1. Superconcentrated hydrochloric acid
Kun Huang, et al. J Phys Chem B. 2011 Jun 23;115(24):7823-9. doi: 10.1021/jp109551z. Epub 2011 May 26.
We report the discovery of a potentially useful superconcentrated HCl at ambient temperature and pressure by using a simple surfactant-based reversed micelle system. Surprisingly, the molar ratios of H(+) to H(2)O (denoted as n(H+)/n(H2O)) in superconcentrated HCl can be larger than 5, while the maximum achievable n(H+)/n(H2O) value for conventional saturated HCl aqueous solution (37 wt %) is only about 0.28. Furthermore, both NMR and FT-IR results indicate that a significant amount of HCl remains in the molecular form rather than being ionized into H(+) and Cl(-). The superconcentrated HCl may promote some organic reactions that are not feasible by using conventional 37 wt % HCl solution. For example, addition reaction between C═C and HCl occurs in superconcentrated HCl solution without using catalysts.
2. Potential energy profile for the Cl + (H2O)3 → HCl + (H2O)2OH reaction. A CCSD(T) study
Guoliang Li, Ying Yao, Shengyao Lü, Yaoming Xie, Gary E Douberly, Henry F Schaefer 3rd Phys Chem Chem Phys. 2021 Dec 8;23(47):26837-26842. doi: 10.1039/d1cp04309a.
Four different reaction pathways are initially located for the reaction of Cl atom plus water trimer Cl + (H2O)3 → HCl + (H2O)2OH using a standard DFT method. As found for the analogous fluorine reaction, the geometrical and energetic results for the four chlorine pathways are closely related. However, the energetics for the Cl reaction are very different from those for fluorine. In the present paper, we investigate the lowest-energy chlorine pathway using the "gold standard" CCSD(T) method in conjunction with correlation-consistent basis sets up to cc-pVQZ. Structurally, the stationary points for the water trimer reaction Cl + (H2O)3 may be compared to those for the water monomer reaction Cl + H2O and water dimer reaction Cl + (H2O)2. Based on the CCSD(T) energies, the title reaction is endothermic by 19.3 kcal mol-1, with a classical barrier height of 16.7 kcal mol-1 between the reactants and the exit complex. There is no barrier for the reverse reaction. The Cl⋯(H2O)3 entrance complex lies 5.3 kcal mol-1 below the separated reactants. The HCl⋯(H2O)2OH exit complex is bound by 8.6 kcal mol-1 relative to the separated products. The Cl + (H2O)3 reaction is somewhat similar to the analogous Cl + (H2O)2 reaction, but qualitatively different from the Cl + H2O reaction. It is reasonable to expect that the reactions between the chlorine atom and larger water clusters may be similar to the Cl + (H2O)3 reaction. The potential energy profile for the Cl + (H2O)3 reaction is radically different from that for the valence isoelectronic F + (H2O)3 system, which may be related to the different bond energies between HCl and HF.
3. Effect of microsolvation on the mode specificity of the OH˙(H2O) + HCl reaction
Subhasish Mallick, Pradeep Kumar Phys Chem Chem Phys. 2021 Nov 17;23(44):25246-25255. doi: 10.1039/d1cp01300a.
The present study investigates the mode specificity in the microsolvated OH˙(H2O) + HCl reaction using on-the-fly direct dynamics simulation. To the best of our knowledge, this is the first study which aims to gain insights into the effect of microsolvation on the mode selectivity. Our investigation reveals that, similar to the gas phase OH˙ + HCl reaction, the microsolvated reaction is also predominantly affected by the vibrational excitation of the HCl mode, whereas the OH vibrational mode behaves as a spectator. Interestingly, in contrast to the behavior of the bare reaction, the integral cross section at the ground state of the microsolvated reaction decreases with an increase in translational energy. However, for the vibrational excited states, the reactivity of the microsolvated reaction is found to be higher than that of the bare reaction within the selected range of translational energies.
