63 Хuм uя ГЕтЕрОГЕННАЯ рЕАКЦИЯ пАрОВ

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´Ý³Ï³Ý ·ÇïáõÃÛáõÝÝ»ñ
1, 2007
Åñòåñòâåííûå íàó êè
ɏɢɦ ɢɹ
ɍȾɄ 541.128.13+541.127+661.491+541.49
Ʌ. Ƚ. ɌȺȾȿȼɈɋəɇ
ȽȿɌ ȿɊɈȽȿɇɇȺə ɊȿȺɄɐɂə ɉȺɊɈȼ ɉȿɊɈɄɋɂȾȺ ȼɈȾɈɊɈȾȺ ɋ MgO
ȼɩɟɪɜɵɟ ɢɡɭɱɟɧɚ ɤɢɧɟɬɢɤɚ ɧɚɤɨɩɥɟɧɢɹ ɜ ɝɚɡɨɜɨɣ ɮɚɡɟ ɩɪɨɦɟɠɭɬɨɱɧɨɝɨ
ɫɨɟɞɢɧɟɧɢɹ (ɉɋ), ɨɛɪɚɡɭɸɳɟɝɨɫɹ ɩɪɢ ɜɡɚɢɦɨɞɟɣɫɬɜɢɢ ɩɚɪɨɜ ɇ 2Ɉ 2 ɫ MgO
ɩɪɢ ɬɟɦɩɟɪɚɬɭɪɟ 273 K ɢ ɞɚɜɥɟɧɢɢ ɩɚɪɨɜ ɩɟɪɨɤɫɢɞɚ 7,5 ɉɚ . Ɉɩɪɟɞɟɥɟɧɵ
ɡɧɚɱɟɧɢɹ ɫɤɨɪɨɫɬɢ ɩɟɪɟɯɨɞɚ ɉɋ ɫ ɩɨɜɟɪɯɧɨɫɬɢ ɜ ɝɚɡɨɜɭɸ ɮɚɡɭ ɢ ɤɨɧɫɬɚɧɬɵ
ɟɝɨ ɞɚɥɶɧɟɣɲɟɝɨ ɝɟɬɟɪɨɝɟɧɧɨɝɨ ɪɚɡɥɨɠɟɧɢɹ.
ȼ ɩɨɫɥɟɞɧɢɟ ɝɨɞɵ ɨɬɤɪɵɬɚ ɪɟɚɤɰɢɹ ɩɚɪɨɜ ɇ2 Ɉ2 ɫ ɧɟɤɨɬɨɪɵɦɢ ɫɨɥɹɦɢ ɢ
ɨɤɫɢɞɚɦɢ [1–3], ɤɨɬɨɪɚɹ ɩɨ ɫɭɬɢ ɹɜɥɹɟɬɫɹ ɧɨɜɨɣ ɯɢɦɢɱɟɫɤɨɣ ɬɪɚɧɫɩɨɪɬɧɨɣ
ɪɟɚɤɰɢɟɣ (ɏɌɊ) [4]. ɉɪɢɱɟɦ, ɜ ɨɬɥɢɱɢɟ ɨɬ ɫɭɳɟɫɬɜɭɸɳɢɯ ɏɌɊ, ɨɬɤɪɵɬɚɹ ɪɟɚɤɰɢɹ ɢɦɟɟɬ ɨɩɪɟɞɟɥɟɧɧɵɟ ɩɪɟɢɦɭɳɟɫɬɜɚ – ɨɧɚ ɩɪɨɬɟɤɚɟɬ ɩɪɢ ɫɪɚɜɧɢɬɟɥɶɧɨ
ɧɢɡɤɢɯ ɬɟɦɩɟɪɚɬɭɪɚɯ (ɜ ɧɟɤɨɬɨɪɵɯ ɫɥɭɱɚɹɯ ɧɚɱɢɧɚɹ ɫ ɤɨɦɧɚɬɧɨɣ), ɢɦɟɟɬ ɦɚɥɨɟ ɱɢɫɥɨ ɷɬɚɩɨɜ, ɩɪɨɫɬɚ ɢ ɥɟɝɤɨ ɪɟɝɭɥɢɪɭɟɦɚ. Ʉɪɨɦɟ ɬɟɨɪɟɬɢɱɟɫɤɨɝɨ ɢɧɬɟɪɟɫɚ, ɧɨɜɚɹ ɏɌɊ ɨɬɥɢɱɚɟɬɫɹ ɛɨɥɶɲɢɦɢ ɩɪɢɤɥɚɞɧɵɦɢ ɜɨɡɦɨɠɧɨɫɬɹɦɢ. ȿɟ ɦɨɠɧɨ ɢɫɩɨɥɶɡɨɜɚɬɶ ɞɥɹ ɦɨɞɢɮɢɰɢɪɨɜɚɧɢɹ ɩɨɜɟɪɯɧɨɫɬɟɣ ɬɜɟɪɞɵɯ ɜɟɳɟɫɬɜ [5],
ɩɨɥɭɱɟɧɢɹ ɤɚɬɚɥɢɡɚɬɨɪɨɜ [6] ɢ ɩɨɤɪɵɬɢɣ ɫ ɪɚɡɥɢɱɧɵɦɢ ɮɢɡɢɤɨ-ɯɢɦɢɱɟɫɤɢɦɢ
ɫɜɨɣɫɬɜɚɦɢ, ɜ ɱɚɫɬɧɨɫɬɢ ɞɥɹ ɩɨɥɭɱɟɧɢɹ ɧɚɧɨɫɬɪɭɤɬɭɪɧɵɯ ɩɥɟɧɨɤ.
Ⱦɥɹ ɭɫɬɚɧɨɜɥɟɧɢɹ ɦɟɯɚɧɢɡɦɚ ɩɪɨɰɟɫɫɚ ɧɟɨɛɯɨɞɢɦɨ ɞɟɬɚɥɶɧɨɟ ɢɡɭɱɟɧɢɟ
ɜɫɟɯ ɚɫɩɟɤɬɨɜ ɪɟɚɤɰɢɢ ɢ, ɜ ɩɟɪɜɭɸ ɨɱɟɪɟɞɶ, ɤɢɧɟɬɢɱɟɫɤɢɯ ɡɚɤɨɧɨɦɟɪɧɨɫɬɟɣ
ɧɚɤɨɩɥɟɧɢɹ ɜ ɝɚɡɨɜɨɣ ɮɚɡɟ ɩɪɨɦɟɠɭɬɨɱɧɨɝɨ ɫɨɟɞɢɧɟɧɢɹ (ɉɋ), ɨɬɜɟɬɫɬɜɟɧɧɨɝɨ
ɡɚ ɩɟɪɟɧɨɫ ɜɟɳɟɫɬɜɚ, ɫ ɩɪɢɜɥɟɱɟɧɢɟɦ ɧɨɜɵɯ ɬɜɟɪɞɵɯ ɫɨɟɞɢɧɟɧɢɣ, ɩɪɨɹɜɥɹɸɳɢɯ ɚɧɚɥɨɝɢɱɧɨɟ ɫɜɨɣɫɬɜɨ. ɂɫɫɥɟɞɨɜɚɧɢɹ ɩɨɤɚɡɚɥɢ, ɱɬɨ ɉɋ ɹɜɥɹɟɬɫɹ ɩɟɪɨɤɫɨɫɨɥɶɜɚɬɨɦ ɫɨɨɬɜɟɬɫɬɜɭɸɳɟɝɨ ɨɤɫɢɞɚ (MemOn ·H2 O2 ). ȼ ɞɚɧɧɨɣ ɪɚɛɨɬɟ ɜɩɟɪɜɵɟ ɢɡɭɱɟɧɚ ɤɢɧɟɬɢɤɚ ɧɚɤɨɩɥɟɧɢɹ ɜ ɝɚɡɨɜɨɣ ɮɚɡɟ ɉɋ, ɨɛɪɚɡɭɸɳɟɝɨɫɹ ɩɪɢ
ɜɡɚɢɦɨɞɟɣɫɬɜɢɢ ɩɚɪɨɜ ɩɟɪɨɤɫɢɞɚ ɜɨɞɨɪɨɞɚ ɫ MgO.
ȼɵɛɨɪ ɨɛɴɟɤɬɚ ɢɫɫɥɟɞɨɜɚɧɢɹ ɛɵɥ ɨɛɭɫɥɨɜɥɟɧ ɬɚɤɠɟ ɬɟɦ, ɱɬɨ MgO ɢ
ɦɧɨɝɨɤɨɦɩɨɧɟɧɬɧɵɟ ɫɢɫɬɟɦɵ ɧɚ ɟɝɨ ɨɫɧɨɜɟ ɢɦɟɸɬ ɲɢɪɨɤɨɟ ɩɪɚɤɬɢɱɟɫɤɨɟ
ɩɪɢɦɟɧɟɧɢɟ. ɇɚɩɪɢɦɟɪ, MgO ɢɫɩɨɥɶɡɭɟɬɫɹ ɜ ɤɚɱɟɫɬɜɟ ɞɨɩɢɪɭɸɳɟɝɨ ɫɨɟɞɢɧɟɧɢɹ ɞɥɹ ɩɥɟɧɨɤ ɨɤɫɢɞɚ ɰɢɧɤɚ, ɚ ɫɢɫɬɟɦɚ MgO+ZnO ɹɜɥɹɟɬɫɹ ɷɮɮɟɤɬɢɜɧɵɦ
ɤɚɬɚɥɢɡɚɬɨɪɨɦ ɝɢɞɪɚɬɚɰɢɢ ɚɰɟɬɢɥɟɧɚ ɢ ɞɟɝɢɞɪɚɬɚɰɢɢ ɜɬɨɪɢɱɧɵɯ ɫɩɢɪɬɨɜ [7].
ɂɡɭɱɟɧɢɟ ɜɨɡɦɨɠɧɨɫɬɢ ɩɟɪɟɧɨɫɚ MgO ɫ ɩɨɦɨɳɶɸ ɩɚɪɨɜ H2 O2 , ɚ ɬɚɤɠɟ
ɤɢɧɟɬɢɱɟɫɤɢɯ ɡɚɤɨɧɨɦɟɪɧɨɫɬɟɣ ɷɬɨɝɨ ɩɪɨɰɟɫɫɚ ɩɨɡɜɨɥɢɬ ɨɛɨɝɚɬɢɬɶ ɧɚɲɢ ɫɜɟ63
ɞɟɧɢɹ ɨɬɧɨɫɢɬɟɥɶɧɨ ɧɨɜɨɣ ɏɌɊ ɢ ɪɚɫɲɢɪɢɬ ɤɪɭɝ ɟɟ ɩɪɚɤɬɢɱɟɫɤɨɝɨ ɩɪɢɦɟɧɟɧɢɹ ɜ ɪɚɡɥɢɱɧɵɯ ɨɛɥɚɫɬɹɯ ɧɚɭɤɢ ɢ ɬɟɯɧɢɤɢ.
ɂɫɫɥɟɞɨɜɚɧɢɹ ɩɪɨɜɨɞɢɥɢɫɶ ɜ ɩɪɨɬɨɱɧɵɯ ɭɫɥɨɜɢɹɯ ɫ ɩɨɦɨɳɶɸ ɫɬɟɤɥɹɧɧɨɣ ɜɚɤɭɭɦɧɨɣ ɭɫɬɚɧɨɜɤɢ ɩɨ ɦɟɬɨɞɢɤɟ, ɨɩɢɫɚɧɧɨɣ ɜ ɪɚɛɨɬɟ [8]. ɂɫɬɨɱɧɢɤɨɦ
ɩɚɪɨɜ ɩɟɪɨɤɫɢɞɚ ɫɥɭɠɢɥ ~85% ɜɨɞɧɵɣ ɪɚɫɬɜɨɪ H2 O2 ɦɚɪɤɢ ɨɫ.ɱ., ɤɨɬɨɪɵɣ
ɜ ɯɨɞɟ ɷɤɫɩɟɪɢɦɟɧɬɚ ɬɟɪɦɨɫɬɚɬɢɪɨɜɚɥɫɹ
1
ɩɪɢ ɬɟɦɩɟɪɚɬɭɪɟ 273 K. ȼ ɤɚɱɟɫɬɜɟ ɬɜɟɪɞɨɝɨ ɤɨɧɬɚɤɬɚ ɛɵɥ ɜɵɛɪɚɧ MgO ɦɚɪɤɢ
ɯ.ɱ., ɤɨɬɨɪɵɣ ɩɨɦɟɳɚɥɫɹ ɜ ɪɟɚɤɬɨɪ ɜ ɜɢɞɟ
ɬɚɛɥɟɬɤɢ (ɪɢɫ. 1), ɱɬɨɛɵ ɢɫɤɥɸɱɢɬɶ ɦɟɯɚɧɢɱɟɫɤɢɣ ɩɟɪɟɧɨɫ MgO. Ɉɛɴɟɦ ɪɟɚɤɬɨɪɚ
ɫɨɫɬɚɜɥɹɥ ɩɪɢɦɟɪɧɨ 1 ɫɦ 3, ɚ ɩɥɨɳɚɞɶ ɬɚɛ4
ɥɟɬɢɪɨɜɚɧɧɨɝɨ ɨɛɪɚɡɰɚ ~2 ɫɦ 2 .
ɉɪɨɯɨɞɹ ɱɟɪɟɡ ɪɟɚɤɬɨɪ, ɩɚɪɵ
H2O2 ɜɡɚɢɦɨɞɟɣɫɬɜɭɸɬ ɫ M gO ɫ
ɨɛɪɚɡɨɜɚɧɢɟɦ ɧɚ ɩɨɜɟɪɯɧɨɫɬɢ ɉɋ,
ɤɨɬɨɪɨɟ ɱɚɫɬɢɱɧɨ
ɩɟɪɟɯɨɞɢɬ ɜ 2
ɝɚɡɨɜɭɸ ɮɚɡɭ ɢ ɩɨɬɨɤɨɦ ɝɚɡɚ ɜɵɯɨɞɢɬ Ɋɢɫ. 1. ɋɯɟɦɚ ɪɟɚɤɬɨɪɚ
3 ɢ ɭɡɥɚ ɧɚɤɨɩɥɟɢɡ ɪɟɚɤɬɨɪɚ 2. ȼ ɯɨɞɟ ɷɤɫɩɟɪɢɦɟɧɬɚ ɧɢɹ: 1 – ɜɯɨɞ ɩɚɪɨɜ ɩɟɪɨɤɫɢɞɚ ɜɨɞɨɪɨɞɚ,
ɝɚɡɨɜɵɣ ɩɨɬɨɤ ɩɨɫɥɟ ɪɟɚɤɬɨɪɚ ɤɨɧ- 2 – ɪɟɚɤɬɨɪ ɫ ɨɛɪɚɡɰɨɦ ɆgO, 3 – ɫɨɫɭɞɵ
Ⱦɶɸɚɪɚ, 4 – ɧɚɤɨɩɢɬɟɥɶ.
ɞɟɧɫɢɪɨɜɚɥɢ ɜ ɧɚɤɨɩɢɬɟɥɟ 4, ɧɚɯɨɞɹɳɟɦɫɹ ɩɪɢ 77 K. ɉɨɫɥɟ ɨɞɧɨɝɨ ɱɚɫɚ ɤɨɧɞɟɧɫɚɰɢɢ ɩɨɬɨɤɚ ɨɩɪɟɞɟɥɹɥɢ
ɤɨɥɢɱɟɫɬɜɨ ɉɋ ɜ ɧɟɦ. Ⱥ ɧɚɥɢɡ ɨɫɭɳɟɫɬɜɥɹɥɢ ɫɥɟɞɭɸɳɢɦ ɨɛɪɚɡɨɦ.
ɇɚɯɨɞɹɳɢɣɫɹ ɜ ɤɨɧɞɟɧɫɚɬɟ ɩɟɪɨɤɫɨɫɨɥɶɜɚɬ ɫ ɩɨɦɨɳɶɸ ɫɨɥɹɧɨɣ
ɤɢɫɥɨɬɵ ɩɪɟɜɪɚɳɚɥɢ ɜ M gCl2 ɢ ɩɨ
[ÏC] ˜ 10 , ÷àñò èö ˜ ñì
ɦɟɬɨɞɢɤɟ, ɨɩɢɫɚɧɧɨɣ ɜ ɪɚɛɨɬɟ [8],
14
ɫ ɩɨɦɨɳɶɸ ɚɬɨɦɧɨ-ɚɛɫɨɪɛɰɢɨɧɧɨɝɨ
ɫɩɟɤɬɪɨɦɟɬɪa AAS30 (ɱɭɜɫɬɜɢɬɟɥɶ12
ɧɨɫɬɶ ɩɨɪɹɞɤɚ 10-8 ɦɨɥɶ˜ɥ-1) ɨɩɪɟɞɟ10
ɥɹɥɢ ɤɨɥɢɱɟɫɬɜɨ ɢɨɧɨɜ ɦɚɝɧɢɹ ɜ
8
ɪɚɫɬɜɨɪɟ.
Ɂɧɚɹ
ɤɨɥɢɱɟɫɬɜɨ
6
ɧɚɤɨɩɥɟɧɧɨɝɨ ɜɟɳɟɫɬɜɚ, ɫɤɨɪɨɫɬɶ
ɩɨɬɨɤɚ ɝɚɡɚ ɢ ɜɪɟɦɹ ɧɚɤɨɩɥɟɧɢɹ,
4
ɪɚɫɫɱɢɬɵɜɚɥɢ ɤɨɧɰɟɧɬɪɚɰɢɸ ɉɋ ɜ
2
ɝɚɡɨɜɨɣ ɮɚɡɟ.
- 10
-3
ɉɪɨɰɟɫɫ ɢɡɭɱɚɥɢ ɜ ɬɟɦɩɟɪɚɬɭɪɧɨɦ
ɢɧɬɟɪɜɚɥɟ
273–323 K ɩɪɢ ɨɛɳɟɦ
Ɋɢɫ. 2. Ʉɢɧɟɬɢɱɟɫɤɚɹ ɤɪɢɜɚɹ ɧɚɤɨɩɥɟɧɢɹ
ɞɚɜɥɟɧɢɢ
ɫɦɟɫɢ
H2 O2 +H2 O 30 ɉɚ ɢ ɫɨɉɋ ɜ ɝɚɡɨɜɨɣ ɮɚɡɟ ɩɪɢ ɬɟɦɩɟɪɚɬɭɪɟ 273 K ɢ
ɞɚɜɥɟɧɢɢ ɩɚɪɨɜ ɇ 2Ɉ 2 7,5 ɉɚ (Ɋ ɨɛɳ = 30 ɉɚ ). ɨɬɧɨɲɟɧɢɢ H2 O2 :H2 O=1:3, ɱɬɨ ɫɨɨɬɜɟɬɫɬɜɭɟɬ ɞɚɜɥɟɧɢɸ H2 O2 ɜ ɪɟɚɤɬɨɪɟ 7,5 ɉɚ .
ȼɪɟɦɹ ɩɪɨɯɨɠɞɟɧɢɹ ɫɦɟɫɢ ɱɟɪɟɡ ɪɟɚɤɬɨɪ ɜɚɪɶɢɪɨɜɚɥɢ ɨɬ 1·10 -2 ɞɨ 7,5·10 -2 ɫ.
ɂɡɭɱɟɧɢɟ ɪɟɚɤɰɢɢ ɩɪɢ ɪɚɡɥɢɱɧɵɯ ɬɟɦɩɟɪɚɬɭɪɚɯ ɩɨɤɚɡɚɥɨ, ɱɬɨ ɜ ɯɨɞɟ
ɩɪɨɰɟɫɫɚ ɫɨɫɬɨɹɧɢɟ ɩɨɜɟɪɯɧɨɫɬɢ ɦɟɧɹɟɬɫɹ, ɩɪɢɱɟɦ ɱɟɦ ɜɵɲɟ ɬɟɦɩɟɪɚɬɭɪɚ,
ɬɟɦ ɛɵɫɬɪɟɟ ɩɪɨɢɫɯɨɞɢɬ ɷɬɨ ɢɡɦɟɧɟɧɢɟ. ɋ ɰɟɥɶɸ ɩɨɥɭɱɟɧɢɹ ɜɨɫɩɪɨɢɡɜɨɞɢɦɵɯ ɞɚɧɧɵɯ ɤɢɧɟɬɢɤɚ ɧɚɤɨɩɥɟɧɢɹ ɉɋ ɜ ɝɚɡɨɜɨɣ ɮɚɡɟ ɩɪɢ ɜɡɚɢɦɨɞɟɣɫɬɜɢɢ
ɩɚɪɨɜ ɩɟɪɨɤɫɢɞɚ ɜɨɞɨɪɨɞɚ ɫ ɆgO ɛɵɥɚ ɢɡɭɱɟɧɚ ɩɪɢ 273 K. ɉɪɢ ɷɬɨɣ ɬɟɦɩɟɪɚɬɭɪɟ ɧɟ ɩɪɨɢɫɯɨɞɹɬ ɫɭɳɟɫɬɜɟɧɧɵɟ ɢɡɦɟɧɟɧɢɹ ɫɨɫɬɨɹɧɢɹ ɩɨɜɟɪɯɧɨɫɬɢ ɢ
ɧɚɛɥɸɞɚɟɬɫɹ ɦɚɤɫɢɦɚɥɶɧɚɹ ɫɤɨɪɨɫɬɶ ɩɟɪɟɧɨɫɚ ɜɟɳɟɫɬɜɚ. ɉɨɥɭɱɟɧɧɚɹ ɤɢɧɟɬɢɱɟɫɤɚɹ ɤɪɢɜɚɹ ɩɪɟɞɫɬɚɜɥɟɧɚ ɧɚ ɪɢɫ. 2. Ʉɚɤ ɜɢɞɧɨ ɢɡ ɪɢɫɭɧɤɚ, ɩɪɢ ɧɟɩɪɨɞɨɥ0
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2
t ˜ 10 , c
ɠɢɬɟɥɶɧɨɦ ɤɨɧɬɚɤɬɟ (t <2· 10 -2 ɫ) ɧɚɤɨɩɥɟɧɢɟ ɉɋ ɜ ɝɚɡɨɜɨɣ ɮɚɡɟ ɩɪɹɦɨ ɩɪɨɩɨɪɰɢɨɧɚɥɶɧɨ ɜɪɟɦɟɧɢ, ɬ.ɟ. ɪɚɫɩɚɞ ɉɋ ɧɟɡɧɚɱɢɬɟɥɟɧ, ɢ ɩɨ ɜɟɥɢɱɢɧɟ ɧɚɤɥɨɧɚ
ɩɪɹɦɨɣ ɜ ɷɬɨɣ ɨɛɥɚɫɬɢ ɦɨɠɧɨ ɨɩɪɟɞɟɥɢɬɶ ɫɤɨɪɨɫɬɶ ɩɟɪɟɯɨɞɚ ɉɋ ɫ ɩɨɜɟɪɯɧɨɫɬɢ ɜ ɝɚɡɨɜɭɸ ɮɚɡɭ. ɋ ɭɜɟɥɢɱɟɧɢɟɦ ɜɪɟɦɟɧɢ ɤɨɧɬɚɤɬɚ ɤɢɧɟɬɢɱɟɫɤɚɹ ɤɪɢɜɚɹ
ɨɬɤɥɨɧɹɟɬɫɹ ɨɬ ɩɪɹɦɨɣ ɥɢɧɢɢ, ɬ.ɟ. ɫɤɨɪɨɫɬɶ ɧɚɤɨɩɥɟɧɢɹ ɉɋ ɜ ɝɚɡɨɜɨɣ ɮɚɡɟ
ɭɦɟɧɶɲɚɟɬɫɹ, ɫɬɪɟɦɹɫɶ ɤ ɧɭɥɸ. Ɍ ɚɤɢɦ ɨɛɪɚɡɨɦ, ɩɨɥɭɱɟɧɧɚɹ ɤɢɧɟɬɢɱɟɫɤɚɹ
ɤɪɢɜɚɹ ɹɜɥɹɟɬɫɹ ɪɟɡɭɥɶɬɚɬɨɦ ɤɨɧɤɭɪɟɧɰɢɢ ɦɟɠɞɭ ɩɪɨɰɟɫɫɚɦɢ ɨɛɪɚɡɨɜɚɧɢɹ
ɉɋ ɧɚ ɩɨɜɟɪɯɧɨɫɬɢ ɫ ɱɚɫɬɢɱɧɵɦ ɩɟɪɟɯɨɞɨɦ ɜ ɝɚɡɨɜɭɸ ɮɚɡɭ ɢ ɟɝɨ ɞɚɥɶɧɟɣɲɟɝɨ ɪɚɡɥɨɠɟɧɢɹ.
ɋɭɞɹ ɩɨ ɥɢɬɟɪɚɬɭɪɧɵɦ ɞɚɧɧɵɦ [2, 3, 6], ɝɨɦɨɝɟɧɧɨɟ ɪɚɡɥɨɠɟɧɢɟ ɉɋ ɜ
ɪɟɚɤɰɢɹɯ ɯɢɦɢɱɟɫɤɨɝɨ ɩɟɪɟɧɨɫɚ ɬɜɟɪɞɵɯ ɫɨɟɞɢɧɟɧɢɣ ɩɪɨɬɟɤɚɟɬ ɩɪɢ ɬɟɦɩɟɪɚɬɭɪɟ ɜɵɲɟ 670 K. Ɍ ɚɤ ɤɚɤ ɩɪɨɰɟɫɫ ɩɟɪɟɧɨɫɚ ɆgO ɧɚɦɢ ɛɵɥ ɢɡɭɱɟɧ ɩɪɢ
ɬɟɦɩɟɪɚɬɭɪɟ 273 K, ɬɨ ɦɨɠɧɨ ɩɨɥɚɝɚɬɶ, ɱɬɨ ɜ ɧɚɲɟɦ ɫɥɭɱɚɟ ɪɚɫɩɚɞ ɉɋ
ɨɫɭɳɟɫɬɜɥɹɟɬɫɹ ɬɨɥɶɤɨ ɝɟɬɟɪɨɝɟɧɧɨ. Ɍ ɚɤ ɤɚɤ ɢɡ-ɡɚ ɧɢɡɤɨɝɨ ɩɚɪɰɢɚɥɶɧɨɝɨ
ɞɚɜɥɟɧɢɹ ɉɋ ɜ ɝɚɡɨɜɨɣ ɮɚɡɟ ( <10 -4 ɉɚ ) ɫɬɟɩɟɧɶ ɡɚɩɨɥɧɟɧɢɹ ɩɨɜɟɪɯɧɨɫɬɢ (ɩɨ
ɤɚɤɨɣ ɛɵ ɢɡɨɬɟɪɦɟ ɚɞɫɨɪɛɰɢɢ ɧɟ ɩɪɟɞɫɬɚɜɥɹɥɢ) ɡɚɜɢɫɢɬ ɨɬ ɟɝɨ ɤɨɧɰɟɧɬɪɚɰɢɢ
ɜ ɩɟɪɜɨɣ ɫɬɟɩɟɧɢ, ɬɨ ɫɤɨɪɨɫɬɶ ɝɟɬɟɪɨɝɟɧɧɨɝɨ ɪɚɡɥɨɠɟɧɢɹ ɉɋ ɦɨɠɧɨ ɩɪɟɞɫɬɚɜɢɬɶ ɜ ɬɚɤɨɦ ɜɢɞɟ:
Wɪɚɫ = Ʉɪɚɫ[ɉɋ],
(1)
ɝɞɟ Ʉɪɚɫ – ɷɮɮɟɤɬɢɜɧɚɹ ɤɨɧɫɬɚɧɬɚ ɷɬɨɣ ɫɤɨɪɨɫɬɢ, [ɉɋ] – ɬɟɤɭɳɚɹ ɤɨɧɰɟɧɬɪɚɰɢɹ ɉɋ ɜ ɝɚɡɨɜɨɣ ɮɚɡɟ..
ȼ ɬɚɤɨɦ ɫɥɭɱɚɟ, ɫɤɨɪɨɫɬɶ ɧɚɤɨɩɥɟɧɢɹ ɉɋ ɜ ɝɚɡɨɜɨɣ ɮɚɡɟ
ɦɨɠɧɨ ɧɚɩɢɫɚɬɶ ɜ ɜɢɞɟ
W = d[ɉɋ]/dt = W ɩɟɪ – Wɪɚɫ = Wɩɟɪ – Ʉɪɚɫ[ɉɋ],
(2)
ɝɞɟ W ɩɟɪ – ɫɤɨɪɨɫɬɶ ɩɟɪɟɯɨɞɚ ɉɋ ɫ ɩɨɜɟɪɯɧɨɫɬɢ ɜ ɝɚɡɨɜɭɸ ɮɚɡɭ.
ɉɪɢ ɭɜɟɥɢɱɟɧɢɢ ɜɪɟɦɟɧɢ ɤɨɧɬɚɤɬɚ, ɤɨɝɞɚ ɤɨɧɰɟɧɬɪɚɰɢɹ ɉɋ ɜ ɝɚɡɨɜɨɣ
ɮɚɡɟ ɞɨɫɬɢɝɚɟɬ ɫɜɨɟɝɨ ɦɚɤɫɢɦɚɥɶɧɨɝɨ ɡɧɚɱɟɧɢɹ ( [ɉɋ]max ), ɫɤɨɪɨɫɬɶ ɧɚɤɨɩɥɟɧɢɹ ɉɋ ɜ ɝɚɡɨɜɨɣ ɮɚɡɟ ɫɬɪɟɦɢɬɫɹ ɤ ɧɭɥɸ ɢ ɭɪɚɜɧɟɧɢɟ (2) ɩɪɢɧɢɦɚɟɬ ɫɥɟɞɭɸɳɢɣ ɜɢɞ:
W ɩɟɪ – Ʉɪɚɫ[ɉɋ]max = 0 ɢɥɢ Ʉɪɚɫ = W ɩɟɪ /[ɉɋ]max .
(3)
ɋɨɝɥɚɫɧɨ ɩɪɢɜɟɞɟɧɧɵɦ ɪɚɫɫɭɠɞɟɧɢɹɦ ɢɡ ɞɚɧɧɵɯ ɪɢɫ. 2 ɨɩɪɟɞɟɥɟɧɵ
ɜɟɥɢɱɢɧɵ W ɩɟɪ (~2,4 · 1012 ɱɚɫɬɢɰ ˜ɫɦ -3 ˜ ɫ -1 ) ɢ [ɉɋ]max (~12,9 · 1010 ɱɚɫɬɢɰ ˜ ɫɦ -3 ).
Ɂɧɚɹ Wɩɟɪ ɢ [ɉɋ]max, ɩɨ ɮɨɪɦɭɥɟ (3) ɨɩɪɟɞɟɥɹɟɦ ɜɟɥɢɱɢɧɭ ɤɨɧɫɬɚɧɬɵ ɫɤɨɪɨɫɬɢ ɝɟɬɟɪɨɝɟɧɧɨɝɨ ɪɚɡɥɨɠɟɧɢɹ ɉɋ (Ʉɪɚɫ). Ɉɧɚ ɫɨɫɬɚɜɥɹɟɬ ɩɪɢɦɟɪɧɨ 18,6 ɫ -1 .
ɂɫɫɥɟɞɨɜɚɧɢɹ ɩɨ ɭɫɬɚɧɨɜɥɟɧɢɸ ɞɪɭɝɢɯ ɤɢɧɟɬɢɱɟɫɤɢɯ ɡɚɤɨɧɨɦɟɪɧɨɫɬɟɣ ɷɬɨɝɨ
ɩɪɨɰɟɫɫɚ ɢ ɫɬɪɭɤɬɭɪɵ ɉɋ ɩɪɨɞɨɥɠɚɸɬɫɹ.
Ɍ ɚɤɢɦ ɨɛɪɚɡɨɦ, ɩɨ ɩɨɥɭɱɟɧɧɵɦ ɞɚɧɧɵɦ ɦɨɠɧɨ ɭɬɜɟɪɠɞɚɬɶ, ɱɬɨ ɩɪɢ
ɨɞɢɧɚɤɨɜɵɯ ɭɫɥɨɜɢɹɯ ɷɤɫɩɟɪɢɦɟɧɬɚ ɆgO ɩɨɞ ɜɨɡɞɟɣɫɬɜɢɟɦ ɩɚɪɨɜ ɇ2 Ɉ2
ɩɟɪɟɧɨɫɢɬɫɹ ɧɚɦɧɨɝɨ ɷɮɮɟɤɬɢɜɧɟɟ, ɱɟɦ ɦɧɨɝɢɟ ɪɚɧɟɟ ɢɡɭɱɟɧɧɵɟ ɨɤɫɢɞɵ
[3, 8], ɩɪɨɹɜɥɹɸɳɢɟ ɚɧɚɥɨɝɢɱɧɵɟ ɫɜɨɣɫɬɜɚ.
Ɋɚɛɨɬɚ ɜɵɩɨɥɧɟɧɚ ɩɪɢ ɮɢɧɚɧɫɨɜɨɣ ɩɨɞɞɟɪɠɤɟ ɆɇɌɐ (ɩɪɨɟɤɬ Ⱥ-629).
ɉɨɫɬɭɩɢɥ ɚ 06.06. 2006
Ʉɚɮɟɞɪɚ ɯɢɦɢɱɟɫɤɨɣ ɮɢɡɢɤɢ
Ʌ ɂ Ɍ ȿ ɊȺ Ɍ ɍ ɊȺ
1. Ⱥɛɪɚɦɹɧ Ⱥ.ɇ., ȽɪɢɝɨɪɹɧȽ.Ʌ., ɇɚɥɛɚɧɞɹɧ Ⱥ.Ȼ. – Ⱦɨɤɥ.Ⱥɇ ɋɋɋɊ, 1986, ɬ. 289, ʋ 4, ɫ. 896.
2. ɋɚɪɤɢɫɹɧ ɇ.ə., Ⱥɛɪɚɦɹɧ Ⱥ.ɇ., Ƚɪɢɝɨɪɹɧ Ƚ.Ʌ. – ɀɎɏ, 1990, ɬ. 64, ɫ. 2548.
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3. Ƚɪɢɝɨɪɹɧ Ƚ.Ʌ., Ⱥɛɪɚɦɹɧ Ⱥ.ɇ., ɋɚɪɤɢɫɹɧ ɇ.ə., Ƚɪɢɝɨɪɹɧ Ƚ.ɋ. – ɏɢɦ. ɠ. Ⱥɪɦɟɧɢɢ, 1998,
ɬ. 51, ʋ 3–4, ɫ. 240.
4. ɒɟɮɮɟɪ Ƚ. ɏɢɦɢɱɟɫɤɢɟ ɬɪɚɧɫɩɨɪɬɧɵɟ ɪɟɚɤɰɢɢ. Ɇ.: Ɇɢɪ, 1964, 190 ɫ.
5. Ƚɪɢɝɨɪɹɧ Ƚ.Ʌ., Ʉɚɦɚɥ ɹɧ Ɍ.Ɉ., Ʉɚɦɚɥ ɹɧ Ɉ.Ⱥ., Ƚɭɤɚɫɹɧ ɉ.ɋ. – ɀɎɏ, 2005, ɬ. 79, ʋ 10,
ɫ. 1908.
6. ɋɚɪɤɢɫɹɧ ɇ.ə., Ⱥɛɪɚɦɹɧ Ⱥ.ɇ., Ƚɪɢɝɨɪɹɧ Ƚ.Ʌ. – Ʉɢɧɟɬɢɤɚ ɢ ɤɚɬɚɥɢɡ, 1992, ɬ. 33, ʋ 5–6,
ɫ. 1205.
7. ɋɚɦɫɨɧɨɜ Ƚ.ȼ . Ɏɢɡɢɤɨ-ɯɢɦɢɱɟɫɤɢɟ ɫɜɨɣɫɬɜɚ ɨɤɢɫɥɨɜ. Ɇ.: Ɇɟɬɚɥɥɭɪɝɢɹ, 1978, 472 ɫ.
8. Ɍɚɞɟɜɨɫɹɧ Ʌ.Ƚ., Ȼɟɝɥ ɚɪɹɧ Ⱥ.Ⱥ., Ƚɪɢɝɨɪɹɧ Ƚ.ɋ., Ƚɪɢɝɨɪɹɧ Ƚ.Ʌ. – ɂɧɮɨɪɦ. ɬɟɯɧɨɥɨɝɢɢ ɢ
ɭɩɪɚɜɥɟɧɢɟ, 2006, ʋ 1, ɫ. 152.
È. ¶. ²¸ºìàêÚ²Ü
MgO-Æ Ðºî æð²ÌÜÆ äºðúøêÆ¸Æ ¶àÈàðÞÆܺðÆ
кîºðà¶ºÜ èº²ÎòƲÜ
² Ù÷á÷ áõÙ
²é³çÇÝ ³Ý·³Ù áõëáõÙݳëÇñí»É ¿ MgO-Ç Ñ»ï H2O2 -Ç ·áÉáñßÇÝ»ñÇ
÷á˳½¹»óáõÃÛáõÝÇó ³é³ç³óáÕ ÙÇç³ÝÏÛ³É ÙdzóáõÃÛ³Ý (ØØ) ·³½³ÛÇÝ ý³½áõÙ Ïáõï³ÏÙ³Ý ÏÇÝ»ïÇÏ³Ý 273 Î ç»ñÙ³ëïÇ׳ÝÇ ¨ å»ñûùëÇ¹Ç 7,5 ä³
×ÝßÙ³Ý å³ÛÙ³ÝÝ»ñáõÙ: àñáßí»É »Ý ØØ Ù³Ï»ñ¨áõÛÃÇó ·³½³ÛÇÝ ý³½ ³ÝóÙ³Ý ³ñ³·áõÃÛ³Ý ¨ Ýñ³ ѻﳷ³ Ñ»ï»ñá·»Ý ù³Ûù³ÛÙ³Ý ³ñ³·áõÃÛ³Ý
ѳëï³ïáõÝÇ ³ñÅ»ùÝ»ñÁ:
L. G. TADEVOSYAN
HET EROGENEOUS REACT ION OF HYDROGEN PEROXIDE VAPORS
WIT H MgO
Su m m ar y
Kinetics of accumulation of intermediate compound (IC) in gas phase being
formed at interaction of H2 O2 vapors with MgO at 273 K and 7,5 Pa pressure of
peroxide has been studied for the first time. Values of IC transportation rate from
surface into gas phase and constant of its futher heterogeneous decomposition rate
has been defined.
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