ɀ ɍ Ɋ ɇ Ⱥ Ʌ ɋ Ɍ Ɋ ɍ... Ɍɨɦ 48, ʋ 2 Ɇɚɪɬ – ɚɩɪɟɥɶ ɋ. 339 – 347

ɀɍɊɇȺɅ ɋɌɊɍɄɌɍɊɇɈɃ ɏɂɆɂɂ
2007. Ɍɨɦ 48, ʋ 2
Ɇɚɪɬ – ɚɩɪɟɥɶ
ɋ. 339 – 347
ɍȾɄ 539.2;543.422;547.466;548.33
ɂɋɋɅȿȾɈȼȺɇɂȿ ȼɅɂəɇɂə ɌȿɆɉȿɊȺɌɍɊɕ ɇȺ ɂɄ ɋɉȿɄɌɊɕ
ɄɊɂɋɌȺɅɅɂɑȿɋɄɂɏ ȺɆɂɇɈɄɂɋɅɈɌ, ȾɂɉȿɉɌɂȾɈȼ ɂ ɉɈɅɂȺɆɂɇɈɄɂɋɅɈɌ.
I. ȽɅɂɐɂɇ
” 2007 Ƚ.Ȼ. ɑɟɪɧɨɛɚɣ1,2*, ɘ.Ⱥ. ɑɟɫɚɥɨɜ1,3, ȿ.Ȼ. Ȼɭɪɝɢɧɚ3 ,
Ɍ.ɇ. Ⱦɪɟɛɭɳɚɤ1,2, ȿ.ȼ. Ȼɨɥɞɵɪɟɜɚ1,2
1
ɇɈɐ sɆȾɗȻɌs **, ɇɨɜɨɫɢɛɢɪɫɤɢɣ ɝɨɫɭɞɚɪɫɬɜɟɧɧɵɣ ɭɧɢɜɟɪɫɢɬɟɬ
ɂɧɫɬɢɬɭɬ ɯɢɦɢɢ ɬɜɟɪɞɨɝɨ ɬɟɥɚ ɢ ɦɟɯɚɧɨɯɢɦɢɢ ɋɈ ɊȺɇ, ɇɨɜɨɫɢɛɢɪɫɤ
3
ɂɧɫɬɢɬɭɬ ɤɚɬɚɥɢɡɚ ɢɦ. Ƚ.Ʉ. Ȼɨɪɟɫɤɨɜɚ ɋɈ ɊȺɇ, ɇɨɜɨɫɢɛɢɪɫɤ
2
ɋɬɚɬɶɹ ɩɨɫɬɭɩɢɥɚ 8 ɞɟɤɚɛɪɹ 2006 ɝ.
ɂɄ ɫɩɟɤɬɪɵ D-, E-, J-ɩɨɥɢɦɨɪɮɧɵɯ ɦɨɞɢɮɢɤɚɰɢɣ ɱɢɫɬɨɝɨ ɝɥɢɰɢɧɚ (ɛɟɡ ɢɫɩɨɥɶɡɨɜɚɧɢɹ
ɤɚɤɢɯ-ɥɢɛɨ ɪɚɡɛɚɜɢɬɟɥɟɣ) ɢɫɫɥɟɞɨɜɚɧɵ ɜ ɢɧɬɟɪɜɚɥɟ ɬɟɦɩɟɪɚɬɭɪ 93—433 K; ɢɡɦɟɧɟɧɢɹ ɜ
ɂɄ ɫɩɟɤɬɪɚɯ ɩɪɢ ɜɚɪɶɢɪɨɜɚɧɢɢ ɬɟɦɩɟɪɚɬɭɪɵ ɫɨɨɬɧɟɫɟɧɵ ɫ ɪɚɧɟɟ ɩɨɥɭɱɟɧɧɵɦɢ ɞɢɮɪɚɤɰɢɨɧɧɵɦɢ ɞɚɧɧɵɦɢ ɨ ɩɨɥɢɦɨɪɮɧɵɯ ɩɟɪɟɯɨɞɚɯ, ɚɧɢɡɨɬɪɨɩɧɨɦ ɫɠɚɬɢɢ ɫɬɪɭɤɬɭɪɵ ɢ ɢɡɦɟɧɟɧɢɹɯ ɩɚɪɚɦɟɬɪɨɜ ɜɨɞɨɪɨɞɧɵɯ ɫɜɹɡɟɣ.
Ʉ ɥ ɸ ɱ ɟ ɜ ɵ ɟ ɫ ɥ ɨ ɜ ɚ : ɩɨɥɢɦɨɪɮɧɵɟ ɦɨɞɢɮɢɤɚɰɢɢ, ɝɥɢɰɢɧ, ɂɄ ɫɩɟɤɬɪɨɫɤɨɩɢɹ, ɜɨɞɨɪɨɞɧɵɟ ɫɜɹɡɢ.
ȼȼȿȾȿɇɂȿ
Ʉɪɢɫɬɚɥɥɵ ɚɦɢɧɨɤɢɫɥɨɬ ɩɪɢɜɥɟɤɚɸɬ ɜɧɢɦɚɧɢɟ ɤɚɤ ɦɨɥɟɤɭɥɹɪɧɵɟ ɦɚɬɟɪɢɚɥɵ (ɩɶɟɡɨɷɥɟɤɬɪɢɤɢ, ɮɟɪɪɨɷɥɟɤɬɪɢɤɢ, ɧɟɥɢɧɟɣɧɵɟ ɨɩɬɢɱɟɫɤɢɟ ɦɚɬɟɪɢɚɥɵ) ɢ ɤɚɤ ɛɢɨɦɢɦɟɬɢɤɢ, ɫɥɭɠɚɳɢɟ
ɫɪɚɜɧɢɬɟɥɶɧɨ ɩɪɨɫɬɵɦɢ ɦɨɞɟɥɹɦɢ ɛɨɥɟɟ ɫɥɨɠɧɵɯ ɛɢɨɩɨɥɢɦɟɪɨɜ, ɬɚɤɢɯ ɤɚɤ ɨɥɢɝɨ- ɢ ɩɨɥɢɩɟɩɬɢɞɵ. ɂ ɜ ɬɨɦ, ɢ ɜ ɞɪɭɝɨɦ ɫɥɭɱɚɟ ɜɚɠɧɨ ɢɫɫɥɟɞɨɜɚɬɶ ɤɨɧɮɨɪɦɚɰɢɢ ɢɧɞɢɜɢɞɭɚɥɶɧɵɯ ɰɜɢɬɬɟɪɢɨɧɨɜ, ɚ ɬɚɤɠɟ ɜɡɚɢɦɨɞɟɣɫɬɜɢɹ ɦɟɠɞɭ ɰɜɢɬɬɟɪ-ɢɨɧɚɦɢ ɜ ɤɪɢɫɬɚɥɥɢɱɟɫɤɨɣ ɫɬɪɭɤɬɭɪɟ. ȼ ɤɚɱɟɫɬɜɟ ɦɟɬɨɞɨɜ ɢɫɫɥɟɞɨɜɚɧɢɹ ɬɚɤɢɯ ɫɢɫɬɟɦ ɲɢɪɨɤɨ ɩɪɢɦɟɧɹɸɬɫɹ ɥɢɛɨ ɞɢɮɪɚɤɰɢɨɧɧɵɟ ɦɟɬɨɞɵ, ɥɢɛɨ ɤɨɥɟɛɚɬɟɥɶɧɚɹ ɫɩɟɤɬɪɨɫɤɨɩɢɹ ɜ ɭɫɥɨɜɢɹɯ ɩɟɪɟɦɟɧɧɵɯ ɬɟɦɩɟɪɚɬɭɪ / ɞɚɜɥɟɧɢɣ [ 1 ]. ɗɬɢ ɦɟɬɨɞɵ ɭɞɚɱɧɨ ɞɨɩɨɥɧɹɸɬ ɞɪɭɝ ɞɪɭɝɚ: ɨɞɢɧ ɞɚɟɬ ɢɧɮɨɪɦɚɰɢɸ ɨɛ ɢɫɤɚɠɟɧɢɹɯ ɜɧɭɬɪɢ- ɢ ɦɟɠɦɨɥɟɤɭɥɹɪɧɵɯ ɪɚɫɫɬɨɹɧɢɣ ɢ ɭɝɥɨɜ, ɞɪɭɝɨɣ — ɨɛ ɢɡɦɟɧɟɧɢɹɯ ɷɧɟɪɝɢɢ ɫɜɹɡɟɣ, ɢɯ ɫɨɩɪɨɜɨɠɞɚɸɳɢɯ.
ɉɨɷɬɨɦɭ ɨɫɨɛɵɣ ɢɧɬɟɪɟɫ ɩɪɟɞɫɬɚɜɥɹɟɬ ɫɪɚɜɧɟɧɢɟ ɪɟɡɭɥɶɬɚɬɨɜ ɢɫɫɥɟɞɨɜɚɧɢɣ ɨɞɧɢɯ ɢ ɬɟɯ ɠɟ
ɫɢɫɬɟɦ ɜ ɨɞɢɧɚɤɨɜɵɯ ɭɫɥɨɜɢɹɯ, ɜɵɩɨɥɧɟɧɧɵɯ ɩɚɪɚɥɥɟɥɶɧɨ ɞɢɮɪɚɤɰɢɨɧɧɵɦɢ ɢ ɫɩɟɤɬɪɨɫɤɨɩɢɱɟɫɤɢɦɢ ɦɟɬɨɞɚɦɢ. ȼ ɫɟɪɢɢ ɫɬɚɬɟɣ ɦɵ ɢɡɥɚɝɚɟɦ ɪɟɡɭɥɶɬɚɬɵ ɬɚɤɢɯ ɢɫɫɥɟɞɨɜɚɧɢɣ, ɩɪɨɜɟɞɟɧɧɵɯ
ɞɥɹ ɪɹɞɚ ɤɪɢɫɬɚɥɥɢɱɟɫɤɢɯ ɚɦɢɧɨɤɢɫɥɨɬ, ɚ ɬɚɤɠɟ, ɞɥɹ ɫɪɚɜɧɟɧɢɹ, — ɞɥɹ ɩɪɨɫɬɟɣɲɢɯ ɞɢɩɟɩɬɢɞɨɜ
ɢ ɩɨɥɢɚɦɢɧɨɤɢɫɥɨɬ.
ɉɟɪɜɚɹ ɫɬɚɬɶɹ ɩɨɫɜɹɳɟɧɚ ɫɪɚɜɧɢɬɟɥɶɧɨɦɭ ɂɄ-ɫɩɟɤɬɪɨɫɤɨɩɢɱɟɫɤɨɦɭ ɢɫɫɥɟɞɨɜɚɧɢɸ ɜ ɢɧɬɟɪɜɚɥɟ ɬɟɦɩɟɪɚɬɭɪ 93—433 K ɬɪɟɯ ɩɨɥɢɦɨɪɮɧɵɯ ɦɨɞɢɮɢɤɚɰɢɣ (D, E ɢ J) ɩɪɨɫɬɟɣɲɟɣ ɚɦɢɧɨɤɢɫɥɨɬɵ — ɝɥɢɰɢɧɚ (NH 3 —CH2—COO–), ɪɚɡɥɢɱɚɸɳɢɯɫɹ ɭɩɚɤɨɜɤɨɣ ɰɜɢɬɬɟɪ-ɢɨɧɨɜ ɜ ɫɬɪɭɤɬɭɪɟ ɢ ɫɬɪɨɟɧɢɟɦ ɫɟɬɨɤ ɦɟɠɦɨɥɟɤɭɥɹɪɧɵɯ ɜɨɞɨɪɨɞɧɵɯ ɫɜɹɡɟɣ NH…O [ 2 — 5 ].
Ɋɚɧɟɟ ɞɥɹ ɬɪɟɯ ɩɨɥɢɦɨɪɮɧɵɯ ɦɨɞɢɮɢɤɚɰɢɣ ɝɥɢɰɢɧɚ ɦɟɬɨɞɨɦ ɦɨɧɨɤɪɢɫɬɚɥɶɧɨɣ ɪɟɧɬɝɟɧɨɜɫɤɨɣ ɞɢɮɪɚɤɰɢɢ ɛɵɥɢ ɢɫɫɥɟɞɨɜɚɧɵ ɫɬɪɭɤɬɭɪɧɵɟ ɢɡɦɟɧɟɧɢɹ ɩɪɢ ɨɯɥɚɠɞɟɧɢɢ ɨɬ ɤɨɦɧɚɬɧɨɣ ɬɟɦɩɟɪɚɬɭɪɵ ɞɨ 100 K [ 6 ]. Ʉɪɨɦɟ ɬɨɝɨ, ɦɟɬɨɞɚɦɢ ɚɞɢɚɛɚɬɢɱɟɫɤɨɣ ɢ ɞɢɮɮɟɪɟɧɰɢɚɥɶɧɨɣ ɫɤɚɧɢ* E-mail: [email protected]
** ɇɚɭɱɧɨ-ɨɛɪɚɡɨɜɚɬɟɥɶɧɵɣ ɰɟɧɬɪ sɆɨɥɟɤɭɥɹɪɧɵɣ ɞɢɡɚɣɧ ɢ ɷɤɨɥɨɝɢɱɟɫɤɢ ɛɟɡɨɩɚɫɧɵɟ ɬɟɯɧɨɥɨɝɢɢs.
340
Ƚ.Ȼ. ɑȿɊɇɈȻȺɃ, ɘ.Ⱥ. ɑȿɋȺɅɈȼ, ȿ.Ȼ. ȻɍɊȽɂɇȺ ɂ ȾɊ.
ɪɭɸɳɟɣ ɤɚɥɨɪɢɦɟɬɪɢɢ ɢɫɫɥɟɞɨɜɚɧɵ ɨɬɧɨɫɢɬɟɥɶɧɚɹ ɭɫɬɨɣɱɢɜɨɫɬɶ ɩɨɥɢɦɨɪɮɨɜ ɝɥɢɰɢɧɚ ɩɪɢ
ɜɚɪɶɢɪɨɜɚɧɢɢ ɬɟɦɩɟɪɚɬɭɪɵ ɢ ɮɚɡɨɜɵɟ ɩɟɪɟɯɨɞɵ ɦɟɠɞɭ ɦɨɞɢɮɢɤɚɰɢɹɦɢ [ 7 — 10 ].
ɂɄ ɫɩɟɤɬɪɵ D-, E- ɢ J-ɦɨɞɢɮɢɤɚɰɢɣ ɝɥɢɰɢɧɚ ɩɪɢ ɤɨɦɧɚɬɧɨɣ ɬɟɦɩɟɪɚɬɭɪɟ ɛɵɥɢ ɨɩɢɫɚɧɵ
ɪɚɧɟɟ. ɇɚ ɞɚɧɧɵɣ ɦɨɦɟɧɬ ɢɡɜɟɫɬɧɨ ɦɧɨɝɨ ɪɚɛɨɬ, ɩɨɫɜɹɳɟɧɧɵɯ ɪɚɫɱɟɬɭ ɤɨɥɟɛɚɬɟɥɶɧɵɯ ɫɩɟɤɬɪɨɜ
ɢ ɭɬɨɱɧɟɧɢɸ ɨɬɧɟɫɟɧɢɣ ɩɨɥɨɫ ɩɨɝɥɨɳɟɧɢɹ ɜ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɯ ɂɄ ɢ ɄɊ ɫɩɟɤɬɪɚɯ D-ɮɨɪɦɵ
ɝɥɢɰɢɧɚ ɩɪɢ ɤɨɦɧɚɬɧɨɣ ɬɟɦɩɟɪɚɬɭɪɟ [ 11 — 14 ]. Ȼɵɥɢ ɨɩɭɛɥɢɤɨɜɚɧɵ ɫɬɚɬɶɢ ɫ ɪɚɫɱɟɬɨɦ, ɨɬɧɟɫɟɧɢɟɦ ɢ ɨɛɳɢɦ ɜɢɞɨɦ ɤɨɥɟɛɚɬɟɥɶɧɵɯ ɫɩɟɤɬɪɨɜ J-ɝɥɢɰɢɧɚ [ 15, 16 ]. ɂɄ ɫɩɟɤɬɪ E-ɝɥɢɰɢɧɚ ɩɨ
ɩɪɢɱɢɧɟ ɦɟɬɚɫɬɚɛɢɥɶɧɨɫɬɢ ɞɚɧɧɨɣ ɮɨɪɦɵ ɢ ɬɪɭɞɧɨɫɬɢ ɟɟ ɩɨɥɭɱɟɧɢɹ [ 4, 5, 17 ] ɞɨɥɝɨɟ ɜɪɟɦɹ
ɛɵɥ ɩɪɟɞɫɬɚɜɥɟɧ ɬɨɥɶɤɨ ɜɵɫɨɤɨɱɚɫɬɨɬɧɨɣ ɨɛɥɚɫɬɶɸ 3400—2800 ɫɦ–1 ɜ ɫɬɚɬɶɟ ɂɬɚɤɢ [ 4 ]. ɋɨɜɫɟɦ ɧɟɞɚɜɧɨ ɩɨɹɜɢɥɚɫɶ ɪɚɛɨɬɚ [ 18 ], ɜ ɤɨɬɨɪɨɣ ɩɚɪɚɥɥɟɥɶɧɨ ɫɪɚɜɧɢɜɚɸɬɫɹ ɂɄ ɫɩɟɤɬɪɵ D- ɢ Eɮɨɪɦ ɝɥɢɰɢɧɚ ɩɪɢ ɤɨɦɧɚɬɧɨɣ ɬɟɦɩɟɪɚɬɭɪɟ ɜ ɞɢɚɩɚɡɨɧɟ ɱɚɫɬɨɬ 4000—400 ɫɦ–1. Ɉɞɧɚɤɨ ɞɥɹ ɂɄ
ɫɩɟɤɬɪɚ, ɩɪɢɜɟɞɟɧɧɨɝɨ ɜ ɫɬɚɬɶɟ [ 18 ], ɤɚɤ ɫɩɟɤɬɪ ɱɢɫɬɨɣ D-ɮɨɪɦɵ, ɦɨɠɧɨ ɩɪɟɞɩɨɥɨɠɢɬɶ ɩɪɢɫɭɬɫɬɜɢɟ ɜ ɨɛɪɚɡɰɟ ɡɚɦɟɬɧɨɝɨ ɤɨɥɢɱɟɫɬɜɚ ɩɪɢɦɟɫɢ J-ɮɨɪɦɵ ɧɚ ɨɫɧɨɜɚɧɢɢ ɩɨɥɨɠɟɧɢɹ ɩɨɥɨɫ ɩɨɝɥɨɳɟɧɢɹ ɜɚɥɟɧɬɧɵɯ ɤɨɥɟɛɚɧɢɣ, ɞɟɮɨɪɦɚɰɢɨɧɧɵɯ ɫɢɦɦɟɬɪɢɱɧɵɯ ɤɨɥɟɛɚɧɢɣ NH3+ , ɜɚɥɟɧɬɧɵɯ
ɤɨɥɟɛɚɧɢɣ ɨɫɬɨɜɚ, ɦɚɹɬɧɢɤɨɜɵɯ ɤɨɥɟɛɚɧɢɣ ɋɇ2-ɝɪɭɩɩɵ, ɚ ɬɚɤɠɟ ɩɥɨɫɤɨɫɬɧɵɯ ɞɟɮɨɪɦɚɰɢɨɧɧɵɯ
ɤɨɥɟɛɚɧɢɣ ɤɚɪɛɨɤɫɢɥɶɧɨɣ ɝɪɭɩɩɵ.
ɋɪɚɜɧɟɧɢɟ ɂɄ ɫɩɟɤɬɪɨɜ ɜɫɟɯ ɬɪɟɯ ɩɨɥɢɦɨɪɮɧɵɯ ɦɨɞɢɮɢɤɚɰɢɣ ɝɥɢɰɢɧɚ ɩɪɢ ɤɨɦɧɚɬɧɨɣ
ɬɟɦɩɟɪɚɬɭɪɟ ɛɵɥɨ ɪɚɧɟɟ ɩɪɨɜɟɞɟɧɨ ɬɨɥɶɤɨ ɞɥɹ ɜɵɫɨɤɨɱɚɫɬɨɬɧɨɣ ɨɛɥɚɫɬɢ 2800—3200 ɫɦ–1 [ 4 ].
ɋɨɩɨɫɬɚɜɥɟɧɢɟ ɪɟɡɭɥɶɬɚɬɨɜ, ɩɪɢɜɟɞɟɧɧɵɯ ɪɚɡɧɵɦɢ ɚɜɬɨɪɚɦɢ ɞɥɹ ɪɚɡɧɵɯ ɩɨɥɢɦɨɪɮɨɜ, ɡɚɬɪɭɞɧɹɟɬɫɹ ɬɟɦ, ɱɬɨ ɞɚɠɟ ɞɥɹ ɨɞɧɨɣ ɢ ɬɨɣ ɠɟ ɮɨɪɦɵ ɩɨɥɨɠɟɧɢɟ ɩɨɥɨɫ ɩɨɝɥɨɳɟɧɢɹ ɜɚɥɟɧɬɧɵɯ ɢ ɞɟɮɨɪɦɚɰɢɨɧɧɵɯ ɤɨɥɟɛɚɧɢɣ ɢɨɧɢɡɨɜɚɧɧɵɯ ɤɚɪɛɨɤɫɢɥɶɧɨɣ ɢ ɚɦɢɧɨɝɪɭɩɩ ɜ ɂɄ ɫɩɟɤɬɪɚɯ ɜ ɧɟɤɨɬɨɪɵɯ ɫɥɭɱɚɹɯ ɪɚɡɥɢɱɚɟɬɫɹ ɧɚ ɜɟɥɢɱɢɧɭ ɨɤɨɥɨ 10 ɫɦ–1. Ɋɚɧɟɟ ɛɵɥɨ ɩɪɨɜɟɞɟɧɨ ɢɫɫɥɟɞɨɜɚɧɢɟ
ɰɜɢɬɬɟɪ-ɢɨɧɨɜ ɝɥɢɰɢɧɚ ɜ ɦɚɬɪɢɰɚɯ ɝɚɥɨɝɟɧɢɞɨɜ ɳɟɥɨɱɧɵɯ ɦɟɬɚɥɥɨɜ ɩɪɢ ɤɨɦɧɚɬɧɨɣ ɬɟɦɩɟɪɚɬɭɪɟ, ɤɨɬɨɪɨɟ ɩɨɤɚɡɚɥɨ, ɱɬɨ ɂɄ ɫɩɟɤɬɪɵ ɦɚɥɨ ɨɬɥɢɱɚɸɬɫɹ ɞɪɭɝ ɨɬ ɞɪɭɝɚ ɩɪɢ ɜɚɪɶɢɪɨɜɚɧɢɢ ɤɚɤ
ɤɚɬɢɨɧɚ, ɬɚɤ ɢ ɚɧɢɨɧɚ ɜ ɫɨɥɢ, ɢɫɩɨɥɶɡɭɟɦɨɣ ɜ ɤɚɱɟɫɬɜɟ ɪɚɡɛɚɜɢɬɟɥɹ [ 19 ]. ȼ ɪɚɛɨɬɟ Ȼɚɪɚɧ ɢ Ɋɚɬɚɣɱɚɤ ɩɨ J-ɝɥɢɰɢɧɭ ɂɄ ɫɩɟɤɬɪɵ ɛɵɥɢ ɫɧɹɬɵ ɩɪɢ ɤɨɦɧɚɬɧɨɣ ɬɟɦɩɟɪɚɬɭɪɟ ɜɨ ɮɬɨɪɭɝɥɟɪɨɞɟ ɢ ɜ
ɜɚɡɟɥɢɧɨɜɨɦ ɦɚɫɥɟ. Ɂɧɚɱɟɧɢɹ ɱɚɫɬɨɬ ɩɨɝɥɨɳɟɧɢɹ ɜ ɂɄ ɫɩɟɤɬɪɚɯ ɩɪɚɤɬɢɱɟɫɤɢ ɧɟ ɨɬɥɢɱɚɥɢɫɶ.
ɉɨɷɬɨɦɭ ɪɚɡɥɢɱɢɹ ɜ ɩɨɥɨɠɟɧɢɢ ɩɨɥɨɫ ɩɨɝɥɨɳɟɧɢɹ, ɧɚɛɥɸɞɚɟɦɵɟ ɭ ɪɚɡɧɵɯ ɚɜɬɨɪɨɜ, ɫɤɨɪɟɟ ɜɫɟɝɨ ɦɨɠɧɨ ɨɛɴɹɫɧɢɬɶ ɥɢɛɨ ɪɚɡɧɨɣ ɮɚɡɨɜɨɣ ɱɢɫɬɨɬɨɣ ɨɛɪɚɡɰɨɜ, ɥɢɛɨ ɜɥɢɹɧɢɟɦ ɧɚ ɂɄ ɫɩɟɤɬɪɵ
ɫɨɨɬɧɨɲɟɧɢɹ ɜɟɳɟɫɬɜɨ—ɦɚɬɪɢɰɚ ɩɪɢ ɩɪɢɝɨɬɨɜɥɟɧɢɢ ɨɛɪɚɡɰɚ. Ɉɞɧɚɤɨ ɜɥɢɹɧɢɟ ɩɪɢɪɨɞɵ ɦɚɬɪɢɰɵ ɦɨɠɟɬ ɜɵɹɜɢɬɶɫɹ ɜ ɂɄ ɫɩɟɤɬɪɚɯ ɩɪɢ ɢɡɦɟɧɟɧɢɢ ɜɧɟɲɧɢɯ ɭɫɥɨɜɢɣ (ɬɟɦɩɟɪɚɬɭɪɵ, ɞɚɜɥɟɧɢɹ).
ɋɥɟɞɭɟɬ ɨɬɦɟɬɢɬɶ, ɱɬɨ ɤɨɥɟɛɚɬɟɥɶɧɵɟ ɫɩɟɤɬɪɵ ɩɨɥɢɦɨɪɮɨɜ ɝɥɢɰɢɧɚ ɩɪɢ ɩɟɪɟɦɟɧɧɨɦ ɞɚɜɥɟɧɢɢ ɢ ɬɟɦɩɟɪɚɬɭɪɟ ɜ ɥɢɬɟɪɚɬɭɪɟ ɩɨɱɬɢ ɧɟ ɩɪɟɞɫɬɚɜɥɟɧɵ. Ɋɚɧɟɟ ɛɵɥɢ ɨɩɭɛɥɢɤɨɜɚɧɵ ɫɬɚɬɶɢ ɩɨ
ɢɫɫɥɟɞɨɜɚɧɢɸ ɫɩɟɤɬɪɨɜ ɤɨɦɛɢɧɚɰɢɨɧɧɨɝɨ ɪɚɫɫɟɹɧɢɹ: ɦɨɧɨ- ɢ ɩɨɥɢɤɪɢɫɬɚɥɥɨɜ ɱɢɫɬɨɝɨ Dɝɥɢɰɢɧɚ ɩɪɢ ɨɯɥɚɠɞɟɧɢɢ ɞɨ 83 K (ɡɚɩɢɫɚɧɧɵɟ ɜ ɞɢɚɩɚɡɨɧɚɯ ɱɚɫɬɨɬ 470—540 ɫɦ–1 ɢ 3200—
3050 ɫɦ–1) [ 20 ] ɢ ɦɨɧɨɤɪɢɫɬɚɥɥɚ E-ɝɥɢɰɢɧɚ (160—3300 ɫɦ–1) ɩɪɢ ɩɟɪɟɦɟɧɧɨɦ ɞɚɜɥɟɧɢɢ [ 21 ].
ɂɄ-ɫɩɟɤɬɪɨɫɤɨɩɢɱɟɫɤɢɟ ɢɫɫɥɟɞɨɜɚɧɢɹ ɩɨɥɢɦɨɪɮɨɜ ɝɥɢɰɢɧɚ ɜ ɭɫɥɨɜɢɹɯ ɩɟɪɟɦɟɧɧɵɯ
ɬɟɦɩɟɪɚɬɭɪ ɪɚɧɟɟ ɧɟ ɩɪɨɜɨɞɢɥɢɫɶ.
ȼ ɧɚɲɟɣ ɥɚɛɨɪɚɬɨɪɢɢ ɛɵɥɢ ɢɫɫɥɟɞɨɜɚɧɵ ɢɧɮɪɚɤɪɚɫɧɵɟ ɫɩɟɤɬɪɵ ɩɨɪɨɲɤɨɜ ɱɢɫɬɵɯ ɩɨɥɢɦɨɪɮɧɵɯ ɦɨɞɢɮɢɤɚɰɢɣ ɝɥɢɰɢɧɚ (D-, E- ɢ J-) ɜ ɢɧɬɟɪɜɚɥɟ ɬɟɦɩɟɪɚɬɭɪ 93—433 K. ɋɴɟɦɤɢ ɂɄ
ɫɩɟɤɬɪɨɜ ɩɪɨɩɭɫɤɚɧɢɹ ɜɫɟɯ ɬɪɟɯ ɮɨɪɦ ɝɥɢɰɢɧɚ ɩɪɨɜɨɞɢɥɢɫɶ ɛɟɡ ɢɫɩɨɥɶɡɨɜɚɧɢɹ ɦɚɬɪɢɰɵ.
ɗɄɋɉȿɊɂɆȿɇɌȺɅɖɇȺə ɑȺɋɌɖ
D-Ɏɨɪɦɚ ɝɥɢɰɢɧɚ ɛɵɥɚ ɩɨɥɭɱɟɧɚ ɩɭɬɟɦ ɩɟɪɟɤɪɢɫɬɚɥɥɢɡɚɰɢɢ ɢɡ ɜɨɞɧɨɝɨ ɪɚɫɬɜɨɪɚ ɱɢɫɬɨɝɨ
ɞɥɹ ɚɧɚɥɢɡɚ ɪɟɚɤɬɢɜɚ Riedel-de-Haen (Sigma-Aldrich Laborchemikalien GmbH). Ⱦɥɹ ɨɫɚɠɞɟɧɢɹ Eɝɥɢɰɢɧɚ ɢɫɩɨɥɶɡɨɜɚɥɢ ɦɟɬɨɞɢɤɭ, ɨɩɢɫɚɧɧɭɸ ɜ ɪɚɛɨɬɟ [ 25 ]: ɧɚɫɵɳɟɧɧɵɣ ɪɚɫɬɜɨɪ D-ɝɥɢɰɢɧɚ ɜ
ɫɦɟɫɢ ɥɟɞɹɧɨɣ ɭɤɫɭɫɧɨɣ ɤɢɫɥɨɬɵ ɢ ɜɨɞɵ (2:1) ɧɚɝɪɟɜɚɥɢ ɞɨ 80 qɋ, ɨɬɮɢɥɶɬɪɨɜɵɜɚɥɢ ɢ ɨɫɬɚɜɥɹɥɢ ɯɪɚɧɢɬɶɫɹ ɜ ɝɟɪɦɟɬɢɱɧɨ ɡɚɤɪɵɬɨɦ ɫɨɫɭɞɟ ɧɚ ɞɜɟ ɧɟɞɟɥɢ. ɉɪɢ ɯɪɚɧɟɧɢɢ ɱɚɫɬɶ ɝɥɢɰɢɧɚ ɜɵɩɚɥɚ
ɜ ɨɫɚɞɨɤ. ɉɨɫɥɟ ɯɪɚɧɟɧɢɹ ɪɚɫɬɜɨɪ ɨɫɬɨɪɨɠɧɨ ɨɬɞɟɥɢɥɢ ɨɬ ɜɵɩɚɜɲɟɝɨ ɨɫɚɞɤɚ ɞɟɤɚɧɬɚɰɢɟɣ ɢ ɞɨɩɨɥɧɢɬɟɥɶɧɵɦ ɮɢɥɶɬɪɨɜɚɧɢɟɦ, ɩɨɫɥɟ ɱɟɝɨ ɞɨɛɚɜɢɥɢ ɤ ɪɚɫɬɜɨɪɭ ɚɰɟɬɨɧ. Ɇɝɧɨɜɟɧɧɨ ɜɵɩɚɜɲɢɟ
ɦɟɥɤɢɟ ɢɝɨɥɶɱɚɬɵɟ ɤɪɢɫɬɚɥɥɵ E-ɝɥɢɰɢɧɚ ɨɬɮɢɥɶɬɪɨɜɚɥɢ ɢ ɜɵɫɭɲɢɥɢ ɩɨɞ ɜɚɤɭɭɦɨɦ, ɩɨɫɥɟ ɱɟɝɨ
341
ɂɄ ɋɉȿɄɌɊɕ ɄɊɂɋɌȺɅɅɂɑȿɋɄɂɏ ȺɆɂɇɈɄɂɋɅɈɌ, ȾɂɉȿɉɌɂȾɈȼ ɂ ɉɈɅɂȺɆɂɇɈɄɂɋɅɈɌ. I
ɯɪɚɧɢɥɢ ɜ ɷɤɫɢɤɚɬɨɪɟ, ɡɚɩɨɥɧɟɧɧɨɦ ɨɫɭɲɟɧɧɵɦ ɧɚɞ ɫɢɥɢɤɚɝɟɥɟɦ ɜɨɡɞɭɯɨɦ. Ɉɛɪɚɡɟɰ ɱɢɫɬɨɣ
ɮɚɡɵ J-ɝɥɢɰɢɧɚ ɛɵɥ ɩɨɥɭɱɟɧ ɩɨ ɦɟɬɨɞɢɤɟ, ɨɩɢɫɚɧɧɨɣ ɜ [ 8 ], ɩɭɬɟɦ ɩɟɪɟɤɪɢɫɬɚɥɥɢɡɚɰɢɢ ɜ ɩɚɪɚɯ
ɜɨɞɧɨɝɨ ɚɦɦɢɚɤɚ ɪɟɚɤɬɢɜɚ ICN Biomedicals(1-800-854-05030 [56-40-6]). Ɏɚɡɨɜɭɸ ɱɢɫɬɨɬɭ ɜɫɟɯ
ɬɪɟɯ ɨɛɪɚɡɰɨɜ ɤɨɧɬɪɨɥɢɪɨɜɚɥɢ ɦɟɬɨɞɨɦ ɪɟɧɬɝɟɧɨɮɚɡɨɜɨɝɨ ɚɧɚɥɢɡɚ ɧɚ ɩɨɪɨɲɤɨɜɨɦ ɞɢɮɪɚɤɬɨɦɟɬɪɟ ɫ ɞɜɭɯɤɨɨɪɞɢɧɚɬɧɵɦ ɫɱɟɬɱɢɤɨɦ GADDS D8 Bruker, CuKD, 2T 10—40q.
ɂɄ ɫɩɟɤɬɪɵ ɩɨɪɨɲɤɨɜ ɱɢɫɬɵɯ ɮɨɪɦ ɝɥɢɰɢɧɚ, ɨɬɩɪɟɫɫɨɜɚɧɧɵɯ ɜ ɬɨɧɤɢɟ ɩɥɚɫɬɢɧɤɢ, ɛɵɥɢ
ɢɡɦɟɪɟɧɵ ɧɚ ɂɄ-Ɏɭɪɶɟ ɫɩɟɤɬɪɨɦɟɬɪɟ Digilab Excalibur 3100 ɫ ɩɪɨɫɜɟɱɢɜɚɸɳɢɦ ɂɄ ɦɢɤɪɨɫɤɨɩɨɦ UMA-400 (ɮɢɪɦɚ Varian) ɜ ɞɢɚɩɚɡɨɧɟ ɱɚɫɬɨɬ 7800—600 ɫɦ–1 ɢ ɪɚɡɪɟɲɟɧɢɟɦ
4 ɫɦ–1. Ⱦɥɹ ɧɚɝɪɟɜɚɧɢɹ ɢ ɨɯɥɚɠɞɟɧɢɹ ɨɛɪɚɡɰɨɜ ɢɫɩɨɥɶɡɨɜɚɥɢ ɫɬɨɥɢɤ ɩɟɪɟɦɟɧɧɨɣ ɬɟɦɩɟɪɚɬɭɪɵ
FTIR 600 ɮɢɪɦɵ Linkam c ɩɪɨɝɪɚɦɦɚɬɨɪɨɦ ɬɟɦɩɟɪɚɬɭɪ (ɬɟɦɩɟɪɚɬɭɪɧɵɣ ɢɧɬɟɪɜɚɥ 93—433 K ɢ
ɲɚɝ ɩɨ ɬɟɦɩɟɪɚɬɭɪɟ 20q, ɬɨɱɧɨɫɬɶ ɨɩɪɟɞɟɥɟɧɢɹ ɬɟɦɩɟɪɚɬɭɪɵ 0,1 K).
ɊȿɁɍɅɖɌȺɌɕ ɂ ɂɏ ɈȻɋɍɀȾȿɇɂȿ
ɋɪɚɜɧɟɧɢɟ ɂɄ ɫɩɟɤɬɪɨɜ ɩɨɥɢɦɨɪɮɨɜ ɝɥɢɰɢɧɚ ɩɪɢ ɤɨɦɧɚɬɧɨɣ ɬɟɦɩɟɪɚɬɭɪɟ. ɋɬɪɭɤɬɭɪɵ ɩɨɥɢɦɨɪɮɧɵɯ ɦɨɞɢɮɢɤɚɰɢɣ ɝɥɢɰɢɧɚ ɪɚɡɥɢɱɚɸɬɫɹ ɭɩɚɤɨɜɤɨɣ ɰɜɢɬɬɟɪ-ɢɨɧɨɜ ɝɥɢɰɢɧɚ ɢ ɫɟɬɤɚɦɢ ɨɛɪɚɡɭɟɦɵɯ ɜɨɞɨɪɨɞɧɵɯ ɫɜɹɡɟɣ NH…O ɦɟɠɞɭ ɤɚɪɛɨɤɫɢɥɶɧɨɣ ɢ ɚɦɢɧɨɝɪɭɩɩɚɦɢ (ɬɚɛɥ. 1)
[ 2 — 5 ]. ɗɬɨ ɨɬɪɚɠɚɟɬɫɹ ɧɚ ɢɯ ɂɄ ɫɩɟɤɬɪɚɯ, ɡɚɩɢɫɚɧɧɵɯ ɩɪɢ ɤɨɦɧɚɬɧɨɣ ɬɟɦɩɟɪɚɬɭɪɟ, ɤɨɬɨɪɵɟ
ɩɪɢɜɟɞɟɧɵ ɧɚ ɪɢɫ. 1.
D- ɂ E-ɮɨɪɦɵ ɹɜɥɹɸɬɫɹ ɩɨɥɢɬɢɩɚɦɢ ɢ ɪɚɡɥɢɱɚɸɬɫɹ ɦɟɠɞɭ ɫɨɛɨɣ ɭɤɥɚɞɤɨɣ ɨɞɢɧɚɤɨɜɨ ɩɨ5
ɫɬɪɨɟɧɧɵɯ ɫɥɨɟɜ: ɦɨɧɨɤɥɢɧɧɚɹ ɫɢɧɝɨɧɢɹ, ɩɪɨɫɬɪɚɧɫɬɜɟɧɧɚɹ ɝɪɭɩɩɚ Ɋ21/n ( C2h
) ɢ Ɋ21 ( C22 ) ɫɨɨɬɜɟɬɫɬɜɟɧɧɨ. ɉɨɷɬɨɦɭ ɢɯ ɂɄ ɫɩɟɤɬɪɵ ɢɦɟɸɬ ɫɯɨɠɢɣ ɯɚɪɚɤɬɟɪ (ɩɪɚɤɬɢɱɟɫɤɢ ɨɞɢɧɚɤɨɜɨɟ ɤɨɥɢɱɟɫɬɜɨ ɩɨɥɨɫ ɩɨɝɥɨɳɟɧɢɹ, ɛɥɢɡɤɢɟ ɡɧɚɱɟɧɢɹ ɱɚɫɬɨɬ ɦɚɤɫɢɦɭɦɨɜ ɢ ɢɯ ɩɨɥɭɲɢɪɢɧɵ). ɉɨɥɨɫɵ
ɩɨɝɥɨɳɟɧɢɹ ɜ ɂɄ ɫɩɟɤɬɪɚɯ D-ɮɨɪɦɵ ɛɵɥɢ ɨɬɧɟɫɟɧɵ ɧɚ ɨɫɧɨɜɚɧɢɢ ɞɚɧɧɵɯ [ 11—14 ]. Ɉɬɧɟɫɟɧɢɟ
ɩɨɥɨɫ ɩɨɝɥɨɳɟɧɢɹ ɜ E-ɝɥɢɰɢɧɟ ɛɵɥɨ ɩɪɨɜɟɞɟɧɨ ɩɨ ɚɧɚɥɨɝɢɢ ɫ D-ɮɨɪɦɨɣ (ɬɚɛɥ. 2). Ʉɪɢɫɬɚɥɥɵ J-
ɮɨɪɦɵ ɝɥɢɰɢɧɚ ɨɬɧɨɫɹɬɫɹ ɤ ɬɪɢɝɨɧɚɥɶɧɨɣ ɫɢɧɝɨɧɢɢ (ɩɪɨɫɬɪɚɧɫɬɜɟɧɧɚɹ ɝɪɭɩɩɚ Ɋ31/Ɋ32 — C32 ).
ȼ ɨɬɥɢɱɢɟ ɨɬ D- ɢ E-ɮɨɪɦ, ɰɟɩɨɱɤɢ ɰɜɢɬɬɟɪ-ɢɨɧɨɜ ɫɜɹɡɚɧɵ ɧɟ ɜ ɫɥɨɢ, ɚ ɜ ɬɪɨɣɧɵɟ ɫɩɢɪɚɥɢ, ɤɨɬɨɪɵɟ ɜ ɫɜɨɸ ɨɱɟɪɟɞɶ ɬɚɤɠɟ ɫɨɟɞɢɧɟɧɵ ɦɟɠɞɭ ɫɨɛɨɣ ɜɨɞɨɪɨɞɧɵɦɢ ɫɜɹɡɹɦɢ ɜ ɬɪɟɯɦɟɪɧɭɸ ɫɟɬɤɭ. ɉɨɷɬɨɦɭ ɧɟ ɭɞɢɜɢɬɟɥɶɧɨ, ɱɬɨ ɨɛɳɢɣ ɜɢɞ ɂɄ ɫɩɟɤɬɪɚ J-ɦɨɞɢɮɢɤɚɰɢɢ ɝɥɢɰɢɧɚ ɡɚɦɟɬɧɨ ɨɬɥɢɱɚɟɬɫɹ ɨɬ ɂɄ ɫɩɟɤɬɪɨɜ ɞɜɭɯ ɞɪɭɝɢɯ ɩɨɥɢɦɨɪɮɧɵɯ ɦɨɞɢɮɢɤɚɰɢɣ (ɫɦ. ɪɢɫ. 1). ɉɨɥɨɫɵ ɩɨɝɥɨɳɟɧɢɹ ɜ ɂɄ ɫɩɟɤɬɪɟ J-ɮɨɪɦɵ ɛɵɥɢ ɨɬɧɟɫɟɧɵ ɫɨɝɥɚɫɧɨ ɞɚɧɧɵɦ [ 16 ]. Ⱦɥɹ ɜɫɟɯ ɬɪɟɯ ɮɨɪɦ ɝɥɢɰɢɧɚ
ɩɨɥɭɱɟɧɧɵɟ ɧɚɦɢ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɟ ɞɚɧɧɵɟ ɫɨɜɩɚɞɚɸɬ ɫ ɥɢɬɟɪɚɬɭɪɧɵɦɢ, ɡɚ ɢɫɤɥɸɱɟɧɢɟɦ
ɧɟɛɨɥɶɲɢɯ ɪɚɫɯɨɠɞɟɧɢɣ (2—3 ɫɦ–1) ɜ ɱɚɫɬɨɬɚɯ ɜɚɥɟɧɬɧɵɯ ɤɨɥɟɛɚɧɢɣ ɢɨɧɢɡɨɜɚɧɧɨɣ ɤɚɪɛɨɤɫɢɥɶɧɨɣ ɝɪɭɩɩɵ ɢ ɞɟɮɨɪɦɚɰɢɨɧɧɵɯ ɤɨɥɟɛɚɧɢɣ ɢɨɧɢɡɨɜɚɧɧɨɣ ɚɦɢɧɨɝɪɭɩɩɵ, ɱɬɨ ɦɨɠɟɬ ɛɵɬɶ
ɫɜɹɡɚɧɨ ɫ ɪɚɡɥɢɱɢɟɦ ɫɩɨɫɨɛɚ ɪɟɝɢɫɬɪɚɰɢɢ ɫɩɟɤɬɪɨɜ.
Ɍɚɛɥɢɰɚ 1
ɂɡɦɟɧɟɧɢɟ ɩɚɪɚɦɟɬɪɨɜ ɜɨɞɨɪɨɞɧɵɯ ɫɜɹɡɟɣ ɩɪɢ ɨɯɥɚɠɞɟɧɢɢ ɨɬ ɤɨɦɧɚɬɧɨɣ ɬɟɦɩɟɪɚɬɭɪɵ ɞɨ 150 K ɞɥɹ
D-, E-, J-ɮɨɪɦ ɝɥɢɰɢɧɚ ɩɨ ɞɚɧɧɵɦ ɦɨɧɨɤɪɢɫɬɚɥɶɧɨɝɨ ɪɟɧɬɝɟɧɨɫɬɪɭɤɬɭɪɧɨɝɨ ɚɧɚɥɢɡɚ [ 6 ]
H-ɫɜɹɡɶ
N(H)…O
(ɜ ɰɟɩɨɱɤɟ)
N(H)…O
(ɜ ɫɥɨɟ)
N(H)…O
(ɦɟɠɞɭ
ɫɥɨɹɦɢ)
N(H)…O
(ɦɟɠɞɭ
ɰɟɩɹɦɢ)
D
E
J
Ɍ = 294 K, Å
', Å
', %
Ɍ = 294 K, Å
2,7703(8)
–0,002
(7)
–0,07
2,7626(11)
–0,006 (3) –0,2
2,804(3)
2,8505(10) –0,012 (9) –0,4
2,8509(13)
–0,021 (3) –0,7
–
–
2,9516(9) –0,008 (8) – 0,3
–0,0464
–1,5
3,0749(10)
(8)
–
–
–
2,9795(15)
–0,030 (3) –1,0
–
–
2,9785(13)
–0,011 (3) –0,4
–
–
–
–
–
ǻ, Å
ǻ, %
Ɍ = 294 K, Å
–
–
–
2,811(4)
–
–
–
2,976(3)
ǻ, Å
ǻ, %
–0,010 (6) –0,3
–
–
–
–0,020 (7) –0,7
–0,7
–0,022 (6)
342
Ƚ.Ȼ. ɑȿɊɇɈȻȺɃ, ɘ.Ⱥ. ɑȿɋȺɅɈȼ, ȿ.Ȼ. ȻɍɊȽɂɇȺ ɂ ȾɊ.
Ɋɢɫ. 1. ɂɄ ɫɩɟɤɬɪɵ D-, E-, J-ɩɨɥɢɦɨɪɮɧɵɯ ɦɨɞɢɮɢɤɚɰɢɣ ɝɥɢɰɢɧɚ, ɡɚɩɢɫɚɧɧɵɟ ɩɪɢ ɤɨɦɧɚɬɧɨɣ ɬɟɦɩɟɪɚɬɭɪɟ
ɉɨɦɢɦɨ ɫɩɨɫɨɛɨɜ ɭɤɥɚɞɤɢ ɰɜɢɬɬɟɪ-ɢɨɧɨɜ ɜ ɫɬɪɭɤɬɭɪɟ, ɩɨɥɢɦɨɪɮɧɵɟ ɦɨɞɢɮɢɤɚɰɢɢ ɝɥɢɰɢɧɚ ɪɚɡɥɢɱɚɸɬɫɹ ɩɚɪɚɦɟɬɪɚɦɢ ɜɨɞɨɪɨɞɧɵɯ ɫɜɹɡɟɣ NH…O ɦɟɠɞɭ ɤɚɪɛɨɤɫɢɥɶɧɨɣ ɢ ɚɦɢɧɨɝɪɭɩɩɚɦɢ (ɫɦ. ɬɚɛɥ. 1), ɱɬɨ ɞɨɥɠɧɨ ɩɪɨɹɜɢɬɶɫɹ ɜ ɢɯ ɂɄ ɫɩɟɤɬɪɚɯ, ɩɪɟɠɞɟ ɜɫɟɝɨ, ɜ ɨɛɥɚɫɬɢ ɱɚɫɬɨɬ ɤɨɥɟɛɚɧɢɣ ɢɨɧɢɡɨɜɚɧɧɵɯ ɤɚɪɛɨɤɫɢɥɶɧɨɣ ɢ ɚɦɢɧɨɝɪɭɩɩ.
ɉɨɥɨɠɟɧɢɟ ɩɨɥɨɫɵ ɩɨɝɥɨɳɟɧɢɹ ɜɚɥɟɧɬɧɵɯ ɤɨɥɟɛɚɧɢɣ Ȟ(NH) ɢɨɧɢɡɨɜɚɧɧɨɣ ɚɦɢɧɨɝɪɭɩɩɵ
ɨɬɥɢɱɚɟɬɫɹ ɛɨɥɟɟ ɱɟɦ ɧɚ 10 ɫɦ–1 ɞɥɹ ɜɫɟɯ ɬɪɟɯ ɮɨɪɦ (ɫɦ. ɬɚɛɥ. 2).
Ɍɚɛɥɢɰɚ 2
–1
–1
ɑɚɫɬɨɬɵ (ɫɦ ), ɨɬɧɟɫɟɧɢɟ ɢ ɫɦɟɳɟɧɢɹ ɩɨɥɨɠɟɧɢɹ ɩɨɥɨɫ ɩɨɝɥɨɳɟɧɢɹ (', ɫɦ ) ɜ ɂɄ ɫɩɟɤɬɪɚɯ
ɩɨɥɢɦɨɪɮɨɜ ɝɥɢɰɢɧɚ ɜ ɢɧɬɟɪɜɚɥɟ ɬɟɦɩɟɪɚɬɭɪ 93—393 K
Ɉɬɧɟɫɟɧɢɟ
Q(NH…O)
Qas(ɋɇ2)
Qs(ɋɇ2)
Ɉɛɟɪɬɨɧ/ɫɨɫɬɚɜɧɚɹ ɱɚɫɬɨɬɚ
Ga(NH3)
Ȟa(COO)
įs(NH3)
į(CH2)
Ȟs(COO)
w(CH2)
W(CH2)
U(NH3)
Ȟa(CCN)
U(CH2)
Q(CC)
į(ɋɈɈ)
D [ 11 — 14 ]
Ɍɤɨɦɧ
', ɫɦ–1
Ɍɤɨɦɧ
', ɫɦ–1
3165
3007
2969
2128
1611
–
1584
1526
1513
1503
1444
1414
1333
1314
1132
1112
1034
911
893
702
3188
3006
2969
2136
1655
–
1606
1562
1543
1526
1445
1416
1336
–
1135
1120
1041
916
894
704
15
*
*
44
*
–
*
3100
2999
2962
2172
1663
1632
1580
–18
*
*
26
*
9
2
*
1496
*
5
4
4
–
9
2
6
1
3
5
1437
1397
1336
1326
1155
1129
1044
930
892
686
2
6
4
*
13
*
5
5
5
6
–14
1
2
55
5
–
4
*
2
5
2
*
10
9
3
10
4
7
E
J [ 15, 16 ]
Ɍɤɨɦɧ
', ɫɦ–1
* Ɉɩɪɟɞɟɥɟɧɢɟ ɩɨɥɨɠɟɧɢɹ ɦɚɤɫɢɦɭɦɚ ɩɨɥɨɫɵ ɩɨɝɥɨɳɟɧɢɹ ɜɵɡɵɜɚɟɬ ɡɚɬɪɭɞɧɟɧɢɹ ɜɫɥɟɞɫɬɜɢɟ ɢɡɦɟɧɟɧɢɹ
ɫɬɟɩɟɧɢ ɩɟɪɟɤɪɵɜɚɧɢɹ ɫɚɦɨɣ ɩɨɥɨɫɵ.
ɂɄ ɋɉȿɄɌɊɕ ɄɊɂɋɌȺɅɅɂɑȿɋɄɂɏ ȺɆɂɇɈɄɂɋɅɈɌ, ȾɂɉȿɉɌɂȾɈȼ ɂ ɉɈɅɂȺɆɂɇɈɄɂɋɅɈɌ. I
343
ɋɚɦɚɹ ɧɢɡɤɚɹ ɱɚɫɬɨɬɚ ɧɚɛɥɸɞɚɟɬɫɹ ɜ ɫɥɭɱɚɟ J-ɝɥɢɰɢɧɚ, ɫɚɦɚɹ ɜɵɫɨɤɚɹ — ɞɥɹ E-ɝɥɢɰɢɧɚ.
ɗɬɢ ɞɚɧɧɵɟ ɂɄ-ɫɩɟɤɬɪɨɫɤɨɩɢɱɟɫɤɢɯ ɢɫɫɥɟɞɨɜɚɧɢɣ ɫɥɨɠɧɨ ɫɨɩɨɫɬɚɜɢɬɶ ɫɨ ɫɬɪɭɤɬɭɪɧɵɦɢ ɞɚɧɧɵɦɢ ɨ ɝɟɨɦɟɬɪɢɱɟɫɤɢɯ ɩɚɪɚɦɟɬɪɚɯ ɜɨɞɨɪɨɞɧɵɯ ɫɜɹɡɟɣ ɜɨ ɜɫɟɯ ɬɪɟɯ ɩɨɥɢɦɨɪɮɚɯ ɝɥɢɰɢɧɚ, ɬɚɤ
ɤɚɤ ɪɚɫɫɬɨɹɧɢɹ ɞɨɧɨɪ—ɚɤɰɟɩɬɨɪ ɞɥɹ ɫɜɹɡɟɣ, ɫɨɟɞɢɧɹɸɳɢɯ ɚɧɚɥɨɝɢɱɧɵɟ ɮɪɚɝɦɟɧɬɵ ɫɬɪɭɤɬɭɪɵ,
ɢ ɫɨɨɬɧɨɲɟɧɢɹ ɦɟɠɞɭ ɧɢɦɢ ɜɨ ɜɫɟɯ ɬɪɟɯ ɩɨɥɢɦɨɪɮɚɯ ɞɨɫɬɚɬɨɱɧɨ ɛɥɢɡɤɢ (ɫɦ. ɬɚɛɥ. 1). Ʉ ɬɨɦɭ
ɠɟ ɮɨɪɦɚ ɤɨɥɟɛɚɧɢɹ, ɨɬɜɟɱɚɸɳɟɝɨ ɷɬɨɣ ɩɨɥɨɫɟ ɩɨɝɥɨɳɟɧɢɹ, ɜɨɡɦɨɠɧɨ, ɢɦɟɟɬ ɫɥɨɠɧɵɣ ɯɚɪɚɤɬɟɪ (ɩɪɢ ɤɨɥɟɛɚɧɢɢ ɦɟɧɹɸɬɫɹ ɞɥɢɧɵ ɜɫɟɯ ɬɪɟɯ ɫɜɹɡɟɣ ɝɪɭɩɩɵ NH3+ ), ɯɨɬɹ ɪɚɧɟɟ ɜ ɥɢɬɟɪɚɬɭɪɟ ɢ
ɜɵɫɤɚɡɵɜɚɥɢ ɩɪɟɞɩɨɥɨɠɟɧɢɟ, ɱɬɨ ɞɚɧɧɚɹ ɩɨɥɨɫɚ ɩɨɝɥɨɳɟɧɢɹ ɨɬɧɨɫɢɬɫɹ ɤ ɤɨɥɟɛɚɧɢɹɦ ɜɨɞɨɪɨɞɚ
ɝɪɭɩɩɵ NH3+ , ɭɱɚɫɬɜɭɸɳɟɝɨ ɜ ɨɛɪɚɡɨɜɚɧɢɢ ɫɚɦɨɣ ɫɥɚɛɨɣ ɜɨɞɨɪɨɞɧɨɣ ɫɜɹɡɢ [ 16, 20 ].
ɂɄ ɫɩɟɤɬɪɵ ɩɨɥɢɦɨɪɮɨɜ ɝɥɢɰɢɧɚ ɡɚɦɟɬɧɨ ɨɬɥɢɱɚɸɬɫɹ ɧɟ ɬɨɥɶɤɨ ɜ ɨɛɥɚɫɬɢ ɜɚɥɟɧɬɧɵɯ ɤɨɥɟɛɚɧɢɣ Q(NH), ɧɚ ɱɬɨ ɜɩɟɪɜɵɟ ɨɛɪɚɬɢɥ ɜɧɢɦɚɧɢɟ ɂɬɚɤɚ [ 4 ], ɧɨ ɢ ɜ ɛɨɥɟɟ ɧɢɡɤɨɱɚɫɬɨɬɧɵɯ ɞɢɚɩɚɡɨɧɚɯ. Ɍɚɤ, ɡɚɦɟɬɧɨ ɪɚɡɥɢɱɚɸɬɫɹ ɱɚɫɬɨɬɵ ɩɨɥɨɫɵ ɩɨɝɥɨɳɟɧɢɹ ɦɚɹɬɧɢɤɨɜɵɯ ɤɨɥɟɛɚɧɢɣ ɚɦɢɧɨɝɪɭɩɩɵ U( NH3+ ). J-Ɏɨɪɦɭ ɦɨɠɧɨ ɨɬɥɢɱɢɬɶ ɨɬ D- ɢ E-ɩɨɥɢɦɨɪɮɧɵɯ ɦɨɞɢɮɢɤɚɰɢɣ ɝɥɢɰɢɧɚ ɩɨ
ɟɞɢɧɫɬɜɟɧɧɨɣ ɭɡɤɨɣ ɩɨɥɨɫɟ ɩɨɝɥɨɳɟɧɢɹ ɫɢɦɦɟɬɪɢɱɧɵɯ ɞɟɮɨɪɦɚɰɢɨɧɧɵɯ ɩɥɨɫɤɨɫɬɧɵɯ ɤɨɥɟɛɚɧɢɣ ɚɦɢɧɨɝɪɭɩɩɵ Gs( NH3+ ) (ɫɦ. ɪɢɫ. 1).
Ɍɚɤɠɟ ɜ ɫɩɟɤɬɪɚɯ ɜɫɟɯ ɬɪɟɯ ɩɨɥɢɦɨɪɮɨɜ ɝɥɢɰɢɧɚ ɧɚɛɥɸɞɚɟɬɫɹ ɪɚɡɥɢɱɢɟ ɜ ɩɨɥɨɠɟɧɢɢ ɩɨɥɨɫɵ ɩɨɝɥɨɳɟɧɢɹ ɦɚɹɬɧɢɤɨɜɵɯ ɤɨɥɟɛɚɧɢɣ ɝɪɭɩɩɵ ɋɇ2, ɫɤɟɥɟɬɧɵɯ ɤɨɥɟɛɚɧɢɣ Q(ɋɋN) ɢ ɩɨɝɥɨɳɟɧɢɹ ɫɨ ɫɥɨɠɧɵɦ ɤɨɧɬɭɪɨɦ ɜ ɞɢɚɩɚɡɨɧɟ ɱɚɫɬɨɬ 2120—2180 ɫɦ–1 (ɫɦ. ɪɢɫ. 1): 2128, 2136,
2172 ɫɦ–1 ɜ ɫɥɭɱɚɟ D-, E- ɢ J-ɮɨɪɦ ɝɥɢɰɢɧɚ ɫɨɨɬɜɟɬɫɬɜɟɧɧɨ ɩɪɢ ɤɨɦɧɚɬɧɨɣ ɬɟɦɩɟɪɚɬɭɪɟ. Ⱦɚɧɧɨɟ
ɩɨɝɥɨɳɟɧɢɟ ɹɜɥɹɟɬɫɹ ɨɛɳɟɣ ɨɫɨɛɟɧɧɨɫɬɶɸ ɂɄ ɫɩɟɤɬɪɨɜ ɤɪɢɫɬɚɥɥɨɜ ɚɦɢɧɨɤɢɫɥɨɬ [ 23 ]. Ɉɞɧɚɤɨ
ɜ ɥɢɬɟɪɚɬɭɪɟ ɧɟɬ ɟɞɢɧɨɝɨ ɦɧɟɧɢɹ ɨɛ ɨɬɧɟɫɟɧɢɢ ɷɬɨɝɨ ɩɨɝɥɨɳɟɧɢɹ. Ɋɹɞ ɢɫɫɥɟɞɨɜɚɬɟɥɟɣ ɨɬɧɨɫɹɬ
ɟɝɨ ɤ ɨɛɟɪɬɨɧɚɦ ɢɥɢ ɫɨɫɬɚɜɧɵɦ ɱɚɫɬɨɬɚɦ [ 30 ], ɞɪɭɝɢɟ ɚɜɬɨɪɵ — ɤ ɜɚɥɟɧɬɧɵɦ ɤɨɥɟɛɚɧɢɹɦ
(N—)ɇ…Ɉ [ 24 ].
ȼɥɢɹɧɢɟ ɩɨɧɢɠɟɧɢɹ ɬɟɦɩɟɪɚɬɭɪɵ ɧɚ ɂɄ ɫɩɟɤɬɪɵ ɩɨɥɢɦɨɪɮɨɜ ɝɥɢɰɢɧɚ. ɂɡ ɞɢɮɪɚɤɰɢɨɧɧɵɯ ɷɤɫɩɟɪɢɦɟɧɬɨɜ ɢɡɜɟɫɬɧɨ, ɱɬɨ ɩɨɧɢɠɟɧɢɟ ɬɟɦɩɟɪɚɬɭɪɵ ɨɬ ɤɨɦɧɚɬɧɨɣ ɞɨ 150 K ɜɵɡɵɜɚɟɬ ɚɧɢɡɨɬɪɨɩɧɨɟ ɫɠɚɬɢɟ ɤɪɢɫɬɚɥɥɢɱɟɫɤɢɯ ɫɬɪɭɤɬɭɪ ɩɨɥɢɦɨɪɮɧɵɯ ɦɨɞɢɮɢɤɚɰɢɣ ɝɥɢɰɢɧɚ, ɩɪɢ
ɤɨɬɨɪɨɦ ɩɪɨɢɫɯɨɞɢɬ ɞɟɮɨɪɦɚɰɢɹ ɦɟɠɦɨɥɟɤɭɥɹɪɧɵɯ ɜɨɞɨɪɨɞɧɵɯ ɫɜɹɡɟɣ [ 6 ].
ɉɪɢ ɩɨɧɢɠɟɧɢɢ ɬɟɦɩɟɪɚɬɭɪɵ ɜ ɂɄ ɫɩɟɤɬɪɚɯ D-, E- ɢ J-ɮɨɪɦ ɝɥɢɰɢɧɚ ɧɚɛɥɸɞɚɟɬɫɹ ɫɦɟɳɟɧɢɟ ɩɨɥɨɫ ɩɨɝɥɨɳɟɧɢɹ (ɫɦ. ɬɚɛɥ. 2) ɢ ɭɫɥɨɠɧɟɧɢɟ ɫɩɟɤɬɪɚ ɡɚ ɫɱɟɬ ɭɦɟɧɶɲɟɧɢɹ ɩɨɥɭɲɢɪɢɧɵ ɩɨɥɨɫ ɩɨɝɥɨɳɟɧɢɹ (ɪɢɫ. 2).
Ɋɚɧɟɟ ɢɡ ɤɚɥɨɪɢɦɟɬɪɢɱɟɫɤɢɯ ɷɤɫɩɟɪɢɦɟɧɬɨɜ ɢ ɢɫɫɥɟɞɨɜɚɧɢɣ ɦɟɬɨɞɨɦ ɂɄ ɫɩɟɤɬɪɨɫɤɨɩɢɢ
ɛɵɥɨ ɢɡɜɟɫɬɧɨ, ɱɬɨ E-ɮɨɪɦɚ ɝɥɢɰɢɧɚ ɩɪɟɬɟɪɩɟɜɚɟɬ ɮɚɡɨɜɵɣ ɩɟɪɟɯɨɞ ɜɬɨɪɨɝɨ ɪɨɞɚ ɩɪɢ ɨɯɥɚɠɞɟɧɢɢ ɞɨ 252 K [ 10, 12 ]. ȼ ɂɄ ɫɩɟɤɬɪɚɯ, ɢɫɫɥɟɞɨɜɚɧɧɵɯ ɜ ɧɚɫɬɨɹɳɟɣ ɪɚɛɨɬɟ, ɷɬɨɬ ɮɚɡɨɜɵɣ ɩɟɪɟɯɨɞ ɧɟ ɩɪɨɹɜɢɥɫɹ. Ⱦɥɹ ɜɫɟɯ ɬɪɟɯ ɮɨɪɦ ɧɚɛɥɸɞɚɥɢ ɧɟɩɪɟɪɵɜɧɨɟ ɢɡɦɟɧɟɧɢɟ ɩɨɥɨɠɟɧɢɹ ɩɨɥɨɫ
ɩɨɝɥɨɳɟɧɢɹ.
ɇɚɢɛɨɥɟɟ ɱɭɜɫɬɜɢɬɟɥɶɧɨ ɤ ɢɡɦɟɧɟɧɢɸ ɬɟɦɩɟɪɚɬɭɪɵ ɫɥɨɠɧɨɟ ɩɨɝɥɨɳɟɧɢɟ ɜ ɞɢɚɩɚɡɨɧɟ ɱɚɫɬɨɬ 2120—2180 ɫɦ–1. ɋɞɜɢɝ ɞɚɧɧɨɝɨ ɩɨɝɥɨɳɟɧɢɹ ɜ ɨɛɥɚɫɬɶ ɜɵɫɨɤɢɯ ɱɚɫɬɨɬ ɩɪɢ ɨɯɥɚɠɞɟɧɢɢ ɜ
ɢɧɬɟɪɜɚɥɟ 433—93 K ɫɨɫɬɚɜɥɹɟɬ ɛɨɥɟɟ 20 ɫɦ–1. ɇɚɢɛɨɥɶɲɟɟ ɚɛɫɨɥɸɬɧɨɟ ɢ ɨɬɧɨɫɢɬɟɥɶɧɨɟ ɫɦɟɳɟɧɢɟ ɧɚɛɥɸɞɚɟɬɫɹ ɞɥɹ D-ɮɨɪɦɵ, ɧɚɢɦɟɧɶɲɟɟ — ɞɥɹ J-ɝɥɢɰɢɧɚ (ɫɦ. ɬɚɛɥ. 2). ȼ ɧɚɫɬɨɹɳɟɟ ɜɪɟɦɹ ɧɟ ɩɪɟɞɫɬɚɜɥɹɟɬɫɹ ɜɨɡɦɨɠɧɵɦ ɨɛɴɹɫɧɢɬɶ ɷɬɢ ɮɚɤɬɵ, ɩɨɫɤɨɥɶɤɭ ɧɟɬ ɬɨɱɧɵɯ ɞɚɧɧɵɯ ɨɛ ɨɬɧɟɫɟɧɢɢ ɷɬɨɝɨ ɩɨɝɥɨɳɟɧɢɹ.
ɉɪɢ ɨɯɥɚɠɞɟɧɢɢ ɡɧɚɱɢɬɟɥɶɧɨ ɫɦɟɳɚɟɬɫɹ ɩɨɥɨɫɚ ɩɨɝɥɨɳɟɧɢɹ ɜɚɥɟɧɬɧɵɯ ɤɨɥɟɛɚɧɢɣ Q(NH).
ȼ ɫɥɭɱɚɟ D- ɢ J-ɮɨɪɦ ɝɥɢɰɢɧɚ ɱɚɫɬɨɬɚ Q(NH) ɨɬ ɬɟɦɩɟɪɚɬɭɪɵ ɦɨɧɨɬɨɧɧɨ ɭɛɵɜɚɟɬ ɩɪɢ ɩɨɧɢɠɟɧɢɢ ɬɟɦɩɟɪɚɬɭɪɵ, ɱɬɨ ɫɜɢɞɟɬɟɥɶɫɬɜɭɟɬ ɨɛ ɭɜɟɥɢɱɟɧɢɢ ɩɪɨɱɧɨɫɬɢ ɜɨɞɨɪɨɞɧɵɯ ɫɜɹɡɟɣ ɩɪɢ ɨɯɥɚɠɞɟɧɢɢ (ɪɢɫ. 3).
Ɋɚɧɟɟ ɭɦɟɧɶɲɟɧɢɟ ɱɚɫɬɨɬɵ ɜɚɥɟɧɬɧɵɯ ɤɨɥɟɛɚɧɢɣ ɚɦɢɧɨɝɪɭɩɩɵ Q(NH) ɩɪɢ ɭɦɟɧɶɲɟɧɢɢ
ɬɟɦɩɟɪɚɬɭɪɵ ɧɚɛɥɸɞɚɥɢ ɩɪɢ ɢɫɫɥɟɞɨɜɚɧɢɢ ɦɟɬɨɞɨɦ ɄɊ-ɫɩɟɤɬɪɨɫɤɨɩɢɢ ɜ ɢɧɬɟɪɜɚɥɟ ɬɟɦɩɟɪɚɬɭɪ
358—123 K ɜ ɪɚɛɨɬɟ [ 20 ]. ɗɬɨɬ ɪɟɡɭɥɶɬɚɬ ɬɚɤɠɟ ɤɨɪɪɟɥɢɪɭɟɬ ɫ ɞɚɧɧɵɦɢ ɦɨɧɨɤɪɢɫɬɚɥɶɧɨɣ ɧɢɡɤɨɬɟɦɩɟɪɚɬɭɪɧɨɣ ɞɢɮɪɚɤɬɨɦɟɬɪɢɢ: ɩɪɢ ɨɯɥɚɠɞɟɧɢɢ ɭɦɟɧɶɲɚɸɬɫɹ ɪɚɫɫɬɨɹɧɢɹ N…O ɞɥɹ ɜɫɟɯ
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Ƚ.Ȼ. ɑȿɊɇɈȻȺɃ, ɘ.Ⱥ. ɑȿɋȺɅɈȼ, ȿ.Ȼ. ȻɍɊȽɂɇȺ ɂ ȾɊ.
Ɋɢɫ. 2. ɍɫɥɨɠɧɟɧɢɟ ɂɄ ɫɩɟɤɬɪɨɜ ɩɨɥɢɦɨɪɮɨɜ ɝɥɢɰɢɧɚ, ɡɚɩɢɫɚɧɧɵɯ ɩɪɢ ɨɯɥɚɠɞɟɧɢɢ ɞɨ 93 K, ɜ ɞɢɚɩɚɡɨɧɟ
1800—1200 ɫɦ–1, ɚ — D-ɮɨɪɦɚ, ɛ — E-ɮɨɪɦɚ, ɜ — J-ɮɨɪɦɚ
Ɋɢɫ. 3. Ɂɚɜɢɫɢɦɨɫɬɶ ɱɚɫɬɨɬ ɤɨɥɟɛɚɧɢɣ ɨɬ ɬɟɦɩɟɪɚɬɭɪɵ: ɚ — ɩɨɥɨɫɚ ɩɨɝɥɨɳɟɧɢɹ ɜɚɥɟɧɬɧɵɯ ɤɨɥɟɛɚɧɢɣ
ɢɨɧɢɡɨɜɚɧɧɨɣ ɚɦɢɧɨɝɪɭɩɩɵ Q(NH), ɛ — ɩɨɥɨɫɚ ɩɨɝɥɨɳɟɧɢɹ ɜ ɨɛɥɚɫɬɢ ɱɚɫɬɨɬ 2120—2180 ɫɦ–1
ɬɪɟɯ ɚɬɨɦɨɜ ɜɨɞɨɪɨɞɚ ɢɨɧɢɡɨɜɚɧɧɨɣ ɚɦɢɧɨɝɪɭɩɩɵ (ɫɦ. ɬɚɛɥ. 2). Ⱦɥɹ E-ɝɥɢɰɢɧɚ ɱɚɫɬɨɬɚ ɤɨɥɟɛɚɧɢɣ Q(NH) ɦɨɧɨɬɨɧɧɨ ɪɚɫɬɟɬ ɩɪɢ ɩɨɧɢɠɟɧɢɢ ɬɟɦɩɟɪɚɬɭɪɵ, ɯɨɬɹ, ɫɨɝɥɚɫɧɨ ɫɬɪɭɤɬɭɪɧɵɦ ɞɚɧɧɵɦ, ɪɚɫɫɬɨɹɧɢɟ N…O ɬɚɤɠɟ ɭɦɟɧɶɲɚɟɬɫɹ. ɉɪɢ ɷɬɨɦ ɜɟɥɢɱɢɧɚ ɫɦɟɳɟɧɢɹ ɫɨɩɨɫɬɚɜɢɦɚ ɫ ɢɡɦɟɧɟɧɢɟɦ ɩɨɥɨɠɟɧɢɹ ɩɨɥɨɫ ɩɨɝɥɨɳɟɧɢɹ ɜ ɂɄ ɫɩɟɤɬɪɚɯ ɞɪɭɝɢɯ ɞɜɭɯ ɩɨɥɢɦɨɪɮɨɜ. ȼɵɫɨɤɨɱɚɫɬɨɬɧɵɣ ɫɞɜɢɝ ɞɚɧɧɨɣ ɩɨɥɨɫɵ ɩɨɝɥɨɳɟɧɢɹ ɧɚɛɥɸɞɚɥɢ ɜ ɛɨɥɟɟ ɪɚɧɧɢɯ ɢɫɫɥɟɞɨɜɚɧɢɹɯ ɩɪɢ ɨɯɥɚɠɞɟɧɢɢ ɬɚɛɥɟɬɤɢ E-ɝɥɢɰɢɧɚ ɫ KBr ɨɬ ɤɨɦɧɚɬɧɨɣ ɬɟɦɩɟɪɚɬɭɪɵ ɞɨ ɬɟɦɩɟɪɚɬɭɪɵ ɠɢɞɤɨɝɨ ɚɡɨɬɚ, ɨɞɧɚɤɨ ɷɮɮɟɤɬ ɛɵɥ ɡɧɚɱɢɬɟɥɶɧɨ ɦɟɧɶɲɟ. ȼ ɫɩɟɤɬɪɚɯ, ɫɧɹɬɵɯ ɜ KBr, ɩɨɥɨɠɟɧɢɟ ɩɨɥɨɫɵ ɩɨɝɥɨɳɟɧɢɹ
Q(NH) ɩɪɢ ɤɨɦɧɚɬɧɨɣ ɬɟɦɩɟɪɚɬɭɪɟ (a3181 ɫɦ–1) ɡɚɦɟɬɧɨ ɨɬɥɢɱɚɥɨɫɶ ɨɬ ɧɚɛɥɸɞɚɜɲɟɝɨɫɹ ɜ ɞɚɧɧɨɣ ɪɚɛɨɬɟ ɛɟɡ ɢɫɩɨɥɶɡɨɜɚɧɢɹ ɪɚɡɛɚɜɢɬɟɥɹ, ɱɬɨ ɦɨɠɟɬ ɛɵɬɶ ɫɜɹɡɚɧɨ ɫ ɜɥɢɹɧɢɟɦ ɦɚɬɪɢɰɵ ɧɚ ɢɫɫɥɟɞɭɟɦɭɸ ɫɢɫɬɟɦɭ ɜɨɞɨɪɨɞɧɵɯ ɫɜɹɡɟɣ (ȿ.Ȼ. Ȼɭɪɝɢɧɚ, ɧɟɨɩɭɛɥɢɤɨɜɚɧɧɵɟ ɞɚɧɧɵɟ). Ɍɚɤɢɦ ɨɛɪɚɡɨɦ, ɢɡɦɟɧɟɧɢɹ ɂɄ ɫɩɟɤɬɪɚ E-ɝɥɢɰɢɧɚ ɩɪɢ ɨɯɥɚɠɞɟɧɢɢ ɭɤɚɡɵɜɚɸɬ ɧɚ ɨɫɥɚɛɥɟɧɢɟ ɜɨɞɨɪɨɞɧɵɯ
ɫɜɹɡɟɣ ɩɪɢ ɭɦɟɧɶɲɟɧɢɢ ɪɚɫɫɬɨɹɧɢɣ ɞɨɧɨɪ—ɚɤɰɟɩɬɨɪ, ɱɬɨ ɦɨɠɧɨ ɫɜɹɡɚɬɶ, ɧɚɩɪɢɦɟɪ, ɫ ɢɡɦɟɧɟɧɢɹɦɢ ɭɝɥɨɜ ɜɨɞɨɪɨɞɧɵɯ ɫɜɹɡɟɣ N—ɇ…Ɉ. ɉɪɢɱɢɧɵ ɷɬɨɝɨ ɧɟ ɜɩɨɥɧɟ ɨɛɵɱɧɨɝɨ ɹɜɥɟɧɢɹ ɬɪɟɛɭɸɬ ɞɚɥɶɧɟɣɲɟɝɨ ɢɡɭɱɟɧɢɹ.
Ⱦɪɭɝɢɟ ɩɨɥɨɫɵ ɩɨɝɥɨɳɟɧɢɹ ɜ ɂɄ ɫɩɟɤɬɪɚɯ ɩɨɥɢɦɨɪɮɨɜ ɝɥɢɰɢɧɚ ɫɦɟɳɚɸɬɫɹ ɜ ɦɟɧɶɲɟɣ
ɫɬɟɩɟɧɢ. ɋɥɟɞɭɸɳɢɟ ɩɨ ɜɟɥɢɱɢɧɟ ɬɟɦɩɟɪɚɬɭɪɧɨɝɨ ɫɞɜɢɝɚ — ɩɨɥɨɫɵ ɩɨɝɥɨɳɟɧɢɹ, ɨɬɧɨɫɹɳɢɟɫɹ
ɤ ɦɚɹɬɧɢɤɨɜɵɦ ɤɨɥɟɛɚɧɢɹɦ U( NH3+ ). ȼ ɫɥɭɱɚɟ J-ɮɨɪɦɵ ɝɥɢɰɢɧɚ ɧɚɛɥɸɞɚɟɬɫɹ ɧɚɢɛɨɥɶɲɟɟ ɫɦɟɳɟɧɢɟ ɫɚɦɨɣ ɜɵɫɨɤɨɱɚɫɬɨɬɧɨɣ ɩɨɥɨɫɵ U( NH3+ ), ɚ ɬɚɤɠɟ ɭɫɥɨɠɧɟɧɢɟ ɤɨɧɬɭɪɚ ɩɨɥɨɫɵ ɩɨɝɥɨɳɟɧɢɹ ɜ ɪɚɣɨɧɟ 1129 ɫɦ–1 (ɪɢɫ. 4, ɚ). Ɍɚɤɠɟ ɞɥɹ ɂɄ ɫɩɟɤɬɪɚ J-ɝɥɢɰɢɧɚ ɩɪɢ ɨɯɥɚɠɞɟɧɢɢ ɧɚɛɥɸɞɚɸɬɫɹ ɡɚɦɟɬɧɵɟ ɢɡɦɟɧɟɧɢɹ ɞɥɹ ɩɨɥɨɫɵ ɩɨɝɥɨɳɟɧɢɹ ɩɥɨɫɤɨɫɬɧɵɯ ɞɟɮɨɪɦɚɰɢɨɧɧɵɯ ɤɨɥɟɛɚɧɢɣ
ɂɄ ɋɉȿɄɌɊɕ ɄɊɂɋɌȺɅɅɂɑȿɋɄɂɏ ȺɆɂɇɈɄɂɋɅɈɌ, ȾɂɉȿɉɌɂȾɈȼ ɂ ɉɈɅɂȺɆɂɇɈɄɂɋɅɈɌ. I
345
Ɋɢɫ. 4. ɉɪɢɦɟɪɵ ɢɡɦɟɧɟɧɢɣ ɜ ɂɄ ɫɩɟɤɬɪɚɯ ɩɨɥɢɦɨɪɮɧɵɯ ɦɨɞɢɮɢɤɚɰɢɣ ɝɥɢɰɢɧɚ ɩɪɢ ɨɯɥɚɠɞɟɧɢɢ ɜ
ɢɧɬɟɪɜɚɥɟ ɬɟɦɩɟɪɚɬɭɪ 413—93 K: ɚ — ɩɨɥɨɫɚ ɩɨɝɥɨɳɟɧɢɹ ɦɚɹɬɧɢɤɨɜɵɯ ɤɨɥɟɛɚɧɢɣ U(NH3) ɜ ɂɄ ɫɩɟɤɬɪɟ
J-ɝɥɢɰɢɧɚ, ɛ — ɩɨɥɨɫɚ ɩɨɝɥɨɳɟɧɢɹ ɫɢɦɦɟɬɪɢɱɧɵɯ ɩɥɨɫɤɨɫɬɧɵɯ ɞɟɮɨɪɦɚɰɢɨɧɧɵɯ ɤɨɥɟɛɚɧɢɣ Gs(NH3) ɜ
ɂɄ ɫɩɟɤɬɪɟ J-ɝɥɢɰɢɧɚ, ɜ — ɩɨɥɨɫɚ ɩɨɝɥɨɳɟɧɢɹ ɦɚɹɬɧɢɤɨɜɵɯ ɤɨɥɟɛɚɧɢɣ U(ɋɇ2) ɜ ɂɄ ɫɩɟɤɬɪɟ D-ɝɥɢɰɢɧɚ
ɢɨɧɢɡɨɜɚɧɧɨɣ ɚɦɢɧɨɝɪɭɩɩɵ: ɫɦɟɳɟɧɢɟ ɨɞɧɨɣ ɢɡ ɩɨɥɨɫ ɩɨɝɥɨɳɟɧɢɹ, ɨɬɧɨɫɹɳɢɯɫɹ ɤ Gɚ(NH3)
ɩɪɢɦɟɪɧɨ ɧɚ 10 ɫɦ–1, ɢ ɢɡɦɟɧɟɧɢɟ ɩɨɥɨɠɟɧɢɹ ɧɚ 12 ɫɦ–1, ɭɫɥɨɠɧɟɧɢɟ ɤɨɧɬɭɪɚ ɩɨɥɨɫɵ ɩɨɝɥɨɳɟɧɢɹ Gs(NH3) (ɫɦ. ɪɢɫ. 4, ɛ).
ɉɨɥɨɫɵ ɩɨɝɥɨɳɟɧɢɹ, ɨɬɧɨɫɹɳɢɟɫɹ ɤ ɜɚɥɟɧɬɧɵɦ ɤɨɥɟɛɚɧɢɹɦ ɤɚɪɛɨɤɫɢɥɶɧɨɣ ɝɪɭɩɩɵ, ɫɦɟɳɚɸɬɫɹ ɩɪɢ ɨɯɥɚɠɞɟɧɢɢ ɜ ɡɚɞɚɧɧɨɦ ɢɧɬɟɪɜɚɥɟ ɬɟɦɩɟɪɚɬɭɪ ɧɚ ɜɟɥɢɱɢɧɭ ɞɨ 6—7 ɫɦ–1. ȼɫɟ ɨɫɬɚɥɶɧɵɟ ɩɨɥɨɫɵ ɩɨɝɥɨɳɟɧɢɹ ɜ ɂɄ ɫɩɟɤɬɪɚɯ ɜɫɟɯ ɬɪɟɯ ɩɨɥɢɦɨɪɮɨɜ ɫɦɟɳɚɸɬɫɹ ɩɪɢ ɨɯɥɚɠɞɟɧɢɢ
ɜ ɨɛɥɚɫɬɶ ɛɨɥɟɟ ɜɵɫɨɤɢɯ ɱɚɫɬɨɬ ɦɟɧɶɲɟ, ɩɪɢɦɟɪɧɨ ɧɚ 2—5 ɫɦ–1 (ɫɦ. ɬɚɛɥ. 1). Ɇɟɧɶɲɟ ɜɫɟɝɨ
346
Ƚ.Ȼ. ɑȿɊɇɈȻȺɃ, ɘ.Ⱥ. ɑȿɋȺɅɈȼ, ȿ.Ȼ. ȻɍɊȽɂɇȺ ɂ ȾɊ.
ɫɦɟɳɚɸɬɫɹ ɩɨɥɨɫɵ ɩɨɝɥɨɳɟɧɢɹ ɝɪɭɩɩɵ ɋɇ2. ɂɫɤɥɸɱɟɧɢɟ ɫɨɫɬɚɜɥɹɟɬ ɡɧɚɱɢɬɟɥɶɧɨɟ (' a 10 ɫɦ–1)
ɫɦɟɳɟɧɢɟ ɩɨɥɨɫɵ ɦɚɹɬɧɢɤɨɜɵɯ ɤɨɥɟɛɚɧɢɣ U(ɋɇ2) ɜ D-ɝɥɢɰɢɧɟ ɩɪɢ ɩɨɧɢɠɟɧɢɢ ɬɟɦɩɟɪɚɬɭɪɵ ɨɬ
ɤɨɦɧɚɬɧɨɣ ɞɨ 93 K. ɂɧɬɟɪɟɫɧɨ, ɱɬɨ ɬɚɤɨɟ ɛɨɥɶɲɨɟ ɫɦɟɳɟɧɢɟ ɧɚɛɥɸɞɚɟɬɫɹ ɬɨɥɶɤɨ ɞɥɹ D-ɮɨɪɦɵ
(ɫɦ. ɪɢɫ. 4, ɜ). ȼ ɂɄ ɫɩɟɤɬɪɟ E-ɝɥɢɰɢɧɚ, ɹɜɥɹɸɳɟɝɨɫɹ ɩɨɥɢɬɢɩɨɦ ɞɥɹ D-ɮɨɪɦɵ, ɩɪɢ ɤɨɦɧɚɬɧɨɣ
ɬɟɦɩɟɪɚɬɭɪɟ ɱɚɫɬɨɬɚ ɤɨɥɟɛɚɧɢɣ U(ɋɇ2) ɛɥɢɡɤɚ ɤ ɡɧɚɱɟɧɢɸ ɷɬɨɣ ɱɚɫɬɨɬɵ D-ɮɨɪɦɵ, ɨɞɧɚɤɨ ɬɟɦɩɟɪɚɬɭɪɧɵɣ ɫɞɜɢɝ ɧɚ ɩɨɪɹɞɨɤ ɦɟɧɶɲɟ (ɫɦ. ɬɚɛɥ. 2). ɉɨɷɬɨɦɭ ɱɭɜɫɬɜɢɬɟɥɶɧɨɫɬɶ ɤ ɬɟɦɩɟɪɚɬɭɪɟ
ɞɚɧɧɨɣ ɩɨɥɨɫɵ ɜ ɂɄ ɫɩɟɤɬɪɟ D-ɮɨɪɦɵ ɦɨɠɧɨ ɫɜɹɡɚɬɶ ɫ ɨɫɨɛɟɧɧɨɫɬɹɦɢ ɟɟ ɫɬɪɭɤɬɭɪɵ. Ɍɨɥɶɤɨ ɜ
D-ɝɥɢɰɢɧɟ ɨɛɪɚɡɭɸɬɫɹ ɝɢɞɪɨɮɨɛɧɵɟ ɫɥɨɢ ɡɚ ɫɱɟɬ ɚɬɨɦɨɜ ɜɨɞɨɪɨɞɚ ɝɪɭɩɩɵ ɋɇ2, ɜɵɯɨɞɹɳɢɯ ɧɚɜɫɬɪɟɱɭ ɞɪɭɝ ɞɪɭɝɭ ɢɡ ɩɥɨɫɤɨɫɬɢ ɞɜɨɣɧɵɯ ɫɜɹɡɚɧɧɵɯ ɫɥɨɟɜ N—H…O. ɉɪɢ ɷɬɨɦ ɚɬɨɦɵ ɜɨɞɨɪɨɞɚ, ɜɵɯɨɞɹɳɢɟ ɢɡ ɩɥɨɫɤɨɫɬɢ ɨɞɧɨɝɨ ɞɜɨɣɧɨɝɨ ɫɥɨɹ, ɜɡɚɢɦɨɞɟɣɫɬɜɭɸɬ ɫ ɚɬɨɦɚɦɢ ɤɢɫɥɨɪɨɞɚ ɢɨɧɢɡɨɜɚɧɧɵɯ ɤɚɪɛɨɤɫɢɥɶɧɵɯ ɝɪɭɩɩ ɦɨɥɟɤɭɥ ɢɡ ɫɨɫɟɞɧɟɝɨ ɫɥɨɹ. ɉɪɢ ɨɯɥɚɠɞɟɧɢɢ ɪɚɫɫɬɨɹɧɢɟ ɦɟɠɞɭ ɚɬɨɦɚɦɢ ɭɝɥɟɪɨɞɚ ɝɪɭɩɩɵ ɋɇ2 ɜɧɭɬɪɢ ɞɜɨɣɧɨɝɨ ɫɥɨɹ ɫɨɤɪɚɳɚɟɬɫɹ ɩɪɢɦɟɪɧɨ ɜ 2 ɪɚɡɚ ɦɟɧɶɲɟ, ɱɟɦ ɦɟɠɞɭ ɞɜɨɣɧɵɦɢ ɫɥɨɹɦɢ (ɫ 3,472(2) ɞɨ 3,451(8) Å ɢ ɫ 2,514(2) ɞɨ 2,472(8) Å ɫɨɨɬɜɟɬɫɬɜɟɧɧɨ). ȼ ɫɥɭɱɚɟ J-ɝɥɢɰɢɧɚ ɬɟɦɩɟɪɚɬɭɪɧɵɣ ɫɞɜɢɝ U(ɋɇ2) ɩɨɥɨɫɵ ɩɨɝɥɨɳɟɧɢɹ ɫɨɫɬɚɜɥɹɟɬ ɩɪɨɦɟɠɭɬɨɱɧɨɟ ɡɧɚɱɟɧɢɟ 5 ɫɦ–1, ɨɞɧɚɤɨ ɢ ɟɟ ɩɨɥɨɠɟɧɢɟ ɜ ɂɄ ɫɩɟɤɬɪɟ, ɡɚɩɢɫɚɧɧɨɦ ɩɪɢ ɤɨɦɧɚɬɧɨɣ
ɬɟɦɩɟɪɚɬɭɪɟ, ɡɧɚɱɢɬɟɥɶɧɨ ɨɬɥɢɱɚɟɬɫɹ (a20 ɫɦ–1) ɨɬ ɂɄ ɫɩɟɤɬɪɨɜ D- ɢ E-ɮɨɪɦ. ȼɫɥɟɞɫɬɜɢɟ ɷɬɨɝɨ,
ɬɚɤɨɣ ɫɞɜɢɝ ɩɨɥɨɫɵ ɩɨɝɥɨɳɟɧɢɹ U(ɋɇ2) ɜ ɂɄ ɫɩɟɤɬɪɟ J-ɝɥɢɰɢɧɚ ɦɨɠɟɬ ɛɵɬɶ ɫɜɹɡɚɧ ɫ ɢɡɦɟɧɟɧɢɟɦ ɮɨɪɦɵ ɤɨɥɟɛɚɧɢɹ, ɤɨɬɨɪɨɦɭ ɨɬɜɟɱɚɟɬ ɞɚɧɧɚɹ ɩɨɥɨɫɚ.
ȼ ɥɢɬɟɪɚɬɭɪɟ ɜɵɫɤɚɡɵɜɚɥɨɫɶ ɩɪɟɞɩɨɥɨɠɟɧɢɟ ɨ ɬɨɦ, ɱɬɨ ɜ ɫɬɪɭɤɬɭɪɟ ɩɨɥɢɦɨɪɮɧɵɯ ɦɨɞɢɮɢɤɚɰɢɣ ɝɥɢɰɢɧɚ ɩɪɢɫɭɬɫɬɜɭɸɬ ɬɚɤɠɟ ɜɨɞɨɪɨɞɧɵɟ ɫɜɹɡɢ CH…O [ 25, 26 ]. ȼɨɞɨɪɨɞɧɵɟ ɫɜɹɡɢ
ɷɬɨɝɨ ɬɢɩɚ ɨɤɚɡɵɜɚɸɬ ɜɥɢɹɧɢɟ ɧɚ ɮɨɪɦɢɪɨɜɚɧɢɟ ɫɬɪɭɤɬɭɪ ɪɹɞɚ ɦɨɥɟɤɭɥɹɪɧɵɯ ɤɪɢɫɬɚɥɥɨɜ, ɛɢɨɩɨɥɢɦɟɪɨɜ ɢ ɫɭɩɪɚɦɨɥɟɤɭɥɹɪɧɵɯ ɚɧɫɚɦɛɥɟɣ [ 28, 29 ]. ȼ ɫɥɭɱɚɟ ɝɥɢɰɢɧɚ ɩɪɟɞɩɨɥɚɝɚɥɨɫɶ, ɱɬɨ
ɷɬɢ ɫɜɹɡɢ ɦɨɝɭɬ ɢɝɪɚɬɶ ɜɚɠɧɭɸ ɪɨɥɶ ɩɪɢ ɤɪɢɫɬɚɥɥɢɡɚɰɢɢ ɩɨɥɢɦɨɪɮɧɵɯ ɦɨɞɢɮɢɤɚɰɢɣ, ɜ ɱɚɫɬɧɨɫɬɢ E-ɮɨɪɦɵ [ 26 ], ɚ ɬɚɤɠɟ ɩɪɢ ɨɬɤɥɢɤɟ ɫɬɪɭɤɬɭɪ ɧɚ ɩɨɜɵɲɟɧɢɟ ɞɚɜɥɟɧɢɹ [ 27 ]. ȼɵɲɟɨɩɢɫɚɧɧɵɟ ɜɵɜɨɞɵ ɛɵɥɢ ɫɞɟɥɚɧɵ ɧɚ ɨɫɧɨɜɚɧɢɢ ɚɧɚɥɢɡɚ ɦɟɠɚɬɨɦɧɵɯ ɪɚɫɫɬɨɹɧɢɣ C(H)…O. ɂɫɫɥɟɞɨɜɚɧɢɹ ɦɟɬɨɞɨɦ ɧɢɡɤɨɬɟɦɩɟɪɚɬɭɪɧɨɣ ɂɄ ɫɩɟɤɬɪɨɫɤɨɩɢɢ ɪɚɧɟɟ ɧɟ ɩɪɨɜɨɞɢɥɢɫɶ. ɉɪɢ ɨɛɪɚɡɨɜɚɧɢɢ ɜɨɞɨɪɨɞɧɵɯ ɫɜɹɡɟɣ C(H)…O ɜ ɂɄ ɫɩɟɤɬɪɚɯ ɞɨɥɠɧɨ ɧɚɛɥɸɞɚɬɶɫɹ ɡɚɦɟɬɧɨɟ ɭɲɢɪɟɧɢɟ ɢ
ɫɞɜɢɝ ɩɨɥɨɫ ɩɨɝɥɨɳɟɧɢɹ, ɫɨɨɬɜɟɬɫɬɜɭɸɳɢɯ ɤɨɥɟɛɚɧɢɹɦ ɫɜɹɡɟɣ ɋ—ɇ, ɱɬɨ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɨ
ɧɚɛɥɸɞɚɥɢ, ɧɚɩɪɢɦɟɪ, ɞɥɹ ɠɢɞɤɨɝɨ 4-ɷɬɨɤɫɢɛɟɧɡɚɥɶɞɟɝɢɞɚ ɜ ɪɚɛɨɬɟ [ 30 ]. ȼ ɢɫɫɥɟɞɨɜɚɧɧɵɯ ɧɚɦɢ ɂɄ ɫɩɟɤɬɪɚɯ ɜɫɟɯ ɬɪɟɯ ɩɨɥɢɦɨɪɮɧɵɯ ɦɨɞɢɮɢɤɚɰɢɣ ɝɥɢɰɢɧɚ ɜ ɢɧɬɟɪɜɚɥɟ ɬɟɦɩɟɪɚɬɭɪ 433—
93 K ɩɨɥɨɫɵ ɩɨɝɥɨɳɟɧɢɹ, ɨɬɧɨɫɹɳɢɟɫɹ ɤ ɜɚɥɟɧɬɧɵɦ ɢ ɞɟɮɨɪɦɚɰɢɨɧɧɵɦ ɤɨɥɟɛɚɧɢɹɦ ɝɪɭɩɩɵ
ɋɇ2, ɭɡɤɢɟ ɢ ɩɪɚɤɬɢɱɟɫɤɢ ɧɟ ɱɭɜɫɬɜɢɬɟɥɶɧɵ ɤ ɬɟɦɩɟɪɚɬɭɪɟ (ɫɦ. ɪɢɫ. 1, ɬɚɛɥ. 2), ɱɬɨ ɧɟ ɩɨɞɬɜɟɪɠɞɚɟɬ ɩɪɢɫɭɬɫɬɜɢɟ ɜ ɞɚɧɧɵɯ ɫɬɪɭɤɬɭɪɚɯ ɜɡɚɢɦɨɞɟɣɫɬɜɢɣ, ɤɨɬɨɪɵɟ ɦɨɠɧɨ ɛɵɥɨ ɛɵ ɨɯɚɪɚɤɬɟɪɢɡɨɜɚɬɶ ɤɚɤ ɜɨɞɨɪɨɞɧɵɟ ɫɜɹɡɢ CH…O.
Ɋɚɛɨɬɚ ɜɵɩɨɥɧɟɧɚ ɩɪɢ ɮɢɧɚɧɫɨɜɨɣ ɩɨɞɞɟɪɠɤɟ ɝɪɚɧɬɚ CRDF ɢ Ɇɢɧɨɛɪɚɡɨɜɚɧɢɹ Ɋɨɫɫɢɣɫɤɨɣ
Ɏɟɞɟɪɚɰɢɢ (REC-008 NO-0008-X1), ɝɪɚɧɬɚ Ɋɨɫɫɢɣɫɤɨɝɨ ɮɨɧɞɚ ɮɭɧɞɚɦɟɧɬɚɥɶɧɵɯ ɢɫɫɥɟɞɨɜɚɧɢɣ
05-03-32468, ɂɧɬɟɝɪɚɰɢɨɧɧɵɯ ɩɪɨɟɤɬɨɜ ɋɈ ɊȺɇ ʋ 49 ɢ ʋ 110, ɚ ɬɚɤɠɟ ɩɪɨɝɪɚɦɦɵ ɊȺɇ sɋɭɩɪɚɦɨɥɟɤɭɥɹɪɧɚɹ ɯɢɦɢɹs.
Ⱥɜɬɨɪɵ ɛɥɚɝɨɞɚɪɹɬ ɘ.ȼ. ɋɟɪɟɬɤɢɧɚ ɢ Ⱥ.Ɏ. Ⱥɱɤɚɫɨɜɚ ɡɚ ɩɨɦɨɳɶ ɜ ɩɪɨɜɟɞɟɧɢɢ ɷɤɫɩɟɪɢɦɟɧɬɨɜ.
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