Theoretical insight into the solvent effect of H2O and formamide on the cooperativity effect in HMX complex.

The cooperativity effects of the H-bonding interactions in HMX (1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane)∙∙∙HMX∙∙∙FA (formamide), HMX∙∙∙HMX∙∙∙H2O and HMX∙∙∙HMX∙∙∙HMX complexes involving the chair and chair-chair HMX are investigated by using the ONIOM2 (CAM-B3LYP/6-31++G(d,p):PM3) and ONIOM2 (M06-2X/6-31++G(d,p):PM3) methods. The solvent effect of FA or H2O on the cooperativity effect in HMX∙∙∙HMX∙∙∙HMX are evaluated by the integral equation formalism polarized continuum model. The results show that the cooperativity and anti-cooperativity effects are not notable in all the systems. Although the effect of solvation on the binding energy of ternary system HMX∙∙∙HMX∙∙∙HMX is not large, that on the cooperativity of H-bonds is notable, which leads to the mutually strengthened H-bonding interaction in solution. This is perhaps the reason for the formation of different conformation of HMX in different solvent. Surface electrostatic potential and reduced density gradient are used to reveal the nature of the solvent effect on cooperativity effect in HMX∙∙∙HMX∙∙∙HMX. Graphical abstract RDG isosurface and electrostatic potential surface of HMX∙∙∙HMX∙∙∙HMX.

Concentration-dependence of the explosion characteristics of chlorine dioxide gas.

The explosion characteristics of chlorine dioxide gas have been studied for the first time in a cylindrical exploder with a shell capacity of 20 L. The experimental results have indicated that the lower concentration limit for the explosive decomposition of chlorine dioxide gas is 9.5% ([ClO(2)]/[air]), whereas there is no corresponding upper concentration limit. Under the experimental conditions, and within the explosion limits, the pressure of explosion increases with increasing concentration of chlorine dioxide gas; the maximum pressure of explosion relative to the initial pressure was measured as 0.024 MPa at 10% ClO(2) and 0.641 MPa at 90% ClO(2). The induction time (the time from the moment of sparking to explosion) has also been found to depend on the concentration of chlorine dioxide gas; thus, at 10% ClO(2) the induction time was 2195 ms, but at 90% ClO(2) the induction time was just 8 ms. The explosion reaction mechanism of ClO(2) is of a degenerate chain-branching type involving the formation of a stable intermediate (Cl(2)O(3)), from which the chain-branching occurs. Chain initiation takes place at the point of ignition and termination takes place at the inner walls of the exploder.