A specimen of Kenya vermiculite contained no mica or chlorite layers either as separate phases or as components of an interstratifled structure. Dehydroxylation occurred in two stages, at 550° and 850°C, with approximately equal amounts of hydroxyl liberated in each stage. Al-saturated Kenya vermiculite showed low temperature dehydration characteristics similar to those of the natural Mg-saturated specimen, but the DTA, TGA and oscillating-heating X-ray diffraction patterns showed that the three stage dehydration process was not as clear-cut with the Al-saturated specimen.

As with montmorillonite, when small amounts of aluminum were precipitated by the addition of Ca(OH)2 in the presence of vermiculite, the Al(OH)x, was taken up and held indefinitely by the clay, the ion product (Al)(OH)3 in solution was maintained at 10-33∙0 and no gibbsite was formed with time. With large amounts, 800 and 1600 me Al(OH)x per 100g vermiculite, the hydroxide was held initially in the interlayer space, but gibbsite was eventually formed as (Al)(OH)3 approached the solubility product of gibbsite. Unlike montmorillonite, the vermiculite specimens retained an appreciable amount of the interlayer hydroxide and did not regain the original C.E.C. values as gibbsite was formed.

Al-vermiculite which was repeatedly suspended in AlCl3 with (Al)(OH)3 maintained at a value less than 10-33∙8 liberated 435 me Mg, took up 208 me Al as an interlayer hydroxide and caused a reduction in C.E.C. from 130 to 28 me per 100g clay. With vermiculite an appreciable amount of the interlayer Al(OH)x was stable with respect to gibbsite whereas with montmorillonite it was not.

The hypothesis tested was that macroscopic swelling of montmorillonitic clays is reduced by the presence of interlayer minerals. Fine and coarse clay fractions of Camargo and Panther Greek bentonite samples were artificially interlayered by reaction of Al2(SO4)3 and NaOH in 0∙5% suspensions of the clays. All four clay fractions reacted similarly to artificial interlayering. At an Al:clay ratio of 16 meq Al/g clay the CEC was completely lost, surface area was reduced and X-ray basal spacings were altered. No macroscopic swelling occurred in samples treated with 16 meq of Al/g of clay. At smaller concentrations of hydroxy-aluminum 8 and 2 meq Al/g clay, the clay properties were less drastically altered. Extraction of interlayered clays with Na citrate restored the original C.E.C., surface area, and basal spacings of all samples and resulted in some slight enhancement of C.E.C. and surface areas of the coarse fractions. Treatment with hot Na citrate resulted in an increase in swelling ability but only slight increases in C.E.C. and surface area. Evidence presented supports the hypothesis that macroscopic swelling of montmorillonitic clays is greatly reduced by interlayer materials. Reduced swelling due to interlayering occurs even when other clay properties may be slightly different from those of nontreated samples. Indications are that interlayer material occurs naturally in the clays studied and this may apply to other bentonite deposits.

X-ray, chemical, and genetic characteristics of a chloritized montmorillonite mineral species, found in The Río Chiflón Formation (La Torre, La Rioja, Argentina) are described. The mineral is associated with illite, montmorillonite, and chlorite, plus the non-clay associates analcite and hematite. The Río Chiflón Formation is of Upper Triassic age, and consists of red sandstones and siltstones representing poorly developed fluviatile cyclothems.

Studies of the Li+, K+ and Mg2+ varieties of the clay, and solvation with glycerol or ethylene glycol have shown that the mineral is a smectite which behaves peculiarly with heating. Between 200° and 600°C the mineral collapses gradually from a basal spacing of 13–10 Å. Regular expansibility with ethylene glycol and glycerol is completely preserved (in the Li+ and K+ clays) up to a preheating of 400°C and partially preserved up to 600°C. This behavior has been interpreted as caused by the presence of interlayer contaminants of a hydroxy-cation type. The interlayer cations may be Al, Mg, and Fe, (in this order).

The environment of the Río Chiflón Formation has been evaluated in the light of well-known occurrences of intergradient clays in soils, and the presence of analcite and hematite. It is proposed that chloritization has taken place during a soil weathering process, under alkaline conditions with great availability of sodium during alternating dry-humid seasonal climates (oxidation conditions). The stability of the interlayer developed under these circumstances was increased during long burial and diagenesis.

A method is described for preparing electron-transparent sections of fine-grained argillaceous rocks suitable for making transmission micrographs. A sediment and a slate are used as examples. Sections perpendicular to bedding or cleavage yield diffraction patterns with clearly defined 00l reflections. These allow immediate identification of 7, 10 and 14 Å structures. The combination of detailed textural information with structural identification of individual phyllosilicate particles affords a powerful method for the investigation of late diagenetic and early metamorphic changes in sediments.

The i.r. spectrum of K depleted biotites (structural OH stretching range) has been studied with monocrystals equilibrated at various water contents. Prior to spectroscopic measurements, the samples were submitted to deuteration treatments which displaced the hydration water spectrum to the OD region and made it possible to observe the behaviour of the structural hydroxyls without interference from hydration water.

In these conditions it was shown that the high frequency absorption of K depleted biotites (N + I bands) is the sum of two absorptions: the first corresponds to the initial mica spectrum, the second corresponds to the hydrated phase in which component bands (according to Vedder and Wilkins) are shifted by 36 cm-1 towards low frequencies.

Simultaneously it was shown that low frequency bands (V bands) decreased in intensity. This unexpected observation has been explained by a partial deuteration of structural OH, which takes place during the preliminary contacts of the samples with D2O vapour.

The b-dimensions of the unit cells of six different Na-saturated montmorillonites were determined by X-ray diffraction at water contents ranging from 0 to 20 g per g of montmorillonite. In every case, the b-dimension increased progressively with water content from its initial value, which was characteristic of each dry montmorillonite, to a final value of ~9•0Å, which was common to all montmorillonites. The latter value was reached when the water contents of the respective montmorillonites were equal to those at maximal swelling. When these water contents were plotted against the corresponding changes in b-dimension, a straight line that passed through the origin was obtained.

Different structure-sensitive properties of the water in montmorillonite-water systems (i.e. the partial specific volume, the amount remaining unfrozen at −5°C and the activation energy required for ions to move through it) were available, as functions of the species of exchangeable cation, from previous studies. Relevant b-dimensions were determined in the present study. It was found that all of these water properties were correlated with the b-dimension of the associated montmorillonite.

Our results indicate that epitaxy exists between the crystal lattices of montmorillonite and adsorbed water and that these lattices undergo mutual adjustment with each increment of water. The resulting loss of free energy causes water adsorption, i.e. swelling, to occur spontaneously. Swelling stops when no further adjustment takes place. This does not happen until the adsorbed water is several hundred angstroms thick and has achieved a preferred configuration.

Artificial alteration of thirty-five trioctahedral and one dioctahedral micas by solutions varying in strength from 0·001 to 1·00 molal magnesium sulfate was found to approximate a normal exchange reaction after surface effects are eliminated. The equilibrium constants for the reaction:

$1/2M{g}^{2+}+K-mica=M{g}_{1/2}-mica+K^{+}\left(vermiculite\right)$$1/2 {Mg^{2+}}+K-mica=Mg_{1/2}-mica+K^+(vermiculite)$

range from 0·0001 to 0·0028 and average 0·0010 in value. X-ray diffraction study reveals that iron-rich micas tend to develop a 1:1 mixed-layer biotite-vermiculite structure in weak magnesium sulfate solutions whereas magnesium-rich biotite and phlogopite alter to vermiculite. Mica composition also influences the degree of alteration of mica to vermiculite. High fluorine and octahedral multivalent cation contents tend to retard the reaction whereas high magnesium content and perhaps high calcium contents tend to favor the alteration. The equilibrium constant data indicate that vermiculite and hydrobiotite are more stable than trioctahedral micas in most weathering environments.

Interlayer potassium was removed from a wide range of mice minerals by treatment with dilute solutions of n-dodecylammonium chloride. On subsequent reaction with the appropriate metal methoxide, the Na+ or Ca2+ form of the altered mica was produced. The properties of the original and sodium saturated samples were compared to assess the changes in water content, charge density and chemical composition (particularly ferrous iron) which resulted from the displacement of potassium.

Calculation of structural formulae was not attempted since it was established that for the altered samples accurate distinction could not be made between adsorbed and structural water. Changes in layer charge are thus expressed on the basis of samples ignited to 1000°C. Charge losses of up to 76 me/100 g were recorded for biotites, smaller charges were noted for phlogopites and no loss was observed for the two muscovites examined.

Oxidation of ferrous iron occurred for all trioctahedral samples, the greatest oxidation occurring in the samples initially high in iron. There was no consistent relationship between the amount of iron oxidized and the loss of layer charge.

All altered samples contained greater amounts of H2O+ than the original materials suggesting that protonation of structural oxygens occurred during, or following, removal of potassium.

It is concluded that the alteration of micas by reaction with organic cations is a complex process, differing in detail for different micas, and following a similar path to alteration by reaction with inorganic salts.

Shaking of water-soluble fulvic acid with Cu2+-montmorillonite at pH 2·5 increased the interlamellar spacing from 10·0 to 15·1 A. The spacings were measured at ≈ 0% relative humidity. The extent of interlayer adsorption decreased with increase in pH. Differential thermal analysis and thermogravimetric examinations showed that in addition to interlayer adsorption, fulvic acid was also retained on external clay surfaces. The FA was held so tightly by the Cu2+-clay that > 3/4 of the total amount adsorbed, including degradation products formed from it, resisted decomposition even when heated to 1000°C. I.R. spectra showed that β-diketone groups in fulvic acid reacted with Cu2+ in or on the clay to form acetylacetonate-type chelates. Indications were obtained that the mechanism postulated for the FA-Cu2+-clay interaction may also apply to reactions between FA and montmorillonite saturated with other di- and trivalent metal ions. Reactions of FA in aqueous solutions with metal ions in the presence of clays differ from those in the absence of clay. Montmorillonite appears to affect the conformation of the fulvic acid polymer in a way that favours reactions between C=O groups and metal ions, a type of reaction that has so far not been observed in aqueous solutions in the absence of clay.

Organic acids in the 0·01M concentration range representing amino-, aliphatic, and aromatic types present in humus dissolve 70–85 ppm Al from Arkansas bauxite at room temperature, whereas 0-03 ppm is dissolved in water. The species of Al in aqueous solution, calculated from stability data, range from Al3+ at pH 3 and lower, through Al2(OH)24+ at a maximum concentration at pH 4·5, Al(OH)2+ at a maximum at pH 4·7, Al(OH)2+ at a maximum at pH 60, to Al(OH)4- at pH 8·5 and higher. In salicylic acid an Al-Sal+ complex occurs between pH 1·5 and 8·5, and is at a maximum at pH 4·2. Solubility of Al obviously is pH dependent; also because of the vulnerability of organic acids to oxidation, the solubility and transport of Al is indirectly Eh dependent. Anions that combine with Al include OH- to form bauxite, PO43- to form lateritic phosphate such as the Bone Valley Formation, Fla., and SiO44- to form allophane or kaolin as noted in the kaolin synthesis by Linares and Huartes. Spongelike, pisolitic or oolitic structures, and mineral veins in bauxites, lateritic phosphates, and some flint clays attest to mobilization of Al in solution. Lignites and humus zones associated with latentes are a logical geologic source of these complexing organic solvents. Although Al is inherently mobile, such commonly available precipitating anions render Al relatively immobile.

A study of the thermal transformation of alkylammonium cations adsorbed on the surface of a montmorillonite in various conditions of hydration has been carried out. The experimental conditions were: inert atmosphere, temperatures below 250°C and time periods up to 270 days. The reactions observed are mainly transalkylations, for which a mechanism of acid catalysis is proposed. A high degree of dissociation of the water remaining on the surface of the clay is required and is attained for an optimal, and rather low, water content of the clay.

The form under which ethylenediamine (EDA) is adsorbed from aqueous solution by hydrogen- and ethylenediammonium-montmorillonite was studied as a function of the amount of amine present in the system.

EDA added to the acid clay in quantities lower than or equal to the cation exchange capacity (C.E.C.) was exclusively adsorbed as ethylenediammonium (EDAH22+) ion. On further addition of diamine the pH of the suspension rose to alkaline values and the monoprotonated species (EDAH+) was the main charge balancing cation.

Evaporating at room temperature “EDA-H-montmorillonite-H2O” or “EDA-EDAH2-mont- morillonite-H2O” systems containing 300 me EDA/100 g clay did not cause loss of nitrogen, but degassing under high vacuum (10−5 mm Hg) did. Nevertheless, excess EDA molecules with respect to the C.E.C. were retained on the clay surface, at the expense of water molecules, through strong asymmetrical hydrogen bonds between their NH2 groups and the NH3+ groups of EDAH+ ions. On heating up to 160°C under vacuum the nitrogen content decreased further, but still remained at a level significantly higher than the C.E.C. value, all NH3+ groups remaining involved in strong hydrogen bonding. It is suggested that a “condensation” process takes place, implying evolution of EDA molecules and giving rise to “polymeric” associations between protonated and unprotonated diamine.

Washing the clay suspensions with distilled water did not completely remove excess EDA either, as a consequence of the equilibrium existing between the ionic species in solution (EDAH22+ and EDAH+) and on the clay surface. It seems that these species were preferentially adsorbed as “trimeric” associations in which two out of four NH3+ groups are hydrogen bonded to NH2 groups.

After heating at 200°C, nitrogen retained on the clay surface was mainly in the form of NH4+ ions. Ammonium formation was enhanced by the presence of excess EDA and was considerably faster than in montmorillonite systems containing EDA coordinated to Cu2+ ions.

A number of variable charge montmorillonites were prepared. One portion of each sample was extracted with ammonium chloride, while a second portion was first saturated with calcium chloride, washed, and then extracted with ammonium chloride. In both cases, the number of cations displaced by ammonium chloride was determined. The number of calcium ions displaced from Ca-saturated samples was higher than the sum of the number of lithium and calcium ions displaced from Li, Ca-mixed samples. The differences, increasing towards Li-rich end of the series are assumed to be due to protons liberated from the reaction of lithium ions with either structural hydroxyl groups or residual water molecules, as has been shown by other investigators. Supplementary X-ray and i.r. data lend support to this idea.

Two mutually exclusive views exist concerning the relative stabilities of gibbsite and boehmite in soils. These are examined in terms of experimental and thermodynamic evidence and it is shown that all three possible divariant assemblages of two phases that can exist between gibbsite, beohmite and H2O, may do so at 25°C and 1 atmosphere total pressure depending on the status of H2O. It is further shown that the conditions of H2O chemical potential needed to stabilize boehmite + H2O relative to gibbsite + H2O or gibbsite + boehmite, are unlikely to occur in natural waters in the zone of weathering.

Kaolinites, catalytically active for the polymerization of styrene, can be deactivated by treatment with 1N aqueous sodium chloride. Subsequent washing of the sodium kaolinite results in a facile hydrolysis yielding an active hydronium/aluminum kaolinite in which the exchangeable cations act as surface Br0onsted acid initiation sites.