The effects of exchangeable Na and Ca and the ionic strength of NaCl and CaCl2 solutions on the boron adsorption by the Na and Ca forms of montmorillonite and illite at pH 9 were studied. The boron adsorption by montmorillonite was greater for the Ca form than for the Na form at any boron activity in solution and at any ionic strength. For example, the amount of boron adsorbed by Na- and Ca-montmo-rillonite was 2.9 and 4.3 μmole/g, respectively, at an ionic strength of 0.36 and a boron activity of 0.875 mmole/liter in equilibrium solution. The boron adsorption by illite was much greater than by montmorillonite. For example, the amount of boron adsorbed by Na-montmorillonite and Na-illite was 1.5 and 8.7 μmole/g, respectively, at an ionic strength of 0.02 and a boron activity of 0.5 mmole/liter. However, the nature of the exchangeable cation had little effect on the boron adsorption by illite. The effect of the ionic strength on the boron adsorption by Na-montmorillonite was greater than that observed for either Camontmorillonite or illite. The data suggest that the negative electric field around the clay particles is one of the main factors controlling boron adsorption at alkaline pHs.

Regular vertical variations in mineralogy and chemistry indicate that underclay beneath the Herrin (No. 6) coal in southwestern Illinois has undergone in situ alteration. Alteration resulted from the downward movement of hydrogen ions, as indicated by the progressive leaching of acid-sensitive minerals adjacent to the coal. Mineralogical trends observed in the underclay with increasing depth below the coal include: (1) a decrease in the expandability of mixed-layer illite/smectite (I/S); (2) an increase in the amount of ordered I/S with respect to randomly interstratified I/S; (3) an increase in the amount of discrete illite with respect to expandable clays; and (4) an increase in chlorite and calcite. Ordered I/S is the dominant mixed-layer clay where calcite is present, but randomly interstratified I/S dominates where calcite is absent. The pH of the underclay also increases with depth. These trends are consistent with an origin by acid leaching of a preexisting mineral assemblage that included illite, chlorite, and calcite. Other acid-alteration trends may be expected for different precursor minerals and for different leaching intensities and durations.

Clayey sediments of marine origin having sensitivities (ratio of undisturbed to remolded shear strength) as high as 1000 at a reduced salt concentration are found around Ariake Bay, Kyushu, Japan. The clay fraction of the sediments contains smectite as a principal mineral (33–42%) in contrast to the illitic composition of most previously described quick-clays. However, this smectite is a low-swelling type, and the Na-form expands only to about the same extent as the Ca-form and gives a sediment volume almost equal to that of the Ca-clay. This low-swelling smectite appears to consist of packets of unit layers even after saturation with Na, and thus reacts like the kaolinite or illite of conventional quick-clays.

Bis-ethyl 2-hexylphosphoric acid (di-2 EHPA) dissolved in decane is chemisorbed on kaolinite and montmorillonite dispersed in an acidic aqueous solution. The adsorption results in the formation of complexes with the surface cations of the clays. The adsorption isotherms are of the Langmuir type and reveal a limiting value of adsorption on H+-kaolinite of 12.2 mg/g, comparable to that measured in the absence of water. For H+-montmorillonite, however, the limiting value in the presence of acid is somewhat less (20.6 mg/g vs. 23.8 mg/g). Di-2 EHPA does not react with the magnesium cations available at the surface. The isotherm is “stepped” and suggests the presence of adsorption sites with distinctly differentiated energies. The sites of di-2 EHPA adsorption can be masked by treating the two clay minerals with polyphosphate anions. Thus, with pyro- and tripolyphosphate anions, di-2 EHPA uptake in acidic medium is very low. Adsorbed di-2 EHPA can be recovered by treating the clays with fluoride, hydroxyl, and dihydrogenphosphate anions. Dihydrogenphosphate anions lead, however, to a state of equilibrium between the organic and inorganic phosphate anions adsorbed.

Viscosity and light-transmission measurements of dilute suspensions of montmorillonites having different exchangeable cations were used to calculate relative particle sizes as a function of cation composition, where particle size is expressed as the number of clay plates per tactoid relative to the number of plates per tactoid for Li-montmorillonite, after exchange of Li, Na, K, Cs, and Mg by Ca. Tactoid sizes increased in the order Li < Na < K < Mg < Ca, with the number of plates per tactoid relative to Li-montmorillonite varying from 1.5 for Na- to 6.1 for Ca-montmorillonite. The results for tactoid sizes derived from light transmission and those derived from viscosity data are in reasonable agreement with each other and with literature data for similar systems. Upon exchange of Ca-counterions for Li-, Na-, or K-coun-terions, a sharp initial decrease in tactoid size was observed over approximately the first 30% of cation exchange. Upon further exchange, tactoid sizes changed only slightly, but when Ca was exchanged for Cs or Mg, a much more gradual decrease in particle size was observed.

The catalytic activity of sepiolite from Amboseli, Tanzania, for the dehydration and dehydrogenation of ethanol at 150°–300°C has been studied using a flow reactor. Both reactions occur, but the catalyst activity decreases with use. The products include water, carbon dioxide, ethene, ethanal (acetaldehyde), diethyl ether, but-1,3-diene, but-2-enal (crotonaldehyde), and an unidentified aromatic compound. The proportions change with temperature, the dehydrogenation reaction being favored at the higher temperatures. The BET surface areas of the sepiolite are 316 m2/g (nitrogen adsorption at — 197°C) and 212 m2/g (ethanol vapor adsorption at 25°C, assuming a molecular cross-sectional area of 24.6 Å2), indicating a possible greater penetration of pores and channels by nitrogen compared with ethanol vapor under these conditions. The pore-size distribution reveals that approximately 55% of the surface area measured by nitrogen adsorption is contributed by micropores.

Nordstrandite was obtained synthetically by precipitation of Al(OH)3 at pH 9.0 to 11.0 in citrate or malate systems with Al: carboxylic acid molar ratios of 10–100 in the absence and in the presence of montmorillonite. Examination by transmission and scanning electron microscopy showed that the nordstrandite had a tabular morphology in the clay-free systems with Al: carboxylic acid ratio >50. Because the inhibiting effect on crystallization of the citrate or malat e anion decreases with increase in pH, the crystal size varied from <2 μm at pH 10 to 5 μm at pH 11. With increasing concentration of citrate or malate, the nordstrandite crystals became more elongated in the c-direction probably due to organic anion occupation of the coordination sites of Al on the edge faces parallel to the c-axis. Irregular growth along the c-axis was probably due to steric hindrance by the organic ligands distorting the arrangement of the unit layers of nordstrandite.

The catalytic effect of montmorillonite on the formation of nordstrandite was confirmed. Nordstrandite synthesized in the presence of montmoriUonite at pH 9.0 presented an ill-defined ovoidal outline (0.2–0.5 μm), some showing shafts of bayerite growing from the center. At higher pH, where conditions for crystalline growth were again more favorable, nordstrandite crystals nucleated on the montmorillonite surfaces and condensed in clusters of weak face-to-face associations of plates.

The solubility of four different gibbsite preparations was measured, including two commercial hydrated aluminas produced by Alcoa, a Fisher ACS-grade Al(OH)3, and a laboratory preparation. The Alcoa samples and the laboratory-prepared sample had been studied previously by other investigators but without using a long-term acid treatment. Scanning electron microscopy showed globular surface material that was removed by a 14-day, 0.1 M HCl treatment. Solubility was determined at pH 4 from both over-and undersaturation with continuous agitation for 228 days. The acid treatment correlated with a decrease in log*Kso[*KSO = (Al3+)/(H+)3] of about 0.5 units. The mean solubility of the three acid-treated commercial gibbsite samples was log*Kso = 7.55 ± 0.055 (*Kso = 3.5 × 107). The solubility of the acid-treated laboratory preparation was log*Kso = 7.86 (*Kso = 7.2 × 107). The greater solubility of the laboratory-prepared gibbsite is attributed to a greater concentration of structural defects in the crystals.

The diffusion of exchanged Yb, Ho, and Eu from interlayer positions in montmorillonite was studied using infrared spectroscopy (IR), X-ray powder diffraction, and cation-exchange measurements. Dehydration of exchanged montmorillonite between 100° and 280°C caused the ions to diffuse into the hexagonal rings of surface oxygens. Subsequent migration into vacant octahedral sites was small regardless of the radius of the cation. Considerable ion fixation in excess of the cation-exchange capacity of the clay was observed at 20°C in both water and a 1:1 water:95% ethanol mixture. Evidence for hydrolysis as a possible mechanism for cation fixation was obtained by observing frequency shifts for deuterated hydroxyl groups using IR spectroscopy. A major IR band centered at 2680 cm−1 was observed for all three lanthanide-exchanged montmorillonites studied and assigned to the OH-stretching frequency of a lanthanide hydroxide. This band intensified on heating at 300°C for 1 hr. An IR band between 690 and 710 cm−1 also was observed for all three lanthanide-exchanged montmorillonites and was assigned to a lanthanide-hydroxyl deformation mode. No hydrolysis was observed for Na-montmorillonite, as expected from the very low hydration energy of Na+.

The Upper Pliocene sediments near Lebrija in southern Spain contain commercial deposits of palygorskite and sepiolite. These sediments of continental origin consist chiefly of carbonate, marl, and clay resting on marine Pliocene quartzose sand. The lowest unit, the “Marly-Calcareous Bed,” consists of sepiolite-rich marl associated with concretions and irregular layers of chert, <0.5 m thick, and local diatomite layers, as well as limestone, sandy limestone, marl, and clayey sandstones. This unit has a maximum thickness of 30 m and contains three clay-mineral suites as follows: (1) bottom—sepiolite ± palygorskite; (2) center—sepiolite and palygorskite ± illite; (3) top—palygorskite and illite, ± sepiolite and smectite. Sepiolite decreases and palygorskite and illite increase toward the top, reflecting the composition of detrital material supplied to the basin. Beds 0.5–1 m thick locally and containing 50 to 60% sepiolite have been called “Tierra del Vino” (wine earth) because the material formerly was used to clarify and purify wine. The sepiolite-rich beds are as much as 15 m thick in the eastern part of the area. The upper unit is called the “Palygorskite Bed” because certain layers, 0.3 to 3 m thick, contain 35 to 75% palygorskite. The palygorskite-rich layers are interbedded with limestone and marl, and the entire unit is 15 m thick. The total resource of palygorskite is estimated at about 9 million tonnes.

The sediments are believed to have been deposited in a brackish, lacustrine environment. Originally, tectonic stability and an arid climate favored the formation of sepiolite at about pH 8. Later, after significant weathering of the source rocks, detrital illite was transformed to palygorskite in the Mg- and Si-rich waters. Here, palygorskite was also precipitated directly.

Imogolites in which a part or all of Si was substituted with Ge were synthesized from solutions containing aluminum ion and silicic and/or germanic acid. The products were similar to natural imogolite in their tubular morphology, electron diffraction patterns, and differential thermal analysis curves. However, the external diameter of the tube increased with increasing Ge substitution up to about 33 Å, and associated changes appeared in the X-ray powder diffraction patterns, suggesting that the substitution of Ge for Si caused a decrease in the curvature of the gibbsite sheet with which SiO- or GeO-tetrahedra are associated. Infrared absorption bands at 995 and 930 cm−1 in imogolite disappeared and new bands appeared at 910 and 810 cm−1 on substitution of Ge for Si, whereas those in the region between 700 and 300 cm−1 remained unchanged or changed little. The former two bands were assigned to Si-O vibrations and the latter bands to Al-O vibrations.

An iron-rich chlorite, ripidolite, was oxidized by air-heating at 480°C, i.e., below the dehydroxylation temperature and subsequently reduced in hydrogen at the same temperature. On the basis of chemical, differential thermal, infrared, Mössbauer, and X-ray powder diffraction analyses, Fe(II) seems to be present only in the 2:1 layer of the original chlorite in a type of site similar to that of Fe(II) in biotite, with OH in cis-positions. These data also suggest that octahedral Al and Fe(III) are located in the hydroxide sheet of the original chlorite. The structural changes of the mineral due to the oxidation and the subsequent reduction appear limited to minor structural rearrangements and, perhaps, to the introduction of OH in both cis- and trans-positions. The results of the investigation are in agreement with a reaction of the form: [Fe(II)OH]+ ⇋ [Fe(III)O]+ + H(H+ + e−).

The nature of organo-phosphate and carboxylate bonding in aqueous suspensions of noncrystalline alumina, boehmite, and gibbsite has been studied using the anionic nitroxide spin probes 3-carboxy-2,2,5,5-tetramethyl-1-pyrrolidinyloxyl and 4-hydroxy-2,2,6,6-tetramethyl-piperidinooxyl dihydrogen phosphate. Analysis of the electron spin resonance (ESR) spectra of these molecules revealed that adsorption of both molecules occurred rapidly on the high surface area alumina and boehmite, whereas only the organophosphate adsorbed on gibbsite. A loss in rotational motion of the molecules accompanied adsorption, with the greater degree of motional restriction observed for the carboxylate attributed to steric restrictions to rotation about the surface-bound C-COO− bond axis. The ease of displacement of adsorbed carboxylate from surface binding sites by weakly adsorbing anions (Cl−, ClO4−) compared to organophosphate suggests that the carboxylate adsorbed by ligand exchange of a single surface OH, whereas the organophosphate probably formed a bidentate bond. The carboxylate bound on noncrystalline alumina showed evidence of nonspecific electrostatic adsorption in addition to ligand exchange of surface OH. This weak bonding was indicated by a moderate loss in rotational motion and ease of exchangeability.

The ferrous iron content of two vermiculitized biotites decreased by treatment with 0.1 N salts of copper at 70°C from 9.1–14% to 1.8–2.6%. Presumably, interlayer copper ions acted as a catalyst (here, an electron carrier) for the oxidation of iron by dissolved oxygen. The oxidized iron was ejected from the structure and formed crystalline iron minerals, such as hematite and goethite. Weight loss determinations, chemical, and X-ray powder diffraction data suggest that Cu(II) ions were polymerized to hydroxy-hydrous compounds in the interlayer space. Poor exchangeability of the resultant complex is attributed to the formation of strong electrostatic attractions between OH groups of the interlayer complexes and silicate oxygens.

A model describing the electric double layers in clay-electrolyte systems containing particles with different surface charge densities was developed and used to calculate the film thickness of water present in a clay paste. The average water film thicknesses (~18 Å) calculated by considering the clay to contain 9 groups of particles of different charge densities did not differ from those calculated by assuming one average charge density; provided the minimum potential between particles remained constant. These values, however, were higher than those obtained from gravimetric water determinations by about 30%. The overestimation of the average thickness of the water films by the theoretical model is most likely due to the assumption of a complete parallel arrangement of particles in the paste and the validity of the Gouy theory for double layers on clays.

Electron spin resonance (ESR) analysis of Cu2+-hectorite suspensions provides evidence for the surface-induced hydrolysis of Cu(H2O)62+ at low pH and surface-inhibited hydrolysis (or precipitation) at high pH. Dehydration of the hectorite by heating to 110°C appears to promote hydrolysis in high pH clays further. Heating to even higher temperatures removes ligand water from Cu2+, allowing the metal ion to coordinate with silicate oxygen atoms. The planar Cu(H2O)42+ ion predominates in the interlamellar regions of hectorite that has been air dried or heated to temperatures of 110°C or lower, but more extreme thermal treatment changes the apparent orientation of the Cu2+-ligand axes as some or all of the four water ligands are removed, A loss in ESR signal intensity upon heating Cu2+-hectorite above 110°C is evidence for lowered symmetry of the dehydrated, surface-coordinated Cu2+ ion.

The acid-catalyzed reaction between methanol and isobutene to give methyl-t-butyl ether may be carried out using a cation-exchanged smectite as the catalyst. In 1,4-dioxan solvent at 60°C smectites exchanged with Al3+, Fe3+, or Cr3+ give yields of ∼60% after 4 hr, whereas smectites exchanged with Cu2+, Pb2+, Ni2+, Co2+, Ca2+, and Na+ give less than ∼8% yield. The reaction is efficient only when certain solvents are used, e.g., with Al3+-smectite the yield is ∼5% when using 1,2-dimethoxyethane, diethyleneglycol diethylether, n-pentane, tetrahydropyran, N-methylmorpholine, or tetrahydrofuran solvents compared with ∼60% using 1,4-dioxan solvent (4 hr). Moreover, the effective solvents depend somewhat on the clay interlayer cation. The use of tetrahydrofuran and tetrahydropyran gives ∼35% yields at 60°C (4 hr) with Fe3+- or Cr3+-smectites but ∼4% yield with Al3+-smectite.

Ferruginous clay partings in limestones of the marine, largely evaporitic, Upper Triassic Mohila Formation (Makhtesh Ramon, Israel) contain hexagonal plates and cube-like bodies up to one millimeter across. Analyses by electron microscopy, infrared and Mössbauer spectroscopy, and X-ray powder diffraction indicate that the matrix contains Fe-rich anhedral kaolinite, up to 100 μm in size; the hexagonal plates are composed of euhedral, Fe-free kaolinite covered with well-developed acicular goethite and platy hematite (0.5 to 2 μm in size), and the cubes consist of fine-grained goethite with minor amounts of kaolinite. The anhedral kaolinite appears to be detrital, the hexagonal plates to be authigenic, and the cubes to be pseudomorphs after pyrite. Oxidation appears to have altered Fe-rich kaolinite and pyrite to Fe-free kaolinite, goethite, and hematite and was accompanied by recrystallization and pseudomorphic replacement. The alteration process was slow and was probably induced by a small increase in pH and in the Al/Fe ratio, resulting from oxidation of reduced components (pyrite, ferrous carbonate, organic matter) in a semiclosed, sediment-mud system. Overlying kaolinitic flint clay deposits may be the final product of a similar process.

Clay/electrolyte systems are best characterized using a new variable, notional interfacial content (NIC). The NIC approach emphasizes that any division of the total amount of a species present in a clay/electrolyte system into that part which ‘belongs’ to the clay and that part which ‘belongs’ to solution is necessarily arbitrary. It carries out this division by choosing one of the species as a reference species and defining it as being completely in a notional bulk solution which had the same composition, but not extent, as the real bulk solution. The NIC of each of the other species present, that is that part of their total amount not in the notional bulk solution, therefore represents the amounts of those species ‘belonging’ to the clay.

The NIC concept is universal and hence encompasses several other, older terms. For example, by choosing different reference species, the variables hitherto called ‘water adsorption’ and ‘negative adsorption’ (which have been used to describe the same phenomenon) may be obtained. Similarly, certain earlier definitions of exchangeable and adsorbed cations (some being pragmatic are not included) as well as that of ion surface excesses may be accounted for. The NIC approach thus provides a rationalization of several earlier terms which are, in fact, plagued by a multiplicity of definition which makes their use very complicated.