First principles computational study on hydrolysis of hazardous chemicals phosphorus trichloride and oxychloride (PCl3 and POCl3) catalyzed by molecular water clusters.

Title First principles computational study on hydrolysis of hazardous chemicals phosphorus trichloride and oxychloride (PCl3 and POCl3) catalyzed by molecular water clusters.
Authors H. Jung; J. Kang; H. Chun; B. Han
Journal J Hazard Mater
DOI 10.1016/j.jhazmat.2017.08.054
Abstract

Using first principles calculations we unveil fundamental mechanism of hydrolysis reactions of two hazardous chemicals PCl3 and POCl3 with explicit molecular water clusters nearby. It is found that the water molecules play a key role as a catalyst significantly lowing activation barrier of the hydrolysis via transferring its protons to reaction intermediates. Interestingly, torsional angle of the molecular complex at transition state is identified as a vital descriptor on the reaction rate. Analysis of charge distribution over the complex further reinforces the finding with atomic level correlation between the torsional angle and variation of the orbital hybridization state of phosphorus (P) in the complex. Electronic charge separation (or polarization) enhances thermodynamic stability of the activated complex and reduces the activation energy through hydrogen bonding network with water molecules nearby. Calculated potential energy surfaces (PES) for the hydrolysis of PCl3 and POCl3 depict their two contrastingly different profiles of double- and triple-depth wells, respectively. It is ascribed to the unique double-bonding O=P in the POCl3. Our results on the activation free energy show well agreements with previous experimental data within 7kcalmol-1 deviation.

Citation H. Jung; J. Kang; H. Chun; B. Han.First principles computational study on hydrolysis of hazardous chemicals phosphorus trichloride and oxychloride (PCl3 and POCl3) catalyzed by molecular water clusters.. J Hazard Mater. 2018;341:457463. doi:10.1016/j.jhazmat.2017.08.054

Related Elements

Phosphorus

15 P 30.973762000 Phosphorus

Phosphorus Bohr ModelSee more Phosphorus products. Phosphorus (atomic symbol: P, atomic number: 15) is a Block P, Group 15, Period 3 element. The number of electrons in each of Phosphorus's shells is 2, 8, 5 and its electronic configuration is [Ne] 3s2 3p3. The phosphorus atom has a radius of 110.5.pm and its Van der Waals radius is 180.pm. Phosphorus is a highly-reactive non-metallic element (sometimes considered a metalloid) with two primary allotropes, white phosphorus and red phosphorus its black flaky appearance is similar to graphitic carbon. Compound forms of phosphorus include phosphates and phosphides. Phosphorous was first recognized as an element by Hennig Brand in 1669 its name (phosphorus mirabilis, or "bearer of light") was inspired from the brilliant glow emitted by its distillation.

Chlorine

17 Cl 35.453000000 Chlorine

Chlorine is a Block P, Group 17, Period 3 element. Its electron configuration is [Ne]3s23p5. The chlorine atom has a covalent radius of 102±4 pm and its Van der Waals radius is 175 pm. Chlorine ModelIn its elemental form, chlorine is a yellow-green gas. Chlorine is the second lightest halogen after fluorine. It has the third highest electronegativity and the highest electron affinity of all elements, making it a strong oxidizing agent. It is rarely found by itself in nature. Chlorine was discovered and first isolated by Carl Wilhelm Scheele in 1774. It was first recognized as an element by Humphry Davy in 1808.

Related Forms & Applications

Chlorides
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