Electric Field-driven Acid-base Transformation: Proton Transfer from Acid(HBr/HF) to Base(NH3/H2O)

doi:10.1007/s40242-015-4464-0

Chemical Research in Chinese Universities ›› 2015, Vol. 31 ›› Issue (3): 418-426.doi: 10.1007/s40242-015-4464-0

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Electric Field-driven Acid-base Transformation: Proton Transfer from Acid(HBr/HF) to Base(NH₃/H₂O)

LIANG Hailong¹, CHAI Baojie², CHEN Guanghui¹, CHEN Wei¹, CHEN Sheng¹, XIAO Hailan¹, LIN Shujuan¹

1. Department of Chemistry, Shantou University, Shantou 515063, P. R. China;
2. School of Technology, Mudanjiang Normal University, Mudanjiang 157012, P. R. China

Received:2014-12-05 Revised:2014-12-29 Online:2015-06-01 Published:2015-03-16
Contact: CHEN Guanghui E-mail:ghchen@stu.edu.cn
Supported by:
Supported by the Natural Science Foundation of Guangdong Province of China(No.S2013010014476) and the Engagement Fund of Shantou University, China(No.NFC13001).

Abstract

Abstract:

The proton-transfer between ammonia/water and HF/HBr without and with the stimulus of external electric fields(E_ext) was investigated with the ab initio calculations. When external electric field is applied, the proton transfer occurs, resulting in ion-paired H₄N⁺X^- and H₃O⁺X^-(X=Br and F) from hydrogen-bonded complexes in view of the great changes of geometrical structures, dipole moments, frontier molecular orbitals and potential energy surfaces in the critical external electric fields(E_c) of 1.131×107 V/cm for H₃N-HBr, 1.378×108 V/cm for H₃N-HF, 9.358×107 V/cm for H₂O-HBr and 2.304×108 V/cm for H₂O-HF, respectively. Furthermore, one or three excess electrons can trigger the proton transfer from H₃N-HBr and H₃N-HF to H₄N⁺Br^- and H₄N⁺F^-, while two and four excess electrons can induce the proton transfer from H₂O-HBr and H₂O-HF to H₃O⁺Br^- and H₃O⁺F^-, respectively. Compared with that of the analogous NH₃/H₂O-HCl systems, the strength of E_c of proton transfer increases from HBr to HCl and HF for either H₃N-HX or H₂O-HX series, which is understandable by the fact that the acidity sequence is HBr>HCl>HF. And the larger of acidity of conjugated acid, the smaller of needed E_c. On the other hand, the E_c for the systems of NH₃ with a stronger basicity is generally smaller than that of H₂O systems for the same conjugated acid.

Key words: Electric field, Proton transfer, H₃N-HX and H₂O-HX(X=Br and F) systems

LIANG Hailong, CHAI Baojie, CHEN Guanghui, CHEN Wei, CHEN Sheng, XIAO Hailan, LIN Shujuan. Electric Field-driven Acid-base Transformation: Proton Transfer from Acid(HBr/HF) to Base(NH₃/H₂O)[J]. Chemical Research in Chinese Universities, 2015, 31(3): 418-426.

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Electric Field-driven Acid-base Transformation: Proton Transfer from Acid(HBr/HF) to Base(NH₃/H₂O)

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