XRD peaks of clay minerals present in the analyzed mixture; for example, increases in estimated kaolinite proportions correspond with larger 7-Å (and other) peaks in analyzed samples. A precision of 7–25% has been routinely achievable.

Hydrated kaolinite (d(001) = 10 Å) can be synthesized by mild heating of a kaolinite-organic suspension, allowing time for the clay to be intercalated by the organic solvent, and then dissolving a fluoride salt in the liquid. After mild heating of the suspension, the salt and organic solvent are removed by repeated water washings. The kaolinite retains interlayer water in the form of a 10-Å kaolinite hydrate. The influence of the intercalating agent, type of salt, concentration of salt, and the time of treatment on the synthesis of 10-Å hydrate was examined for several kaolinites. The most effective salt is NH4F; much smaller yields were obtained using KF and RbF. Not all organic molecules gave high yields of the hydrate; dimethyl sulfoxide, formamide, and hydrazine worked well but N-methyl formamide did not. The reaction between clay and salt resulted in the replacement of some hydroxyls by fluoride. This replacement was rapid; after 1 min of fluoride treatment a substantial yield of hydrate was obtained. The intercalation step separated the layers and also disordered the kaolinite, facilitating the F for OH replacement at or near crystallite edges. This replacement weakens the interlayer bonding at the edges and thereby reduces the possibility of layer collapse and attendant dehydration.

The unit-cell dimensions of synthetic, Al-substituted goethites showed that the c dimension is a linear function of Al substitution in the range 0–33 mole % Al, but that the a dimension is variable over this same range. The b dimension is also linearly related to Al substitution but is slightly more variable than the c dimension for Al substitutions of 20–33 mole %. The variability of the a dimension is postulated to be the result of structural defects. An improved procedure for estimating Al substitution from x-ray powder diffraction positions requires (1) calculation of the c dimension from the positions of the 110 and 111 diffraction lines using the formula: c = (1/d(111)2 − 1/d(110)2)−1/2, and (2) estimation of Al substitution from the relationship: mole % Al = 1730 − 572.0c. The 95% confidence interval of the estimate is ±2.6 mole % Al when using this procedure, in contrast to ±4.0 mole % Al when the position of the 111 reflection alone is used.

Adsorption of Mo(VI) on 2-0.2-μm size fraction of sodium-saturated kaolinite at 25 ± 2°C and at a constant pH of 7.00 ± 0.05 was studied. The kaolinite sample was pretreated to remove any surface oxide and hydroxide coatings. The initial concentrations of Mo in solution ranged from 1 to 11 mg/liter in a NaClO4 background electrolyte at a constant ionic strength of 0.09 ± 0.01. Calculations of speciation using the GEOCHEM computer program indicated that under experimental conditions Mo(VI) was mainly in the MoO42− form. The experimental conditions were also shown to fulfill the requirements for applying the Langmuir equation in interpreting adsorption data. The Langmuir parameter for the adsorption maximum, n°, and the affinity parameter, $K_{Mo{O}_{4^{2-}}-Cl{O}_{4^{-}}}$ were computed to be 3.33 × 10−4 mole/ mole of adsorbent and 5.969 × 105, respectively. The large affinity parameter indicated that the Na-saturated kaolinite surface has a very high affinity for MoO42− ions relative to ClO4− ions.

Polycations of limited molecular size were prepared from 0.1 M solutions of Fe(III)(NO3)3 and A1(NO3)3 by ultrafiltration. Various amounts of the polycations were added to Na-kaolinite, Na-mont-morillonite, and a Na-soil clay and the effect on the flocculation of the clay and electrophoretic mobility compared. Flocculation occurred just before zero net charge was obtained. Addition of further polycation resulted in the dispersion of clay with a net positive charge. The Al polycations possessed a high positive charge (0.49 per gram atom of Al), and their interaction with the clays indicated a planar shape. Adsorption of Al polycations decreased markedly the cation-exchange capacities of the kaolinite and the soil clay but had little effect on surface areas determined by low-temperature N2 adsorption. The Fe polycations were spheres 10–100 Å in diameter with a positive charge of 0.2 per gram atom. The surface areas of the kaolinite and the soil clay were substantially increased by the addition of the Fe polycations but their cation-exchange capacities were reduced by one fifth. Al polycations increased the surface areas of the montmorillonite (to 300 m2) presumably by propping open the interlamellar spaces and rendering the a-b planes accessible for nitrogen adsorption. The Al polycations in interlamellar spaces prevented collapse to 14 Å on heating to 150°C. There was no evidence of regular interlayer Fe as might be anticipated from the size of the spheres.

Several new, room-temperature luminescent phenomena, resulting from the interaction of kaolin and various amino compounds, have been observed. The emission of light from kaolin pastes (treated with quinoline, pyridine, hydrazine, monoethanolamine, n-butylamine, and piperidine) was shown to decay monotonically over a period of hours to days. More light was released by a given amino compound after it was dried and purified. Hydrazine, in addition to the monotonically decaying photon release, produces delayed pulses of light with peak emission wavelength of 365 nm which last between several hours and several days. These photon bursts are acutely sensitive to the initial dryness of the hydrazine, both in the number of bursts and the integrated photon output. The amount of light and the capacity of the kaolin to produce the delayed burst appeared to be strongly dependent on preliminary heating and on gamma-irradiation, analogous to the dehydration-induced light pulse previously reported from the Ames Research Center. A small, delayed burst of photons occurred when piperidine and n-butylamine were removed by evaporation into an H2SO4 reservoir.

The effect of the surface acidity of montmorillonite and kaolinite on the hydrolysis rate constants of different agricultural chemicals was studied at variable moisture contents. Ethyl acetate, cyclohexene oxide, isopropyl bromide, 1-(4-methoxyphenyl)-2,3-epoxypropane, and N-methyl p-tolyl carbamate were chosen as representatives of classes of chemicals that exhibit acid-catalyzed, base-catalyzed, and neutral hydrolysis. In addition to being commercially available in pure forms, these chemicals have well-characterized homogeneous kinetics. The presence of montmorillonite or kaolinite in water suspensions had a small effect on the hydrolysis rate constants (kh), whereas, the addition of moisture to oven-dried clays up to the limits of sorbed water resulted in an increase in the rate of hydrolysis of the epoxide by a factor of 10.

The increase in the hydrolysis rate constant suggests that the surface pH of montmorillonite or kaolinite might be 1–2 pH units lower than the bulk pH. The kh value for the carbamate on Na-montmorillonite surface (bulk pH = 8.5) is 6.4 × 10−8/sec which is equivalent to the rate constant at pH values ≤7. The hydrolysis rate constant of the epoxide was reduced by a factor of 4 when the moisture content exceeded the limit of sorbed water. The addition of humic acid to the clay minerals resulted in about a 40% reduction of the epoxide hydrolysis rate constant.

The gas-phase adsorption of trimethylphosphine onto hectorite, exchanged with Co(II) and Ni(II), gives trigonal complexes of the type [M(Ol)3(PMe3)]2+ (M = Co, Ni). Ten Dq values of PMe3 are 2.1 and 2.4 times larger than those of the structural oxygens or solvent molecules. The same complexes form between dimethylphenylphosphine and Ni(II) on hectorite and on synthetic zeolite Y. Co(II) forms pseudotetrahedral complexes with dimethylphenylphosphine ligands. These surface-immobilized transition-metal complexes interact strongly with NO and CH ≡ CH and to a lesser extent with CO and CH2=CH2, giving new types of complexes.