Products resulting from the reaction of toluene with Cu(II)-montmorillonite were analyzed using GC/MS, HPLC/MS, GPC, and FTIR methods. Numerous oligomers of toluene were observed, extending at least as high as the resolution limit (1500 g/mol) of the GPC column. The FTIR spectrum of the nonvolatile components of the extract was very similar to that of liquid toluene. GC/MS data on the volatile components revealed dimers, trimers, and a multitude of transmethylated products. Oligomerization proceeded via both ring-ring (i.e., polyphenyl) and ring-methyl linkages. The primary trans-methylated products were tert-butylbenzene and isopropylxylene, indicating a competition between ringand side-chain methylations. The side-chain substitutions cannot be explained in terms of the aromatic radical cation intermediate which typically forms in arene/clay reactions. A consideration of alkylbenzene reactions observed in various other media suggests that the present transmethylation reactions occur via a benzyl cation intermediate.

Desorption processes of low-molecular-weight compounds from the surface of smectites into the gas phase determine a number of processes, e.g. those involved in drug delivery and the release of herbicides. The desorption has not been investigated thoroughly and is not well understood. The present study was undertaken in order to understand better the factors influencing these desorption mechanisms. Starting with a very pure standard (Na+-rich) montmorillonite (Kunipia-F), which was exchanged against cations with different hydration properties (Ca2+, Li+, phenyltrimethylammonium, hexyltrimethyl-ammonium), the experiments explored the rate of desorption of volatiles with different chemical functionalities (water, ethanol, ethyl acetate, and toluene). The desorption was monitored by thermogravimetry and differential scanning calorimetry under isothermal conditions, and by ramping the temperature at a constant rate. The experiments were compared with numerical calculations based on finite-element methods and with analytical models. These data point to a two-step mechanism where the desorption follows the curve of the equilibrium desorption isotherms of those molecules on the montmorillonite. The bulk-like volatiles (i.e. volatiles with release kinetics close to that of the bulk liquids) were desorbed in a first step. With a decrease in the degree of coverage of the volatile on the montmorillonite, the desorption was increasingly dominated by the strength of interaction between the volatile and the interlayer cations of the montmorillonite.

X-ray basal reflections of several HDTMA-vermiculites show that when these contain co-adsorbed molecules of HDTMA-Br, their interlayer spacings are ∼29.5 Å. After HDTMA-Br has been leached out with ethanol, spacings decrease to ∼26 Å, but when exposed to toluene vapor the spacings increase to ∼36 Å, and to ∼45 Å in toluene liquid. Transmission X-ray diffraction photographs of HDTMA-vermiculites, both with and without co-adsorbed HDTMA-Br, indicate that they have highly ordered interlayer structures. The structure of HDTMA-Br-free vermiculite flakes is more open with the interlayer cations arranged in a 3a × b superstructure. In the HDTMA-Br containing HDTMA vermiculite flakes, HDTMA-Br molecules occupy interstitial positions between the HDTMA cations. Swelling in toluene vapor does not disorder the 2-dimensional arrangement of interlayer cations, but disorder does occur in toluene liquid. In toluene vapor, the aliphatic chains of the cations remain partially interdigitated, but in toluene liquid the interdigitation disappears. In response to the layer-charge density, the organization of the interlayer HDTMA units is caused by the self-assembly process responsible for hydrocarbon close packing.

The development and application of Fe-rich palygorskite clay has been restricted significantly by its red colour and low grade. Moreover, the nano-structured properties of palygorskite and the relatively large Fe content of Fe-rich palygorskite clay have received insufficient attention. The present study involved the synthesis of Ni-based catalysts via a coprecipitation method using Fe-rich palygorskite clay as the support. The catalysts were then evaluated for their performance for catalytic steam reforming of toluene (CSRT). The experimental findings revealed that the Fe in Fe-rich palygorskite clay interacted strongly with Ni and formed Fe-Ni alloys. The catalyst with a Ni/Fe mass ratio of 14 (Ni14/FePal) calcined in air at 600°C exhibited superior performance for CSRT under the reaction temperature 700°C and S/C molar ratio of 1.0. According to the kinetics study, Ni14/FePal exhibited the lowest apparent activation energy (33.99 kJ mol−1) among the catalysts, which further confirmed the superior catalytic activity in CSRT. The characterizations of the catalysts used demonstrated that the excellent stability and resistance to coke formation of Ni14/FePal were attributable to the presence of a sufficient amount of highly dispersed Fe-Ni alloys on its surface.

Toluene sniffing, frequently described under the generic category of “glue sniffing,” is a potential cause of normal anion gap metabolic acidosis due to distal renal tubular acidosis. Urine anion gap is used to diagnose metabolic acidosis of a normal anion gap variety; however, pitfalls exist when using urine anion gap in the setting of toluene sniffing. We present the case of a young woman who had a normal anion gap metabolic acidosis due to toluene sniffing and an unexpectedly low urine anion gap. In such a scenario, the urine anion gap will underestimate the rate of ammonia excretion when the conjugate bases of acids other than HCl are excreted in large quantities. Estimation of the urine osmolal gap will provide a more accurate ammonia excretion rate in these circumstances. The challenges in interpretation of the urine anion gap and ammonia excretion in the setting of distal renal tubular acidosis due to toluene toxicity are discussed.