Peptization Resistance of Selected Samples of Kaolinitic, Montmorillonitic, and Illitic Clay Materials
TL;DR: In this article, the peptization resistance of selected samples of clay mineralogical materials toward alkaline dispersing agents was discussed from a quantitative point of view. But, the authors did not consider the effect of the type of clay types on the performance of these agents.
Abstract: Variations in the peptization resistance of selected samples of clay mineralogical materials toward alkaline dispersing agents are discussed from a quantitative point of view. Clay samples, collected from South Carolina, Wyoming, Illinois, New Mexico, South Wales, Great Britain and Cornwall, England were subjected to the action of solutions of Calgon (“sodium hexametaphosphate”), ammonia, sodium hydroxide, sodium carbonate, sodium pyrophosphate, and “sodium lignosulfonate.” The resulting apparent dispersion, in each case, was expressed as a function of the employed concentration and chemical nature of the dispersing agent. Pipette analysis and Oden balance techniques at constant temperature were used to measure the degree of dispersion. All clay samples employed were identified as to type by X-ray diffraction, chemical analysis, thermal analysis, and electron microscopy. All samples examined exhibited a maximum in apparent dispersion (suspension stability) at a specific concentration of dispersing agent. Such maximum was followed by a sudden decrease in apparent dispersion, i.e., flocculation, at higher concentrations of dispersing agent. Concentrations of dispersing agent were varied in steps of one part per thousand. One hundred and twenty experimental runs were made on each type of material examined. Differences in the degree of apparent dispersion attained by use of different dispersing agents were expressed in terms of a threshold concentration which altered “equivalent diameter” one tenth of a phi unit. Among dispersing agents employed, “sodium lignosulfonate” was found to be least selective of clay mineral type in its peptizing action. An equation for the calculation of a “peptization resistance factor” is presented. Results obtained by application of this equation indicate that differences in the response of the same clay material to different alkaline dispersing agents may be attributed, in part, to differences in degree of peptization achieved by “threshold mechanisms” of peptization and by “adjustment mechanisms” along the peptization path. Such equation may have future value in the differentiation of marine and terrestrial clay deposits.
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TL;DR: In this article, the authors used pipette analysis, Oden balance techniques, Kelley-Wiegner manometer methods, and spectrophotometric methods, using artificial sea-water and filtered Gulf of Mexico water.
Abstract: Differential settling velocities of individual clay mineral types and clay mineral mixtures in quiet saline water are reported for ocean water chlorinity range 0–18‰, brackish water ionic strength range 0.0–0.686 moles-(unit charge)2/kg, temperature range 6–26°C, clay mineral concentration range 0.01–3.6 g/1., and pH range 6.5–9.8. The materials employed included natural deposit clay minerals and clay minerals extracted from marine sedimentary matter and from terrestrial soils. Settling velocities at 26°C for illitic and kaolinitic materials reached values of 15.8 and 11.8 m/day, respectively, at an ocean water chlorinity of 18‰ and exhibited little dependence upon chlorinity above a chlorinity of 2‰. Settling velocities for montmorillonites were found to be functions of chlorinity over the entire chlorinity range 0–18‰ and to increase exponentially to a limit of 1.3 m/day at 26°C. The settling velocities were determined by pipette analysis, Oden balance techniques, Kelley-Wiegner manometer methods, and spectrophotometric methods, using artificial sea-water and filtered Gulf of Mexico water. In quiet brackish water, variations in ionic ratio composition alter the settling rates of illites and kaolinites less than 15 percent from such rates in ocean water, at constant, brackish water, ionic strength of 14 or greater. In contrast, montmorillonitic settling rates in such water varied by 40 percent or more from ocean water rates, at constant ionic strength unless the magnesium—potassium or magnesiun-strontium ionic ratios of the brackish water were kept constant. These induced variations were not sufficient in magnitude, however, to change the general relative order of settling rates for the clay minerals. Decreasing temperatures over the range 26°-6°C decreased settling rates (of all clay types) progressively up to about 40 percent in accordance with temperature-induced changes in the viscosity and density of the saline water medium. The influences of fifty-seven different organic compounds or materials (carbohydrates and proteins dissolved or dispersed in the water) upon the settling velocities are cited. In general, carbohydrates increased the settling rates of montmorillonitic materials as much as 25 percent, and proteins decreased such rates a maximum of 1–5 percent. Kaolinitic materials suffered a 30–40 percent decrease in settling velocity under the influence of some proteins. So-called “humic acids,” derived from quinone and soil fractions, decreased kaolinitic and montmorillonitic settling rates to lesser extent. No significant alterations of illitic settling rates by organic materials were noted. Chlorite-montmorillonites were found to settle slightly faster than sodium and calcium montmorillonites. Potassium-saturated montmorillonites settled from two to three times as rapidly as the reference montmorillonites. Chlorite settling rates, of magnitude comparable to rates found for kaolinites, and vermiculite settling rates, comparable at higher chlorinities to illite settling rates, are also reported. The apparent interaction of illite and montmorillonite to form illitic-montmorillonitic settling entities in some clay mineral mixtures was noted. Other mixtures, exposed to artificial sea-water for 3–6 years, exhibited a tendency to transport 5–20 percent kaolinite within a developed illitic-chloritic mix, when reagitated. Evidence is also presented to support the argument that clay minerals do not settle in single solid particulate units in saline waters. The effective settling unit, after flocculation, is described as a coacervate, i.e. as a thermodynamically reversible assembly of solid clay particles or strands within a settling solid-rich liquid unit phase. Settling rate increases are thereby not a consequence of any irreversible formation of larger solid particles or solid aggregates by coalescence of fresh water particles at or beyond the fresh-water-saline-water interface. Differential transport of clay minerals by the turbulent flow of saline water in a pipe is quantitatively described. Flow rates of about 6 miles/hr were required to eliminate differential transport of the clay minerals. Clay mineral concentrations over the range 0.01–15.0 g/l. were considered. Chemical data, electron and x-ray diffraction data, base exchange data, and electron micrographs support the settling velocity information.
190 citations
TL;DR: In this article, it was shown that the detrital basic lattice is not altered to a measurable extent in Recent marine sediments. But, it remains to be proved whether this is caused by chemical modification of the basic lattices with burial, or if the Detrital clay lattice has the inherent ability to contract, without chemical rearrangement, when buried to a sufficient depth.
Abstract: Studies of the Recent indicate that, at the most, somewhat less than half the clay minerals are altered to any extent in a marine environment. Probably most of this alteration is in the form of cation adsorption or reconstitution of slightly weathered illites and chlorites to their original form. There appears to be little if any evidence that the detrital basic lattice is being altered to a measurable extent in Recent marine sediments. In the near-shore environments there is usually a coincidence of clay mineral suites and environments. A major change in the clay mineral composition of sedimentary rock occurs within the Mississippian. Illite is the dominant clay mineral of the pre-Upper Mississippian sediments. Post-Lower Mississippian clay suites are more variable in composition; illite becomes less abundant and montmorillonite and kaolinite more abundant. This change is best related to a change in regional tectonics. The clay minerals seem to have no preferred lithologie associations, although owing to epigenetie alterations porous sandstones commonly have different clay mineral suites from those of adjacent shales and carbonate rocks. In many instances clay mineral facies coincide with environmental facies. As the clay mineral criteria for distinguishing any given type environment are extremely variable, it is thought that segregation of clay mineral suites by sorting is usually more effective than by diagenesis. Expanded clay minerals appear to be partially contracted by the time they have been buried to 10,000–15,000 ft. It remains to be proved whether this is caused by chemical modification of the basic lattice with burial or if the detrital clay lattice has the inherent ability to contract, without chemical rearrangement, when buried to a sufficient depth.
85 citations
TL;DR: In this paper, it is suggested that K+ is adsorbed preferentially to Mg2+ by clays when they have been buried to a depth that is greater than that of the K+ equivalence level.
Abstract: Further x-ray and chemical work on suspended sediment samples and cored samples from the James River and its estuary support earlier proposals by the author. A chlorite-like clay is forming from weathered illite through a mixed-layer illite—vermiculite-chlorite stage, and some illite is seemingly regenerated to a better illite by potassium fixation. Chemical analyses of interstitial water, hydrochloric acid-leachate, and fused samples offer explanations regarding the chemical changes occurring in clays as composition of the environment changes. Magnesium is adsorbed by clays to a far greater degree than potassium in the marine and brackish environment. The variance between clays found in Recent and ancient sediments is related to and explained by the concept of the equivalence level. It is suggested that K+ is adsorbed preferentially to Mg2+ by clays when they have been buried to a depth that is greater than that of the Mg2+ — K+ — equivalence level; above this level Mg2+ is preferentially adsorbed by the clays. The trifold nature of clay minerals in terms of their origin and distribution is briefly discussed.
72 citations
TL;DR: The history of St. Joseph Bay, on the west coast of Florida, begins with the last rise in sea level about 5,000 years ago as discussed by the authors, and the formation of an extensive cuspate spit has formed a basin which is now in the process of being filled by detrital sands delivered via longshore drift from the eastern Apalachicola River.
Abstract: SUMMARY
The history of St. Joseph Bay, on the west coast of Florida, begins with the last rise in sea level about 5,000 years ago. The formation of an extensive cuspate spit has formed a basin which is now in the process of being filled by detrital sands delivered via longshore drift from the eastern Apalachicola River. Prior to or during early stages of spit development, a wedge of fine material was deposited over the old terrace surface from an old distributary of the Apalachicola. Present sedimentation has as yet failed to obscure portions of this older surface within the lagoon.
Clean quartz sand and biological carbonates comprise the bulk of the present sediment contribution. The typical East Gulf “kyanite-staurolite” heavy mineral suite is present, as is the kaolinite-montmorillonite-illite clay mineral suite common to this coast.
Sediments in this area have an average organic content of about 1.4%. A high organic carbon/organic nitrogen average of 15.4 has resulted from the accumulation of highly carbonaceo us plant debris under the restrictive environment of the lagoon.
29 citations
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TL;DR: In this paper, the problem of terminology in geology has been discussed and the need for greater uniformity of usage and hence much confusion has arisen due to the indiscriminate use of the terms both in the old and new senses.
Abstract: In no other science does the problem of terminology present so many difficulties as in geology. With the growth of knowledge in any field of investigation, men devise new terms or redefine old ones in the attempt to convey more precise and definite ideas. In all the branches of science much confusion has followed the redefinition of old terms because of the indiscriminate use of the terms both in the old and the new senses. But in geology, difficulties of this kind are peculiarly great. Because geology is a field science and has followed in the footsteps of exploration, it has acquired terms from all parts of the world. Many of the names for the less common special features have come from the dialect or colloquial speech of that part of the world where they are best developed. With the use of these terms of geologists of other regions, much irregularity of usage and hence much confusion has arisen. Since '917, the writer had been engaged in the study of abrasion and shaping of cobbles and pebbles by the action of running water. In the course of this study the loose usage of cobble, pebble, and related terms (in which his own practice was no exception) has impressed him with the need of greater uniformity of usage and
5,425 citations
01 Jul 2009
TL;DR: In this paper, the reduction to a vacuum correction is considered, which is the only correction that is necessary for a simple pendulum to swing in a vacuum environment, due to the buoyancy of the fluid.
Abstract: T he great importance of the results obtained by means of the pendulum has induced philosophers to devote so much attention to the subject, and to perform the experiments with such a scrupulous regard to accuracy in every particular, that pendulum observations may justly be ranked among those most distinguished by modern exactness. It is unnecessary here to enumerate the different methods which have been employed, and the several corrections which must be made, in order to deduce from the actual observations the result which would correspond to the ideal case of a simple pendulum performing indefinitely small oscillations in vacuum. There is only one of these corrections which bears on the subject of the present paper, namely, the correction usually termed the reduction to a vacuum . On account of the inconvenience and expense attending experiments in a vacuum apparatus, the observations are usually made in air, and it then becomes necessary to apply a small correction, in order to reduce the observed result to what would have been observed had the pendulum been swung in a vacuum. The most obvious effect of the air consists in a diminution of the moving force, and consequent increase in the time of vibration, arising from the buoyancy of the fluid. The correction for buoyancy is easily calculated from the first principles of hydrostatics, and formed for a considerable time the only correction which it was thought necessary to make for reduction to a vacuum.
2,016 citations
Book•
01 Jan 1929
TL;DR: The first edition of the Applied Inorganic Analysis (AIA) was published in 1929 by the National Bureau of Standards (NBS) and the second edition appeared in 1953 by the same authors.
Abstract: The 1929 first edition of Applied Inorganic Analysis [1] was a classic of its time, commonly referred to as the " analyst's bible. " Co-authored by two Chief Chemists of the National Bureau of Standards, Gustav Ernst Fredrik Lundell and William Francis Hillebrand, the book represented the authors' comprehensive knowledge and broad practical experience. The 1953 second edition [2] was a thorough revision by Harry Aaron Bright and James Irvin Hoffman, who were Chief of the Analytical Chemistry Section and Assistant Chief of the Chemistry Division, respectively. Both editions of Applied Inorganic Analysis presented critical expositions of the chemical methods of analysis as applied to a broad range of complex matrices including metals, alloys, rocks, minerals, ores, ore concentrates, and glass. Each of the two editions stood alone as the authoritative single-volume reference for inorganic analysis for many years, and even today remains a valuable resource for pre-instrumental, classical methods of chemical analysis. The story of the development of this remarkable book began in 1878 after the young American chemist William Francis Hillebrand completed a course in metallurgy and assaying at the mining academy in Freiberg, Germany. Fully intent on returning to America and impressed with the opportunities for young chemists as assayers, he took this course in order to supplement the training in mineral analysis that he had received from Bunsen, under whom he had earned his Ph.D., magna cum laude, at the University of Heidelberg, in 1875. Upon returning, he failed to find suitable work in the East, so he made his way in 1879 to Leadville, Colorado, where he became the third partner in a small assaying firm. Samuel F. Emmons, an occasional customer who was in charge of the Rocky Mountain Division of the newly formed United States Geological Survey (USGS), offered Hillebrand a job as a chemist. Considering this offer to be the opportunity of a lifetime, he quickly accepted, remaining in the Denver laboratory of USGS until 1885, when he was transferred to the Washington USGS laboratory. During his 28 years at USGS, Hillebrand made more than 400 complete (for that day) analyses of various rock samples [3]. In 1897 Hillebrand wrote a 50-page introduction to USGS Bulletin No. 148 [4] on the methods of analysis of silicate rocks, and this was translated into German and published in Germany in 1899. In 1900 this material was rewritten and enlarged to 114 pages and issued …
677 citations
TL;DR: In this paper, it was shown that the Coulomb attraction between the micelles and the oppositely charged ions in the solution gives an excess of attractive force which must be balanced by the dispersive action of thermal agitation and another repulsive force.
Abstract: The formation of tactoids from thixotropic sols, of Schiller layers from iron‐oxide sols, the separation of tobacco virus solutions and bentonite sols into two liquid layers and the crystallization of proteins are regarded as examples of unipolar coacervation (micelles having like charges) which must involve attractive forces.Kallmann, Willstatter, Freundlich, De Boer, Hamaker, Houwink and others have assumed that the attraction is due to van der Waals forces. They have also analyzed the stability of colloid systems by diagrams giving the potential energy as a function of the distance between micelles. It is now shown that the Coulomb attraction between the micelles and the oppositely charged ions in the solution gives an excess of attractive force which must be balanced by the dispersive action of thermal agitation and another repulsive force. Thus there is no need to assume long range van der Waals forces. The past use of energy diagrams is criticized because it has ignored the effect of the thermal agitation and the attraction of the ``gegenions'' in solution. Instead of potential energy it is proposed that osmotic pressure p be used, which includes these previously neglected factors. A maximum in p as the colloid concentration increases is the condition for the separation into two phases (coacervation).The Debye‐Huckel theory (1st approximation) for the osmotic pressure of electrolytes takes into account both these factors and permits a rough calculation of the conditions under which coacervation occurs. The 2nd approximation, which considers particle size, does not agree as well with experiment as the first approximation. The reasons for this lack of agreement are discussed.The micelles in unipolar coacervates are not in contact, but are separated by relatively large distances (10–5000A). Either a specific repulsive force or a decrease in the Coulomb attraction as the concentration increases (due to decreased charges on micelles) can account for stable coacervates. The assumption of a definite ζ‐potential, rather than a definite charge on the micelles, gives automatically just such a decrease in attraction.The general mathematical theory of coacervation presents great difficulties because the approximations of the Debye‐Huckel theory cannot be used. However, the one‐dimensional problem of the forces acting between parallel colloidal platelets can be solved rigorously in terms of elliptic integrals. For highly charged particles in sufficiently dilute solutions of electrolytes, the pressure p in the liquid between the two plates is given by p = (π/2)D(kT/eb)2 = 8.9×10—7/b2 dynes/cm2 where b is the distance in cm between the plates and D is the dielectric constant (81 for water at T = 293°K). This pressure which tends to force the plates apart is independent of the charge on the plates and on the electrolyte concentration (univalent ions only). Polyvalent ions decrease the force. This force is of the right magnitude to account for the stability of unipolar coacervates. It also furnishes a quantitative explanation of the Jones‐Ray effect, by which low salt concentrations decrease the capillary rise in surface tension experiments with water.Experimental determinations were made of the relaxation times τ for the decay of birefringence in bentonite and vanadium pentoxide sols, after stirring was stopped. In one sample of bentonite, τ varied with the 22nd power of the concentration, while in V2O5 sols the exponent was 1.8. The temperature coefficients of τ were also measured and the activation energies were calculated.A theory of the relaxation of birefringence was developed, according to which the micelles in dilute thixotropic bentonite sols are arranged normally in a cubic lattice (isotropic). Temporary shear in the liquid orients the micelles and produces birefringence although the lattice remains cubic. The experimental data confirm the theory and indicate that the energy barrier opposing reorientation of micelles in a particular bentonite sol varied with the inverse 20th power of the distance between the micelles. With V2O5 this exponent was about 4. Further support for the theory was obtained by experiments which gave ``angles of isocline'' for bentonite particles in a flowing sol that varied from 65° to 78°.In bipolar coacervates (which contain micelles of unlike polarities) the electric fields and the charges on the micelles increase as the micellar concentration increases. When a certain concentration is reached, the field rises to a value so high as to cause increased hydration which holds the micelles apart and gives stability to the coacervate.
634 citations