The basal spacing of a set of smectites, with layer charges between 0.74 and 1.14 electrons per unit cell, have been measured while the smectites were in equilibrium with NaCl solutions having concentrations of 0.25 to 2.5 molal. Except for the most highly charged smectites, an expansion from ~15.5 to ~18.5 Å occurred as the NaCl concentrations were reduced. This expansion (or “crystalline swelling”) corresponds to the transition from two to three sheets of water between the silicate layers. A random interstratification of 15.5 and 18.5 Å structure units was present during the change and gave rise to broad diffraction peaks for the 001 reflections. A balance between cation hydration forces, interlamellar electrostatic forces, and van der Waals forces was apparently the basis of the relationship between surface charge and swelling. The results can be expressed in terms of the relative vapor pressures at which the transitions were half complete; these pressures increased with surface density of charge, and over the range of surface charge studied, the P/P0 values ranged from 0.943 to 0.974.

The prevailing concept that positive-edge to negative-face attraction accounts for the rheological behavior of montmorillonite suspensions at low electrolyte concentration was investigated. In one experiment, Mg2+ released from Na-montmorillonite was measured at several NaCl concentrations; in a second experiment, the viscosity, η, and the extrapolated shear stress, θ, were measured at several clay concentrations, pHs, and NaCl concentrations; and in a third experiment, the absorbance, A, was measured at two wavelengths (450 and 760 nm) at different clay and electrolyte concentrations. The released Mg2+ decreased with increasing NaCl concentration until it became zero at a NaCl concentration between 0.01 and 0.02 M, depending on pH. Thereafter, it increased with increasing NaCl concentration. Both θ and η were highly correlated with the amount of released Mg2+. Also, A remained constant until the NaCl concentration corresponded to that at the minimum of θ. Thereafter, it increased and became linearly related to θ. These results suggest: (1) positive-edge to negative-face interaction cannot solely account for the rheological properties of montmorillonite at low electrolyte concentration, and (2) the release of octahedral Mg2+ from montmorillonite affects θ, because it reduces the negative charge on the particles and, thereby, the repulsive force between them.

A model based on Gouy-Chapman theory, describing the ion exchange behavior of clays in mixed electrolyte solutions is presented. Computed ionic distributions, taking into account variations in relative permittivity, ion activity, and closeness of approach of ions to clay surfaces, are compared with experimental data for smectite and kaolinite in contact with river and saline waters. To obtain reasonable agreement between theoretical prediction and observation the most important extension of Gouy-Chapman theory involves the introduction of a closeness of approach term. Furthermore, the aggregated nature of smectites plays an important part in controlling its exchange properties, whereas a fixed-charge model provides a poor description for the ion exchange properties of kaolinite.

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.

The specific conductivity, κg, of Na/Ca montmorillonite gels (0.02 and 0.04 g clay/cm3) as a function of the specific conductivity of the interclay solution, κw, was measured. For low values of κw (<3 mmho/cm) the conductivity curves were convex with respect to xw; at higher values they were linear. The κw at which deviation from linearity began increased with increasing sodium content from 0.7 mmho/cm for the Ca-montmorillonite gel to 2.6 mmho/cm for Na-montmorillonite gel. The intercept of the linear portion of the conductivity curve increased and its slope decreased with increasing exchangeable sodium. The experimental results were described by a conductance model comprised of two elements connected in parallel: an element consisting of the solid and solution phases connected in series, and another consisting of the solution phase. At low electrolyte concentrations, the first element accounts for the curvature of the κg-κw curve, whereas at high electrolyte concentrations, the second element dominates, and the curve is linear with a slope determined by a formation factor and an intercept determined by exchangeable cation mobility.

An adjustable parameter in the conductivity term for the first element, which accounts for the thickness of the clay particles, increased with exchangeable Na, and its numerical value indicated that the solid phase also includes the diffuse double layer. The mobility of the exchangeable cation relative to that in water increased from 4% for Ca to 41% for Na with the largest increase occurring between 20 and 40% exchangeable Na. Similar effects of exchangeable Na were evident on the axial ratio of the clay particles calculated from the slopes of the linear lines. These observations are consistent with an exchangeable-ion demixing model where the initial exchangeable Na is adsorbed on the external surfaces of the Ca-montmorillonite tactoids without affecting exchangeable ion mobility or tactoid size. Further additions of exchangeable Na result in Na adsorption on the internal surfaces of the tactoid and tactoid breakdown with a subsequent increase in both exchangeable ion mobility and the axial ratio of the clay particles.

The influence of added sodium and calcium nitrate electrolyte on the particle aggregates in the colloid fraction of natural bentonite and kaolin was studied. Clays were flocculated in distilled water and various electrolyte concentrations. Aggregate size was studied by sedimentation analysis; the mean radius of the aggregates was plotted against the concentrations of Na+ and Ca2+. For bentonite, the mean radii decreased with an increase of Na+ and Ca2+ concentration, reaching a minimum; and further increases in concentration led to an increase of the mean radii of the aggregates. For kaolin, an increase in Na+ and Ca2+ concentration gave rise to an increase in the mean radii of aggregates.

Scanning electron micrographs showed different types of aggregates, depending on the physico-chemical conditions of a sedimentation process. In bentonite and kaolin sediments formed from a distilled water slurry, the dominant aggregate was an edge-face type. The small addition of salts to a bentonite slurry led to the formation of edge-edge-type aggregates; for kaolin edge-face-type aggregates formed, although within the microaggregate face-face associations were observed. The highest concentrations of electrolytes for sediments of both clays led to formation of compact, face-face-type aggregates.

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.

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.

The speciation of vanadium in the electrolyte of vanadium redox flow batteries (VRFBs) is important to determine the state of charge of the battery. To obtain a better understanding of the transport of the different vanadium species through the separator polymer electrolyte membranes, it is necessary to be able to determine concentration and species of the vanadium ions inside the nanoscopic water body of the membranes. The speciation of V in the electrolyte of VRFBs has been performed by others at the synchrotron by X-ray absorption near-edge structure analysis (XANES). However, the concentrations are quite high and not necessarily justify the use of a large-scale facility. Here, we show that vanadium species in the electrolyte and inside the ionomeric membranes can be determined by laboratory XANES. We were able to determine V species in the 1.6 M electrolyte with a measurement time of 2.3 h and V species having a concentration of 9.8 g kg−1 inside the membranes (178 µm thick) with a measurement time of 5 h. Our results show that laboratory XANES is an appropriate tool to study these kind of samples.

The present study used the physicochemical approach to characterize the changes in acid–base status that occur in Standardbreds after post-exercise electrolyte supplementation. Jugular venous blood was sampled from six conditioned Standardbreds on two separate occasions, at rest and for 24 h following a competitive exercise test (CET) designed to simulate the speed and endurance test of a 3-day event. After the CETs, horses were given water ad libitum and either a hypotonic commercial electrolyte solution, via nasogastric tube followed by a typical hay/grain meal, or a hay/grain meal alone. The electrolyte supplementation resulted in c. 2 mmol l− 1 decreased plasma [TCO2] during the recovery period as compared with control. The primary contributor to the decreased [TCO2] with electrolyte supplementation was a decreased strong ion difference ([SID]), as a result of the non-significant increase in plasma [Cl− ]. Additionally, electrolyte supplementation resulted in faster restoration of hydration status compared with control, as evidenced by faster recovery of plasma [protein] and total weak acid concentration ([Atot]). It is concluded that oral administration of a hypotonic electrolyte solution after prolonged moderate-intensity exercise diminishes the post-exercise alkalosis, and that recovery of hydration status is still incomplete 24 h after exercise when no electrolytes are given. Thus, supplementation with electrolytes according to estimated sweat losses may attenuate post-exercise increases in plasma [TCO2], which is of significant practical interest to the horse racing community, as a testing threshold of greater than 37 mmol l− 1 is used by many racing jurisdictions to determine whether a horse has been administered an alkalinizing agent.

Their higher production performance and feed conversion efficiency make today's chickens more susceptible to heat stress than ever before. The increasing proportion of poultry production in tropical and subtropical regions makes it necessary to reconsider the long-term selection strategy of today's commercial breeding programmes. Also, the importance of the potential use of Naked neck and Frizzle genes is accentuated. Nutritional strategies aimed to alleviate the negative effects of heat stress by maintaining feed intake, electrolytic and water balance or by supplementing micronutrients such as Vitamins and minerals to satisfy the special needs during heat stress have been proven advantageous. To enhance the birds' thermotolerance by early heat conditioning or feed restriction seems to be one of the most promising management methods in enhancing the heat resistance of broiler chickens in the short run.

This study used a randomized crossover design, with investigators blind to the treatment given, to test the hypothesis that seven commercially available electrolyte supplements would alter plasma concentrations of Na+, K+, Cl−, lactate, total protein (TP) and total carbon dioxide (tCO2) as well as plasma strong ion difference (SID) and haematocrit (HCT). Ten unfit Standardbred mares (∼450 kg, 4–9 years) completed a series of simulated race exercise tests (SRT) during which venous blood was collected at five sampling intervals (prior to receiving electrolyte treatment, prior to the SRT, immediately following exercise and at 60 and 90 min post-SRT). Plasma electrolyte and tCO2 concentrations were measured in duplicate using a Beckman EL-ISE electrolyte analyser. No difference (P>0.05) between treatments was detected at any of the five sampling intervals for plasma [Na+], [K+], [Cl−] or [tCO2]. Similarly, no significant difference was detected between treatments across each of the five sampling intervals for plasma SID, HCT or TP concentration. There were differences (P<0.05) in plasma [Na+], [K+] and [tCO2] (as well as plasma SID, HCT, and TP concentration) in the immediately post-SRT samples that were attributable to the physiological pressures associated with acute exercise. No differences (P>0.05) were detected between treatments across the pre-electrolyte and pre-SRT sampling intervals for plasma lactate concentration. There was, however, a significant time by treatment interaction during the 0, 60 and 90 min post-SRT sampling intervals for this parameter. The electrolyte supplements featured in this investigation did not affect either plasma tCO2 concentration or SID; however, this result does not rule out the potential for other supplements, especially those containing alkalinizing ingredients, to exert an effect that could push a horse towards threshold values.