Hydrogen bonding systems containing hydrogen fluoride. II. Formation constants and enthalpies of complexes with organic compounds from infrared study

Abstract

The hydrogen bonding complex of hydrogen fluoride (HF) with organic compounds having a proton-accepting group was studied by measuring the infrared F-H band of HF. Equilibrium constants (K) and enthalpies (AH) of complex formation were determined in a temperature range between 10 and 50 °C for the 1:1 complex of HF with the following proton acceptor molecules: acetone, acetonitrile, diethyl ether, dimethylformamide, ethanol, methanol, and tetrahydrofuran. The enthalpies of formation of these complexes are between -5.2 ± 0.5 and -9.6 ± 0.5 kcal mol-1. Linear correlations were found to exist between AH and (hydrogen bond shift), AH and AS, and log K and p , except for the case when methanol or ethanol was used as the proton acceptor.

STRUCTURE OF HYDROGEN FLUORIDE COMPLEXES WITH DIETHYLKETONE IN A HF-Et2CO SOLUTION

“…ɉɨɥɭɱɟɧɢɟ ɚɧɚɥɨɝɢɱɧɵɯ ɫɜɟɞɟɧɢɣ ɨ ɤɨɦɩɥɟɤɫɚɯ, ɜɤɥɸɱɚɸɳɢɯ ɦɨɥɟɤɭɥɵ HF, ɜ ɠɢɞɤɢɯ ɫɦɟɫɹɯ ɹɜɥɹɟɬɫɹ ɚɤɬɭɚɥɶɧɨɣ ɡɚɞɚɱɟɣ ɯɢɦɢɢ ɪɚɫɬɜɨɪɨɜ, ɢɦɟɸɳɟɣ ɤɚɤ ɮɭɧɞɚɦɟɧɬɚɥɶɧɨɟ, ɬɚɤ ɢ ɩɪɚɤɬɢɱɟɫɤɨɟ ɡɧɚɱɟɧɢɟ (ɬɚɤɢɟ ɫɢɫɬɟɦɵ ɦɨɝɭɬ ɜɵɫɬɭɩɚɬɶ ɜ ɤɚɱɟɫɬɜɟ ɮɬɨɪɢɪɭɸɳɢɯ ɫɪɟɞ [1][2][3][4]). Ɉɞ-ɧɚɤɨ ɢɡ-ɡɚ ɨɛɴɟɤɬɢɜɧɵɯ ɫɥɨɠɧɨɫɬɟɣ ɪɚɛɨɬ, ɩɨɫɜɹɳɟɧɧɵɯ ɪɟɲɟɧɢɸ ɷɬɨɣ ɡɚɞɚɱɢ, ɞɨ ɩɨɫɥɟɞɧɟɝɨ ɜɪɟɦɟɧɢ ɛɵɥɨ ɧɟɦɧɨɝɨ [ 7,[9][10][11]. ɂɯ ɚɜɬɨɪɵ, ɚɧɚɥɢɡɢɪɭɹ ɫɞɜɢɝɢ ɱɚɫɬɨɬ ɜɚɥɟɧɬɧɵɯ ɤɨɥɟɛɚɧɢɣ HF ('Q HF ) ɜ ɂɄ ɫɩɟɤɬɪɚɯ ɪɚɫɬɜɨɪɨɜ HF-ɨɪɝɚɧɢɱɟɫɤɢɣ ɪɚɫɬɜɨɪɢɬɟɥɶ (Solv), ɩɪɟɞɩɨɥɚɝɚɥɢ, ɱɬɨ ɜ ɷɬɢɯ ɪɚɫɬɜɨɪɚɯ ɨɛɪɚɡɭɸɬɫɹ ɰɟɩɨɱɟɱɧɵɟ ɦɨɥɟɤɭɥɹɪɧɵɟ (ɫɨɫɬɚɜɚ 1:1 [ 7,10,11 ] ɢɥɢ t3:1 [ 11 ]) ɢ ɢɨɧɧɵɟ ( 2 HF ) [ 9 ] ɤɨɦɩɥɟɤɫɵ, ɨɰɟɧɢɜɚɥɢ ɷɧɬɚɥɶɩɢɸ ɨɛɪɚɡɨɜɚɧɢɹ ('H) ȽȺ ɫɨɫɬɚɜɚ 1:1, ɧɚɯɨɞɢɥɢ ɤɨɪɪɟɥɹɰɢɢ ɦɟɠɞɭ ɡɧɚɱɟɧɢɹɦɢ 'H ɢ 'Q HF [ 10 ].…”

“…Ɉɞ-ɧɚɤɨ ɢɡ-ɡɚ ɨɛɴɟɤɬɢɜɧɵɯ ɫɥɨɠɧɨɫɬɟɣ ɪɚɛɨɬ, ɩɨɫɜɹɳɟɧɧɵɯ ɪɟɲɟɧɢɸ ɷɬɨɣ ɡɚɞɚɱɢ, ɞɨ ɩɨɫɥɟɞɧɟɝɨ ɜɪɟɦɟɧɢ ɛɵɥɨ ɧɟɦɧɨɝɨ [ 7,[9][10][11]. ɂɯ ɚɜɬɨɪɵ, ɚɧɚɥɢɡɢɪɭɹ ɫɞɜɢɝɢ ɱɚɫɬɨɬ ɜɚɥɟɧɬɧɵɯ ɤɨɥɟɛɚɧɢɣ HF ('Q HF ) ɜ ɂɄ ɫɩɟɤɬɪɚɯ ɪɚɫɬɜɨɪɨɜ HF-ɨɪɝɚɧɢɱɟɫɤɢɣ ɪɚɫɬɜɨɪɢɬɟɥɶ (Solv), ɩɪɟɞɩɨɥɚɝɚɥɢ, ɱɬɨ ɜ ɷɬɢɯ ɪɚɫɬɜɨɪɚɯ ɨɛɪɚɡɭɸɬɫɹ ɰɟɩɨɱɟɱɧɵɟ ɦɨɥɟɤɭɥɹɪɧɵɟ (ɫɨɫɬɚɜɚ 1:1 [ 7,10,11 ] ɢɥɢ t3:1 [ 11 ]) ɢ ɢɨɧɧɵɟ ( 2 HF ) [ 9 ] ɤɨɦɩɥɟɤɫɵ, ɨɰɟɧɢɜɚɥɢ ɷɧɬɚɥɶɩɢɸ ɨɛɪɚɡɨɜɚɧɢɹ ('H) ȽȺ ɫɨɫɬɚɜɚ 1:1, ɧɚɯɨɞɢɥɢ ɤɨɪɪɟɥɹɰɢɢ ɦɟɠɞɭ ɡɧɚɱɟɧɢɹɦɢ 'H ɢ 'Q HF [ 10 ].…”