PubMed · 15445113
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M LAPEYRE, P MAESTRACCI, A M MICHEL. [Acute sodium fluoride poisoning].. https://pubmed.ncbi.nlm.nih.gov/15445113/
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The strongest and most robust carborane acid, H(CHB11Cl11), has a monomeric structure in the gas phase. IR spectra show two nuH-Cl bands at 2357(br) and 2066(br) cm-1 which, together with DFT calculations, indicate the coexistence of at least two isomers. The acidic proton bridges adjacent chlorine atoms with asymmetric Cl-H...Cl hydrogen bonding. The 12,7 isomer is more stable than the 7,8 isomer. These monomers can be condensed into an amorphous solid phase but are metastable. They quickly decay, first to an amorphous dimeric structure, then to a crystalline polymeric phase that has been characterized by X-ray crystallography. In the polymeric structure, the acidic proton bridges chlorine atoms from the 7-11 positions of carborane anions in linear chains. The dimeric phase (nuCl-H...Cl = 1100-2200 cm-1) and polymeric phase (nuasClHCl ca. 1100 cm-1, v broad) have more nearly symmetrical, low-barrier H-bonding. These findings have implications for the dependency of acid strength upon phase.
Many industrial unit operations and unit processes require near-complete removal of hardness to avoid scaling in heat-transfer equipment, fouling in membranes, and high consumption of detergents and sequestering chemicals in cooling and wash water. Lime softening and cation exchange are the most commonly used processes practiced to date for hardness removal. Herein, we report and discuss the results and attributes of a new hardness removal process using ion-exchange fibers (IX-fibers). Most importantly, the process uses harvested snowmelt (or rainwater) as the regenerant chemical along with sparged carbon dioxide. Consequently, the spent regenerant does not contain a high concentration of aggressive chemicals such as sodium chloride or acid like traditional ion-exchange processes nor does the process produce voluminous sludges similar to lime softening. The bulk of carbon dioxide consumed during regeneration remains sequestered in the aqueous phase as alkalinity. IX-fibers form the heart of the process. They are essentially thin cylindrical polymeric strands 10-20 microm in diameter. The weak-acid carboxylate functional groups reside near to the surface of these cylindrical fibers. Low intraparticle diffusional resistance is the underlying reason IX-fibers are amenable to efficient regeneration with snowmelt sparged with carbon dioxide. When the carbon dioxide partial pressure is increased to 6.8 atm, over 90% calcium desorption efficiency is obtained. On the contrary, commercial weak-acid ion-exchange resins in spherical bead forms are ineffective for regeneration with carbon-dioxide-sparged snowmelt due to extremely slow ion-exchange kinetics involving counter-transport of Ca2+ and H+.
BGIA has organised round robins for the analysis of samples of inorganic acids in workplace air for a number of years. Test samples of the volatile acids HCl and HNO(3) are collected from a standard atmosphere and samples of the non-volatile acids H(3)PO(4) and H(2)SO(4) are prepared by spiking filters with acid solution. The last two round robins have also covered the sampling of volatile acids, with up to 15 "active" participants able to visit the test facility in Dresden and take samples themselves. For other "passive" participants, BGIA takes samples from the same atmosphere. The acid concentrations generated lie between 0,1 and 1 times the German limit values for HCl and HNO(3). The results for the last round robin showed no significant difference between the performance of the "active" and "passive" participants. The participant means were in good agreement with the theoretical concentrations and the quality control measurements. For "active" participants RSDs were between 7% and 14% and for all participants between 8% and 16%. The round robin for the non-volatile acids showed similar results. The participant means were again in excellent agreement with the quality control measurements and RSDs were between 12% and 15%. The BGIA round robins have demonstrated the proficiency of laboratories measuring exposure to inorganic acids in air. However, concerns remain about the performance of published methods. It has shown that the sampling efficiency of sorbent tubes falls off with increasing particle size and hence silica gel tube methods may give low results for acid mists. Another issue with silica gel tubes is that a substantial proportion of the sample can be collected on the glass wool plugs that retain the sorbent. This can be up to 50% for HCl and 100% for HNO(3). Hence, low results may be obtained if the glass wool plugs are discarded. Similarly, methods for volatile inorganic acids that use a pre-filter to remove particulates usually overlook the fact that the acids can react with co-particulate matter on the pre-filter. Low recoveries in the range 30%-50% have been found when sampling HCl through filters loaded with potential interferents. Finally, particulate salts interfere with filter sampling methods for non-volatile inorganic acids. A two-part International Standard is in preparation for inorganic acids by ion chromatography and the issues discussed above are being taken into consideration during its development.