ɀ ɍ Ɋ ɇ Ⱥ Ʌ ɋ Ɍ Ɋ ɍ... ɘ Ɍɨɦ 48, ʋ 5 ɋɟɧɬɹɛɪɶ – ɨɤɬɹɛɪɶ
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ɀɍɊɇȺɅ ɋɌɊɍɄɌɍɊɇɈɃ ɏɂɆɂɂ 2007. Ɍɨɦ 48, ʋ 5 ɋɟɧɬɹɛɪɶ – ɨɤɬɹɛɪɶ ɋ. 849 – 856 ɍȾɄ 548.31 ɏɂɆɂɑȿɋɄȺə ɋȼəɁɖ ȼ ɋɍɅɖɎȺɌȺɏ ɓȿɅɈɑɇɕɏ ɆȿɌȺɅɅɈȼ 2007 ɘ.ɇ. ɀɭɪɚɜɥɟɜ*, Ʌ.ȼ. ɀɭɪɚɜɥɟɜɚ, Ɉ.ȼ. Ƚɨɥɨɜɤɨ ȽɈɍ ȼɉɈ sɄɟɦɟɪɨɜɫɤɢɣ ɝɨɫɭɞɚɪɫɬɜɟɧɧɵɣ ɭɧɢɜɟɪɫɢɬɟɬs ɋɬɚɬɶɹ ɩɨɫɬɭɩɢɥɚ 30 ɧɨɹɛɪɹ 2006 ɝ. ȼ ɪɚɦɤɚɯ ɬɟɨɪɢɢ ɮɭɧɤɰɢɨɧɚɥɚ ɥɨɤɚɥɶɧɨɣ ɷɥɟɤɬɪɨɧɧɨɣ ɩɥɨɬɧɨɫɬɢ ɦɟɬɨɞɨɦ ɩɫɟɜɞɨɩɨɬɟɧɰɢɚɥɚ ɜ ɛɚɡɢɫɟ ɱɢɫɥɟɧɧɵɯ ɚɬɨɦɧɵɯ ɩɫɟɜɞɨɨɪɛɢɬɚɥɟɣ ɪɚɫɫɱɢɬɚɧɨ ɪɚɫɩɪɟɞɟɥɟɧɢɟ ɜɚɥɟɧɬɧɨɣ ɢ ɪɚɡɧɨɫɬɧɨɣ ɩɥɨɬɧɨɫɬɢ ɜ ɤɪɢɫɬɚɥɥɢɱɟɫɤɢɯ ɫɭɥɶɮɚɬɚɯ M2SO4 (M: Li, Rb, Cs) ɢ ɞɜɨɣɧɵɯ ɫɭɥɶɮɚɬɚɯ MLiSO4. ɉɨɤɚɡɚɧɨ, ɱɬɨ ɜ ɫɭɥɶɮɚɬɟ ɥɢɬɢɹ ɧɟɷɤɜɢɜɚɥɟɧɬɧɵɟ ɜ ɤɪɢɫɬɚɥɥɨɝɪɚɮɢɱɟɫɤɨɦ ɨɬɧɨɲɟɧɢɢ ɚɬɨɦɵ ɤɢɫɥɨɪɨɞɚ ɧɚɯɨɞɹɬɫɹ ɜ ɪɚɡɧɨɦ ɡɚɪɹɞɨɜɨɦ ɫɨɫɬɨɹɧɢɢ ɢ ɢɦɟɸɬ ɪɚɡɧɭɸ ɫɢɥɭ ɯɢɦɢɱɟɫɤɨɝɨ ɫɜɹɡɵɜɚɧɢɹ ɫ ɫɟɪɨɣ. Ⱥɧɢɨɧɵ ɫɜɹɡɚɧɵ ɦɟɠɞɭ ɫɨɛɨɣ ɩɨɫɪɟɞɫɬɜɨɦ ɚɬɨɦɨɜ ɥɢɬɢɹ, ɤɨɬɨɪɵɟ ɨɛɪɚɡɭɸɬ ɫ ɤɢɫɥɨɪɨɞɨɦ ɬɟɬɪɚɷɞɪɢɱɟɫɤɢɟ ɤɨɦɩɥɟɤɫɵ. ȼ ɫɭɥɶɮɚɬɟ ɪɭɛɢɞɢɹ ɷɥɟɤɬɪɨɧɧɵɟ ɨɛɥɚɤɚ ɚɧɢɨɧɨɜ ɩɟɪɟɤɪɵɜɚɸɬɫɹ ɢ ɨɛɪɚɡɭɸɬɫɹ ɰɟɩɨɱɟɱɧɵɟ ɫɬɪɭɤɬɭɪɵ. ɏɢɦɢɱɟɫɤɚɹ ɫɜɹɡɶ ɦɟɠɞɭ ɚɧɢɨɧɨɦ ɢ ɤɚɬɢɨɧɨɦ ɢɦɟɟɬ ɢɨɧɧɵɣ ɯɚɪɚɤɬɟɪ. ɗɬɢ ɨɫɨɛɟɧɧɨɫɬɢ ɷɥɟɤɬɪɨɧɧɨɝɨ ɫɬɪɨɟɧɢɹ ɩɪɨɹɜɥɹɸɬɫɹ ɜ ɞɜɨɣɧɵɯ ɫɭɥɶɮɚɬɚɯ, ɝɞɟ ɬɚɤɠɟ ɨɛɪɚɡɭɸɬɫɹ ɤɨɦɩɥɟɤɫɵ LiO4, ɫɜɹɡɵɜɚɸɳɢɟ ɚɧɢɨɧɧɵɟ ɰɟɩɨɱɤɢ, ɚ ɬɹɠɟɥɵɟ ɦɟɬɚɥɥɵ ɹɜɥɹɸɬɫɹ ɤɚɬɢɨɧɚɦɢ. Ʉ ɥ ɸ ɱ ɟ ɜ ɵ ɟ ɫ ɥ ɨ ɜ ɚ : ɮɭɧɤɰɢɨɧɚɥ ɩɥɨɬɧɨɫɬɢ, ɷɥɟɤɬɪɨɧɧɚɹ ɩɥɨɬɧɨɫɬɶ, ɩɨɞɪɟɲɟɬɤɢ, ɪɚɡɧɨɫɬɧɚɹ ɩɥɨɬɧɨɫɬɶ, ɯɢɦɢɱɟɫɤɚɹ ɫɜɹɡɶ, ɫɭɥɶɮɚɬ ɥɢɬɢɹ, ɫɭɥɶɮɚɬ ɪɭɛɢɞɢɹ, ɫɭɥɶɮɚɬ ɰɟɡɢɹ, ɞɜɨɣɧɵɟ ɫɭɥɶɮɚɬɵ. ȼȼȿȾȿɇɂȿ ɋɭɥɶɮɚɬɵ ɳɟɥɨɱɧɵɯ ɦɟɬɚɥɥɨɜ M2SO4 (M: Li, Rb, Cs) ɨɛɥɚɞɚɸɬ ɪɹɞɨɦ ɭɧɢɤɚɥɶɧɵɯ ɷɥɟɤɬɪɢɱɟɫɤɢɯ, ɨɩɬɢɱɟɫɤɢɯ, ɦɟɯɚɧɢɱɟɫɤɢɯ ɫɜɨɣɫɬɜ, ɱɬɨ ɞɟɥɚɟɬ ɢɯ ɨɛɴɟɤɬɨɦ ɩɪɢɫɬɚɥɶɧɨɝɨ ɜɧɢɦɚɧɢɹ ɦɧɨɝɢɯ ɢɫɫɥɟɞɨɜɚɬɟɥɟɣ [ 1 ]. ɇɟ ɦɟɧɟɟ ɢɧɬɟɪɟɫɧɵɟ ɫɜɨɣɫɬɜɚ ɢɦɟɸɬ ɢɯ ɞɜɨɣɧɵɟ ɫɨɥɢ MLiSO4. ɉɪɟɠɞɟ ɜɫɟɝɨ, ɷɬɨ ɫɜɹɡɚɧɨ ɫ ɢɡɭɱɟɧɢɟɦ ɦɧɨɝɨɱɢɫɥɟɧɧɵɯ ɟɞɢɧɢɱɧɵɯ ɢɥɢ ɩɨɫɥɟɞɨɜɚɬɟɥɶɧɵɯ ɨɛɪɚɬɢɦɵɯ ɫɬɪɭɤɬɭɪɧɵɯ ɩɟɪɟɯɨɞɨɜ ɜ ɩɶɟɡɨɷɥɟɤɬɪɢɱɟɫɤɢɟ, ɫɟɝɧɟɬɨɷɥɟɤɬɪɢɱɟɫɤɢɟ, ɫɟɝɧɟɬɨɷɥɚɫɬɢɱɟɫɤɢɟ ɢ ɧɟɫɨɪɚɡɦɟɪɧɵɟ ɮɚɡɵ. ɍɩɨɪɹɞɨɱɟɧɧɵɟ ɮɚɡɵ ɫɭɥɶɮɚɬɨɜ ɦɟɬɚɥɥɨɜ ɨɬɧɨɫɹɬɫɹ ɤ ɬɪɟɦ ɫɬɪɭɤɬɭɪɧɵɦ ɬɢɩɚɦ: ɦɨɧɨ5 ɤɥɢɧɧɚɹ ɫ ɩɪɨɫɬɪɚɧɫɬɜɟɧɧɨɣ ɝɪɭɩɩɨɣ C2h , ɱɢɫɥɨ ɮɨɪɦɭɥɶɧɵɯ ɟɞɢɧɢɰ Z = 4 (E-Li2SO4); ɨɪɬɨ16 17 ɪɨɦɛɢɱɟɫɤɚɹ — D2h , Z = 4 (E-K2SO4); ɨɪɬɨɪɨɦɛɢɱɟɫɤɚɹ — D2h , Z = 2 (Na2SO4). ȼɵɫɨɤɨɬɟɦɩɟ4 , ɪɚɬɭɪɧɵɟ ɮɚɡɵ ɢɦɟɸɬ ɝɟɤɫɚɝɨɧɚɥɶɧɭɸ ɫɬɪɭɤɬɭɪɭ ɬɢɩɚ D-K2SO4 (ɩɪɨɫɬɪɚɧɫɬɜɟɧɧɚɹ ɝɪɭɩɩɚ D6h Z = 2), ɤɨɬɨɪɚɹ ɦɨɠɟɬ ɫɭɳɟɫɬɜɨɜɚɬɶ ɥɢɲɶ ɩɪɢ ɧɚɥɢɱɢɢ ɨɪɢɟɧɬɚɰɢɨɧɧɨɝɨ ɪɚɡɭɩɨɪɹɞɨɱɟɧɢɹ ɬɟɬɪɚɷɞɪɢɱɟɫɤɢɯ ɝɪɭɩɩ SO4. ȼ ɞɜɨɣɧɵɯ ɫɭɥɶɮɚɬɚɯ MLiSO4 ɚɧɢɨɧɵ ɨɛɪɚɡɭɸɬ ɤɚɪɤɚɫɧɭɸ ɫɬɪɭɤɬɭɪɭ ɬɢɩɚ ɬɪɢɞɢɦɢɬɚ ɡɚ ɫɱɟɬ ɫɜɹɡɢ ɦɟɠɞɭ ɫɨɛɨɣ ɱɟɪɟɡ ɬɟɬɪɚɷɞɪɵ LiO4. ȼ ɧɟɤɨɬɨɪɨɦ ɢɧɬɟɪɜɚɥɟ ɬɟɦɩɟɪɚɬɭɪ ɫɢɦɦɟɬɪɢɹ 16 ɷɬɢɯ ɤɪɢɫɬɚɥɥɨɜ ɹɜɥɹɟɬɫɹ ɨɪɬɨɪɨɦɛɢɱɟɫɤɨɣ ɫ ɩɪɨɫɬɪɚɧɫɬɜɟɧɧɨɣ ɝɪɭɩɩɨɣ D2h . ȼ ɡɚɜɢɫɢɦɨɫɬɢ ɨɬ ɪɚɡɦɟɪɚ ɤɚɬɢɨɧɚ M ɮɚɡɨɜɵɟ ɩɟɪɟɯɨɞɵ ɜ ɫɟɝɧɟɬɨɷɥɚɫɬɢɱɟɫɤɭɸ ɮɚɡɭ ɫ ɩɪɨɫɬɪɚɧɫɬɜɟɧɧɨɣ ɝɪɭɩɩɨɣ * E-mail: [email protected] 850 ɘ.ɇ. ɀɍɊȺȼɅȿȼ, Ʌ.ȼ. ɀɍɊȺȼɅȿȼȺ, Ɉ.ȼ. ȽɈɅɈȼɄɈ 5 C2h ɩɪɨɢɫɯɨɞɹɬ ɩɪɢ ɩɨɧɢɠɟɧɢɢ ɬɟɦɩɟɪɚɬɭɪɵ, ɥɢɛɨ ɧɟɩɨɫɪɟɞɫɬɜɟɧɧɨ (CsLiSO4), ɥɢɛɨ ɱɟɪɟɡ ɪɹɞ ɩɪɨɦɟɠɭɬɨɱɧɵɯ ɫɬɪɭɤɬɭɪɧɵɯ ɮɨɪɦ, ɜɤɥɸɱɚɹ ɧɟɫɨɪɚɡɦɟɪɧɭɸ ɮɚɡɭ (RbLiSO4). ɇɚ ɨɫɧɨɜɟ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɯ ɢɫɫɥɟɞɨɜɚɧɢɣ [ 2—6 ] ɫɮɨɪɦɢɪɨɜɚɥɨɫɶ ɩɪɟɞɫɬɚɜɥɟɧɢɟ ɨ ɬɨɦ, ɱɬɨ ɜ ɨɫɧɨɜɟ ɮɚɡɨɜɵɯ ɩɟɪɟɯɨɞɨɜ D64h o D216h o C25h ɥɟɠɚɬ ɩɪɨɰɟɫɫɵ ɭɩɨɪɹɞɨɱɟɧɢɹ ɬɟɬɪɚɷɞɪɢɱɟɫɤɢɯ ɝɪɭɩɩ. ɉɪɢ ɷɬɨɦ ɜɨɩɪɨɫɵ ɨɛɪɚɡɨɜɚɧɢɹ ɯɢɦɢɱɟɫɤɨɣ ɫɜɹɡɢ ɤɚɤ ɜ ɱɢɫɬɵɯ, ɬɚɤ ɢ ɞɜɨɣɧɵɯ ɫɭɥɶɮɚɬɚɯ, ɯɚɪɚɤɬɟɪ ɟɟ ɢɡɦɟɧɟɧɢɹ ɩɪɢ ɮɚɡɨɜɵɯ ɩɟɪɟɯɨɞɚɯ ɜ ɥɢɬɟɪɚɬɭɪɟ ɩɪɚɤɬɢɱɟɫɤɢ ɧɟ ɨɛɫɭɠɞɚɥɢɫɶ, ɡɚ ɢɫɤɥɸɱɟɧɢɟɦ [7—9 ]. ɉɨɷɬɨɦɭ ɜ ɧɚɫɬɨɹɳɟɣ ɪɚɛɨɬɟ ɩɪɨɜɨɞɢɬɫɹ ɫɢɫɬɟɦɚɬɢɱɟɫɤɨɟ ɢɡɭɱɟɧɢɟ ɩɪɨɫɬɪɚɧɫɬɜɟɧɧɨɝɨ ɪɚɫɩɪɟɞɟɥɟɧɢɹ ɜɚɥɟɧɬɧɨɣ ɢ ɪɚɡɧɨɫɬɧɨɣ ɩɥɨɬɧɨɫɬɢ, ɢ ɧɚ ɨɫɧɨɜɟ ɷɬɨɝɨ ɞɟɥɚɸɬɫɹ ɜɵɜɨɞɵ ɨ ɦɟɯɚɧɢɡɦɚɯ ɨɛɪɚɡɨɜɚɧɢɹ ɯɢɦɢɱɟɫɤɨɣ ɫɜɹɡɢ ɜ ɤɪɢɫɬɚɥɥɢɱɟɫɤɢɯ ɫɭɥɶɮɚɬɚɯ, ɯɚɪɚɤɬɟɪɟ ɟɟ ɢɡɦɟɧɟɧɢɹ ɩɪɢ ɮɚɡɨɜɵɯ ɩɟɪɟɯɨɞɚɯ. ȼɚɥɟɧɬɧɭɸ ɩɥɨɬɧɨɫɬɶ ɪɚɫɫɱɢɬɵɜɚɥɢ ɜ ɪɚɦɤɚɯ ɬɟɨɪɢɢ ɮɭɧɤɰɢɨɧɚɥɚ ɥɨɤɚɥɶɧɨɣ ɷɥɟɤɬɪɨɧɧɨɣ ɩɥɨɬɧɨɫɬɢ ɫ ɢɫɩɨɥɶɡɨɜɚɧɢɟɦ ɧɟɥɨɤɚɥɶɧɵɯ BSH-ɩɫɟɜɞɨɩɨɬɟɧɰɢɚɥɨɜ ɜ ɛɚɡɢɫɟ ɱɢɫɥɟɧɧɵɯ ɚɬɨɦɧɵɯ ɩɫɟɜɞɨɨɪɛɢɬɚɥɟɣ sp3d 5, ɤɨɬɨɪɵɟ ɩɨɥɭɱɚɥɢ ɩɭɬɟɦ ɪɟɲɟɧɢɹ ɭɪɚɜɧɟɧɢɹ ɒɪɟɞɢɧɝɟɪɚ ɫ ɬɟɦɢ ɠɟ ɩɫɟɜɞɨɩɨɬɟɧɰɢɚɥɚɦɢ, ɚ ɱɢɫɥɚ ɡɚɩɨɥɧɟɧɢɹ ɜɚɪɶɢɪɨɜɚɥɢ ɬɚɤɢɦ ɨɛɪɚɡɨɦ, ɱɬɨɛɵ ɩɨɥɭɱɢɬɶ ɛɥɢɡɤɭɸ ɤ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɨ ɧɚɛɥɸɞɚɟɦɨɣ ɞɢɚɝɪɚɦɦɭ ɷɧɟɪɝɟɬɢɱɟɫɤɢɯ ɭɪɨɜɧɟɣ ɚɬɨɦɚ. Ⱦɥɹ ɚɧɚɥɢɡɚ ɦɟɯɚɧɢɡɦɨɜ ɨɛɪɚɡɨɜɚɧɢɹ ɯɢɦɢɱɟɫɤɨɣ ɫɜɹɡɢ ɢɫɩɨɥɶɡɨɜɚɧ ɦɟɬɨɞ ɩɨɞɪɟɲɟɬɨɤ [ 10 ], ɩɨɫɪɟɞɫɬɜɨɦ ɤɨɬɨɪɨɝɨ ɪɚɫɫɱɢɬɵɜɚɸɬ ɪɚɡɧɨɫɬɧɭɸ ɩɥɨɬɧɨɫɬɶ 'U ɜɵɱɢɬɚɧɢɟɦ ɢɡ ɜɚɥɟɧɬɧɨɣ ɤɪɢɫɬɚɥɥɢɱɟɫɤɨɣ ɩɥɨɬɧɨɫɬɢ ɜɫɟɯ ɫɨɫɬɚɜɥɹɸɳɢɯ ɤɪɢɫɬɚɥɥ ɩɨɞɪɟɲɟɬɨɤ. ɂɡ ɭɫɥɨɜɢɹ ɧɨɪɦɢɪɨɜɤɢ ɷɥɟɤɬɪɨɧɧɵɯ ɩɥɨɬɧɨɫɬɟɣ ɧɚ ɱɢɫɥɨ ɷɥɟɤɬɪɨɧɨɜ ɫɥɟɞɭɟɬ, ɱɬɨ ɤɚɪɬɵ 'U ɛɭɞɭɬ ɫɨɞɟɪɠɚɬɶ ɨɛɥɚɫɬɢ ɤɚɤ ɩɨɥɨɠɢɬɟɥɶɧɵɯ, ɬɚɤ ɢ ɨɬɪɢɰɚɬɟɥɶɧɵɯ ɡɧɚɱɟɧɢɣ, ɤɨɬɨɪɵɟ ɞɚɸɬ ɧɚɝɥɹɞɧɨɟ ɩɪɟɞɫɬɚɜɥɟɧɢɟ ɨ ɩɟɪɟɬɨɤɟ ɡɚɪɹɞɚ ɦɟɠɞɭ ɩɨɞɪɟɲɟɬɤɚɦɢ ɩɪɢ ɢɯ ɜɡɚɢɦɨɞɟɣɫɬɜɢɢ. ɄɊɂɋɌȺɅɅɂɑȿɋɄȺə ɋɌɊɍɄɌɍɊȺ ɉɪɢ ɨɛɵɱɧɵɯ ɭɫɥɨɜɢɹɯ ɫɭɥɶɮɚɬ ɥɢɬɢɹ ɢɦɟɟɬ ɭɩɨɪɹɞɨɱɟɧɧɭɸ ɦɨɧɨɤɥɢɧɧɭɸ ɫɬɪɭɤɬɭɪɭ [ 11 ] ɫɨ ɫɥɚɛɨ ɢɫɤɚɠɟɧɧɵɦ ȽɐɄ ɨɤɪɭɠɟɧɢɟɦ ɫɭɥɶɮɚɬɧɵɯ ɝɪɭɩɩ ɢ ɢɨɧɚɦɢ ɥɢɬɢɹ ɜ ɬɟɬɪɚɷɞɪɢɱɟɫɤɢɯ ɩɨɥɨɫɬɹɯ. ȼ ɬɟɬɪɚɷɞɪɟ SO4 ɜɫɟ ɫɜɹɡɢ ɹɜɥɹɸɬɫɹ ɧɟɷɤɜɢɜɚɥɟɧɬɧɵɦɢ: S—O1 1,470, S—O2 1,471, S—O3 1,474, S—O4 1,478 Å. Ⱥɬɨɦɵ ɥɢɬɢɹ ɨɛɪɚɡɭɸɬ ɞɜɟ ɧɟɷɤɜɢɜɚɥɟɧɬɧɵɟ ɩɨɞɪɟɲɟɬɤɢ ɢ ɧɚɯɨɞɹɬɫɹ ɜ ɬɟɬɪɚɷɞɪɢɱɟɫɤɨɦ ɨɤɪɭɠɟɧɢɢ ɢɡ ɚɬɨɦɨɜ ɤɢɫɥɨɪɨɞɚ, ɩɪɢɧɚɞɥɟɠɚɳɢɯ ɪɚɡɧɵɦ ɫɭɥɶɮɚɬɧɵɦ ɝɪɭɩɩɚɦ, ɚ ɜɫɟ ɪɚɫɫɬɨɹɧɢɹ Li—O ɬɚɤɠɟ ɪɚɡɥɢɱɧɵ: Li1—O4 1,914, 1,976, Li1—O1 1,963, Li1—O3 1,976 Å; Li2—O2 1,928, 1,990, Li2—O1 1,962, Li2—O3 1,981 Å. ɉɪɢ 851 K ɨɛɪɚɡɭɟɬɫɹ ɫɭɩɟɪɢɨɧɧɚɹ ɮɚɡɚ D-Li2SO4 [ 12 ], ɤɨɬɨɪɚɹ ɨɛɧɚɪɭɠɢɜɚɟɬ ɜɵɫɨɤɭɸ ɢɨɧɧɭɸ ɩɪɨɜɨɞɢɦɨɫɬɶ, ɢɨɧɵ Li+ ɜ ɧɟɣ ɡɚɧɢɦɚɸɬ ɪɚɡɭɩɨɪɹɞɨɱɟɧɧɵɟ ɩɨɡɢɰɢɢ, ɚ ɚɬɨɦɵ ɤɢɫɥɨɪɨɞɚ ɜɪɚɳɚɸɬɫɹ ɨɬɧɨɫɢɬɟɥɶɧɨ ɚɬɨɦɨɜ ɫɟɪɵ. ɉɪɢ ɬɟɦɩɟɪɚɬɭɪɟ 723 K ɢ ɞɚɜɥɟɧɢɢ 7,2 Ƚɉɚ H-Li2SO4 17 ɢɦɟɟɬ ɫɬɪɭɤɬɭɪɭ, ɩɨɞɨɛɧɭɸ Na2SO4(III) ɫ ɝɪɭɩɩɨɣ ɫɢɦɦɟɬɪɢɢ D2h ɢ Z = 2 [ 13 ]. ɉɪɢ ɤɨɦɧɚɬɧɨɣ ɬɟɦɩɟɪɚɬɭɪɟ ɤɪɢɫɬɚɥɥɨɝɪɚɮɢɱɟɫɤɢɟ ɩɚɪɚɦɟɬɪɵ Rb2SO4 ɩɪɢɜɟɞɟɧɵ ɜ [ 14 ], Cs2SO4 — ɜ [ 15 ]. Ⱥɬɨɦɵ ɤɢɫɥɨɪɨɞɚ ɨɛɪɚɡɭɸɬ ɜ ɫɭɥɶɮɚɬɟ ɪɭɛɢɞɢɹ ɬɪɢ ɩɨɞɪɟɲɟɬɤɢ: S—O1 1,492, S—O2 1,473, S—O3(4) 1,466 Å, ɦɟɬɚɥɥɵ — ɞɜɟ: Rb1—S 3,415, Rb2—S 3,544 Å, ɚ ɫɟɪɚ — ɨɞɧɭ. ɋɬɪɭɤɬɭɪɵ ɷɬɢɯ ɤɪɢɫɬɚɥɥɨɜ ɨɩɢɫɚɧɵ ɜ [ 16 ]. ɋɭɥɶɮɚɬ ɥɢɬɢɹ ɨɛɪɚɡɭɟɬ ɫ ɞɪɭɝɢɦɢ ɫɭɥɶɮɚɬɚɦɢ ɤɪɢɫɬɚɥɥɢɱɟɫɤɢɟ ɬɜɟɪɞɵɟ ɪɚɫɬɜɨɪɵ. ɇɚɢɛɨɥɟɟ ɪɚɫɩɪɨɫɬɪɚɧɟɧɧɵɦ ɫɩɨɫɨɛɨɦ ɢɯ ɩɨɥɭɱɟɧɢɹ ɹɜɥɹɟɬɫɹ ɪɨɫɬ ɤɪɢɫɬɚɥɥɨɜ MLiSO4 ɢɫɩɚɪɟɧɢɟɦ ɢɡ ɜɨɞɧɨɝɨ ɪɚɫɬɜɨɪɚ ɷɤɜɢɦɨɥɟɤɭɥɹɪɧɨɝɨ ɫɨɫɬɚɜɚ Li2SO44H2O ɢ M2SO4. Ⱦɜɨɣɧɨɣ ɫɭɥɶɮɚɬ RbLiSO4 (RLS) ɩɪɢ ɤɨɦɧɚɬɧɨɣ ɬɟɦɩɟɪɚɬɭɪɟ ɢɦɟɟɬ ɦɨɧɨɤɥɢɧɧɭɸ ɫɬɪɭɤɬɭɪɭ (ɩɪɨɫɬɪɚɧɫɬɜɟɧɧɚɹ 5 , Z = 4), ɜ ɤɨɬɨɪɨɣ ɞɥɢɧɵ ɫɜɹɡɟɣ S—O1 1,4332, S—O2 1,4427, S—O3 1,4505, ɝɪɭɩɩɚ C2h S—O4 1,4509, Li—O1 1,881, Li—O4 1,905, Li—O2 1,943, Li—O3 1,967 Å [17 ]. ȼ ɢɧɬɟɪɜɚɥɟ 438—474,5 K ɧɚɛɥɸɞɚɸɬɫɹ 6 ɮɚɡɨɜɵɯ ɩɟɪɟɯɨɞɨɜ, ɯɚɪɚɤɬɟɪɢɫɬɢɤɚ ɤɨɬɨɪɵɯ ɩɪɢɜɟɞɟɧɚ ɜ [ 6 ]. ȼɵɲɟ 474,5 K ɪɚɡɭɩɨɪɹɞɨɱɟɧɧɚɹ ɩɚɪɚɷɥɟɤɬɪɢɱɟɫɤɚɹ ɮɚɡɚ ɨɪɬɨɪɨɦɛɢɱɟɫɤɚɹ. ɗɬɚ ɫɬɪɭɤɬɭɪɚ ɹɜɥɹɟɬɫɹ ɪɟɡɭɥɶɬɚɬɨɦ ɪɚɜɧɨɦɟɪɧɨɝɨ ɪɚɫɩɪɟɞɟɥɟɧɢɹ ɫɭɥɶɮɚɬ-ɢɨɧɨɜ ɦɟɠɞɭ ɞɜɭɯ ɪɚɡɪɟɲɟɧɧɵɯ ɩɨɡɢɰɢɣ, ɥɨɤɚɥɢɡɨɜɚɧɧɵɯ ɫɢɦɦɟɬɪɢɱɧɨ ɩɥɨɫɤɨɫɬɢ bc. Ʉɪɢɫɬɚɥɥɢɱɟɫɤɚɹ ɫɬɪɭɤɬɭɪɚ CsLiSO4 (CLS) ɨɩɢɫɚɧɚ ɜ [ 18 ]: ɩɪɢ ɤɨɦɧɚɬɧɨɣ ɬɟɦɩɟɪɚɬɭɪɟ ɫɬɪɭɤɬɭɪɚ ɨɪɬɨɪɨɦɛɢɱɟɫɤɚɹ, ɚ ɩɪɢ 163 K — ɦɨɧɨɤɥɢɧɧɚɹ. Ɇɟɠɚɬɨɦɧɵɟ ɪɚɫɫɬɨɹɧɢɹ ɜ ɪɨɦɛɢɱɟ- ɏɂɆɂɑȿɋɄȺə ɋȼəɁɖ ȼ ɋɍɅɖɎȺɌȺɏ ɓȿɅɈɑɇɕɏ ɆȿɌȺɅɅɈȼ 851 ɫɤɨɣ ɮɚɡɟ ɪɚɜɧɵ S—O1 1,436, S—O2 1,449, S—O3(4) 1,462 Å ɢ Li—O1 1,854, Li—O2 1,894, Li—O3(4) 1,956 Å. ɊȿɁɍɅɖɌȺɌɕ ɂ ɂɏ ɈȻɋɍɀȾȿɇɂȿ SO4 — ɫɥɚɛɨɭɫɬɨɣɱɢɜɚɹ ɦɨɥɟɤɭɥɚ, ɤɨɬɨɪɚɹ ɫɬɚɛɢɥɢɡɢɪɭɟɬɫɹ, ɩɪɢɫɨɟɞɢɧɹɹ ɤ ɫɟɛɟ ɞɜɚ ɷɥɟɤɬɪɨɧɚ, ɜ ɪɟɡɭɥɶɬɚɬɟ ɱɟɝɨ ɩɨɥɭɱɚɟɬɫɹ ɚɧɢɨɧ SO 24 . ȼ ɫɜɨɸ ɨɱɟɪɟɞɶ, ɢɡɨɥɢɪɨɜɚɧɧɵɣ ɚɧɢɨɧ ɬɚɤɠɟ ɧɟɫɬɚɛɢɥɟɧ, ɢ ɜ [ 19 ] ɩɨɤɚɡɚɧɨ, ɱɬɨ ɨɧ ɫɬɚɧɨɜɢɬɫɹ ɭɫɬɨɣɱɢɜɵɦ, ɩɪɢɫɨɟɞɢɧɢɜ ɱɟɬɵɪɟ ɦɨɥɟɤɭɥɵ ɜɨɞɵ. ȼ ɚɧɢɨɧɟ SO 24 ɡɚɪɹɞ ɚɬɨɦɚ ɫɟɪɵ ɛɥɢɡɨɤ ɤ ɧɭɥɸ, ɢ ɟɝɨ ɷɥɟɤɬɪɨɧɧɚɹ ɤɨɧɮɢɝɭɪɚɰɢɹ 3s3p2,43d2,6, ɬ.ɟ. ɜɧɟɲɧɢɟ 6 ɷɥɟɤɬɪɨɧɨɜ ɚɬɨɦɚ ɫɟɪɵ ɧɚɯɨɞɹɬɫɹ ɜ ɜɨɡɛɭɠɞɟɧɧɨɦ ɫɨɫɬɨɹɧɢɢ ɢ ɡɚɪɹɞɵ ɧɚ ɚɬɨɦɚɯ ɤɢɫɥɨɪɨɞɚ ɪɚɜɧɵ 0,5 ɟ (ɟ — ɡɚɪɹɞ ɷɥɟɤɬɪɨɧɚ). Ɋɚɫɩɪɟɞɟɥɟɧɢɟ ɜɚɥɟɧɬɧɨɣ ɩɥɨɬɧɨɫɬɢ U ɢ ɪɚɡɧɨɫɬɧɨɣ ɩɥɨɬɧɨɫɬɢ 'U ɩɪɢɜɨɞɢɬɫɹ ɜ ɚɤɬɭɚɥɶɧɵɯ ɤɪɢɫɬɚɥɥɨɝɪɚɮɢɱɟɫɤɢɯ ɩɥɨɫɤɨɫɬɹɯ ɜ ɟɞɢɧɢɰɚɯ e/Å3. ɂɫɩɨɥɶɡɭɟɬɫɹ ɪɚɜɧɨɦɟɪɧɚɹ ɲɤɚɥɚ. Ⱦɥɹ ɭɤɚɡɚɧɢɹ ɩɪɨɫɬɪɚɧɫɬɜɟɧɧɨɝɨ ɦɚɫɲɬɚɛɚ ɫɥɟɞɭɟɬ ɩɪɢɦɟɧɹɬɶ ɩɪɢɜɟɞɟɧɧɵɟ ɜɵɲɟ ɦɟɠɚɬɨɦɧɵɟ ɪɚɫɫɬɨɹɧɢɹ. ɋɭɥɶɮɚɬ ɥɢɬɢɹ. Ɋɚɫɩɪɟɞɟɥɟɧɢɟ ɜɚɥɟɧɬɧɨɣ ɢ ɪɚɡɧɨɫɬɧɨɣ ɩɥɨɬɧɨɫɬɢ ɜ ɩɥɨɫɤɨɫɬɢ ab ɩɪɢɜɟɞɟɧɨ ɧɚ ɪɢɫ. 1, ɝɞɟ ɧɚ ɜɫɬɚɜɤɚɯ ɭɤɚɡɚɧɵ ɩɪɨɮɢɥɢ 'U ɜɞɨɥɶ ɥɢɧɢɣ S—O ɢ Li—O. Ⱥɬɨɦɵ Ɉ1 ɧɚɯɨɞɹɬɫɹ ɧɚ ɪɚɫɫɬɨɹɧɢɢ 0,319 Å ɧɚɞ ɢ ɩɨɞ ɭɤɚɡɚɧɧɨɣ ɩɥɨɫɤɨɫɬɶɸ, Ɉ2 — 0,029, Ɉ3 — 0,708, Ɉ4 — 0,251, S — 0,317, Li1 — 0,343, Li2 — 0,374 Å. Ɋɚɫɫɬɨɹɧɢɟ ɦɟɠɞɭ ɚɬɨɦɚɦɢ ɤɢɫɥɨɪɨɞɚ ɫɨɫɟɞɧɢɯ ɚɧɢɨɧɧɵɯ ɝɪɭɩɩ Ɉ2—Ɉ2 2,735 Å ɢ ɚɬɨɦɚɦɢ Li2—Li2 2,806 Å. ɗɬɢ ɱɟɬɵɪɟ ɚɬɨɦɚ ɨɛɪɚɡɭɸɬ ɩɚɪɚɥɥɟɥɨɝɪɚɦɦ ɫɨ ɫɬɨɪɨɧɚɦɢ 1,928 ɢ 1,990 Å. ɇɚ ɜɫɬɚɜɤɟ ɞɥɹ ɥɢɧɢɢ S—O ɢɫɩɨɥɶɡɨɜɚɧɵ ɫɥɟɞɭɸɳɢɟ ɨɛɨɡɧɚɱɟɧɢɹ: S—O1 — ɫɩɥɨɲɧɚɹ ɠɢɪɧɚɹ, S—O2 — ɩɭɧɤɬɢɪɧɚɹ, S—O4 — ɫɩɥɨɲɧɚɹ ɬɨɧɤɚɹ, ɚ ɞɥɹ ɥɢɧɢɣ Li—O — ɩɭɧɤɬɢɪɧɚɹ ɤɪɢɜɚɹ ɫɨɨɬɜɟɬɫɬɜɭɟɬ ɤɨɪɨɬɤɨɣ ɢɡ ɧɢɯ. Ɇɚɤɫɢɦɚɥɶɧɚɹ ɜɚɥɟɧɬɧɚɹ ɩɥɨɬɧɨɫɬɶ ɩɪɢɯɨɞɢɬɫɹ ɧɚ ɩɨɡɢɰɢɢ ɚɧɢɨɧɚ, ɢ ɨɧɚ ɦɚɥɚ ɧɚ ɤɚɬɢɨɧɟ. ɇɟ ɧɚɛɥɸɞɚɟɬɫɹ ɨɛɳɢɯ ɥɢɧɢɣ ɭɪɨɜɧɹ U ɞɥɹ ɫɨɫɟɞɧɢɯ ɚɧɢɨɧɨɜ, ɱɬɨ ɫɜɢɞɟɬɟɥɶɫɬɜɭɟɬ ɨ ɫɥɚɛɨɦ ɩɟɪɟɤɪɵɜɚɧɢɢ ɢɯ ɜɨɥɧɨɜɵɯ ɮɭɧɤɰɢɣ. ɉɥɨɬɧɨɫɬɶ ɧɚ ɚɬɨɦɚɯ ɫɟɪɵ ɫɨɫɬɚɜɥɹɟɬ 0,6 ɟÅ–3, ɢ ɷɬɨ ɡɧɚɱɢɬɟɥɶɧɨ ɦɟɧɶɲɟ, ɱɟɦ ɧɚ ɤɢɫɥɨɪɨɞɟ. ɉɥɨɬɧɨɫɬɶ ɧɚ ɚɬɨɦɚɯ ɤɢɫɥɨɪɨɞɚ ɬɚɤɠɟ ɧɚ ɩɨɪɹɞɨɤ ɛɨɥɶɲɟ, ɱɟɦ ɧɚ ɥɢɬɢɢ, ɢ ɞɥɹ ɷɬɢɯ ɚɬɨɦɨɜ ɧɟ ɧɚɛɥɸɞɚɟɬɫɹ ɨɛɳɢɯ ɤɨɧɬɭɪɧɵɯ ɥɢɧɢɣ. Ʉɨɧɬɭɪɵ ɜɚɥɟɧɬɧɨɣ ɩɥɨɬɧɨɫɬɢ ɡɚɦɟɬɧɨɣ ɜɟɥɢɱɢɧɵ ɨɯɜɚɬɵɜɚɸɬ ɚɬɨɦɵ ɤɢɫɥɨɪɨɞɚ ɢ ɚɧɢɨɧ ɜ ɰɟɥɨɦ. Ɋɚɫɩɪɟɞɟɥɟɧɢɟ ɪɚɡɧɨɫɬɧɨɣ ɩɥɨɬɧɨɫɬɢ ɭɤɚɡɵɜɚɟɬ ɧɚ ɬɨ, ɱɬɨ ɡɚɪɹɞ ɜɵɬɟɤɚɟɬ ɢɡ ɜɧɭɬɪɢɚɬɨɦɧɵɯ ɨɛɥɚɫɬɟɣ ɚɬɨɦɨɜ ɢ ɧɚɬɟɤɚɟɬ ɜɨ ɜɧɟɲɧɢɟ ɨɛɥɚɫɬɢ. Ⱦɥɹ ɚɬɨɦɨɜ ɤɢɫɥɨɪɨɞɚ ɨɧɢ ɢɦɟɸɬ ɚɫɢɦɦɟɬɪɢɱɧɭɸ ɮɨɪɦɭ p-ɨɪɛɢɬɚɥɟɣ V- ɢ S-ɬɢɩɚ (ɩɨ ɨɬɧɨɲɟɧɢɸ ɤ ɥɢɧɢɢ S—O). Ⱦɥɹ ɚɬɨɦɨɜ Ɉ1 ɢ Ɉ2 ɡɚɪɹɞ ɜɵɬɟɤɚɟɬ ɢɡ ɪS-ɨɛɥɚɫɬɢ ɢ ɧɚɬɟɤɚɟɬ ɜ ɪV-ɨɛɥɚɫɬɶ, ɜ ɪɟɡɭɥɶɬɚɬɟ ɱɟɝɨ ɧɚ ɥɢɧɢɹɯ ɫɜɹɡɟɣ Ɋɢɫ. 1. Li2SO4: ɪɚɫɩɪɟɞɟɥɟɧɢɟ ɜɚɥɟɧɬɧɨɣ (ɫɥɟɜɚ) ɢ ɪɚɡɧɨɫɬɧɨɣ (ɫɩɪɚɜɚ) ɩɥɨɬɧɨɫɬɟɣ ɜ ɩɥɨɫɤɨɫɬɢ ab 852 ɘ.ɇ. ɀɍɊȺȼɅȿȼ, Ʌ.ȼ. ɀɍɊȺȼɅȿȼȺ, Ɉ.ȼ. ȽɈɅɈȼɄɈ Ɋɢɫ. 2. Rb2SO4: ɪɚɫɩɪɟɞɟɥɟɧɢɟ ɜɚɥɟɧɬɧɨɣ ɩɥɨɬɧɨɫɬɢ ɜ ɩɥɨɫɤɨɫɬɢ ɚɫ (ɫɥɟɜɚ) ɢ ɪɚɡɧɨɫɬɧɨɣ ɩɥɨɬɧɨɫɬɢ (ɫɩɪɚɜɚ) ɜ ɩɥɨɫɤɨɫɬɢ S—O1—O2 (ɫɜɟɪɯɭ), ɩɥɨɫɤɨɫɬɢ O3—S—O4 (ɫɧɢɡɭ) S—O1, Ɉ2 ɩɨɹɜɥɹɸɬɫɹ ɦɚɤɫɢɦɭɦɵ 'U ɡɚɦɟɬɧɨɣ ɜɟɥɢɱɢɧɵ. Ⱦɥɹ ɚɬɨɦɨɜ Ɉ3, Ɉ4 ɡɚɪɹɞ ɜɵɬɟɤɚɟɬ ɢɡ ɪV-ɨɛɥɚɫɬɟɣ ɢ ɧɚɬɟɤɚɟɬ ɜ ɪS-ɨɛɥɚɫɬɶ ɬɚɤ, ɱɬɨ ɧɚ ɥɢɧɢɢ ɫɜɹɡɢ S—O4 ɩɨɹɜɥɹɟɬɫɹ ɧɟɡɧɚɱɢɬɟɥɶɧɵɣ ɩɨɥɨɠɢɬɟɥɶɧɵɣ ɪɚɡɧɨɫɬɧɵɣ ɡɚɪɹɞ, ɚ ɞɥɹ S—Ɉ3 ɨɧ ɢ ɜɨɜɫɟ ɨɬɫɭɬɫɬɜɭɟɬ. Ɍɚɤɢɦ ɨɛɪɚɡɨɦ, ɯɢɦɢɱɟɫɤɢɟ ɫɜɹɡɢ ɜ ɫɭɥɶɮɚɬɟ ɥɢɬɢɹ ɛɭɞɭɬ ɧɟ ɪɚɜɧɨɡɧɚɱɧɵ, ɢ ɫɜɹɡɶ S—O3 ɹɜɥɹɟɬɫɹ ɧɚɢɦɟɧɟɟ ɩɪɨɱɧɨɣ ɢɡ ɜɫɟɯ ɨɫɬɚɥɶɧɵɯ. Ɉɱɟɜɢɞɧɨ, ɡɞɟɫɶ ɪɟɚɥɢɡɭɟɬɫɹ ɤɨɜɚɥɟɧɬɧɚɹ ɫɜɹɡɶ S-ɬɢɩɚ. Ɋɚɡɥɢɱɧɵɣ ɯɚɪɚɤɬɟɪ ɩɟɪɟɬɨɤɚ ɡɚɪɹɞɚ ɜ ɚɬɨɦɚɯ ɤɢɫɥɨɪɨɞɚ ɫɜɢɞɟɬɟɥɶɫɬɜɭɟɬ ɨ ɬɨɦ, ɱɬɨ ɨɧɢ ɧɚɯɨɞɹɬɫɹ ɜ ɪɚɡɧɨɦ ɡɚɪɹɞɨɜɨɦ ɫɨɫɬɨɹɧɢɢ. ɇɚ ɩɨɡɢɰɢɢ ɚɬɨɦɨɜ ɫɟɪɵ ɩɪɢɯɨɞɢɬɫɹ ɨɬɪɢɰɚɬɟɥɶɧɚɹ ɨɛɥɚɫɬɶ 'U, ɢ ɨɧɢ ɢɦɟɸɬ ɩɨɥɨɠɢɬɟɥɶɧɵɣ ɷɮɮɟɤɬɢɜɧɵɣ ɡɚɪɹɞ. ɗɥɟɤɬɪɨɧɧɵɣ ɡɚɪɹɞ ɜɵɬɟɤɚɟɬ ɢɡ ɨɤɪɟɫɬɧɨɫɬɢ ɹɞɪɚ ɥɢɬɢɹ, ɬɚɤ ɱɬɨ ɷɮɮɟɤɬɢɜɧɵɣ ɡɚɪɹɞ ɚɬɨɦɚ ɩɨɥɨɠɢɬɟɥɶɧɵɣ. Ⱦɥɹ ɚɬɨɦɨɜ Li2 ɨɛɥɚɫɬɢ ɧɚɬɟɤɚɧɢɹ ɡɚɪɹɞɚ ɚɬɨɦɨɜ ɤɢɫɥɨɪɨɞɚ ɨɪɢɟɧɬɢɪɨɜɚɧɵ ɬɚɤ, ɱɬɨ ɧɚ ɥɢɧɢɢ Li2—O ɩɪɢɯɨɞɢɬɫɹ ɧɟɛɨɥɶɲɨɣ ɢɡɛɵɬɨɱɧɵɣ ɷɥɟɤɬɪɨɧɧɵɣ ɡɚɪɹɞ, ɢ ɜ ɷɬɨɦ ɫɥɭɱɚɟ ɦɨɠɧɨ ɝɨɜɨɪɢɬɶ ɨ ɧɚɥɢɱɢɢ ɫɥɚɛɨɣ ɫɜɹɡɢ ɦɟɠɞɭ ɤɢɫɥɨɪɨɞɨɦ ɢ ɥɢɬɢɟɦ. Ⱥɧɚɥɨɝɢɱɧɨɟ ɪɚɫɩɪɟɞɟɥɟɧɢɟ 'U ɧɚɛɥɸɞɚɟɬɫɹ ɢ ɞɥɹ ɚɬɨɦɨɜ Li1. Ɍɚɤɢɦ ɨɛɪɚɡɨɦ, ɜ Li2SO4, ɩɨɦɢɦɨ ɫɭɥɶɮɚɬɧɵɯ ɤɨɦɩɥɟɤɫɨɜ SO4, ɨɛɪɚɡɭɸɬɫɹ ɭɫɬɨɣɱɢɜɵɟ ɨɛɪɚɡɨɜɚɧɢɹ Li1O4, Li2O4. ȼ ɰɟɧɬɪɟ ɩɚɪɚɥɥɟɥɨɝɪɚɦɦɚ Ɉ2—Li2—O2—Li2 ɢɦɟɟɬɫɹ ɥɨɤɚɥɶɧɵɣ ɦɚɤɫɢɦɭɦ ɜɚɥɟɧɬɧɨɣ ɢ ɪɚɡɧɨɫɬɧɨɣ ɩɥɨɬɧɨɫɬɢ, ɤɨɬɨɪɵɣ ɹɜɥɹɟɬɫɹ ɫɜɹɡɭɸɳɢɦ ɡɜɟɧɨɦ ɞɥɹ ɦɨɥɟɤɭɥɹɪɧɵɯ ɝɪɭɩɩ. ɗɬɨɬ ɦɚɤɫɢɦɭɦ ɨɛɟɫɩɟɱɢɜɚɟɬɫɹ, ɜ ɬɨɦ ɱɢɫɥɟ, ɡɚ ɫɱɟɬ ɩɟɪɟɞɚɱɢ ɡɚɪɹɞɚ ɩɨɞɪɟɲɟɬɤɨɣ Li2. Ⱥɧɚɥɨɝɢɱɧɵɦ ɨɛɪɚɡɨɦ ɩɨɞɪɟɲɟɬɤɚ Li1 ɩɟɪɟɞɚɟɬ ɛɨɥɶɲɭɸ ɱɚɫɬɶ ɫɜɨɟɝɨ ɜɚɥɟɧɬɧɨɝɨ ɡɚɪɹɞɚ ɜ ɨɛɥɚɫɬɶ ɦɟɠɞɭ ɚɬɨɦɚɦɢ Ɉ4—Ɉ4 3,118 Å. Ɋɚɫɩɪɟɞɟɥɟɧɢɟ ɜɚɥɟɧɬɧɨɣ ɩɥɨɬɧɨɫɬɢ ɜ ɩɨɞɪɟɲɟɬɤɚɯ Li1, Li2 ɯɚɪɚɤɬɟɪɢɡɭɟɬɫɹ ɟɟ ɦɚɤɫɢɦɚɥɶɧɵɦɢ ɡɧɚɱɟɧɢɹɦɢ ɧɚ ɫɟɪɟɞɢɧɚɯ ɥɢɧɢɣ, ɫɨɟɞɢɧɹɸɳɢɯ ɛɥɢɠɚɣɲɢɟ ɚɬɨɦɵ, ɢ ɦɢɧɢɦɚɥɶɧɵɦɢ ɧɚ ɩɨɡɢɰɢɹɯ ɹɞɟɪ. ɗɬɨ ɨɡɧɚɱɚɟɬ, ɱɬɨ ɜɡɚɢɦɨɞɟɣɫɬɜɢɟ ɚɬɨɦɨɜ ɜ ɩɨɞɪɟɲɟɬɤɚɯ ɩɪɢɜɨɞɢɬ ɤ ɜɧɭɬɪɢɚɬɨɦɧɨɣ s—p-ɝɢɛɪɢɞɢɡɚɰɢɢ, ɢ ɭɠɟ ɜ ɬɚɤɨɣ ɮɨɪɦɟ ɥɢɬɢɣ ɭɱɚɫɬɜɭɟɬ ɜ ɨɛɪɚɡɨɜɚɧɢɢ ɯɢɦɢɱɟɫɤɨɣ ɫɜɹɡɢ. Ɍɚɤɢɦ ɨɛɪɚɡɨɦ, ɢɦɟɧɧɨ ɦɟɬɚɥɥɢɱɟɫɤɢɟ ɩɨɞɪɟɲɟɬɤɢ ɨɛɟɫɩɟɱɢɜɚɸɬ ɭɫɬɨɣɱɢɜɭɸ ɤɨɧɮɢɝɭɪɚɰɢɸ ɚɧɢɨɧɧɵɯ ɝɪɭɩɩ ɨɬɧɨɫɢɬɟɥɶɧɨ ɞɪɭɝ ɞɪɭɝɚ. Ɋɚɫɩɪɟɞɟɥɟɧɢɟ ɜɚɥɟɧɬɧɨɣ ɢ ɪɚɡɧɨɫɬɧɨɣ ɩɥɨɬɧɨɫɬɢ ɜ H-Li2SO4 ɨɬɥɢɱɚɟɬɫɹ ɨɬ E-Li2SO4 ɢ ɩɨɞɨɛɧɨ Na2SO4 [ 8 ]. ȼ H-ɮɚɡɟ ɚɬɨɦɵ ɥɢɬɢɹ ɢ ɤɢɫɥɨɪɨɞɚ ɨɛɪɚɡɭɸɬ ɩɨ ɞɜɟ ɩɨɞɪɟɲɟɬɤɢ, ɩɪɢɱɟɦ Li1—O2 (4 ɚɬɨɦɚ) 1,955, Li1—O1(2) 1,982, ɚ Li2—O2 (2) 1,898, Li2—O1(2) 2,214 Å. ɂɦɟɟɬɫɹ ɡɚɦɟɬɧɨɟ ɩɟɪɟɤɪɵɜɚɧɢɟ ɷɥɟɤɬɪɨɧɧɵɯ ɨɛɥɚɤɨɜ ɩɪɟɠɞɟ ɜɫɟɝɨ ɚɬɨɦɨɜ ɤɢɫɥɨɪɨɞɚ ɜɞɨɥɶ ɧɚɩɪɚɜɥɟ- ɏɂɆɂɑȿɋɄȺə ɋȼəɁɖ ȼ ɋɍɅɖɎȺɌȺɏ ɓȿɅɈɑɇɕɏ ɆȿɌȺɅɅɈȼ 853 ɧɢɣ Ɉ1—Ɉ1 (ɨɫɶ z) ɢ Ɉ2—Ɉ2 (ɨɫɶ ɯ). Ɋɚɡɧɨɫɬɧɚɹ ɩɥɨɬɧɨɫɬɶ ɩɨɤɚɡɵɜɚɟɬ ɜɵɬɟɤɚɧɢɟ ɡɚɪɹɞɚ ɜɞɨɥɶ ɥɢɧɢɢ Ɉ2—Ɉ2 ɢ ɧɚɬɟɤɚɧɢɟ ɧɚ Ɉ1—Ɉ1 ɬɚɤ, ɱɬɨ ɧɚ ɫɜɹɡɢ S—O ɨɛɪɚɡɭɸɬɫɹ ɩɪɢɦɟɪɧɨ ɨɞɢɧɚɤɨɜɵɟ ɦɚɤɫɢɦɭɦɵ (ɦɟɯɚɧɢɡɦ ɩɟɪɟɬɨɤɚ ɡɚɪɹɞɚ pSopV), ɧɨ Ɉ2 ɢɦɟɟɬ ɫɭɳɟɫɬɜɟɧɧɨ ɛɨɥɶɲɢɣ ɨɬɪɢɰɚɬɟɥɶɧɵɣ ɡɚɪɹɞ. Li2 ɩɟɪɟɞɚɟɬ ɫɜɨɣ ɜɚɥɟɧɬɧɵɣ ɡɚɪɹɞ ɜ ɨɛɥɚɫɬɶ ɦɟɠɞɭ ɚɬɨɦɚɦɢ Ɉ1 ɫɨɫɟɞɧɢɯ ɚɧɢɨɧɨɜ, ɚ Li1 — ɜ ɨɛɥɚɫɬɶ ɦɟɠɞɭ ɚɬɨɦɚɦɢ Ɉ2, ɫɬɚɛɢɥɢɡɢɪɭɹ ɬɟɦ ɫɚɦɵɦ ɤɚɪɤɚɫɧɭɸ ɫɬɪɭɤɬɭɪɭ ɢɡ ɚɧɢɨɧɧɵɯ ɰɟɩɨɱɟɤ. ɋɭɥɶɮɚɬɵ ɪɭɛɢɞɢɹ ɢ ɰɟɡɢɹ. Ɋɚɫɩɪɟɞɟɥɟɧɢɟ ɜɚɥɟɧɬɧɨɣ ɢ ɪɚɡɧɨɫɬɧɨɣ ɩɥɨɬɧɨɫɬɢ ɜ Rb2SO4 ɩɪɢɜɟɞɟɧɨ ɧɚ ɪɢɫ. 2. ȼɚɥɟɧɬɧɚɹ ɩɥɨɬɧɨɫɬɶ, ɬɚɤ ɠɟ ɤɚɤ ɢ ɜ ɫɭɥɶɮɚɬɟ ɥɢɬɢɹ, ɦɚɤɫɢɦɚɥɶɧɚ ɧɚ ɚɧɢɨɧɟ ɢ ɦɢɧɢɦɚɥɶɧɚ ɜ ɦɟɠɚɧɢɨɧɧɨɦ ɩɪɨɫɬɪɚɧɫɬɜɟ. Ɉɛɥɚɫɬɶ 0,7 ɟÅ–3 ɜɛɥɢɡɢ ɚɬɨɦɚ ɫɟɪɵ ɜ ɚɧɢɨɧɟ ɹɜɥɹɟɬɫɹ ɫɥɟɞɫɬɜɢɟɦ ɩɟɪɟɫɟɱɟɧɢɹ ɩɥɨɫɤɨɫɬɢ ɚɫ ɥɢɧɢɹɦɢ ɩɥɨɬɧɨɫɬɢ, ɨɯɜɚɬɵɜɚɸɳɢɦɢ ɷɤɜɢɜɚɥɟɧɬɧɵɟ ɚɬɨɦɵ Ɉ3(4), ɪɚɫɩɨɥɨɠɟɧɧɵɦɢ ɜ ɩɟɪɩɟɧɞɢɤɭɥɹɪɧɨɣ ɩɥɨɫɤɨɫɬɢ. ȼ ɷɬɨɦ ɧɚɩɪɚɜɥɟɧɢɢ ɧɚɛɥɸɞɚɟɬɫɹ ɡɚɦɟɬɧɨɟ ɩɟɪɟɤɪɵɜɚɧɢɟ ɜɨɥɧɨɜɵɯ ɮɭɧɤɰɢɣ ɫɨɫɟɞɧɢɯ ɚɧɢɨɧɨɜ ɬɚɤ, ɱɬɨ ɨɧɢ ɨɛɪɚɡɭɸɬ ɰɟɩɨɱɤɢ. Ɏɨɪɦɵ ɷɥɟɤɬɪɨɧɧɵɯ ɨɛɥɚɤɨɜ ɚɬɨɦɨɜ Ɉ1, Ɉ2 ɢɦɟɸɬ ɮɨɪɦɭ ɷɥɥɢɩɫɨɢɞɨɜ ɜɪɚɳɟɧɢɹ. Ɋɚɫɩɪɟɞɟɥɟɧɢɟ ɪɚɡɧɨɫɬɧɨɣ ɩɥɨɬɧɨɫɬɢ Rb2SO4 ɜ ɰɟɥɨɦ ɩɨɞɨɛɧɨ ɫɭɥɶɮɚɬɭ ɤɚɥɢɹ [ 9 ]. Ɉɛɥɚɫɬɢ ɩɟɪɟɬɨɤɚ ɷɥɟɤɬɪɨɧɧɨɝɨ ɡɚɪɹɞɚ ɡɞɟɫɶ ɧɟ ɢɦɟɸɬ ɬɚɤɨɣ ɱɟɬɤɨɣ ɧɚɩɪɚɜɥɟɧɧɨɫɬɢ, ɤɚɤ ɜ E-Li2SO4. Ɂɚɪɹɞ ɧɚɬɟɤɚɟɬ ɜ ɫɜɹɡɵɜɚɸɳɢɟ ɢ ɚɧɬɢɫɜɹɡɵɜɚɸɳɢɟ ɨɛɥɚɫɬɢ ɜɞɨɥɶ ɥɢɧɢɢ S—O. ɇɚɢɛɨɥɶɲɢɣ ɢɡɛɵɬɨɱɧɵɣ ɷɥɟɤɬɪɨɧɧɵɣ ɡɚɪɹɞ ɩɪɢɯɨɞɢɬɫɹ ɧɚ ɥɢɧɢɸ ɫɜɹɡɢ S—O1 ɢ ɧɚɢɦɟɧɶɲɢɣ — S—O3(4). Ɂɚɪɹɞ ɜɵɬɟɤɚɟɬ ɢɡ ɨɛɥɚɫɬɢ ɜɞɨɥɶ ɥɢɧɢɢ Ɉ3—Ɉ4 ɢ ɧɚɬɟɤɚɟɬ ɜɨ ɜɧɟɲɧɸɸ ɨɛɥɚɫɬɶ ɬɚɤ, ɱɬɨ ɨɛɪɚɡɭɟɬɫɹ ɩɨɞɨɛɢɟ ɡɚɪɹɞɨɜɨɣ ɬɪɭɛɤɢ, ɛɥɚɝɨɞɚɪɹ ɤɨɬɨɪɨɣ ɢ ɨɛɪɚɡɭɟɬɫɹ ɭɫɬɨɣɱɢɜɚɹ ɰɟɩɨɱɟɱɧɚɹ ɫɬɪɭɤɬɭɪɚ ɢɡ ɚɧɢɨɧɨɜ. Ⱥɬɨɦɵ ɫɟɪɵ ɧɚɯɨɞɹɬɫɹ ɜ ɨɛɥɚɫɬɢ ɩɨɥɨɠɢɬɟɥɶɧɵɯ ɡɧɚɱɟɧɢɣ 'U ɢ ɢɯ ɷɮɮɟɤɬɢɜɧɵɣ ɡɚɪɹɞ, ɜ ɨɬɥɢɱɢɟ ɨɬ ɫɭɥɶɮɚɬɚ ɥɢɬɢɹ, ɹɜɥɹɟɬɫɹ ɫɤɨɪɟɟ ɨɬɪɢɰɚɬɟɥɶɧɵɦ. Ɂɚɪɹɞ ɬɚɤɠɟ ɜɵɬɟɤɚɟɬ ɢɡ ɨɛɲɢɪɧɵɯ ɨɛɥɚɫɬɟɣ ɚɬɨɦɨɜ ɪɭɛɢɞɢɹ, ɩɨɷɬɨɦɭ ɫɜɹɡɶ ɚɧɢɨɧɨɜ ɢ ɤɚɬɢɨɧɨɜ ɡɞɟɫɶ ɢɦɟɟɬ ɩɪɟɢɦɭɳɟɫɬɜɟɧɧɨ ɢɨɧɧɵɣ ɯɚɪɚɤɬɟɪ. Ⱦɜɨɣɧɵɟ ɫɭɥɶɮɚɬɵ. ɇɚ ɪɢɫ. 3 ɩɪɢɜɟɞɟɧɨ ɪɚɫɩɪɟɞɟɥɟɧɢɟ ɜɚɥɟɧɬɧɨɣ ɢ ɪɚɡɧɨɫɬɧɨɣ ɩɥɨɬɧɨɫɬɢ ɜ ɩɥɨɫɤɨɫɬɢ ac ɦɨɧɨɤɥɢɧɧɨɣ ɮɚɡɵ RLS. Ⱥɬɨɦɵ ɪɭɛɢɞɢɹ ɪɚɫɩɨɥɨɠɟɧɵ ɧɚ ɪɚɫɫɬɨɹɧɢɢ 0,06, 0,04 Å, ɥɢɬɢɹ — 0,02, 0,03 Å, ɫɟɪɵ — 0,01, 0,02 Å, Ɉ1 — 0,01, 0,006 Å, Ɉ4 — 0,48, 0,49 Å ɨɬ ɪɚɫɫɦɚɬɪɢɜɚɟɦɨɣ ɩɥɨɫɤɨɫɬɢ. ɇɚ ɜɫɬɚɜɤɟ ɩɪɢɜɟɞɟɧɚ ɜɚɥɟɧɬɧɚɹ ɢ ɪɚɡɧɨɫɬɧɚɹ ɩɥɨɬɧɨɫɬɶ ɜ ɩɥɨɫɤɨɫɬɢ O1—S—O2, ɪɚɡɧɨɫɬɧɚɹ ɩɥɨɬɧɨɫɬɶ ɜ ɩɥɨɫɤɨɫɬɢ O3—S—O4, ɚ ɬɚɤɠɟ ɩɪɨɮɢɥɢ 'U ɜɞɨɥɶ ɥɢɧɢɣ Ɋɢɫ. 3. Ɋɚɫɩɪɟɞɟɥɟɧɢɹ ɜɚɥɟɧɬɧɨɣ (ɫɥɟɜɚ) ɢ ɪɚɡɧɨɫɬɧɨɣ (ɫɩɪɚɜɚ) ɩɥɨɬɧɨɫɬɢ ɜ ɩɥɨɫɤɨɫɬɢ ac ɦɨɧɨɤɥɢɧɧɨɝɨ RbLiSO4 854 ɘ.ɇ. ɀɍɊȺȼɅȿȼ, Ʌ.ȼ. ɀɍɊȺȼɅȿȼȺ, Ɉ.ȼ. ȽɈɅɈȼɄɈ S—O (ɫɩɥɨɲɧɚɹ ɥɢɧɢɹ) ɢ Li—O (ɩɭɧɤɬɢɪ). Ɋɚɫɩɪɟɞɟɥɟɧɢɟ ɜɚɥɟɧɬɧɨɣ ɢ ɪɚɡɧɨɫɬɧɨɣ ɩɥɨɬɧɨɫɬɢ ɜ ɦɨɧɨɤɥɢɧɧɨɣ ɮɚɡɟ CLS ɢɦɟɟɬ ɤɚɱɟɫɬɜɟɧɧɨ ɩɨɞɨɛɧɵɣ ɜɢɞ. ȼɚɥɟɧɬɧɚɹ ɩɥɨɬɧɨɫɬɶ ɦɚɤɫɢɦɚɥɶɧɚ ɧɚ ɚɧɢɨɧɟ ɢ ɦɢɧɢɦɚɥɶɧɚ ɧɚ ɚɬɨɦɚɯ ɪɭɛɢɞɢɹ. ɗɥɟɤɬɪɨɧɧɨɟ ɨɛɥɚɤɨ ɚɬɨɦɨɜ Ɉ1 ɢɦɟɟɬ ɮɨɪɦɭ ɷɥɥɢɩɫɨɢɞɚ, ɢ ɷɬɨ ɫɨɝɥɚɫɭɟɬɫɹ ɫ ɞɚɧɧɵɦɢ ɪɚɛɨɬɵ [ 20 ], ɝɞɟ RLS ɢɡɭɱɚɥɢ ɦɟɬɨɞɨɦ ɪɟɧɬɝɟɧɨɜɫɤɨɣ ɞɢɮɪɚɤɰɢɢ. Ɍɚɤ ɠɟ ɤɚɤ ɢ ɜ ɫɭɥɶɮɚɬɟ ɪɭɛɢɞɢɹ, ɧɚɛɥɸɞɚɟɬɫɹ ɨɛɪɚɡɨɜɚɧɢɟ ɚɧɢɨɧɧɵɯ ɰɟɩɨɱɟɤ ɜ ɨɫɧɨɜɧɨɦ ɡɚ ɫɱɟɬ ɩɟɪɟɤɪɵɜɚɧɢɹ ɷɥɟɤɬɪɨɧɧɵɯ ɨɛɥɚɤɨɜ ɚɬɨɦɨɜ ɤɢɫɥɨɪɨɞɚ Ɉ1, Ɉ4 ɢ ɫɟɪɵ ɜ ɧɚɩɪɚɜɥɟɧɢɢ ɨɫɢ ɫ. Ɋɨɥɶ ɫɜɹɡɵɜɚɸɳɢɯ ɦɨɫɬɢɤɨɜ ɦɟɠɞɭ ɧɢɦɢ ɢɝɪɚɸɬ ɚɬɨɦɵ Li. Ɋɚɫɩɪɟɞɟɥɟɧɢɟ ɜɚɥɟɧɬɧɨɣ ɩɥɨɬɧɨɫɬɢ ɜ ɩɨɞɪɟɲɟɬɤɟ ɥɢɬɢɹ ɨɬɥɢɱɚɟɬɫɹ ɨɬ ELi2SO4: ɬɟɩɟɪɶ ɟɟ ɦɚɤɫɢɦɭɦ ɩɪɢɯɨɞɢɬɫɹ ɧɚ ɩɨɡɢɰɢɢ, ɜɛɥɢɡɢ ɤɨɬɨɪɵɯ ɜ ɤɪɢɫɬɚɥɥɟ ɪɚɫɩɨɥɚɝɚɸɬɫɹ ɚɬɨɦɵ Ɉ1. Ⱦɥɹ ɚɬɨɦɨɜ Ɉ1 ɢ Ɉ2 ɡɚɪɹɞ ɜɵɬɟɤɚɟɬ ɢɡ ɪS-ɨɛɥɚɫɬɢ ɢ ɧɚɬɟɤɚɟɬ ɜ ɪV-ɨɛɥɚɫɬɶ. ȼ ɪɟɡɭɥɶɬɚɬɟ ɧɚ ɥɢɧɢɢ ɫɜɹɡɢ ɧɚɛɥɸɞɚɟɬɫɹ ɦɚɤɫɢɦɭɦ ɪɚɡɧɨɫɬɧɨɝɨ ɡɚɪɹɞɚ, ɢ ɯɢɦɢɱɟɫɤɚɹ ɫɜɹɡɶ ɢɦɟɟɬ ɜɵɪɚɠɟɧɧɵɣ ɤɨɜɚɥɟɧɬɧɵɣ ɯɚɪɚɤɬɟɪ. ɇɚɨɛɨɪɨɬ, ɞɥɹ ɚɬɨɦɨɜ Ɉ3, Ɉ4 ɡɚɪɹɞ ɜɵɬɟɤɚɟɬ ɢɡ ɪV-ɨɛɥɚɫɬɢ ɢ ɧɚɬɟɤɚɟɬ ɜ ɪS-ɨɛɥɚɫɬɶ (ɦɟɯɚɧɢɡɦ pVopS). Ɋɚɡɧɨɫɬɧɵɣ ɡɚɪɹɞ ɧɚ ɫɜɹɡɹɯ S—O3(4) ɬɟɩɟɪɶ ɡɧɚɱɢɬɟɥɶɧɨ ɦɟɧɶɲɟ, ɱɟɦ ɞɥɹ S—O1(2), ɩɨɷɬɨɦɭ ɨɧɢ ɦɟɧɟɟ ɩɪɨɱɧɵɟ. ɋ ɞɪɭɝɨɣ ɫɬɨɪɨɧɵ, ɜ RLS ɡɚɪɹɞ 'U ɧɚ ɫɜɹɡɢ S—O ɛɨɥɶɲɟ, ɱɟɦ ɜ ɱɢɫɬɵɯ ɫɭɥɶɮɚɬɚɯ. ɉɨɷɬɨɦɭ ɦɨɠɧɨ ɩɪɟɞɩɨɥɨɠɢɬɶ, ɱɬɨ ɨɛɪɚɡɨɜɚɧɢɟ ɞɜɨɣɧɵɯ ɫɭɥɶɮɚɬɨɜ ɫ ɬɨɱɤɢ ɡɪɟɧɢɹ ɯɢɦɢɱɟɫɤɨɣ ɫɜɹɡɢ ɛɨɥɟɟ ɩɪɟɞɩɨɱɬɢɬɟɥɶɧɨ. Ɍɚɤ ɠɟ ɤɚɤ ɢ ɜ ɫɭɥɶɮɚɬɟ ɪɭɛɢɞɢɹ, ɜ ɚɧɢɬɢɫɜɹɡɵɜɚɸɳɟɣ ɨɛɥɚɫɬɢ S—O1(2) ɢɦɟɟɬɫɹ ɢɡɛɵɬɨɱɧɵɣ ɷɥɟɤɬɪɨɧɧɵɣ ɡɚɪɹɞ. Ɉɧ ɩɪɢɯɨɞɢɬɫɹ ɧɚ ɥɢɧɢɸ O1—Li, ɢ, ɬɚɤɢɦ ɨɛɪɚɡɨɦ, ɟɝɨ ɦɨɠɧɨ ɪɚɫɫɦɚɬɪɢɜɚɬɶ ɤɚɤ ɡɚɪɹɞ, ɫɜɹɡɵɜɚɸɳɢɣ ɷɬɢ ɚɬɨɦɵ. Ⱥɧɚɥɨɝɢɱɧɨɟ ɪɚɫɩɪɟɞɟɥɟɧɢɟ 'U ɧɚɛɥɸɞɚɟɬɫɹ ɢ ɞɥɹ ɚɬɨɦɚ Ɉ3. Ⱦɥɹ ɚɬɨɦɨɜ Ɉ2, Ɉ4 ɧɟɛɨɥɶɲɨɣ ɪɚɡɧɨɫɬɧɵɣ ɡɚɪɹɞ ɧɚ ɥɢɧɢɢ Li—O ɜɨɡɧɢɤɚɟɬ ɡɚ ɫɱɟɬ ɩɨɥɨɠɢɬɟɥɶɧɵɯ ɪS-ɨɛɥɚɫɬɟɣ. Ɍɚɤɢɦ ɨɛɪɚɡɨɦ, ɜ ɦɨɧɨɤɥɢɧɧɨɦ RLS, ɬɚɤ ɠɟ ɤɚɤ ɢ ɜ E-Li2SO4, ɨɛɪɚɡɭɸɬɫɹ ɬɟɬɪɚɷɞɪɢɱɟɫɤɢɟ ɤɨɦɩɥɟɤɫɵ LiO4 ɫ ɩɪɢɡɧɚɤɚɦɢ ɤɨɜɚɥɟɧɬɧɨɝɨ ɫɜɹɡɵɜɚɧɢɹ ɚɬɨɦɨɜ. Ⱥɬɨɦɵ ɫɟɪɵ ɧɚɯɨɞɹɬɫɹ ɜ ɨɛɥɚɫɬɹɯ ɫ ɨɬɪɢɰɚɬɟɥɶɧɨɣ 'U, ɱɬɨ ɨɡɧɚɱɚɟɬ ɢɯ ɩɨɥɨɠɢɬɟɥɶɧɵɣ ɷɮɮɟɤɬɢɜɧɵɣ ɡɚɪɹɞ. ȼɛɥɢɡɢ ɚɬɨɦɨɜ ɪɭɛɢɞɢɹ ɪɚɡɧɨɫɬɧɚɹ ɩɥɨɬɧɨɫɬɶ ɨɬɪɢɰɚɬɟɥɶɧɚ, ɢ ɨɧɢ ɢɦɟɸɬ ɩɨɥɨɠɢɬɟɥɶɧɵɣ ɡɚɪɹɞ. ɇɚ ɪɢɫ. 4 ɩɪɢɜɟɞɟɧɨ ɪɚɫɩɪɟɞɟɥɟɧɢɟ ɜɚɥɟɧɬɧɨɣ ɢ ɪɚɡɧɨɫɬɧɨɣ ɩɥɨɬɧɨɫɬɟɣ ɜ ɩɥɨɫɤɨɫɬɢ ac ɨɪɬɨɪɨɦɛɢɱɟɫɤɨɣ ɮɚɡɵ ɋLS. ɇɚ ɜɫɬɚɜɤɟ — ɪɚɫɩɪɟɞɟɥɟɧɢɟ U, 'U ɜ ɩɥɨɫɤɨɫɬɢ S—Ɉ3(4), ɜ ɤɨɬɨɪɨɣ ɧɚɛɥɸɞɚɟɬɫɹ ɡɧɚɱɢɬɟɥɶɧɨɟ ɩɟɪɟɤɪɵɜɚɧɢɟ ɜɨɥɧɨɜɵɯ ɮɭɧɤɰɢɣ ɚɧɢɨɧɨɜ ɢ ɪɚɡɧɨɫɬɧɨɣ ɩɥɨɬɧɨɫɬɢ ɜ ɩɥɨɫɤɨɫɬɢ Li—O3—S, ɝɞɟ ɛɥɢɡɤɨ ɪɚɫɩɨɥɨɠɟɧɵ ɚɬɨɦɵ Ɉ1 ɫɨɫɟɞɧɢɯ ɚɧɢɨɧɨɜ. Ɋɢɫ. 4. Ɋɚɫɩɪɟɞɟɥɟɧɢɟ ɜɚɥɟɧɬɧɨɣ (ɫɥɟɜɚ) ɢ ɪɚɡɧɨɫɬɧɨɣ (ɫɩɪɚɜɚ) ɩɥɨɬɧɨɫɬɢ ɜ ɩɥɨɫɤɨɫɬɢ ac ɨɪɬɨɪɨɦɛɢɱɟɫɤɨɝɨ CsLiSO4 ɏɂɆɂɑȿɋɄȺə ɋȼəɁɖ ȼ ɋɍɅɖɎȺɌȺɏ ɓȿɅɈɑɇɕɏ ɆȿɌȺɅɅɈȼ 855 Ɍɚɤ ɠɟ ɤɚɤ ɢ ɜ ɦɨɧɨɤɥɢɧɧɨɣ ɮɚɡɟ, ɷɥɟɤɬɪɨɧɧɨɟ ɨɛɥɚɤɨ Ɉ1 ɜɛɥɢɡɢ ɹɞɪɚ ɢɦɟɟɬ ɷɥɥɢɩɫɨɢɞɚɥɶɧɭɸ ɮɨɪɦɭ. ɗɥɟɤɬɪɨɧɧɵɟ ɨɛɥɚɤɚ ɚɧɢɨɧɨɜ ɩɟɪɟɤɪɵɜɚɸɬɫɹ ɜ ɧɚɩɪɚɜɥɟɧɢɢ Ɉ3—Ɉ4, ɩɟɪɩɟɧɞɢɤɭɥɹɪɧɨɦ ɭɤɚɡɚɧɧɨɣ ɩɥɨɫɤɨɫɬɢ, ɝɞɟ ɬɚɤɠɟ ɨɛɪɚɡɭɸɬɫɹ ɰɟɩɨɱɤɢ. ȼ ɪɚɫɩɪɟɞɟɥɟɧɢɢ U ɢɦ ɨɬɜɟɱɚɸɬ ɦɚɤɫɢɦɭɦɵ ɫɨ ɡɧɚɱɟɧɢɟɦ 0,7 eÅ–3. ȼ ɪɚɡɧɨɫɬɧɨɣ ɩɥɨɬɧɨɫɬɢ ɞɥɹ ɚɬɨɦɨɜ ɤɢɫɥɨɪɨɞɚ Ɉ1, Ɉ2, ɫ ɤɪɚɬɱɚɣɲɢɦɢ ɪɚɫɫɬɨɹɧɢɹɦɢ S—O ɢ Li—O, ɡɚɪɹɞ ɜɵɬɟɤɚɟɬ ɢɡ ɪS-ɨɛɥɚɫɬɢ ɢ ɧɚɬɟɤɚɟɬ ɜ ɪV-ɨɛɥɚɫɬɶ, ɜ ɪɟɡɭɥɶɬɚɬɟ ɱɟɝɨ ɧɚ ɷɬɢɯ ɥɢɧɢɹɯ ɨɛɪɚɡɭɸɬɫɹ ɩɨɥɨɠɢɬɟɥɶɧɵɟ ɦɚɤɫɢɦɭɦɵ ɪɚɡɧɨɫɬɧɨɝɨ ɡɚɪɹɞɚ. ɇɚɬɟɤɚɧɢɟ ɡɚɪɹɞɚ ɧɚɛɥɸɞɚɟɬɫɹ ɢ ɧɚ ɥɢɧɢɢ Li—O3(4), ɢ ɜ CLS ɬɚɤɠɟ ɨɛɪɚɡɭɸɬɫɹ ɤɨɦɩɥɟɤɫɵ LiO4. Ɂɚɪɹɞ ɜɵɬɟɤɚɟɬ ɢɡ ɨɛɲɢɪɧɨɣ ɪV-ɨɛɥɚɫɬɢ ɹɞɟɪ Ɉ3(4) ɢ ɧɚɬɟɤɚɟɬ ɜ ɪS-ɨɛɥɚɫɬɶ, ɜ ɪɟɡɭɥɶɬɚɬɟ ɱɟɝɨ ɧɚ ɥɢɧɢɹɯ S—O3(4), Li— O3(4) ɨɛɪɚɡɭɸɬɫɹ ɦɚɤɫɢɦɭɦɵ 'U ɦɟɧɶɲɟɣ, ɱɟɦ ɞɥɹ ɚɬɨɦɨɜ Ɉ1(2), ɜɟɥɢɱɢɧɵ. ɉɪɢ ɩɟɪɟɯɨɞɟ ɢɡ ɧɢɡɤɨɬɟɦɩɟɪɚɬɭɪɧɨɣ ɭɩɨɪɹɞɨɱɟɧɧɨɣ ɦɨɧɨɤɥɢɧɧɨɣ ɮɚɡɵ ɜ ɨɪɬɨɪɨɦɛɢɱɟɫɤɭɸ ɜ CLS, RLS ɪɚɫɫɬɨɹɧɢɹ S—O, Li—O ɫɬɚɧɨɜɹɬɫɹ ɦɟɧɶɲɟ (ɡɚ ɢɫɤɥɸɱɟɧɢɟɦ ɜ CLS ɪɚɫɫɬɨɹɧɢɹ Li—O3 (CLS), Li—O4 (RLS)). ȼ ɪɚɡɧɨɫɬɧɨɣ ɩɥɨɬɧɨɫɬɢ ɷɬɨ ɩɪɨɹɜɥɹɟɬɫɹ ɜ ɭɦɟɧɶɲɟɧɢɢ ɦɚɤɫɢɦɭɦɚ 'U ɧɚ ɥɢɧɢɢ ɫɚɦɨɣ ɤɨɪɨɬɤɨɣ ɫɜɹɡɢ S—O ɢ ɭɜɟɥɢɱɟɧɢɢ ɧɚ ɥɢɧɢɹɯ S—O3(4). ɉɪɢ ɷɬɨɦ, ɜɟɥɢɱɢɧɵ ɢɡɛɵɬɨɱɧɨɝɨ ɡɚɪɹɞɚ ɧɚ ɚɬɨɦɚɯ Ɉ1, Ɉ2 ɩɪɚɤɬɢɱɟɫɤɢ ɧɟ ɢɡɦɟɧɹɸɬɫɹ, ɬɨɝɞɚ ɤɚɤ ɧɚ Ɉ3(4) ɡɧɚɱɢɬɟɥɶɧɨ ɜɨɡɪɚɫɬɚɸɬ. Ɂɚɪɹɞɨɜɵɟ ɫɨɫɬɨɹɧɢɹ ɷɬɢɯ ɚɬɨɦɨɜ ɢɡɦɟɧɹɸɬɫɹ, ɢ ɨɧɢ ɢɦɟɸɬ ɦɟɧɶɲɢɣ ɨɬɪɢɰɚɬɟɥɶɧɵɣ ɡɚɪɹɞ. Ɍɚɤɠɟ ɜ ɫɬɨɪɨɧɭ ɭɦɟɧɶɲɟɧɢɹ ɢɡɦɟɧɹɟɬɫɹ ɡɚɪɹɞ ɚɬɨɦɨɜ ɫɟɪɵ. ɉɪɢ ɩɟɪɟɯɨɞɟ ɨɬ ɦɨɧɨɤɥɢɧɧɨɣ ɤ ɨɪɬɨɪɨɦɛɢɱɟɫɤɨɣ ɮɚɡɟ ɧɚɛɥɸɞɚɟɬɫɹ ɭɦɟɧɶɲɟɧɢɟ ɪɚɡɧɨɫɬɧɨɝɨ ɡɚɪɹɞɚ ɜ ɨɛɥɚɫɬɹɯ ɦɟɠɞɭ ɚɬɨɦɚɦɢ ɥɢɬɢɹ ɢ ɤɢɫɥɨɪɨɞɚ. Ɍɚɤɢɦ ɨɛɪɚɡɨɦ, ɮɚɡɨɜɵɣ ɩɟɪɟɯɨɞ ɜ ɞɜɨɣɧɵɯ ɫɭɥɶɮɚɬɚɯ ɫɨɩɪɨɜɨɠɞɚɟɬɫɹ ɢɡɦɟɧɟɧɢɟɦ ɫɢɥɵ ɯɢɦɢɱɟɫɤɨɝɨ ɫɜɹɡɵɜɚɧɢɹ ɦɟɠɞɭ ɚɬɨɦɚɦɢ ɤɢɫɥɨɪɨɞɚ ɢ ɥɢɬɢɹ, ɱɬɨ ɢ ɩɪɢɜɨɞɢɬ ɤ ɛɨɥɶɲɟɣ ɫɬɟɩɟɧɢ ɫɜɨɛɨɞɵ ɜɪɚɳɚɬɟɥɶɧɨɝɨ ɞɜɢɠɟɧɢɹ ɫɭɥɶɮɚɬɧɵɯ ɝɪɭɩɩ. ɁȺɄɅɘɑȿɇɂȿ Ⱦɥɹ ɢɫɫɥɟɞɨɜɚɧɢɹ ɯɢɦɢɱɟɫɤɨɣ ɫɜɹɡɢ ɜ ɫɭɥɶɮɚɬɚɯ ɳɟɥɨɱɧɵɯ ɦɟɬɚɥɥɨɜ ɢɫɩɨɥɶɡɭɟɬɫɹ ɪɚɡɧɨɫɬɧɚɹ ɩɥɨɬɧɨɫɬɶ, ɤɨɬɨɪɚɹ ɭɤɚɡɵɜɚɟɬ ɧɚɩɪɚɜɥɟɧɢɹ ɩɟɪɟɬɨɤɚ ɷɥɟɤɬɪɨɧɧɨɝɨ ɡɚɪɹɞɚ, ɜɵɡɜɚɧɧɨɝɨ ɜɡɚɢɦɨɞɟɣɫɬɜɢɟɦ ɫɨɫɬɚɜɥɹɸɳɢɯ ɤɪɢɫɬɚɥɥ ɩɨɞɪɟɲɟɬɨɤ. ȼ ɫɭɥɶɮɚɬɟ ɥɢɬɢɹ ɡɚɪɹɞ ɜɵɬɟɤɚɟɬ ɢɡ ɜɧɭɬɪɢɚɬɨɦɧɵɯ ɨɛɥɚɫɬɟɣ ɢ ɧɚɬɟɤɚɟɬ ɜɨ ɜɧɟɲɧɢɟ ɨɛɥɚɫɬɢ ɤɢɫɥɨɪɨɞɚ ɬɚɤɢɦ ɨɛɪɚɡɨɦ, ɱɬɨ ɧɚ ɥɢɧɢɹɯ S—O ɢ O—Li ɨɛɪɚɡɭɸɬɫɹ ɦɚɤɫɢɦɭɦɵ ɪɚɡɥɢɱɧɨɣ ɜɟɥɢɱɢɧɵ. ɗɬɨ ɩɪɢɜɨɞɢɬ ɤ ɨɛɪɚɡɨɜɚɧɢɸ ɦɟɠɞɭ ɚɬɨɦɚɦɢ ɤɢɫɥɨɪɨɞɚ ɢ ɫɟɪɵ V- ɢ S-ɤɨɜɚɥɟɧɬɧɨɣ ɯɢɦɢɱɟɫɤɨɣ ɫɜɹɡɢ. ɇɚɥɢɱɢɟ ɢɡɛɵɬɨɱɧɨɝɨ ɡɚɪɹɞɚ ɜ ɫɜɹɡɵɜɚɸɳɢɯ ɨɛɥɚɫɬɹɯ O—Li ɭɤɚɡɵɜɚɟɬ ɧɚ ɫɜɹɡɶ ɦɟɠɞɭ ɧɢɦɢ, ɨɞɧɚɤɨ ɨɬɫɭɬɫɬɜɢɟ ɡɚɦɟɬɧɨɝɨ ɩɟɪɟɤɪɵɜɚɧɢɹ ɷɥɟɤɬɪɨɧɧɵɯ ɨɛɥɚɤɨɜ ɚɬɨɦɨɜ ɧɟ ɩɨɡɜɨɥɹɟɬ ɬɪɚɤɬɨɜɚɬɶ ɟɟ ɤɚɤ ɤɨɜɚɥɟɧɬɧɭɸ. Ɍɚɤɢɦ ɨɛɪɚɡɨɦ, ɜ ɷɬɨɦ ɫɨɟɞɢɧɟɧɢɢ ɫɭɥɶɮɚɬɧɵɟ ɝɪɭɩɩɵ SO4 ɫɜɹɡɚɧɵ ɦɟɠɞɭ ɫɨɛɨɣ ɤɨɧɰɟɜɵɦɢ ɚɬɨɦɚɦɢ ɤɢɫɥɨɪɨɞɚ ɱɟɪɟɡ ɚɬɨɦɵ ɥɢɬɢɹ, ɤɨɬɨɪɵɟ ɛɥɚɝɨɞɚɪɹ ɜɧɭɬɪɢɚɬɨɦɧɨɣ s— pɝɢɛɪɢɞɢɡɚɰɢɢ ɨɛɪɚɡɭɸɬ ɭɫɬɨɣɱɢɜɵɟ ɤɨɦɩɥɟɤɫɵ LiO4. ȼ ɫɭɥɶɮɚɬɚɯ ɪɭɛɢɞɢɹ, ɰɟɡɢɹ ɡɚɪɹɞɨɜɵɟ ɫɨɫɬɨɹɧɢɹ ɤɢɫɥɨɪɨɞɚ ɢ ɫɢɥɚ ɢɯ ɯɢɦɢɱɟɫɤɨɝɨ ɫɜɹɡɵɜɚɧɢɹ ɫ ɫɟɪɨɣ ɬɚɤɠɟ ɪɚɡɥɢɱɚɸɬɫɹ, ɨɞɧɚɤɨ ɞɨɦɢɧɢɪɭɸɳɢɦ ɮɚɤɬɨɪɨɦ ɨɛɪɚɡɨɜɚɧɢɹ ɤɪɢɫɬɚɥɥɚ ɹɜɥɹɟɬɫɹ ɢɨɧɧɨɟ ɜɡɚɢɦɨɞɟɣɫɬɜɢɟ ɫɭɥɶɮɚɬ-ɢɨɧɨɜ ɢ ɤɚɬɢɨɧɨɜ. ȼ ɞɜɨɣɧɵɯ ɫɭɥɶɮɚɬɚɯ ɧɚɛɥɸɞɚɟɬɫɹ ɤɨɦɛɢɧɢɪɨɜɚɧɧɨɟ ɜɡɚɢɦɨɞɟɣɫɬɜɢɟ, ɤɨɝɞɚ ɩɟɪɟɤɪɵɜɚɧɢɟ ɷɥɟɤɬɪɨɧɧɵɯ ɨɛɥɚɤɨɜ SO4 ɩɪɢɜɨɞɢɬ ɤ ɨɛɪɚɡɨɜɚɧɢɸ ɰɟɩɨɱɟɱɧɨɣ ɫɬɪɭɤɬɭɪɵ, ɫɜɹɡɭɸɳɢɦ ɡɜɟɧɨɦ ɤɨɬɨɪɨɣ ɹɜɥɹɸɬɫɹ ɢɨɧɵ ɥɢɬɢɹ, ɚ ɬɹɠɟɥɵɟ ɦɟɬɚɥɥɵ—ɤɚɬɢɨɧɵ, ɨɛɟɫɩɟɱɢɜɚɸɬ ɫɬɚɛɢɥɢɡɚɰɢɸ ɤɚɪɤɚɫɧɨɣ ɫɬɪɭɤɬɭɪɵ ɜ ɰɟɥɨɦ. ɉɪɢ ɮɚɡɨɜɵɯ ɩɟɪɟɯɨɞɚɯ ɩɪɨɢɫɯɨɞɢɬ ɨɫɥɚɛɥɟɧɢɟ ɜɡɚɢɦɨɞɟɣɫɬɜɢɹ ɥɢɬɢɹ ɫ ɤɢɫɥɨɪɨɞɨɦ ɢ ɩɨɜɵɲɟɧɢɟ ɜɪɚɳɚɬɟɥɶɧɵɯ ɫɬɟɩɟɧɟɣ ɫɜɨɛɨɞɵ ɫɭɥɶɮɚɬɧɵɯ ɝɪɭɩɩ. ɋɉɂɋɈɄ ɅɂɌȿɊȺɌɍɊɕ 1. 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