ɀ ɍ Ɋ ɇ Ⱥ Ʌ ɋ Ɍ Ɋ ɍ... Ɍɨɦ 47, ʋ 1 əɧɜɚɪɶ – ɮɟɜɪɚɥɶ ɋ. 163 – 169
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ɀɍɊɇȺɅ ɋɌɊɍɄɌɍɊɇɈɃ ɏɂɆɂɂ 2006. Ɍɨɦ 47, ʋ 1 əɧɜɚɪɶ – ɮɟɜɪɚɥɶ ɋ. 163 – 169 ɍȾɄ 544.23.02;541.64 ɄɈɇɎɈɊɆȺɐɂɈɇɇɕȿ ɂɁɆȿɇȿɇɂə ɆɈɅȿɄɍɅɕ ȾɇɄ ɉɊɂ ȿȿ ȼɁȺɂɆɈȾȿɃɋɌȼɂɂ ɋ ȻɂɈɅɈȽɂɑȿɋɄɂ ȺɄɌɂȼɇɕɆɂ ɋɈȿȾɂɇȿɇɂəɆɂ. I. ȼɅɂəɇɂȿ ɂɈɇɈȼ ɆȿɌȺɅɅɈȼ ɇȺ ɄɈɇɎɈɊɆȺɐɂɘ ɆɈɅȿɄɍɅɕ ȾɇɄ ȼ ɊȺɋɌȼɈɊȿ 2006 ɇ.Ⱥ. Ʉɚɫɶɹɧɟɧɤɨ* ɋɚɧɤɬ-ɉɟɬɟɪɛɭɪɝɫɤɢɣ ɝɨɫɭɞɚɪɫɬɜɟɧɧɵɣ ɭɧɢɜɟɪɫɢɬɟɬ ɋɬɚɬɶɹ ɩɨɫɬɭɩɢɥɚ 7 ɚɩɪɟɥɹ 2005 ɝ. Ɋɚɫɫɦɨɬɪɟɧɨ ɜɥɢɹɧɢɟ ɢɨɧɨɜ ɦɟɬɚɥɥɨɜ ɪɚɡɧɨɣ ɜɚɥɟɧɬɧɨɫɬɢ ɧɚ ɤɨɧɮɨɪɦɚɰɢɸ ɦɨɥɟɤɭɥɵ ȾɇɄ ɜ ɪɚɫɬɜɨɪɟ. ɉɪɨɜɟɞɟɧ ɚɧɚɥɢɡ ɜɥɢɹɧɢɹ ɤɨɧɰɟɧɬɪɚɰɢɢ ɢ ɡɚɪɹɞɚ ɩɪɨɬɢɜɨɢɨɧɨɜ ɧɚ ɨɛɴɟɦ, ɩɟɪɫɢɫɬɟɧɬɧɭɸ ɞɥɢɧɭ ɢ ɜɬɨɪɢɱɧɭɸ ɫɬɪɭɤɬɭɪɭ ɦɚɤɪɨɦɨɥɟɤɭɥɵ. ȼɵɩɨɥɧɟɧɚ ɨɰɟɧɤɚ ɩɪɨɬɟɤɚɟɦɨɫɬɢ ɦɨɥɟɤɭɥɹɪɧɨɝɨ ɤɥɭɛɤɚ ȾɇɄ ɞɥɹ ɪɚɫɬɜɨɪɢɬɟɥɹ ɩɪɢ ɪɚɡɧɨɣ ɢɨɧɧɨɣ ɫɢɥɟ ɪɚɫɬɜɨɪɚ. ɉɨɞɪɨɛɧɨ ɪɚɫɫɦɨɬɪɟɧɨ ɫɨɫɬɨɹɧɢɟ ɦɨɥɟɤɭɥɵ ȾɇɄ ɜ ɪɚɫɬɜɨɪɚɯ ɛɨɥɶɲɨɣ ɢɨɧɧɨɣ ɫɢɥɵ, ɤɨɝɞɚ ɩɪɢɫɭɬɫɬɜɢɟ ɧɟɤɨɬɨɪɵɯ ɢɨɧɨɜ ɜɵɡɵɜɚɟɬ ɪɟɡɤɨɟ ɢɡɦɟɧɟɧɢɟ ɨɩɬɢɱɟɫɤɨɣ ɚɧɢɡɨɬɪɨɩɢɢ ɦɚɤɪɨɦɨɥɟɤɭɥɵ. Ʉ ɥ ɸ ɱ ɟ ɜ ɵ ɟ ɫ ɥ ɨ ɜ ɚ : ɩɨɥɢɷɥɟɤɬɪɨɥɢɬɧɵɟ ɫɜɨɣɫɬɜɚ ȾɇɄ, ɢɨɧɵ ɦɟɬɚɥɥɨɜ, ɩɟɪɫɢɫɬɟɧɬɧɚɹ ɞɥɢɧɚ. Ɋɚɫɬɜɨɪɵ ȾɇɄ ɱɚɫɬɨ ɢɫɩɨɥɶɡɭɸɬ ɜ ɤɚɱɟɫɬɜɟ ɭɞɨɛɧɵɯ ɦɨɞɟɥɶɧɵɯ ɫɢɫɬɟɦ ɞɥɹ ɢɡɭɱɟɧɢɹ ɦɨɥɟɤɭɥɹɪɧɨɝɨ ɦɟɯɚɧɢɡɦɚ ɞɟɣɫɬɜɢɹ ɪɚɡɥɢɱɧɵɯ ɥɟɤɚɪɫɬɜɟɧɧɵɯ ɩɪɟɩɚɪɚɬɨɜ. ȼ ɪɚɫɬɜɨɪɚɯ ɜ ɲɢɪɨɤɨɣ ɨɛɥɚɫɬɢ pH ȾɇɄ ɹɜɥɹɟɬɫɹ ɩɨɥɢɢɨɧɨɦ ɫ ɜɵɫɨɤɨɣ ɩɥɨɬɧɨɫɬɶɸ ɨɬɪɢɰɚɬɟɥɶɧɨɝɨ ɡɚɪɹɞɚ, ɩɨɷɬɨɦɭ ɞɥɹ ɩɨɧɢɦɚɧɢɹ ɯɚɪɚɤɬɟɪɚ ɟɟ ɜɡɚɢɦɨɞɟɣɫɬɜɢɹ ɫ ɛɢɨɥɨɝɢɱɟɫɤɢ ɚɤɬɢɜɧɵɦɢ ɫɨɟɞɢɧɟɧɢɹɦɢ ɧɟɨɛɯɨɞɢɦɨ ɨɛɥɚɞɚɬɶ ɢɧɮɨɪɦɚɰɢɟɣ ɨ ɜɥɢɹɧɢɢ ɢɨɧɧɵɯ ɯɚɪɚɤɬɟɪɢɫɬɢɤ ɫɪɟɞɵ ɧɚ ɤɨɧɮɨɪɦɚɰɢɸ ɦɚɤɪɨɦɨɥɟɤɭɥɵ. ȼ ɦɨɞɟɥɶɧɵɯ ɫɢɫɬɟɦɚɯ ɩɪɨɰɟɫɫ ɨɛɪɚɡɨɜɚɧɢɹ ɛɢɨɥɨɝɢɱɟɫɤɢ ɡɧɚɱɢɦɵɯ ɤɨɦɩɥɟɤɫɨɜ ɭɞɨɛɧɨ ɪɚɫɫɦɚɬɪɢɜɚɬɶ ɤɚɤ ɜ ɭɫɥɨɜɢɹɯ ɧɟɞɨɫɬɚɬɤɚ ɩɪɨɬɢɜɨɢɨɧɨɜ (ɷɬɨ, ɤɚɤ ɩɪɚɜɢɥɨ, ɨɛɟɫɩɟɱɢɜɚɟɬ ɛɨɥɟɟ ɹɪɤɨɟ ɩɪɨɹɜɥɟɧɢɟ ɤɨɧɮɨɪɦɚɰɢɨɧɧɵɯ ɢɡɦɟɧɟɧɢɣ ɦɚɤɪɨɦɨɥɟɤɭɥɵ ɩɪɢ ɤɨɦɩɥɟɤɫɨɨɛɪɚɡɨɜɚɧɢɢ), ɬɚɤ ɢ ɩɪɢ ɛɨɥɶɲɨɣ ɢɨɧɧɨɣ ɫɢɥɟ ɪɚɫɬɜɨɪɚ, ɩɨɫɤɨɥɶɤɭ ɩɪɢ ɩɨɞɚɜɥɟɧɢɢ ɩɨɥɢɷɥɟɤɬɪɨɥɢɬɧɨɝɨ ɧɚɛɭɯɚɧɢɹ ȾɇɄ ɦɨɠɧɨ ɜɵɞɟɥɢɬɶ ɧɟɷɥɟɤɬɪɨɫɬɚɬɢɱɟɫɤɭɸ ɫɨɫɬɚɜɥɹɸɳɭɸ ɜɡɚɢɦɨɞɟɣɫɬɜɢɹ. ɍɋɅɈȼɂə ɗɄɋɉȿɊɂɆȿɇɌȺ ȼɟɥɢɱɢɧɭ ɯɚɪɚɤɬɟɪɢɫɬɢɱɟɫɤɨɣ ɜɹɡɤɨɫɬɢ [Ș] lim (Kr 1) / c , ɩɪɨɩɨɪɰɢɨɧɚɥɶɧɭɸ ɭɞɟɥɶɧɨɦɭ g o0, c o0 ɨɛɴɟɦɭ ɦɚɤɪɨɦɨɥɟɤɭɥɵ, ɨɩɪɟɞɟɥɹɥɢ ɩɭɬɟɦ ɷɤɫɬɪɚɩɨɥɹɰɢɢ ɩɪɢɜɟɞɟɧɧɨɣ ɜɹɡɤɨɫɬɢ ɪɚɫɬɜɨɪɨɜ (Kr–1)/ɫ ɤ ɧɭɥɟɜɨɣ ɤɨɧɰɟɧɬɪɚɰɢɢ ȾɇɄ. Ɉɬɧɨɫɢɬɟɥɶɧɭɸ ɜɹɡɤɨɫɬɶ Kr ɢɡɦɟɪɹɥɢ ɩɪɢ ɪɚɡɧɵɯ ɝɪɚɞɢɟɧɬɚɯ ɫɤɨɪɨɫɬɢ ɩɨɬɨɤɚ g ɫ ɩɨɦɨɳɶɸ ɧɢɡɤɨɝɪɚɞɢɟɧɬɧɨɝɨ ɪɨɬɚɰɢɨɧɧɨɝɨ ɜɢɫɤɨɡɢɦɟɬɪɚ ɬɢɩɚ Ɂɢɦɦɚ — Ʉɪɨɡɟɪɫɚ [ 1 ]. Ɇɨɥɟɤɭɥɹɪɧɭɸ ɦɚɫɫɭ ȾɇɄ ɨɩɪɟɞɟɥɹɥɢ ɩɨ ɡɧɚɱɟɧɢɸ [ K ] ɜ 0,15 M NaCl. ȼɟɥɢɱɢɧɭ ɞɜɨɣɧɨɝɨ ɥɭɱɟɩɪɟɥɨɦɥɟɧɢɹ 'n ɪɚɫɬɜɨɪɨɜ ȾɇɄ ɢɡɦɟɪɹɥɢ ɧɚ ɭɫɬɚɧɨɜɤɟ ɫ ɩɨɥɭɬɟɧɟɜɵɦ ɷɥɥɢɩɬɢɱɟɫɤɢɦ ɤɨɦɩɟɧɫɚɬɨɪɨɦ [ 2 ]. Ɉɩɪɟɞɟɥɹɥɢ ɞɢɧɚɦɨɨɩɬɢɱɟɫɤɭɸ ɩɨɫɬɨɹɧɧɭɸ > n@ lim 'n / gCȘ0 . Ⱦɥɹ ɪɚɫɬɜɨɪɨɜ ȾɇɄ ɫɩɪɚɜɟɞɥɢɜɨ [ 3 ]: g o0, C o0 * E-mail: kasyan@paloma.spbu.ru 164 ɇ.Ⱥ. ɄȺɋɖəɇȿɇɄɈ 'n g g o0 > n@ Șr 1 Ș0 > Ș@ n 2 s 2 2 4ʌ S ȕ1 ȕ 2 . ns 45kT Ɂɞɟɫɶ ns — ɩɨɤɚɡɚɬɟɥɶ ɩɪɟɥɨɦɥɟɧɢɹ ɪɚɫɬɜɨɪɢɬɟɥɹ; S — ɱɢɫɥɨ ɡɜɟɧɶɟɜ ɜ ɫɬɚɬɢɫɬɢɱɟɫɤɨɦ ɫɟɝɦɟɧɬɟ; ( ȕ1 ȕ 2 ) — ɨɩɬɢɱɟɫɤɚɹ ɚɧɢɡɨɬɪɨɩɢɹ ɩɚɪɵ ɧɭɤɥɟɨɬɢɞɨɜ. Ɉɬɧɨɲɟɧɢɟ [ n ]/[ K ] ɩɪɨɩɨɪɰɢɨɧɚɥɶɧɨ ɨɩɬɢɱɟɫɤɨɣ ɚɧɢɡɨɬɪɨɩɢɢ ɦɚɤɪɨɦɨɥɟɤɭɥɵ (J1 – J2), ɝɞɟ J1 ɢ J2 — ɟɟ ɩɨɥɹɪɢɡɭɟɦɨɫɬɶ ɨɬɧɨɫɢɬɟɥɶɧɨ ɝɥɚɜɧɵɯ ɨɫɟɣ ɦɨɥɟɤɭɥɹɪɧɨɝɨ ɷɥɥɢɩɫɨɢɞɚ. ɍɝɥɨɜɭɸ ɡɚɜɢɫɢɦɨɫɬɶ ɩɪɢɜɟɞɟɧɧɨɣ ɢɧɬɟɧɫɢɜɧɨɫɬɢ ɢɡɛɵɬɨɱɧɨɝɨ ɪɚɫɫɟɹɧɢɹ I ɜ ɪɚɫɬɜɨɪɚɯ ɛɨɥɶɲɨɣ ɢɨɧɧɨɣ ɫɢɥɵ ɨɩɪɟɞɟɥɹɥɢ ɩɪɢ ɪɚɡɧɨɣ ɤɨɧɰɟɧɬɪɚɰɢɢ ȾɇɄ ɧɚ ɭɫɬɚɧɨɜɤɟ Sofica. Ɇɨɥɟɤɭɥɹɪɧɭɸ ɦɚɫɫɭ ɨɛɪɚɡɰɚ ɨɩɪɟɞɟɥɹɥɢ ɫ ɩɨɦɨɳɶɸ ɦɟɬɨɞɚ ɞɜɨɣɧɨɣ ɷɤɫɬɪɚɩɨɥɹɰɢɢ ɜɟɥɢɱɢɧɵ ɫK/I (ɝɞɟ K — ɨɩɬɢɱɟɫɤɚɹ ɤɨɧɫɬɚɧɬɚ, c — ɤɨɧɰɟɧɬɪɚɰɢɹ ɪɚɫɬɜɨɪɚ) ɤ ɫ = 0 ɢ ș = 0 (ș — ɭɝɨɥ ɪɚɫɫɟɹɧɢɹ) [ 4 ]. ɋɩɟɤɬɪɵ ɤɪɭɝɨɜɨɝɨ ɞɢɯɪɨɢɡɦɚ (ɄȾ) ɪɟɝɢɫɬɪɢɪɨɜɚɥɢ ɫ ɩɨɦɨɳɶɸ ɚɜɬɨɞɢɯɪɨɝɪɚɮɚ JobinYvon Mark 4 (Ɏɪɚɧɰɢɹ). ȼ ɪɚɛɨɬɟ ɢɫɩɨɥɶɡɨɜɚɥɢ ɤɨɦɦɟɪɱɟɫɤɢɟ ɩɪɟɩɚɪɚɬɵ ȾɇɄ ɬɢɦɭɫɚ ɬɟɥɟɧɤɚ ɮɢɪɦɵ Sigma. ȼ ɪɹɞɟ ɫɥɭɱɚɟɜ (ɩɪɢ ɩɪɨɜɟɞɟɧɢɢ ɷɤɫɩɟɪɢɦɟɧɬɨɜ ɜ ɪɚɫɬɜɨɪɚɯ ɛɨɥɶɲɨɣ ɢɨɧɧɨɣ ɫɢɥɵ) ɞɨɩɨɥɧɢɬɟɥɶɧɭɸ ɨɱɢɫɬɤɭ ȾɇɄ ɨɫɭɳɟɫɬɜɥɹɥɢ ɫɨɝɥɚɫɧɨ ɫɬɚɧɞɚɪɬɧɨɣ ɩɪɨɰɟɞɭɪɟ [ 5 ]. ɂɡɦɟɪɟɧɢɹ ɩɪɨɜɨɞɢɥɢ ɩɪɢ ɬɟɦɩɟɪɚɬɭɪɟ 21 qɋ. ɊȿɁɍɅɖɌȺɌɕ ɂ ɂɏ ɈȻɋɍɀȾȿɇɂȿ ɉɨɜɟɞɟɧɢɟ ɜɵɫɨɤɨɦɨɥɟɤɭɥɹɪɧɨɣ ȾɇɄ ɜ ɪɚɫɬɜɨɪɟ ɩɪɢ ɢɡɦɟɧɟɧɢɢ ɢɨɧɧɨɣ ɫɢɥɵ I ɢɡɭɱɟɧɨ ɞɨɫɬɚɬɨɱɧɨ ɯɨɪɨɲɨ. ȼ ɲɢɪɨɤɨɣ ɨɛɥɚɫɬɢ I ɧɚɛɥɸɞɚɟɬɫɹ ɩɨɥɢɷɥɟɤɬɪɨɥɢɬɧɨɟ ɧɚɛɭɯɚɧɢɟ ȾɇɄ ɛɟɡ ɢɡɦɟɧɟɧɢɹ ɟɟ ɪɚɜɧɨɜɟɫɧɨɣ ɠɟɫɬɤɨɫɬɢ. ɉɪɢ ɦɚɥɵɯ ɡɧɚɱɟɧɢɹɯ I < 0,003 M NaCl ɩɪɨɢɫɯɨɞɢɬ ɜɨɡɪɚɫɬɚɧɢɟ ɩɟɪɫɢɫɬɟɧɬɧɨɣ ɞɥɢɧɵ ɦɚɤɪɨɦɨɥɟɤɭɥɵ ɚ ɜ ɪɟɡɭɥɶɬɚɬɟ ɢɡɦɟɧɟɧɢɹ ɛɥɢɠɧɢɯ ɷɥɟɤɬɪɨɫɬɚɬɢɱɟɫɤɢɯ ɜɡɚɢɦɨɞɟɣɫɬɜɢɣ. ɉɪɢ ɛɨɥɶɲɢɯ ɠɟ ɡɧɚɱɟɧɢɹɯ I > 1 M ɧɚɛɥɸɞɚɟɬɫɹ ɩɨɞɚɜɥɟɧɢɟ ɩɨɥɢɷɥɟɤɬɪɨɥɢɬɧɨɝɨ ɧɚɛɭɯɚɧɢɹ, ɚ ɨɛɴɟɦ ɦɚɤɪɨɦɨɥɟɤɭɥɵ ɨɩɪɟɞɟɥɹɟɬɫɹ ɬɟɪɦɨɞɢɧɚɦɢɱɟɫɤɢɦɢ ɨɛɴɟɦɧɵɦɢ ɷɮɮɟɤɬɚɦɢ ɧɟɷɥɟɤɬɪɨɫɬɚɬɢɱɟɫɤɨɣ ɩɪɢɪɨɞɵ [ 6 ]. Ɂɚɜɢɫɢɦɨɫɬɶ ɯɚɪɚɤɬɟɪɢɫɬɢɱɟɫɤɨɣ ɜɹɡɤɨɫɬɢ [ K ] ȾɇɄ ɨɬ I –1/2 ɞɨɫɬɚɬɨɱɧɨ ɩɨɥɧɨ ɢɥɥɸɫɬɪɢɪɭɟɬ ɷɬɢ ɜɵɜɨɞɵ (ɪɢɫ. 1). ɗɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɟ ɞɚɧɧɵɟ ɜ ɰɟɥɨɦ ɫɨɝɥɚɫɭɸɬɫɹ ɫ ɬɟɨɪɟɬɢɱɟɫɤɨɣ ɡɚɜɢɫɢɦɨɫɬɶɸ [ K ] ɨɬ I –1/2 ɞɥɹ ȾɇɄ, ɩɨɥɭɱɟɧɧɨɣ ɜ ɪɚɛɨɬɟ [ 7 ]: >K@ >K@ 0 (at / a0 )3/2 Į3 , Ɋɢɫ. 1. Ɂɚɜɢɫɢɦɨɫɬɶ ɨɬɧɨɫɢɬɟɥɶɧɨɝɨ ɢɡɦɟɧɟɧɢɹ ɯɚɪɚɤɬɟɪɢɫɬɢɱɟɫɤɨɣ ɜɹɡɤɨɫɬɢ ɢ ɩɟɪɫɢɫɬɟɧɬɧɨɣ ɞɥɢɧɵ ȾɇɄ (ɧɚ ɜɫɬɚɜɤɟ) ɨɬ I –1/2 ɜ ɪɚɫɬɜɨɪɚɯ NaCl (1) ɢ MgCl2 (3). Ʉɪɢɜɚɹ 2 ɫɨɨɬɜɟɬɫɬɜɭɟɬ ɬɟɨɪɟɬɢɱɟɫɤɨɣ ɡɚɜɢɫɢɦɨɫɬɢ [ K ] ɨɬ I –1/2 [ 7 ] (1) ɄɈɇɎɈɊɆȺɐɂɈɇɇɕȿ ɂɁɆȿɇȿɇɂə ɆɈɅȿɄɍɅɕ ȾɇɄ 165 ɝɞɟ [ Ș ]0 — ɡɧɚɱɟɧɢɟ ɯɚɪɚɤɬɟɪɢɫɬɢɱɟɫɤɨɣ ɜɹɡɤɨɫɬɢ ɩɪɢ sɛɟɫɤɨɧɟɱɧɨ ɦɚɥɨɣ ɢɨɧɧɨɣ ɫɢɥɟs ɪɚɫɬɜɨɪɚ; at = a0 + ae, ɝɞɟ at — ɩɨɥɧɚɹ ɩɟɪɫɢɫɬɟɧɬɧɚɹ ɞɥɢɧɚ ɰɟɩɢ, ɹɜɥɹɸɳɚɹɫɹ ɫɭɦɦɨɣ sɫɤɟɥɟɬɧɨɣs ɩɟɪɫɢɫɬɟɧɬɧɨɣ ɞɥɢɧɵ a0 ɢ ɟɟ ɷɥɟɤɬɪɨɫɬɚɬɢɱɟɫɤɨɣ ɫɨɫɬɚɜɥɹɸɳɟɣ ae; D — ɤɨɷɮɮɢɰɢɟɧɬ ɥɢɧɟɣɧɨɝɨ ɧɚɛɭɯɚɧɢɹ, ɨɬɜɟɱɚɸɳɢɣ ɡɚ ɭɜɟɥɢɱɟɧɢɟ ɜɹɡɤɨɫɬɢ ɜɫɥɟɞɫɬɜɢɟ ɩɨɥɢɷɥɟɤɬɪɨɥɢɬɧɨɝɨ ɧɚɛɭɯɚɧɢɹ. ȼ ɪɚɛɨɬɟ [ 7 ] ɞɥɹ ɜɵɱɢɫɥɟɧɢɹ Į ɢɫɩɨɥɶɡɭɟɬɫɹ ɜɵɪɚɠɟɧɢɟ [ 8 ] D2 = 0,541 + 0,459(1 + 6,04Zel)0,46. (2) ɉɚɪɚɦɟɬɪ ɢɫɤɥɸɱɟɧɧɨɝɨ ɨɛɴɟɦɚ Zel [ 9 ]: 33 / 2 1/ 2 3 / 2 Z el L rD at . (3) 4S1/ 2 Ɂɞɟɫɶ L — ɝɢɞɪɨɞɢɧɚɦɢɱɟɫɤɚɹ ɞɥɢɧɚ ɰɟɩɢ; rD — ɪɚɞɢɭɫ Ⱦɟɛɚɹ; rD = (8SlB I )–1/2, ɝɞɟ lB = q2/(HkT) — ɛɶɟɪɪɭɦɨɜɫɤɚɹ ɞɥɢɧɚ; q — ɷɥɟɦɟɧɬɚɪɧɵɣ ɡɚɪɹɞ; İ — ɞɢɷɥɟɤɬɪɢɱɟɫɤɚɹ ɩɨɫɬɨɹɧɧɚɹ ɫɪɟɞɵ; k — ɩɨɫɬɨɹɧɧɚɹ Ȼɨɥɶɰɦɚɧɚ; T — ɚɛɫɨɥɸɬɧɚɹ ɬɟɦɩɟɪɚɬɭɪɚ. ɏɨɞ ɬɟɨɪɟɬɢɱɟɫɤɨɣ ɡɚɜɢɫɢɦɨɫɬɢ [ K ] ɨɬ I –1/2 ɯɨɪɨɲɨ ɫɨɝɥɚɫɭɟɬɫɹ ɫ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɨɣ ɜ ɨɛɥɚɫɬɢ ɦɚɥɵɯ ɢɨɧɧɵɯ ɫɢɥ (ɫɦ. ɪɢɫ. 1). Ɉɞɧɚɤɨ ɬɟɨɪɢɹ ɩɪɟɞɫɤɚɡɵɜɚɟɬ ɧɚɪɭɲɟɧɢɟ ɥɢɧɟɣɧɨɣ ɡɚɜɢɫɢɦɨɫɬɢ ɩɪɢ ɛóɥɶɲɢɯ I, ɱɟɦ ɷɬɨ ɧɚɛɥɸɞɚɟɬɫɹ ɧɚ ɨɩɵɬɟ. ɗɬɨ ɫɜɹɡɚɧɨ ɫ ɩɟɪɟɨɰɟɧɤɨɣ ɪɨɥɢ ɛɥɢɠɧɢɯ ɷɥɟɤɬɪɨɫɬɚɬɢɱɟɫɤɢɯ ɜɡɚɢɦɨɞɟɣɫɬɜɢɣ ɜ ɨɛɥɚɫɬɢ ɭɦɟɪɟɧɧɵɯ ɢɨɧɧɵɯ ɫɢɥ. ɋɥɟɞɭɟɬ ɨɬɦɟɬɢɬɶ, ɱɬɨ ɨɩɪɟɞɟɥɟɧɢɟ ɬɟɪɦɨɞɢɧɚɦɢɱɟɫɤɨɣ ɠɟɫɬɤɨɫɬɢ ɜɫɟɝɞɚ ɹɜɥɹɟɬɫɹ ɫɚɦɨɣ ɫɥɨɠɧɨɣ ɡɚɞɚɱɟɣ ɩɪɢ ɨɩɢɫɚɧɢɢ ɤɨɧɮɨɪɦɚɰɢɢ ɦɚɤɪɨɦɨɥɟɤɭɥ. Ʉɨɦɛɢɧɚɰɢɹ ɦɟɬɨɞɨɜ ɞɢɧɚɦɢɱɟɫɤɨɝɨ ɞɜɨɣɧɨɝɨ ɥɭɱɟɩɪɟɥɨɦɥɟɧɢɹ ɢ ɜɢɫɤɨɡɢɦɟɬɪɢɢ ɩɨɡɜɨɥɹɟɬ ɨɩɪɟɞɟɥɢɬɶ ɨɩɬɢɱɟɫɤɭɸ ɚɧɢɡɨɬɪɨɩɢɸ ɫɬɚɬɢɫɬɢɱɟɫɤɨɝɨ ɫɟɝɦɟɧɬɚ (D1 – D2), ɫɜɹɡɚɧɧɭɸ ɫ ɩɟɪɫɢɫɬɟɧɬɧɨɣ ɞɥɢɧɨɣ ȾɇɄ ɚt ɫɨɨɬɧɨɲɟɧɢɟɦ (D1 – D2) = (2ɚt / b)'E (ɡɞɟɫɶ 'E — ɫɪɟɞɧɹɹ ɨɩɬɢɱɟɫɤɚɹ ɚɧɢɡɨɬɪɨɩɢɹ; b = 0,34 ɧɦ — ɩɪɨɟɤɰɢɹ ɞɥɢɧɵ ɩɚɪɵ ɧɭɤɥɟɨɬɢɞɨɜ ɧɚ ɨɫɶ ɫɩɢɪɚɥɢ). Ɉɩɪɟɞɟɥɟɧɧɚɹ ɜ ɧɚɲɟɦ ɷɤɫɩɟɪɢɦɟɧɬɟ ɡɚɜɢɫɢɦɨɫɬɶ ɜɟɥɢɱɢɧɵ ɚt ɨɬ rD ɜ ɪɚɫɬɜɨɪɚɯ NaCl (ɫɦ. ɪɢɫ. 1, ɜɫɬɚɜɤɚ) ɞɨɫɬɚɬɨɱɧɨ ɯɨɪɨɲɨ ɫɨɝɥɚɫɭɟɬɫɹ ɫ ɪɟɡɭɥɶɬɚɬɚɦɢ ɬɚɤ ɧɚɡɵɜɚɟɦɨɣ ɬɟɨɪɢɢ OSF (ɬɟɨɪɢɢ Ɉɞɚɣɤɚ — ɒɤɨɥɶɧɢɤɚ — Ɏɢɤɫɦɚɧɚ) [ 9 — 11 ], ɫɨɝɥɚɫɧɨ ɤɨɬɨɪɨɣ ɷɥɟɤɬɪɨɫɬɚɬɢɱɟɫɤɚɹ ɫɨɫɬɚɜɥɹɸɳɚɹ ɩɟɪɫɢɫɬɟɧɬɧɨɣ ɞɥɢɧɵ ae = r 2D /(4lB). ɉɪɢ ɩɟɪɟɯɨɞɟ ɨɬ ɨɞɧɨɜɚɥɟɧɬɧɵɯ ɩɪɨɬɢɜɨɢɨɧɨɜ ɤ ɞɜɭɯɜɚɥɟɧɬɧɵɦ ɷɮɮɟɤɬɢɜɧɨɫɬɶ ɷɤɪɚɧɢɪɨɜɤɢ ɡɚɪɹɞɚ ȾɇɄ ɜɨɡɪɚɫɬɚɟɬ (ɪɢɫ. 2, ɜɫɬɚɜɤɚ). ɉɪɢ ɷɬɨɦ ɩɨɥɢɷɥɟɤɬɪɨɥɢɬɧɨɟ ɧɚɛɭɯɚɧɢɟ ɦɚɤɪɨɦɨɥɟɤɭɥɵ ɭɦɟɧɶɲɚɟɬɫɹ ɧɟɡɚɜɢɫɢɦɨ ɨɬ ɦɟɫɬɚ ɫɜɹɡɵɜɚɧɢɹ ɞɜɭɯɜɚɥɟɧɬɧɵɯ ɢɨɧɨɜ [ 12 ], ɚ ɩɟɪɫɢɫɬɟɧɬɧɚɹ ɞɥɢɧɚ ȾɇɄ ɫɨɯɪɚɧɹɟɬ ɧɟɢɡɦɟɧɧɨɟ ɡɧɚɱɟɧɢɟ ɜ ɛɨɥɟɟ ɲɢɪɨɤɨɣ ɨɛɥɚɫɬɢ ɢɨɧɧɵɯ ɫɢɥ (ɫɦ. ɪɢɫ. 1). Ⱦɨɛɚɜɥɟɧɢɟ ɜ ɪɚɫɬɜɨɪ ȾɇɄ ɞɨɫɬɚɬɨɱɧɨ ɦɚɥɵɯ ɤɨɧɰɟɧɬɪɚɰɢɣ ɬɪɟɯɜɚɥɟɧɬɧɵɯ ɩɪɨɬɢɜɨɢɨɧɨɜ CM3+ ɜɵɡɵɜɚɟɬ ɪɟɡɤɨɟ ɭɦɟɧɶɲɟɧɢɟ ɨɛɴɟɦɚ ɦɚɤɪɨɦɨɥɟɤɭɥɵ ɞɚɠɟ ɜ ɪɚɫɬɜɨɪɚɯ ɛɨɥɶɲɨɣ ɢɨɧɧɨɣ ɫɢɥɵ (ɫɦ. ɪɢɫ. 2), ɚ ɩɪɢ ɞɨɫɬɢɠɟɧɢɢ ɨɩɪɟɞɟɥɟɧɧɨɣ CM3+ ȾɇɄ ɜɵɩɚɞɚɟɬ ɜ ɨɫɚɞɨɤ. ɗɬɨɦɭ ɜ ɪɹɞɟ ɫɥɭɱɚɟɜ ɩɪɟɞɲɟɫɬɜɭɟɬ ɨɛɪɚɡɨɜɚɧɢɟ ɤɨɧɞɟɧɫɢɪɨɜɚɧɧɵɯ ɫɬɪɭɤɬɭɪ ɨɩɪɟɞɟɥɟɧɧɨɣ ɦɨɪɮɨɥɨɝɢɢ. Ɂɚɦɟɬɢɦ, ɱɬɨ ɧɚɛɥɸɞɚɟɦɨɟ ɩɪɢ ɞɨɛɚɜɥɟɧɢɢ ɬɪɟɯɜɚɥɟɧɬɧɵɯ ɩɪɨɬɢɜɨɊɢɫ. 2. Ɂɚɜɢɫɢɦɨɫɬɶ ɨɬɧɨɫɢɬɟɥɶɧɨɝɨ ɢɡɦɟɧɟɧɢɹ ɯɚɪɚɤɬɟɪɢɫɬɢɱɟɫɤɨɣ ɜɹɡɤɨɫɬɢ ȾɇɄ [ K ]/[ K ]0 ɨɬ ɤɨɧɰɟɧɬɪɚɰɢɢ [Co(NH3)6]Cl3 (1), LaCl3 (2, 5), FeCl3 (3, 4) ɜ 0,005 M (1, 2, 3) ɢ 1 M NaCl (4, 5). ɇɚ ɜɫɬɚɜɤɟ — ɡɚɜɢɫɢɦɨɫɬɶ [ K ]/[ K ]0 ȾɇɄ ɨɬ ɜɤɥɚɞɚ, ɜɧɨɫɢɦɨɝɨ ɜ ɢɨɧɧɭɸ ɫɢɥɭ ɪɚɫɬɜɨɪɚ ɢɨɧɚɦɢ Mg2+ (1, 5), Mn2+ (2, 6), Ba2+ (3), Cu2+ (4) ɩɪɢ I = 0,005 M (1–4), 1 M (5, 6) 166 ɇ.Ⱥ. ɄȺɋɖəɇȿɇɄɈ ɢɨɧɨɜ ɜ ɪɚɫɬɜɨɪ ȾɇɄ ɛɨɥɶɲɨɣ ɢɨɧɧɨɣ ɫɢɥɵ (1 Ɇ NaCl) ɭɦɟɧɶɲɟɧɢɟ ɪɚɡɦɟɪɨɜ ɦɚɤɪɨɦɨɥɟɤɭɥɵ ɫɜɹɡɚɧɨ ɧɟ ɫ ɢɡɦɟɧɟɧɢɟɦ ɷɤɪɚɧɢɪɨɜɤɢ ɟɟ ɡɚɪɹɞɚ, ɚ ɫ ɜɧɭɬɪɢɦɨɥɟɤɭɥɹɪɧɵɦ ɫɬɪɭɤɬɭɪɢɪɨɜɚɧɢɟɦ ɜɫɥɟɞɫɬɜɢɟ ɩɨɹɜɥɟɧɢɹ ɜɡɚɢɦɧɨ ɨɪɢɟɧɬɢɪɨɜɚɧɧɵɯ ɭɱɚɫɬɤɨɜ ȾɇɄ, ɫɜɹɡɚɧɧɵɯ ɬɪɟɯɜɚɥɟɧɬɧɵɦɢ ɢɨɧɚɦɢ [ 13, 14 ]. ɂɡ ɪɚɫɫɦɨɬɪɟɧɧɵɯ ɪɟɡɭɥɶɬɚɬɨɜ ɹɫɧɨ, ɱɬɨ ɩɪɢ ɥɸɛɵɯ ɢɫɫɥɟɞɨɜɚɧɢɹɯ ɤɨɧɰɟɧɬɪɚɰɢɹ ɢ ɫɨɫɬɚɜ ɩɨɞɞɟɪɠɢɜɚɸɳɟɝɨ ɷɥɟɤɬɪɨɥɢɬɚ ɡɚɞɚɸɬ ɫɨɫɬɨɹɧɢɟ ɦɨɥɟɤɭɥɵ ȾɇɄ ɜ ɪɚɫɬɜɨɪɟ. Ʉɚɤ ɭɠɟ ɨɬɦɟɱɚɥɨɫɶ, ɢɫɫɥɟɞɨɜɚɧɢɟ ɜɡɚɢɦɨɞɟɣɫɬɜɢɹ ɛɢɨɥɨɝɢɱɟɫɤɢ ɚɤɬɢɜɧɵɯ ɫɨɟɞɢɧɟɧɢɣ ɫ ɦɨɥɟɤɭɥɨɣ ȾɇɄ ɭɞɨɛɧɨ ɩɪɨɜɨɞɢɬɶ, ɜɚɪɶɢɪɭɹ ɤɨɧɰɟɧɬɪɚɰɢɸ ɩɪɨɬɢɜɨɢɨɧɨɜ. ȼ ɪɚɫɬɜɨɪɚɯ ɦɚɥɨɣ ɢɨɧɧɨɣ ɫɢɥɵ ɞɥɹ ɢɫɤɥɸɱɟɧɢɹ ɞɟɫɬɚɛɢɥɢɡɚɰɢɢ ɜɬɨɪɢɱɧɨɣ ɫɬɪɭɤɬɭɪɵ ȾɇɄ ɫɥɟɞɭɟɬ ɨɝɪɚɧɢɱɢɜɚɬɶɫɹ ɨɛɥɚɫɬɶɸ I, ɜ ɤɨɬɨɪɨɣ ɧɟ ɢɡɦɟɧɹɸɬɫɹ ɛɥɢɠɧɢɟ ɷɥɟɤɬɪɨɫɬɚɬɢɱɟɫɤɢɟ ɜɡɚɢɦɨɞɟɣɫɬɜɢɹ. ɋɨɝɥɚɫɧɨ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɦ ɞɚɧɧɵɦ, ɷɬɢ ɭɫɥɨɜɢɹ ɜɵɩɨɥɧɹɸɬɫɹ ɩɪɢ I > 0,003. ȼɵɛɨɪ ɨɩɬɢɦɚɥɶɧɨɝɨ ɡɧɚɱɟɧɢɹ I ɜ ɨɛɥɚɫɬɢ ɜɵɫɨɤɨɣ ɤɨɧɰɟɧɬɪɚɰɢɢ ɩɨɞɞɟɪɠɢɜɚɸɳɟɝɨ ɷɥɟɤɬɪɨɥɢɬɚ (ɨɛɵɱɧɨ ɢɫɩɨɥɶɡɭɸɬ ɪɚɫɬɜɨɪ NaCl) ɨɛɭɫɥɨɜɥɟɧ ɫɥɟɞɭɸɳɢɦɢ ɨɛɫɬɨɹɬɟɥɶɫɬɜɚɦɢ. ɗɤɫɩɟɪɢɦɟɧɬ ɩɨɤɚɡɚɥ, ɱɬɨ ɩɪɢ ɢɫɩɨɥɶɡɨɜɚɧɢɢ ɨɞɧɨ- ɢ ɞɜɭɯɜɚɥɟɧɬɧɵɯ ɩɪɨɬɢɜɨɢɨɧɨɜ ɜ ɨɛɥɚɫɬɢ I > 1 M ɜɟɥɢɱɢɧɚ [ K ], ɩɪɨɩɨɪɰɢɨɧɚɥɶɧɚɹ ɨɛɴɟɦɭ ɦɨɥɟɤɭɥɵ ȾɇɄ, ɩɟɪɟɫɬɚɟɬ ɡɚɜɢɫɟɬɶ ɨɬ ɢɨɧɧɨɣ ɫɢɥɵ ɪɚɫɬɜɨɪɚ (ɪɢɫ. 3), ɱɬɨ ɫɜɢɞɟɬɟɥɶɫɬɜɭɟɬ ɨ ɩɨɥɧɨɦ ɩɨɞɚɜɥɟɧɢɢ ɞɚɥɶɧɢɯ ɷɥɟɤɬɪɨɫɬɚɬɢɱɟɫɤɢɯ ɜɡɚɢɦɨɞɟɣɫɬɜɢɣ (ɤɚɤ ɨɬɦɟɱɚɥɨɫɶ ɪɚɧɟɟ, ɛɥɢɠɧɢɟ ɷɥɟɤɬɪɨɫɬɚɬɢɱɟɫɤɢɟ ɜɡɚɢɦɨɞɟɣɫɬɜɢɹ ɦɟɧɹɸɬɫɹ ɥɢɲɶ ɩɪɢ ɜɟɫɶɦɚ ɦɚɥɵɯ ɡɧɚɱɟɧɢɹɯ I ). ȼ ɷɬɨɣ ɨɛɥɚɫɬɢ ɢɨɧɧɵɯ ɫɢɥ ɨɩɬɢɱɟɫɤɚɹ ɚɧɢɡɨɬɪɨɩɢɹ ȾɇɄ ɦɟɧɹɟɬɫɹ ɫɥɨɠɧɵɦ ɨɛɪɚɡɨɦ (ɪɢɫ. 4). ɇɟɫɦɨɬɪɹ ɧɚ ɩɨɥɧɨɟ ɩɨɞɚɜɥɟɧɢɟ ɩɨɥɢɷɥɟɤɬɪɨɥɢɬɧɨɝɨ ɧɚɛɭɯɚɧɢɹ, ɜ ɨɛɥɚɫɬɢ ɛɨɥɶɲɢɯ ɢɨɧɧɵɯ ɫɢɥ ɪɚɫɬɜɨɪɢɬɟɥɶ ɜɫɟ ɟɳɟ ɨɫɬɚɟɬɫɹ ɯɨɪɨɲɢɦ ɞɥɹ ȾɇɄ [ 6 ]. ɉɪɢ ɷɬɨɦ ɜɬɨɪɨɣ ɜɢɪɢɚɥɶɧɵɣ ɤɨɷɮɮɢɰɢɟɧɬ ɛɨɥɶɲɟ ɧɭɥɹ, ɤɚɤ ɷɬɨ ɫɥɟɞɭɟɬ ɢɡ ɞɚɧɧɵɯ, ɩɨɥɭɱɟɧɧɵɯ ɦɟɬɨɞɨɦ ɫɜɟɬɨɪɚɫɫɟɹɧɢɹ (ɫɦ. ɜɫɬɚɜɤɭ ɧɚ ɪɢɫ. 4). ɂɧɵɦɢ ɫɥɨɜɚɦɢ, ɞɚɠɟ ɜ ɭɫɥɨɜɢɹɯ ɢɡɛɵɬɤɚ ɫɨɥɢ ɜɡɚɢɦɨɞɟɣɫɬɜɢɟ ɩɪɨɬɢɜɨɢɨɧɨɜ ɫ ɦɚɤɪɨɦɨɥɟɤɭɥɨɣ ɨɫɭɳɟɫɬɜɥɹɟɬɫɹ ɱɟɪɟɡ ɜɨɞɭ, ɬɚɤ ɤɚɤ ɩɪɢ sɩɨɫɚɞɤɟs ɢɨɧɨɜ ɧɚ ɮɨɫɮɚɬɧɵɟ ɝɪɭɩɩɵ ȾɇɄ ɧɟɢɡɛɟɠɧɨ ɬɟɪɹɟɬ ɫɜɨɸ ɝɢɞɪɨɮɢɥɶɧɨɫɬɶ, ɱɬɨ ɫɩɨɫɨɛɫɬɜɭɟɬ ɟɟ ɜɵɩɚɞɟɧɢɸ ɜ ɨɫɚɞɨɤ. Ⱦɥɹ ɞɟɧɚɬɭɪɢɪɨɜɚɧɧɨɣ ȾɇɄ, ɝɢɞɪɨɮɨɛɧɵɟ ɨɫɧɨɜɚɧɢɹ ɤɨɬɨɪɨɣ ɧɚɯɨɞɹɬɫɹ ɜ ɛɨɥɶɲɟɦ ɤɨɧɬɚɤɬɟ ɫ ɜɨɞɨɣ, ɜɵɫɚɥɢɜɚɧɢɟ ɩɪɨɢɫɯɨɞɢɬ ɩɪɢ I > 2 M NaCl [ 15 ]. ȼ ɨɛɥɚɫɬɢ ɛɨɥɶɲɢɯ ɢɨɧɧɵɯ ɫɢɥ, ɤɨɝɞɚ ɨɛɴɟɦɧɵɟ ɷɮɮɟɤɬɵ ɦɚɥɵ [ 6 ], ɞɥɹ ɚɧɚɥɢɡɚ ɝɢɞɪɨɞɢɧɚɦɢɱɟɫɤɨɝɨ ɩɨɜɟɞɟɧɢɹ ȾɇɄ ɦɨɠɧɨ ɜɨɫɩɨɥɶɡɨɜɚɬɶɫɹ ɜɵɪɚɠɟɧɢɟɦ [ 16 ]: M = Q(A)–3/2M 1/2 + (R/A)[ln(A/d) – 1,43], >K@ ɝɞɟ Q ɢ R — ɤɨɧɫɬɚɧɬɵ ɞɥɹ ɞɚɧɧɨɣ ɫɢɫɬɟɦɵ ɩɨɥɢɦɟɪ — ɪɚɫɬɜɨɪɢɬɟɥɶ; Ⱥ — ɞɥɢɧɚ ɫɬɚɬɢɫɬɢɱɟɫɤɨɝɨ ɫɟɝɦɟɧɬɚ; d — ɟɝɨ ɷɮɮɟɤɬɢɜɧɵɣ ɞɢɚɦɟɬɪ. ȼɵɪɚɠɟɧɢɟ ɫɩɪɚɜɟɞɥɢɜɨ, ɤɨɝɞɚ ɱɢɫɥɨ ɫɟɝɦɟɧɬɨɜ N #1. ɋɨɝɥɚɫɧɨ ɷɬɨɣ ɬɟɨɪɢɢ, ɪɚɡɜɢɬɨɣ ɞɥɹ ɠɟɫɬɤɨɰɟɩɧɵɯ ɩɪɨɬɟɤɚɟɦɵɯ ɩɨɥɢɦɟɪɨɜ ɛɟɡ ɨɛɴɟɦɧɵɯ ɷɮɮɟɤɬɨɜ, ɡɚɜɢɫɢɦɨɫɬɶ M / [ K ] ɨɬ Ɇ 1/2 ɩɨɡɜɨɥɹɟɬ ɨɰɟɧɢɬɶ ɩɪɨɬɟɤɚɟɦɨɫɬɶ ɤɥɭɛɤɚ (ɩɨ ɨɬɪɟɡɤɭ, ɨɬɫɟɤɚɟɦɨɦɭ ɧɚ ɨɫɢ ɨɪɞɢɧɚɬ) ɢ ɠɟɫɬɤɨɫɬɶ ɦɚɤɪɨɦɨɥɟɤɭɥ (ɢɡ ɧɚɤɥɨɧɚ ɡɚɜɢɫɢɦɨɫɬɢ). ɗɬɢ Ɋɢɫ. 3. Ɂɚɜɢɫɢɦɨɫɬɶ ɯɚɪɚɤɬɟɪɢɫɬɢɱɟɫɤɨɣ ɜɹɡɤɨɫɬɢ ȾɇɄ ɨɬ I –1/2 ɞɥɹ ȾɇɄ ɜ ɪɚɫɬɜɨɪɚɯ NaCl (1, 6, 7), LiCl (2), MgCl2 (3), MnCl2 (4), NiCl2 (5). Ɇɨɥɟɤɭɥɹɪɧɚɹ ɦɚɫɫɚ ȾɇɄ Ɇ = 9106 (1–5), 14106 (6), 2,6106 Ⱦɚ (7) ɄɈɇɎɈɊɆȺɐɂɈɇɇɕȿ ɂɁɆȿɇȿɇɂə ɆɈɅȿɄɍɅɕ ȾɇɄ 167 Ɋɢɫ. 4. Ɂɚɜɢɫɢɦɨɫɬɶ ɨɬɧɨɫɢɬɟɥɶɧɨɝɨ ɢɡɦɟɧɟɧɢɹ ɨɩɬɢɱɟɫɤɨɣ ɚɧɢɡɨɬɪɨɩɢɢ ȾɇɄ (J1 – J2)/(J1 – J2)0 ɨɬ ɤɨɧɰɟɧɬɪɚɰɢɢ NaCl (1) ɢ MgCl2 (2). ɇɚ ɜɫɬɚɜɤɟ — ɪɟɡɭɥɶɬɚɬɵ ɢɫɫɥɟɞɨɜɚɧɢɹ ɪɚɫɬɜɨɪɨɜ ȾɇɄ ɜ 2,8 M NaCl ɦɟɬɨɞɨɦ ɫɜɟɬɨɪɚɫɫɟɹɧɢɹ. ɉɨɥɭɱɟɧɧɨɟ ɡɧɚɱɟɧɢɟ Ɇ = (11r1)106 Ⱦɚ ɫɨɜɩɚɞɚɟɬ ɫɨ ɡɧɚɱɟɧɢɟɦ Ɇ = 11,5106 Ⱦɚ, ɨɩɪɟɞɟɥɟɧɧɵɦ ɜ 0,15 Ɇ NaCl ɩɚɪɚɦɟɬɪɵ ɦɨɠɧɨ ɨɰɟɧɢɬɶ ɢ ɩɨ ɦɨɞɟɥɢ ɱɟɪɜɟɨɛɪɚɡɧɨɝɨ ɫɮɟɪɨɰɢɥɢɧɞɪɚ [ 17 ]. Ɉɩɵɬ ɩɨɤɚɡɚɥ, ɱɬɨ ɞɚɠɟ ɩɪɢ ɛɨɥɶɲɢɯ ɤɨɧɰɟɧɬɪɚɰɢɹɯ NaCl ɢ MgCl2 ɜ ɪɚɫɬɜɨɪɟ ɧɟ ɧɚɛɥɸɞɚɟɬɫɹ ɥɢɧɟɣɧɨɣ ɡɚɜɢɫɢɦɨɫɬɢ M / [ K ] ɨɬ Ɇ 1/2 (ɪɢɫ. 5). ɗɬɨ ɫɜɢɞɟɬɟɥɶɫɬɜɭɟɬ ɨ ɡɚɦɟɬɧɨɣ ɪɨɥɢ ɨɛɴɟɦɧɵɯ ɷɮɮɟɤɬɨɜ ɜ ɪɚɫɬɜɨɪɚɯ ȾɇɄ ɜ ɭɫɥɨɜɢɹɯ ɩɨɞɚɜɥɟɧɢɹ ɷɥɟɤɬɪɨɫɬɚɬɢɱɟɫɤɢɯ ɜɡɚɢɦɨɞɟɣɫɬɜɢɣ. ɍɱɟɬ ɨɛɴɟɦɧɵɯ ɷɮɮɟɤɬɨɜ ɞɥɹ ɬɚɤɢɯ ɫɢɫɬɟɦ ɦɨɠɧɨ ɨɫɭɳɟɫɬɜɢɬɶ [ 18 ], ɨɬɤɥɚɞɵɜɚɹ M / [ K ] ɧɟ ɨɬ Ɇ 1/2, ɚ ɨɬ ɩɚɪɚɦɟɬɪɚ Ɇ (1–3H)/2, ɝɞɟ H — ɩɚɪɚɦɟɬɪ ɝɢɞɪɨɞɢɧɚɦɢɱɟɫɤɨɝɨ ɜɡɚɢɦɨɞɟɣɫɬɜɢɹ, ɫɜɹɡɚɧɧɵɣ ɫ ɤɨɷɮɮɢɰɢɟɧɬɨɦ ɥɢɧɟɣɧɨɝɨ ɧɚɛɭɯɚɧɢɹ ɦɚɤɪɨɦɨɥɟɤɭɥɵ H = (D2 – 1)/(5D2 – 3). ȿɝɨ ɦɨɠɧɨ ɨɩɪɟɞɟɥɢɬɶ, ɧɚɩɪɢɦɟɪ, ɢɡ ɤɨɷɮɮɢɰɢɟɧɬɚ ɚ ɜ ɭɪɚɜɧɟɧɢɢ Ɇɚɪɤɚ—Ʉɭɧɚ—ɏɚɭɜɢɧɤɚ: [ K ] = KɆ ɚ, ɝɞɟ ɚ = (1+3H)/2. Ɇɵ ɨɫɭɳɟɫɬɜɢɥɢ ɬɚɤɢɟ ɪɚɫɱɟɬɵ, ɩɨɥɭɱɢɜ ɜɟɥɢɱɢɧɭ ɚ ɢɡ ɡɚɜɢɫɢɦɨɫɬɢ lg[ K ] ɨɬ lgɆ ɞɥɹ ɪɚɫɬɜɨɪɨɜ ȾɇɄ ɩɪɢ ɪɚɡɧɵɯ ɤɨɧɰɟɧɬɪɚɰɢɹɯ NaCl ɢ MgCl2 ɜ ɪɚɫɬɜɨɪɟ. ɗɬɢ ɪɟɡɭɥɶɬɚɬɵ ɢɫɩɨɥɶɡɨɜɚɥɢ ɞɥɹ ɩɨɫɬɪɨɟɧɢɹ ɤɪɢɜɵɯ ɡɚɜɢɫɢɦɨɫɬɢ, ɤɨɬɨɪɵɟ ɬɚɤɠɟ ɩɪɟɞɫɬɚɜɥɟɧɵ ɧɚ ɪɢɫ. 5. Ʉɚɤ ɜɢɞɧɨ ɢɡ ɪɢɫɭɧɤɚ, ɜ ɷɬɨɦ ɫɥɭɱɚɟ ɞɟɣɫɬɜɢɬɟɥɶɧɨ ɧɚɛɥɸɞɚɟɬɫɹ ɥɢɧɟɣɧɚɹ ɡɚɜɢɫɢɦɨɫɬɶ M / [ K ] ɨɬ Ɇ (1–3H)/2. ɉɪɢɱɟɦ ɝɪɚɮɢɤ ɩɪɨɯɨɞɢɬ ɱɟɪɟɡ ɧɚɱɚɥɨ ɤɨɨɪɞɢɧɚɬ; ɞɥɹ ɜɫɟɯ ɢɨɧɧɵɯ ɫɢɥ, ɤɪɨɦɟ ɜɟɫɶɦɚ ɦɚɥɵɯ, ɤɨɬɨɪɵɟ ɫɨɨɬɜɟɬɫɬɜɭɸɬ ɭɜɟɥɢɱɟɧɢɸ ɩɟɪɫɢɫɬɟɧɬɧɨɣ ɞɥɢɧɵ ȾɇɄ ɜ ɪɟɡɭɥɶɬɚɬɟ ɢɡɦɟɧɟɧɢɹ ɛɥɢɠ- Ɋɢɫ. 5. Ɂɚɜɢɫɢɦɨɫɬɶ Ɇ/[ K ] ɨɬ Ɇ1/2 (1) ɢ M(1–3H)/2 (2) ɞɥɹ ȾɇɄ ɜ 1 Ɇ NaCl ɢ 1 Ɇ MgCl2 168 ɇ.Ⱥ. ɄȺɋɖəɇȿɇɄɈ ɧɢɯ ɷɥɟɤɬɪɨɫɬɚɬɢɱɟɫɤɢɯ ɜɡɚɢɦɨɞɟɣɫɬɜɢɣ. Ɍɚɤɢɦ ɨɛɪɚɡɨɦ, ɦɨɥɟɤɭɥɚ ȾɇɄ ɧɟɩɪɨɬɟɤɚɟɦɚ ɞɥɹ ɪɚɫɬɜɨɪɢɬɟɥɹ ɜ ɲɢɪɨɤɨɣ ɨɛɥɚɫɬɢ ɢɨɧɧɵɯ ɫɢɥ. Ʌɢɲɶ ɩɪɢ I < 0,003 Ɇ, ɤɨɝɞɚ ɩɪɨɢɫɯɨɞɢɬ ɭɜɟɥɢɱɟɧɢɟ ɠɟɫɬɤɨɫɬɢ ɦɚɤɪɨɦɨɥɟɤɭɥɵ ɢɡ-ɡɚ ɢɡɦɟɧɟɧɢɹ ɛɥɢɠɧɢɯ ɷɥɟɤɬɪɨɫɬɚɬɢɱɟɫɤɢɯ ɜɡɚɢɦɨɞɟɣɫɬɜɢɣ, ɤɥɭɛɨɤ ɱɚɫɬɢɱɧɨ ɩɪɨɬɟɤɚɟɦ. Ɂɚɦɟɬɢɦ ɬɚɤɠɟ, ɱɬɨ ɨɛɴɟɦɧɵɟ ɷɮɮɟɤɬɵ ɜ ɨɛɥɚɫɬɢ ɛɨɥɶɲɢɯ ɢɨɧɧɵɯ ɫɢɥ (I > 1 Ɇ) ɧɟ ɡɚɜɢɫɹɬ ɨɬ ɤɨɧɰɟɧɬɪɚɰɢɢ ɢ ɜɚɥɟɧɬɧɨɫɬɢ ɩɪɨɬɢɜɨɢɨɧɨɜ, ɢɧɵɦɢ ɫɥɨɜɚɦɢ, ɨɧɢ ɨɛɭɫɥɨɜɥɟɧɵ ɧɟ ɩɨɥɢɷɥɟɤɬɪɨɥɢɬɧɵɦ ɧɚɛɭɯɚɧɢɟɦ, ɚ ɬɟɪɦɨɞɢɧɚɦɢɱɟɫɤɢɦ ɫɪɨɞɫɬɜɨɦ ɩɨɥɢɦɟɪ— ɪɚɫɬɜɨɪɢɬɟɥɶ. Ɉɛɪɚɳɚɟɬ ɧɚ ɫɟɛɹ ɜɧɢɦɚɧɢɟ ɪɟɡɤɨɟ ɭɜɟɥɢɱɟɧɢɟ ɨɩɬɢɱɟɫɤɨɣ ɚɧɢɡɨɬɪɨɩɢɢ ȾɇɄ (J1–J2) ɜ ɪɚɫɬɜɨɪɟ ɧɚ ɮɨɧɟ ɧɟɢɡɦɟɧɧɨɫɬɢ ɪɚɡɦɟɪɨɜ ɦɚɤɪɨɦɨɥɟɤɭɥɵ ɫ ɜɨɡɪɚɫɬɚɧɢɟɦ ɤɨɧɰɟɧɬɪɚɰɢɢ ɩɪɨɬɢɜɨɢɨɧɨɜ ɩɪɢ ɞɨɫɬɢɠɟɧɢɢ 2,4 Ɇ NaCl ɢɥɢ 0,7 Ɇ MgCl2 (ɫɦ. ɪɢɫ. 4), ɜ ɬɨ ɜɪɟɦɹ ɤɚɤ ɢɫɩɨɥɶɡɨɜɚɧɢɟ KCl, NH4Cl ɢ LiCl ɧɟ ɜɵɡɵɜɚɟɬ ɞɨɫɬɨɜɟɪɧɨ ɮɢɤɫɢɪɭɟɦɨɝɨ ɜɨɡɪɚɫɬɚɧɢɹ ɷɬɨɣ ɜɟɥɢɱɢɧɵ. Ⱦɥɹ ɜɫɟɯ ɪɚɫɬɜɨɪɨɜ ɩɪɨɜɨɞɢɥɫɹ ɬɟɫɬ ɧɚ ɧɚɥɢɱɢɟ ɚɝɪɟɝɚɬɨɜ ɩɭɬɟɦ ɢɡɦɟɪɟɧɢɹ ɢɯ ɨɩɬɢɱɟɫɤɨɣ ɩɥɨɬɧɨɫɬɢ ɧɚ ɞɥɢɧɟ ɜɨɥɧɵ 310 ɧɦ ɜɧɟ ɩɨɥɨɫɵ ɩɨɝɥɨɳɟɧɢɹ ȾɇɄ. Ɉɛ ɨɬɫɭɬɫɬɜɢɢ ɚɝɪɟɝɚɰɢɢ ɫɜɢɞɟɬɟɥɶɫɬɜɭɸɬ ɢ ɪɟɡɭɥɶɬɚɬɵ, ɩɨɥɭɱɟɧɧɵɟ ɦɟɬɨɞɨɦ ɫɬɚɬɢɱɟɫɤɨɝɨ ɫɜɟɬɨɪɚɫɫɟɹɧɢɹ: ɜ ɪɚɫɫɦɚɬɪɢɜɚɟɦɨɣ ɨɛɥɚɫɬɢ ɢɨɧɧɵɯ ɫɢɥ ɦɨɥɟɤɭɥɹɪɧɚɹ ɦɚɫɫɚ ȾɇɄ ɧɟ ɦɟɧɹɟɬɫɹ (ɫɦ. ɜɫɬɚɜɤɭ ɧɚ ɪɢɫ. 4). ɏɨɪɨɲɨ ɢɡɜɟɫɬɧɨ, ɱɬɨ ɞɥɹ ȾɇɄ ɜ ɜɨɞɧɨɦ ɪɚɫɬɜɨɪɟ ɪɟɚɥɢɡɭɟɬɫɹ ȼ-ɤɨɧɮɨɪɦɚɰɢɹ, ɜ ɤɨɬɨɪɨɣ ɩɥɨɫɤɨɫɬɢ ɚɡɨɬɢɫɬɵɯ ɨɫɧɨɜɚɧɢɣ ɩɟɪɩɟɧɞɢɤɭɥɹɪɧɵ ɨɫɢ ɫɩɢɪɚɥɢ, ɱɬɨ ɢ ɨɩɪɟɞɟɥɹɟɬ ɦɚɤɫɢɦɚɥɶɧɨɟ ɡɧɚɱɟɧɢɟ ɫɨɛɫɬɜɟɧɧɨɣ ɨɩɬɢɱɟɫɤɨɣ ɚɧɢɡɨɬɪɨɩɢɢ ɦɚɤɪɨɦɨɥɟɤɭɥɵ. Ʌɸɛɨɟ ɢɡɦɟɧɟɧɢɟ ɟɟ ɜɬɨɪɢɱɧɨɣ ɫɬɪɭɤɬɭɪɵ ɦɨɠɟɬ ɩɪɢɜɟɫɬɢ ɬɨɥɶɤɨ ɤ ɭɦɟɧɶɲɟɧɢɸ ɷɬɨɣ ɜɟɥɢɱɢɧɵ. Ɍɚɤɢɦ ɨɛɪɚɡɨɦ, ɪɟɡɤɨɟ ɜɨɡɪɚɫɬɚɧɢɟ ɨɩɬɢɱɟɫɤɨɣ ɚɧɢɡɨɬɪɨɩɢɢ ɦɚɤɪɨɦɨɥɟɤɭɥɵ ɜ ɪɚɫɬɜɨɪɚɯ ɛɨɥɶɲɨɣ ɢɨɧɧɨɣ ɫɢɥɵ ɧɟɜɨɡɦɨɠɧɨ ɨɛɴɹɫɧɢɬɶ ɥɨɤɚɥɶɧɵɦɢ ɫɬɪɭɤɬɭɪɧɵɦɢ ɢɡɦɟɧɟɧɢɹɦɢ ȾɇɄ. Ɉɛ ɷɬɨɦ ɫɜɢɞɟɬɟɥɶɫɬɜɭɟɬ ɬɚɤɠɟ ɧɟɢɡɦɟɧɧɨɫɬɶ ɫɩɟɤɬɪɨɜ ɤɪɭɝɨɜɨɝɨ ɞɢɯɪɨɢɡɦɚ ɢ ɍɎ ɩɨɝɥɨɳɟɧɢɹ ȾɇɄ, ɜɟɫɶɦɚ ɱɭɜɫɬɜɢɬɟɥɶɧɵɯ ɤ ɫɨɫɬɨɹɧɢɸ ɟɟ ɜɬɨɪɢɱɧɨɣ ɫɬɪɭɤɬɭɪɵ. Ɇɵ ɧɟ ɦɨɠɟɦ ɨɛɴɹɫɧɢɬɶ ɩɨɥɭɱɟɧɧɵɟ ɞɚɧɧɵɟ ɢ ɭɜɟɥɢɱɟɧɢɟɦ ɬɟɪɦɨɞɢɧɚɦɢɱɟɫɤɨɣ ɠɟɫɬɤɨɫɬɢ ɦɚɤɪɨɦɨɥɟɤɭɥɵ, ɬɚɤ ɤɚɤ ɷɬɨ ɩɪɨɬɢɜɨɪɟɱɢɬ ɧɚɛɥɸɞɚɟɦɨɦɭ ɧɚ ɨɩɵɬɟ ɩɨɫɬɨɹɧɫɬɜɭ ɟɟ ɨɛɴɟɦɚ. Ɉɫɬɚɟɬɫɹ ɩɪɟɞɩɨɥɨɠɢɬɶ, ɱɬɨ ɩɪɢ ɜɵɫɨɤɢɯ ɤɨɧɰɟɧɬɪɚɰɢɹɯ ɫɨɥɢ ɜ ɪɚɫɬɜɨɪɟ ɦɨɠɟɬ ɢɡɦɟɧɢɬɶɫɹ ɫɨɫɬɨɹɧɢɟ ɩɟɪɜɨɝɨ ɝɢɞɪɚɬɧɨɝɨ ɫɥɨɹ ɜɛɥɢɡɢ ɦɚɤɪɨɦɨɥɟɤɭɥɵ. ɗɬɨ ɦɨɠɟɬ ɛɵɬɶ ɫɜɹɡɚɧɨ ɫ ɫɭɳɟɫɬɜɨɜɚɧɢɟɦ ɛɥɢɠɧɟɝɨ ɨɪɢɟɧɬɚɰɢɨɧɧɨɝɨ ɩɨɪɹɞɤɚ ɦɨɥɟɤɭɥ ɪɚɫɬɜɨɪɢɬɟɥɹ ɜɛɥɢɡɢ ɩɨɥɢɦɟɪɚ (ɷɮɮɟɤɬ Ɏɪɢɫɦɚɧ—Ⱦɚɞɢɜɚɧɹɧɚ [ 19 ] ). ɉɨɥɭɱɟɧɧɵɟ ɜ ɪɚɛɨɬɟ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɟ ɞɚɧɧɵɟ ɦɨɝɭɬ ɭɤɚɡɵɜɚɬɶ ɧɚ ɭɦɟɧɶɲɟɧɢɟ ɭɩɨɪɹɞɨɱɟɧɧɨɫɬɢ ɦɨɥɟɤɭɥ ɜɨɞɵ ɜ ɝɢɞɪɚɬɧɨɦ ɫɥɨɟ ȾɇɄ: ɢɨɧɵ, ɧɚɯɨɞɹɳɢɟɫɹ ɜɛɥɢɡɢ ɦɚɤɪɨɦɨɥɟɤɭɥɵ, ɫɬɪɟɦɹɬɫɹ ɜɤɥɸɱɢɬɶ ɜ ɫɜɨɸ ɝɢɞɪɚɬɧɭɸ ɫɮɟɪɭ ɦɨɥɟɤɭɥɵ ɜɨɞɵ ɢɡ ɝɢɞɪɚɬɧɨɣ ɨɛɨɥɨɱɤɢ ȾɇɄ. ɉɪɢ ɷɬɨɦ ɝɢɞɪɚɬɧɵɣ ɫɥɨɣ ɧɟ ɧɚɪɭɲɚɟɬɫɹ, ɩɪɨɢɫɯɨɞɢɬ ɥɢɲɶ ɢɡɦɟɧɟɧɢɟ ɜɡɚɢɦɧɨɣ ɨɪɢɟɧɬɚɰɢɢ ɦɨɥɟɤɭɥ ɜɨɞɵ. Ɋɟɡɭɥɶɬɚɬɵ ɜɵɱɢɫɥɟɧɢɹ ɨɬɧɨɫɢɬɟɥɶɧɨɝɨ ɢɡɦɟɧɟɧɢɹ ɨɩɬɢɱɟɫɤɨɣ ɚɧɢɡɨɬɪɨɩɢɢ ɫɬɚɬɢɫɬɢɱɟɫɤɨɝɨ ɫɟɝɦɟɧɬɚ ɢɡ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɯ ɞɚɧɧɵɯ ɩɨɤɚɡɚɥɢ, ɱɬɨ ɷɬɚ ɜɟɥɢɱɢɧɚ ɜɨɡɪɚɫɬɚɟɬ ɩɪɢɛɥɢɡɢɬɟɥɶɧɨ ɧɚ 20 %. ɉɪɢ ɪɚɫɱɟɬɚɯ ɭɱɢɬɵɜɚɥɢ ɢɡɦɟɧɟɧɢɟ ɩɨɤɚɡɚɬɟɥɹ ɩɪɟɥɨɦɥɟɧɢɹ ɢ ɜɹɡɤɨɫɬɢ ɪɚɫɬɜɨɪɢɬɟɥɹ ɩɪɢ ɩɟɪɟɯɨɞɟ ɜ ɨɛɥɚɫɬɶ ɛɨɥɶɲɢɯ ɤɨɧɰɟɧɬɪɚɰɢɣ ɫɨɥɢ. Ɉɰɟɧɤɚ ɩɨɤɚɡɚɥɚ, ɱɬɨ ɮɢɤɫɢɪɭɟɦɨɟ ɧɚ ɨɩɵɬɟ ɢɡɦɟɧɟɧɢɟ ɨɩɬɢɱɟɫɤɨɣ ɚɧɢɡɨɬɪɨɩɢɢ ɦɚɤɪɨɦɨɥɟɤɭɥɵ ɦɨɠɟɬ ɛɵɬɶ ɨɛɭɫɥɨɜɥɟɧɨ ɢɡɦɟɧɟɧɢɟɦ ɨɪɢɟɧɬɚɰɢɢ (ɜ ɫɪɟɞɧɟɦ ɧɚ ɭɝɨɥ ɨɤɨɥɨ 45q) ɩɪɢɦɟɪɧɨ ɩɹɬɢ ɦɨɥɟɤɭɥ ɜɨɞɵ ɧɚ ɧɭɤɥɟɨɬɢɞ. Ɋɚɫɱɟɬɵ ɨɫɭɳɟɫɬɜɥɹɥɢ ɩɨ ɦɟɬɨɞɭ Ɏɪɢɫɦɚɧ—Ⱦɚɞɢɜɚɧɹɧɚ [ 19 ] ɫ ɢɫɩɨɥɶɡɨɜɚɧɢɟɦ ɫɯɟɦɵ ɬɟɧɡɨɪɧɨɣ ɚɞɞɢɬɢɜɧɨɫɬɢ ɩɨɥɹɪɢɡɭɟɦɨɫɬɟɣ ɫɜɹɡɟɣ. ɉɪɨɜɟɞɟɧɧɵɟ ɪɚɫɱɟɬɵ, ɛɟɡɭɫɥɨɜɧɨ, ɧɨɫɹɬ ɨɰɟɧɨɱɧɵɣ ɯɚɪɚɤɬɟɪ, ɧɨ ɩɨɥɭɱɟɧɧɵɟ ɪɟɡɭɥɶɬɚɬɵ ɧɟ ɩɪɨɬɢɜɨɪɟɱɚɬ ɥɢɬɟɪɚɬɭɪɧɵɦ ɞɚɧɧɵɦ, ɫɨɝɥɚɫɧɨ ɤɨɬɨɪɵɦ ɝɢɞɪɚɬɧɚɹ ɜɨɞɚ ɭɥɨɠɟɧɚ ɜ ɫɬɨɩɤɢ, ɩɪɢɱɟɦ sɫɜɹɡɚɧɧɚɹ ɜɨɞɚs ɢɡ ɩɟɪɜɨɝɨ ɝɢɞɪɚɬɧɨɝɨ ɫɥɨɹ ɫɨɫɬɚɜɥɹɟɬ 11—12 ɦɨɥɟɤɭɥ ɧɚ ɧɭɤɥɟɨɬɢɞ [ 20 ]. ɂɧɬɟɪɟɫɧɨ ɨɬɦɟɬɢɬɶ, ɱɬɨ ɞɥɹ ɨɫɭɳɟɫɬɜɥɟɧɢɹ ɤɨɧɮɨɪɦɚɰɢɨɧɧɨɝɨ ɩɟɪɟɯɨɞɚ ȼ—ɋ ɧɟɨɛɯɨɞɢɦɚ ɩɨɬɟɪɹ ɞɟɫɹɬɢ ɦɨɥɟɤɭɥ ɫɜɹɡɚɧɧɨɣ ɜɨɞɵ ɧɚ ɧɭɤɥɟɨɬɢɞ, ɜ ɬɨ ɜɪɟɦɹ ɤɚɤ ɩɟɪɟɯɨɞ ȼ—Ⱥ, ɨɛɭɫɥɨɜɥɟɧɧɵɣ ɞɟɝɢɞɪɚɬɚɰɢɟɣ ɦɨɥɟɤɭɥɵ ȾɇɄ, ɨɫɭɳɟɫɬɜɥɹɟɬɫɹ ɫ ɩɨɬɟɪɟɣ ɞɜɚɞɰɚɬɢ ɦɨɥɟɤɭɥ ɜɨɞɵ [ 21 ]. ɍɜɟɥɢɱɟɧɢɟ ɨɩɬɢɱɟɫɤɨɣ ɚɧɢɡɨɬɪɨɩɢɢ ȾɇɄ ɜ ɪɚɫɬɜɨɪɚɯ NaCl ɧɚɛɥɸɞɚɥɢ ɞɥɹ ɨɛɪɚɡɰɨɜ ɪɚɡɥɢɱɧɨɣ ɦɨɥɟɤɭɥɹɪɧɨɣ ɦɚɫɫɵ (ɫɦ. ɪɢɫ. 4), ɱɬɨ ɩɨɞɬɜɟɪɠɞɚɟɬ ɜɵɫɤɚɡɚɧɧɨɟ ɩɪɟɞɩɨɥɨɠɟɧɢɟ ɨɛ ɢɡɦɟɧɟɧɢɢ ɢɦɟɧɧɨ ɫɟɝɦɟɧɬɧɨɣ ɚɧɢɡɨɬɪɨɩɢɢ. ɇɚ ɨɫɧɨɜɚɧɢɢ ɧɚɲɢɯ ɪɟɡɭɥɶɬɚɬɨɜ ɦɨɠɧɨ ɝɨɜɨɪɢɬɶ ɨ ɪɚɡɥɢɱɧɨɦ ɜɥɢɹɧɢɢ ɤɚɬɢɨɧɨɜ ɧɚ ɢɡɦɟɪɹɟɦɭɸ ɨɩɬɢɱɟɫɤɭɸ ɚɧɢɡɨɬɪɨɩɢɸ ȾɇɄ. ɉɨɫɥɟ ɪɟɡɤɨɝɨ ɜɨɡɪɚɫɬɚɧɢɹ ɚɛɫɨɥɸɬɧɨɝɨ ɡɧɚɱɟɧɢɹ ɜɟɥɢɱɢɧɵ (J1 – J2) ɩɪɢ ɨɩɪɟɞɟɥɟɧɧɵɯ ɤɨɧɰɟɧɬɪɚɰɢɹɯ NaCl ɢ MgCl2 ɧɚɛɥɸɞɚɟɬɫɹ ɟɟ ɩɨɫɬɨɹɧɫɬɜɨ ɜ ɞɨɫɬɚɬɨɱɧɨ ɲɢɪɨɤɨɣ ɨɛɥɚɫɬɢ ɤɨɧɰɟɧɬɪɚɰɢɣ ɷɬɢɯ ɫɨɥɟɣ. ȼ ɄɈɇɎɈɊɆȺɐɂɈɇɇɕȿ ɂɁɆȿɇȿɇɂə ɆɈɅȿɄɍɅɕ ȾɇɄ 169 ɪɚɫɬɜɨɪɚɯ ɠɟ ɞɪɭɝɢɯ ɫɨɥɟɣ, ɢɫɩɨɥɶɡɭɟɦɵɯ ɜ ɷɤɫɩɟɪɢɦɟɧɬɟ, ɧɟɬ ɱɟɬɤɨ ɮɢɤɫɢɪɭɟɦɨɝɨ ɜɨɡɪɚɫɬɚɧɢɹ ɜɟɥɢɱɢɧɵ (J1 – J2). ȿɫɥɢ ɦɵ ɨɛɴɹɫɧɹɟɦ ɧɚɛɥɸɞɚɟɦɨɟ ɜɨɡɪɚɫɬɚɧɢɟ ɨɩɬɢɱɟɫɤɨɣ ɚɧɢɡɨɬɪɨɩɢɢ ɧɚɪɭɲɟɧɢɟɦ ɨɪɢɟɧɬɚɰɢɢ ɜɨɞɵ ɜɛɥɢɡɢ ȾɇɄ, ɦɨɠɧɨ ɩɪɟɞɩɨɥɨɠɢɬɶ, ɱɬɨ ɫɢɥɶɧɨ ɝɢɞɪɚɬɢɪɨɜɚɧɧɵɣ ɢɨɧ Li+, ɜɟɫɶɦɚ ɧɟɨɯɨɬɧɨ ɨɬɞɚɸɳɢɣ ɜɨɞɭ ɢɡ ɫɜɨɟɣ ɩɟɪɜɨɣ ɝɢɞɪɚɬɧɨɣ ɫɮɟɪɵ, ɨɤɚɡɵɜɚɟɬ ɦɟɧɶɲɟɟ ɜɥɢɹɧɢɟ ɧɚ ɛɥɢɠɧɢɣ ɨɪɢɟɧɬɚɰɢɨɧɧɵɣ ɩɨɪɹɞɨɤ ɦɨɥɟɤɭɥ ɜɨɞɵ ɜɛɥɢɡɢ ȾɇɄ, ɱɟɦ Na+ ɢɥɢ Mg2+. ɋɭɳɟɫɬɜɭɸɬ ɞɚɧɧɵɟ, ɱɬɨ ɢɨɧɵ Li+, ɜ ɨɬɥɢɱɢɟ ɨɬ Na+, ɫɜɹɡɵɜɚɸɬɫɹ ɫ ȾɇɄ ɱɟɪɟɡ ɜɨɞɭ ɞɚɠɟ ɜ ɭɫɥɨɜɢɹɯ ɜɟɫɶɦɚ ɦɚɥɨɣ ɜɥɚɠɧɨɫɬɢ [ 22 ]. Ʉɪɨɦɟ ɬɨɝɨ, Na+ ɫɞɜɢɝɚɟɬ ɪɚɜɧɨɜɟɫɢɟ ɩɟɪɟɯɨɞɚ ȼ—Ⱥ ɜ ɫɬɨɪɨɧɭ Ⱥ-ɮɨɪɦɵ, ɜ ɬɨ ɜɪɟɦɹ ɤɚɤ Li+ ɫɬɚɛɢɥɢɡɢɪɭɟɬ ȼ-ɮɨɪɦɭ [ 23 ]. ɗɬɢ ɞɚɧɧɵɟ ɤɨɫɜɟɧɧɨ ɩɨɞɬɜɟɪɠɞɚɸɬ ɜɵɫɤɚɡɚɧɧɭɸ ɬɨɱɤɭ ɡɪɟɧɢɹ. ɂɧɬɟɪɟɫɧɨ ɨɬɦɟɬɢɬɶ, ɱɬɨ NaCl ɢ MgCl2 ɩɪɢ ɢɯ ɤɨɧɰɟɧɬɪɚɰɢɢ ɜ ɪɚɫɬɜɨɪɟ ɛɨɥɟɟ 2,5 Ɇ ɢ 0,7 Ɇ ɫɨɨɬɜɟɬɫɬɜɟɧɧɨ ɩɟɪɟɜɨɞɹɬ ɩɪɚɜɭɸ ɞɜɨɣɧɭɸ ɫɩɢɪɚɥɶ poly(dG—dC).poly(dG—dC) ɜ ɥɟɜɨɡɚɤɪɭɱɟɧɧɭɸ Z-ɤɨɧɮɨɪɦɚɰɢɸ. ɗɬɢ ɤɨɧɰɟɧɬɪɚɰɢɢ ɫɨɥɟɣ ɫɨɜɩɚɞɚɸɬ ɫ ɭɫɥɨɜɢɹɦɢ ɢɡɦɟɧɟɧɢɹ ɨɩɬɢɱɟɫɤɨɣ ɚɧɢɡɨɬɪɨɩɢɢ ȾɇɄ ɜ ɧɚɲɟɦ ɷɤɫɩɟɪɢɦɟɧɬɟ. ȼɨɡɦɨɠɧɨ, ɩɨɦɢɦɨ ɩɨɫɥɟɞɨɜɚɬɟɥɶɧɨɫɬɢ ɨɫɧɨɜɚɧɢɣ ɢ ɷɤɪɚɧɢɪɨɜɤɢ ɮɨɫɮɚɬɧɵɯ ɝɪɭɩɩ, ɨɩɪɟɞɟɥɟɧɧɭɸ ɪɨɥɶ ɜ ɨɫɭɳɟɫɬɜɥɟɧɢɢ ɩɟɪɟɯɨɞɚ ȼ—Z ɢɝɪɚɟɬ ɢ ɫɨɫɬɨɹɧɢɟ ɩɟɪɜɨɣ ɝɢɞɪɚɬɧɨɣ ɨɛɨɥɨɱɤɢ ȾɇɄ. ɂɡɭɱɟɧɢɟ ɫɜɹɡɵɜɚɧɢɹ ɦɨɥɟɤɭɥɵ ȾɇɄ ɫ ɛɢɨɥɨɝɢɱɟɫɤɢ ɚɤɬɢɜɧɵɦɢ ɫɨɟɞɢɧɟɧɢɹɦɢ ɩɪɟɞɩɨɥɚɝɚɟɬ ɜ ɱɢɫɥɟ ɞɪɭɝɢɯ ɡɚɞɚɱ ɢɫɫɥɟɞɨɜɚɧɢɟ ɪɨɥɢ ɷɥɟɤɬɪɨɫɬɚɬɢɱɟɫɤɢɯ ɜɡɚɢɦɨɞɟɣɫɬɜɢɣ ɜ ɮɨɪɦɢɪɨɜɚɧɢɢ ɤɨɦɩɥɟɤɫɨɜ. 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