Magnesium chloride | EPFL Graph Search

Magnesium chloride is an inorganic compound with the formula . It forms hydrates , where n can range from 1 to 12. These salts are colorless or white solids that are highly soluble in water. These compounds and their solutions, both of which occur in nature, have a variety of practical uses. Anhydrous magnesium chloride is the principal precursor to magnesium metal, which is produced on a large scale. Hydrated magnesium chloride is the form most readily available. Magnesium chloride can be extracted from brine or sea water. In North America, it is produced primarily from Great Salt Lake brine. In the Jordan Valley, it is obtained from the Dead Sea. The mineral bischofite () is extracted (by solution mining) out of ancient seabeds, for example, the Zechstein seabed in northwest Europe. Some deposits result from high content of magnesium chloride in the primordial ocean. Some magnesium chloride is made from evaporation of seawater. In the Dow process, magnesium chloride is regenerated from magnesium hydroxide using hydrochloric acid: It can also be prepared from magnesium carbonate by a similar reaction. crystallizes in the cadmium chloride motif, which features octahedral Mg centers. Several hydrates are known with the formula , and each loses water upon heating: n = 12 (−16.4 °C), 8 (−3.4 °C), 6 (116.7 °C), 4 (181 °C), 2 (about 300 °C). In the hexahydrate, the is also octahedral, but is coordinated to six water ligands. The thermal dehydration of the hydrates (n = 6, 12) does not occur straightforwardly. Anhydrous is produced industrially by heating the complex salt named hexamminemagnesium dichloride . As suggested by the existence of hydrates, anhydrous is a Lewis acid, although a weak one. One derivative is tetraethylammonium tetrachloromagnesate . The adduct is another. In the coordination polymer with the formula , Mg adopts an octahedral geometry. The Lewis acidity of magnesium chloride is reflected in its deliquescence, meaning that it attracts moisture from the air to the extent that the solid turns into a liquid.

Investigation of Sulfate Attack by Experimental and Thermodynamic Means

Wolfgang Kunther

This work investigates sulfate attack in complex sulfate environments by exposing different binder types to various sulfate solutions and comparing predicted phase and volume changes with experimental data. The most important aspects of this work can be grouped in three topics: The comparison of the predicted volume increase with the experimentally observed length changes. This part of the work shows that volume increase cannot be linked directly to the observed expansions. Additionally, the volume increase model does not provide an explanation for the driving force for the space filling to overcome mechanical constraints. A more plausible explanation of expansion lies in the theory of crystallization pressure, in which crystals forming from a supersaturated solution seem to be a more applicable explanation for the deterioration differences. However, this is difficult to verify directly as it is impossible to measure the solution concentration or individual crystals exert pressure on their surroundings. It is observed that expansion occurs in systems where thermodynamic modelling predicts the co-existence of ettringite with gypsum. In such a case, if monosulfate and gypsum are both present locally, the solution can be highly supersaturated with respect to ettringite within the exposed materials. An increase of sulfate contents in the C-S-H phase has been observed for these cases, indicating increased sulfate concentrations in the pore solution while providing the necessary confinement for the crystals in intimate phase mixtures to exceed pressure. The presence of bicarbonate ions in the sulfate solution reduces the expansion significantly for the CEM I and CEM III/B binders, and reduced the sulfate uptake in the phase assemblage. The CEM III/B mortars showed a highly leached zone at the surface in which also calcite was observed, this is attributed to the destabilisation of ettringite in the presence of high concentrations of bicarbonate ions. The microstructural characterization combined with the information from thermodynamic modelling suggests that conditions of high supersaturation with respect to ettringite are unlikely to occur in samples exposed to solutions containing bicarbonate ions. Degradation of mortars exposed to complex magnesium containing sulfate solutions showed that the presence of sodium, potassium and calcium in a magnesium solution reduce the deterioration symptoms significantly for the CEM I and CEM III/B mortars. The experimental observations suggest that sulfate attack in natural environments is not only less severe, due to reduced sulfate concentrations in the field, but are likely to be affected by the presence of bicarbonate anions and the common occurrence of different cations. Both of these aspects reduce the deterioration significantly and can be assumed to occur in most natural waters.

EPFL2012

Influence of pH on dehalorespiring consortia & first steps in the development of a methodology for acid neutralization in enhanced in situ bioremediation

Nicole Munz

Enhanced in situ bioremediation of chlorinated solvents is, especially in source zone remediation, often limited through the accompanied high acidification of groundwater. This acid built-up originating from the dechlorination itself and fermentation products, such as organic acids, presents a draw-back in the efficiency of dehalorespiring bacteria. It is therefore indispensable to develop and implement appropriate buffering strategies to ensure a constant transformation of toxic chloroethenes to the final non-toxic product ethene. In this study pH tolerance of different dehalorespiring bacteria was tested. The limiting acidic pH varies significantly among the consortia. The consortium SL23b4 (PCE to ethene) grows at all the examined pH (pH 5 to pH 7.5) with a pH optimum between 6 and 7 (depending on the dechlorination step), whereas Maroc 6b (PCE to ethene) was only found to grow at incubation pH of 7, and very slowly at pH 6.5. The consortium 2SO (cis-DCE to ethene) seems to be inhibited at acidic pH (no growth at pH 5 and 5.5) having a pH optimum above neutral pH. In most cases incomplete dechlorination was observed in cultures growing at acidic pH or below the pH optima, accumulating toxic intermediate dechlorination products as a consequence. Additionally, high rates of dechlorination were always accompanied by pH drops up to 1.2 pH units, giving evidence of high acid production. pH had also influence on the community composition. In the consortium SL23b4 a shift from a Dehalococcoides- (pH 6-7.5) to a Sulfurospirillum spp.- (pH5 -5.5) dominated community was observed. Consortium Maroc 6b showed significantly different community compositions due to a pH change of only 0.5 pH units. Dehalococcoides spp. and Dehalobacter spp. were dominating at pH 7 and pH 6.5, respectively. Consortium 2SO is dominated by Dehalococcoides spp. at all pH, although at pH 7 a much higher diversity seems to prevail, with the threefold number of OTUs. Tests on the tolerance of the dehalorespiring consortia for elevated PCE concentration showed similar patterns for the different dechlorination steps, as for pH cultures, and confirmed a generally higher sensitivity towards PCE and pH changes for the last steps of dechlorination. Conclusively, Dehalococcoides spp., the only known genera able to perform complete dechlorination, seem to be highly sensitive to pH and PCE changes. Further, abiotic experiments on silicate mineral dissolution, using forsteritic olivine, were performed to simulate the buffer capacity of the minerals for the acid production during microbial reductive dechlorination. In these experiments, the buffer capacity was insufficient to counterbalance the constant acid titration rate, resulting in a final pH between 3 and 4 (initial pH of 7). The formation of precipitates, such as iron oxide, and the re-precipitation of magnesium were observed in some cases, showing a decrease in magnesium concentrations.

2010