The role of CS₂ in CS₂/NMP mixed solvent in weakening the hydrogen bond of OH-N in coal: a DFT investigation.

The interaction processes of trace amounts of N-methyl-2-pyrrolidinone (NMP), CS(2)/NMP (1:1 by volume) and pure NMP solvent with the hydrogen bond of OH⋯N in coal were constructed and simulated by density functional theory methods. The distances and bond orders between the main related atoms, and the hydrogen bond energy of OH⋯N were calculated. The calculated results show that pure NMP solvent does not weaken the hydrogen bond of OH⋯N in coal. However, trace amounts of NMP and CS(2)/NMP (1:1 by volume) have a strong capacity to weaken the hydrogen bond of OH⋯N in coal. The H2-N3 distances are elongated from 1.87 Å to 3.80 Å and 3.44 Å, the bond orders of H2-N3 all disappear, and the corresponding hydrogen bond energies of OH⋯N in coal decrease from 45.72 kJ mol(-1) to 7.06 and 11.24 kJ mol(-1), respectively. These results show that CS(2) added to pure NMP solvent plays an important role in releasing the original capacity of NMP to weaken the hydrogen bond of OH⋯N in coal, in agreement with experimental observations.