Химическая кинетика. Наумов А.В. - 13 стр.

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11. Ɂɚɜɢɫɢɦɨɫɬɶ ɤɨɧɫɬɚɧɬɵ ɪɚɜɧɨɜɟɫɢɹ
ɨɬ ɬɟɦɩɟɪɚɬɭɪɵ ɢ ɞɚɜɥɟɧɢɹ. ɉɪɢɧɰɢɩ Ʌɟ ɒɚɬɟɥɶɟ
Ʉɚɤ ɫɥɟɞɭɟɬ ɢɡ (I.22), ɨ ɡɚɜɢɫɢɦɨɫɬɢ K ɨɬ ɬɟɦɩɟɪɚɬɭɪɵ ɦɨɠɧɨ ɫɭɞɢɬɶ ɩɨ
ɫɨɨɬɜɟɬɫɬɜɭɸɳɢɦ ɡɚɜɢɫɢɦɨɫɬɹɦ ɤɨɧɫɬɚɧɬ ɫɤɨɪɨɫɬɟɣ
k
+
, k
–
. ɉɨ ɭɪɚɜɧɟɧɢɸ
Ⱥɪɪɟɧɢɭɫɚ ɩɨɥɭɱɚɟɬɫɹ, ɱɬɨ
0
0
()
aa
EE
RT
KT e

k
k
,
ɝɞɟ
E
a+
ɢ E
a–
– ɷɧɟɪɝɢɢ ɚɤɬɢɜɚɰɢɢ ɩɪɹɦɨɣ ɢ ɨɛɪɚɬɧɨɣ ɪɟɚɤɰɢɣ. Ɉɬɧɨɲɟɧɢɟ
ɩɪɟɞɷɤɫɩɨɧɟɧɰɢɚɥɶɧɵɯ ɦɧɨɠɢɬɟɥɟɣ, ɤɚɤ ɧɚɦ ɢɡɜɟɫɬɧɨ, ɩɨɱɬɢ ɧɟ ɡɚɜɢɫɢɬ ɨɬ
ɬɟɦɩɟɪɚɬɭɪɵ. Ɍɨɝɞɚ, ɨɛɨɡɧɚɱɚɹ ɷɬɨ ɨɬɧɨɲɟɧɢɟ ɱɟɪɟɡ
K
0
, ɦɨɠɧɨ ɡɚɩɢɫɚɬɶ:
0
()
H
RT
K
TKe
'
, (I.24)
ɝɞɟ ɪɚɡɧɨɫɬɶ ɷɧɟɪɝɢɣ ɚɤɬɢɜɚɰɢɢ
'H = E
a+
– E
a–
ɩɪɟɞɫɬɚɜɥɹɟɬ ɫɨɛɨɣ ɬɟɩɥɨɬɭ
ɪɟɚɤɰɢ
ɢ.
Ɏɨɪɦɭɥɚ (I.24) ɩɨɤɚɡɵɜɚɟɬ, ɱɬɨ ɡɚɜɢɫɢɦɨɫɬɶ
K(T) ɨɩɪɟɞɟɥɹɟɬɫɹ, ɝɥɚɜ-
ɧɵɦ ɨɛɪɚɡɨɦ, ɜɟɥɢɱɢɧɨɣ
'H. ȼ ɨɬɥɢɱɢɟ ɨɬ ɷɧɟɪɝɢɢ ɚɤɬɢɜɚɰɢɢ ɷɬɚ ɜɟɥɢɱɢɧɚ
ɦɨɠɟɬ ɛɵɬɶ ɤɚɤ ɩɨɥɨɠɢɬɟɥɶɧɨɣ, ɬɚɤ ɢ ɨɬɪɢɰɚɬɟɥɶɧɨɣ. ɉɨɷɬɨɦɭ ɮɭɧɤɰɢɹ
K(T) ɦɨɠɟɬ ɛɵɬɶ ɤɚɤ ɜɨɡɪɚɫɬɚɸɳɟɣ, ɬɚɤ ɢ ɭɛɵɜɚɸɳɟɣ.
ɉɪɨɞɢɮɮɟɪɟɧɰɢɪɭɟɦ (I.24) ɩɨ ɬɟɦɩɟɪɚɬɭɪɟ:
0
2
H
RT
K
H
Ke
TR
'
T
w'
w
,
ɢɧɚɱɟ
2
ln
H
K
TR
T
w'
w
(I.25)
(ɫɪ. ɫ (I.14)). Ɇɵ ɢɫɩɨɥɶɡɭɟɦ ɡɞɟɫɶ ɫɢɦɜɨɥ ɱɚɫɬɧɨɣ ɩɪɨɢɡɜɨɞɧɨɣ ɩɨɬɨɦɭ,
ɱɬɨ ɛɭɞɟɦ ɢɫɫɥɟɞɨɜɚɬɶ ɡɚɜɢɫɢɦɨɫɬɶ ɤɨɧɫɬɚɧɬɵ ɧɟ ɬɨɥɶɤɨ ɨɬ ɬɟɦɩɟɪɚɬɭɪɵ,
ɧɨ ɢ ɨɬ ɞɚɜɥɟɧɢɹ, ɬɚɤ ɱɬɨ
K ɜɵɫɬɭɩɚɟɬ ɤɚɤ ɮɭɧɤɰɢɹ ɞɜɭɯ ɩɟɪɟɦɟɧɧɵɯ
K(T, p). ɍɪɚɜɧɟɧɢɟ (I.25) ɢɡɜɟɫɬɧɨ ɤɚɤ ɭɪɚɜɧɟɧɢɟ ȼɚɧɬ-Ƚɨɮɮɚ (1884). ɂɡ
ɧɟɝɨ ɫɥɟɞɭɟɬ, ɱɬɨ
0
K
T
w
!
w
, ɟɫɥɢ 'H > 0, ɬɨ ɟɫɬɶ ɬɟɩɥɨɬɚ ɩɨɝɥɨɳɚɟɬɫɹ,
0
K
T
w
w
, ɟɫɥɢ 'H < 0, ɬɨ ɟɫɬɶ ɬɟɩɥɨɬɚ ɜɵɞɟɥɹɟɬɫɹ
ɩɪɢ ɩɪɨɯɨɞɟ ɪɟɚɤɰɢɢ ɫɥɟɜɚ ɧɚɩɪɚɜɨ ɫɨɝɥɚɫɧɨ ɨɪɢɟɧɬɢɪɨɜɚɧɧɨɣ ɡɚɩɢɫɢ ɫɬɟ-
ɯɢɨɦɟɬɪɢɱɟɫɤɨɝɨ ɭɪɚɜɧɟɧɢɹ. ȼ ɩɟɪɜɨɦ ɫɥɭɱɚɟ ɪɚɜɧɨɜɟɫɢɟ ɩɪɢ ɭɜɟɥɢɱɟɧɢɢ
ɬɟɦɩɟɪɚɬɭɪɵ ɫɦɟɳɚɟɬɫɹ
ɜɩɪɚɜɨ, ɬɨ ɟɫɬɶ ɫɨɝɥɚɫɧɨ ɫɨɨɬɧɨɲɟɧɢɸ (I.22) ɜɟɳɟɫɬ-
ɜɚ
BB
j
ɧɚɤɚɩɥɢɜɚɸɬɫɹ, ɚ ɜɟɳɟɫɬɜɚ A
i
ɢɫɱɟɡɚɸɬ; ɜɨ ɜɬɨɪɨɦ – ɫɦɟɳɚɟɬɫɹ .ɜɥɟɜɨ
Ɇɨɠɧɨ ɩɨɤɚɡɚɬɶ, ɱɬɨ ɡɚɜɢɫɢɦɨɫɬɶ ɤɨɧɫɬɚɧɬɵ ɨɬ ɞɚɜɥɟɧɢɹ ɜɵɪɚɠɚɟɬɫɹ
ɭɪɚɜɧɟɧɢɟɦ, ɩɨɞɨɛɧɵɦ (I.25):
25
ln
V
K
pR
T
w'
w
, (I.26)
ɝɞɟ
'V – ɢɡɦɟɧɟɧɢɟ ɨɛɴɟɦɚ ɜ ɪɟɚɤɰɢɢ. ȼ ɩɥɚɧɟ ɫɦɟɳɟɧɢɹ ɪɚɜɧɨɜɟɫɢɹ ɷɬɨ
ɩɪɢɜɨɞɢɬ ɤ ɚɧɚɥɨɝɢɱɧɨɦɭ ɩɪɚɜɢɥɭ, ɭɫɬɚɧɚɜɥɢɜɚɸɳɟɦɭ ɧɚɩɪɚɜɥɟɧɢɟ ɫɦɟ-
ɳɟɧɢɹ, ɫɦɨɬɪɹ ɩɨ ɡɧɚɤɭ
'V.
ɉɨɥɭɱɢɦ ɹɜɧɭɸ ɡɚɜɢɫɢɦɨɫɬɶ ɤɨɧɫɬɚɧɬɵ ɨɬ ɞɚɜɥɟɧɢɹ ɞɥɹ ɝɚɡɨɜɨɣ ɪɟɚɤɰɢɢ. ɋɢɫɬɟɦɚ
ɪɟɚɝɢɪɭɸɳɢɯ ɢɞɟɚɥɶɧɵɯ ɝɚɡɨɜ ɯɨɪɨɲɚ ɬɟɦ, ɱɬɨ ɞɥɹ ɧɟɟ ɥɟɝɤɨ ɜɵɱɢɫɥɢɬɶ ɢɡɦɟɧɟɧɢɟ
ɨɛɴɟɦɚ. ȿɫɥɢ ɪɟɚɤɰɢɹ ɨɬɜɟɱɚɟɬ ɭɪɚɜɧɟɧɢɸ (I.16), ɬɨ
11
nm
j
i
ji
RT
V
p
' ¦Q¦Q
.
ȼɯɨɞɹɳɭɸ ɫɸɞɚ ɪɚɡɧɨɫɬɶ ɫɬɟɯɢɨɦɟɬɪɢɱɟɫɤɢɯ ɤɨɷɮɮɢɰɢɟɧɬɨɜ ɨɛɵɱɧɨ ɨɛɨɡɧɚɱɚɸɬ ɤɚɤ 'Q.
Ɍɨɝɞɚ
00
()
11
Kp p
Kp
dK dp
K
p
'Q
yy
, ɚ ɨɬɫɸɞɚ

0
0
p
KK
p
'Q
.
Ɍɚɤɢɦ ɨɛɪɚɡɨɦ, ɤɨɧɫɬɚɧɬɚ ɝɚɡɨɜɨɝɨ ɪɚɜɧɨɜɟɫɢɹ ɨɛɧɚɪɭɠɢɜɚɟɬ ɫɬɟɩɟɧɧɭɸ ɡɚɜɢɫɢɦɨɫɬɶ
ɨɬ ɞɚɜɥɟɧɢɹ, ɚ ɜɟɥɢɱɢɧɨɣ, ɨɩɪɟɞɟɥɹɸɳɟɣ ɷɬɭ ɡɚɜɢɫɢɦɨɫɬɶ, ɹɜɥɹɟɬɫɹ ɪɚɡɧɨɫɬɶ ɫɬɟɯɢɨ-
ɦɟɬɪɢɱɟɫɤɢɯ ɤɨɷɮɮɢɰɢɟɧɬɨɜ 'Q.
ȼ ɢɬɨɝɟ ɦɨɠɧɨ ɧɚɡɜɚɬɶ ɫɥɟɞɭɸɳɢɟ ɡɚɤɨɧɨɦɟɪɧɨɫɬɢ.
1. ɋɦɟɳɟɧɢɟ ɪɚɜɧɨɜɟɫɢɹ ɫɬɨɪɨɧɭ ɪɚɫɯɨɞɨɜɚɧɢɹ ɜɟɳɟɫɬɜɚ ɩɪɢ ɟɝɨ ɜɜɟ-
ɞɟɧɢɢ ɜ ɫɢɫɬɟɦɭ (ɜ ɨɬɤɪɵɬɨɣ ɫɢɫɬɟɦɟ).
2. ɋɦɟɳɟɧɢɟ ɪɚɜɧɨɜɟɫɢɹ ɜ ɫɬɨɪɨɧɭ ɩɨɝɥɨɳɟɧɢɹ ɬɟɩɥɨɬɵ ɩɪɢ ɭɜɟɥɢɱɟ-
ɧɢɢ ɬɟɦɩɟɪɚɬɭɪɵ (ɜ ɡɚɤɪɵɬɨɣ ɫɢɫɬɟɦɟ).
3. ɋɦɟɳɟɧɢɟ ɪɚɜɧɨɜɟɫɢɹ ɜ ɫɬɨɪɨɧɭ ɭɦɟɧɶɲɟɧɢɹ ɨɛɴɟɦɚ ɩɪɢ ɭɜɟɥɢɱɟɧɢɢ
ɞɚɜɥɟɧɢɹ (ɜ ɡɚɤɪɵɬɨɣ ɫɢɫɬɟɦɟ).
Ⱥɧɚɥɢɡɢɪɭɹ ɩɨɞɨɛɧɵɟ ɡɚɤɨɧɨɦɟɪɧɨɫɬɢ, Ʌɟ ɒɚɬɟɥɶɟ (H. L. Le Chatelier,
1884) ɫɮɨɪɦɭɥɢɪɨɜɚɥ ɨɛɳɢɣ ɩɪɢɧɰɢɩ: ɜɨɡɞɟɣɫɬɜɢɟ, ɜɵɜɨɞɹɳɟɟ ɫɢɫɬɟɦɭ ɢɡ
ɪɚɜɧɨɜɟɫɢɹ, ɜɵɡɵɜɚɟɬ ɜ ɧɟɣ ɢɡɦɟɧɟɧɢɹ, ɩɪɢɜɨɞɹɳɢɟ ɤ ɨɫɥɚɛɥɟɧɢɸ ɷɬɨɝɨ
ɜɨɡɞɟɣɫɬɜɢɹ. ɉɪɢɧɰɢɩ ɛɵɥ ɬɟɪɦɨɞɢɧɚɦɢɱɟɫɤɢ ɨɛɨɫɧɨɜɚɧ Ȼɪɚɭɧɨɦ
(C. Braun, 1887), ɩɨɷɬɨɦɭ ɧɨɫɢɬ ɧɚɡɜɚɧɢɟ
ɩɪɢɧɰɢɩɚ Ʌɟ ɒɚɬɟɥɶɟ – Ȼɪɚɭɧɚ.
ȼ ɡɚɤɥɸɱɟɧɢɟ ɨɬɦɟɬɢɦ, ɱɬɨ ɩɪɢɫɭɬɫɬɜɢɟ ɤɚɬɚɥɢɡɚɬɨɪɚ ɧɟ ɨɤɚɡɵɜɚɟɬ
ɜɥɢɹɧɢɹ ɧɚ ɤɨɧɫɬɚɧɬɭ ɪɚɜɧɨɜɟɫɢɹ, ɯɨɬɹ ɫɭɳɟɫɬɜɟɧɧɨ ɢɡɦɟɧɹɟɬ ɤɨɧɫɬɚɧɬɵ
ɫɤɨɪɨɫɬɟɣ ɩɪɹɦɨɝɨ ɢ ɨɛɪɚɬɧɨɝɨ ɩɪɨɰɟɫɫɨɜ. Ⱦɟɥɨ ɜ ɬɨɦ, ɱɬɨ ɤɚɬɚɥɢɡɚɬɨɪ ɜ
ɪɚɜɧɨɣ ɫɬɟɩɟɧɢ ɭɫɤɨɪɹɟɬ (ɢɧɝɢɛɢɬɨɪ – ɡɚɦɟɞɥɹɟɬ) ɷɬɢ ɩɪɨɰɟɫɫɵ, ɬɚɤ ɱɬɨ
ɟɝɨ ɧɚɥɢɱɢɟ ɜɥɢɹɟɬ ɥɢɲɶ ɧɚ ɫɤɨɪɨɫɬɶ ɭɫɬɚɧɨɜɥɟɧɢɹ ɪɚɜɧɨɜɟɫɢɹ, ɚɧɟɧɚɟɝɨ
ɩɨɥɨɠɟɧɢɟ.
26
                11. Ɂɚɜɢɫɢɦɨɫɬɶ ɤɨɧɫɬɚɧɬɵ ɪɚɜɧɨɜɟɫɢɹ                                                              w                 'V
          ɨɬ ɬɟɦɩɟɪɚɬɭɪɵ ɢ ɞɚɜɥɟɧɢɹ. ɉɪɢɧɰɢɩ Ʌɟ ɒɚɬɟɥɶɟ                                                              ln K             ,                           (I.26)
                                                                                                                  wp                RT
   Ʉɚɤ ɫɥɟɞɭɟɬ ɢɡ (I.22), ɨ ɡɚɜɢɫɢɦɨɫɬɢ K ɨɬ ɬɟɦɩɟɪɚɬɭɪɵ ɦɨɠɧɨ ɫɭɞɢɬɶ ɩɨ    ɝɞɟ 'V – ɢɡɦɟɧɟɧɢɟ ɨɛɴɟɦɚ ɜ ɪɟɚɤɰɢɢ. ȼ ɩɥɚɧɟ ɫɦɟɳɟɧɢɹ ɪɚɜɧɨɜɟɫɢɹ ɷɬɨ
ɫɨɨɬɜɟɬɫɬɜɭɸɳɢɦ ɡɚɜɢɫɢɦɨɫɬɹɦ ɤɨɧɫɬɚɧɬ ɫɤɨɪɨɫɬɟɣ k+, k–. ɉɨ ɭɪɚɜɧɟɧɢɸ        ɩɪɢɜɨɞɢɬ ɤ ɚɧɚɥɨɝɢɱɧɨɦɭ ɩɪɚɜɢɥɭ, ɭɫɬɚɧɚɜɥɢɜɚɸɳɟɦɭ ɧɚɩɪɚɜɥɟɧɢɟ ɫɦɟ-
Ⱥɪɪɟɧɢɭɫɚ ɩɨɥɭɱɚɟɬɫɹ, ɱɬɨ                                                   ɳɟɧɢɹ, ɫɦɨɬɪɹ ɩɨ ɡɧɚɤɭ 'V.
                                       k0  EaRT Ea                         ɉɨɥɭɱɢɦ ɹɜɧɭɸ ɡɚɜɢɫɢɦɨɫɬɶ ɤɨɧɫɬɚɧɬɵ ɨɬ ɞɚɜɥɟɧɢɹ ɞɥɹ ɝɚɡɨɜɨɣ ɪɟɚɤɰɢɢ. ɋɢɫɬɟɦɚ
                            K (T )         e            ,                   ɪɟɚɝɢɪɭɸɳɢɯ ɢɞɟɚɥɶɧɵɯ ɝɚɡɨɜ ɯɨɪɨɲɚ ɬɟɦ, ɱɬɨ ɞɥɹ ɧɟɟ ɥɟɝɤɨ ɜɵɱɢɫɥɢɬɶ ɢɡɦɟɧɟɧɢɟ
                                       k0                                  ɨɛɴɟɦɚ. ȿɫɥɢ ɪɟɚɤɰɢɹ ɨɬɜɟɱɚɟɬ ɭɪɚɜɧɟɧɢɸ (I.16), ɬɨ
ɝɞɟ Ea+ ɢ Ea– – ɷɧɟɪɝɢɢ ɚɤɬɢɜɚɰɢɢ ɩɪɹɦɨɣ ɢ ɨɛɪɚɬɧɨɣ ɪɟɚɤɰɢɣ. Ɉɬɧɨɲɟɧɢɟ                                                  RT n        m

ɩɪɟɞɷɤɫɩɨɧɟɧɰɢɚɥɶɧɵɯ ɦɧɨɠɢɬɟɥɟɣ, ɤɚɤ ɧɚɦ ɢɡɜɟɫɬɧɨ, ɩɨɱɬɢ ɧɟ ɡɚɜɢɫɢɬ ɨɬ                                       'V            ¦ Q j  ¦ Qi .
                                                                                                                         p j1      i 1
ɬɟɦɩɟɪɚɬɭɪɵ. Ɍɨɝɞɚ, ɨɛɨɡɧɚɱɚɹ ɷɬɨ ɨɬɧɨɲɟɧɢɟ ɱɟɪɟɡ K0, ɦɨɠɧɨ ɡɚɩɢɫɚɬɶ:
                                                  'H
                                                                            ȼɯɨɞɹɳɭɸ ɫɸɞɚ ɪɚɡɧɨɫɬɶ ɫɬɟɯɢɨɦɟɬɪɢɱɟɫɤɢɯ ɤɨɷɮɮɢɰɢɟɧɬɨɜ ɨɛɵɱɧɨ ɨɛɨɡɧɚɱɚɸɬ ɤɚɤ 'Q.
                                                                           Ɍɨɝɞɚ
                                                  RT
                            K (T )     K 0e            ,           (I.24)                   K ( p)                p                                      'Q
                                                                                                     1                 1                            p
ɝɞɟ ɪɚɡɧɨɫɬɶ ɷɧɟɪɝɢɣ ɚɤɬɢɜɚɰɢɢ 'H = Ea+ – Ea– ɩɪɟɞɫɬɚɜɥɹɟɬ ɫɨɛɨɣ ɬɟɩɥɨɬɭ
ɪɟɚɤɰɢɢ.
                                                                                            yK0
                                                                                                     K
                                                                                                       dK     y
                                                                                                            'Q
                                                                                                                  p0
                                                                                                                       p
                                                                                                                         dp , ɚ ɨɬɫɸɞɚ     K   K0
                                                                                                                                                    p0
                                                                                                                                                               .

    Ɏɨɪɦɭɥɚ (I.24) ɩɨɤɚɡɵɜɚɟɬ, ɱɬɨ ɡɚɜɢɫɢɦɨɫɬɶ K(T) ɨɩɪɟɞɟɥɹɟɬɫɹ, ɝɥɚɜ-     Ɍɚɤɢɦ ɨɛɪɚɡɨɦ, ɤɨɧɫɬɚɧɬɚ ɝɚɡɨɜɨɝɨ ɪɚɜɧɨɜɟɫɢɹ ɨɛɧɚɪɭɠɢɜɚɟɬ ɫɬɟɩɟɧɧɭɸ ɡɚɜɢɫɢɦɨɫɬɶ
ɧɵɦ ɨɛɪɚɡɨɦ, ɜɟɥɢɱɢɧɨɣ 'H. ȼ ɨɬɥɢɱɢɟ ɨɬ ɷɧɟɪɝɢɢ ɚɤɬɢɜɚɰɢɢ ɷɬɚ ɜɟɥɢɱɢɧɚ      ɨɬ ɞɚɜɥɟɧɢɹ, ɚ ɜɟɥɢɱɢɧɨɣ, ɨɩɪɟɞɟɥɹɸɳɟɣ ɷɬɭ ɡɚɜɢɫɢɦɨɫɬɶ, ɹɜɥɹɟɬɫɹ ɪɚɡɧɨɫɬɶ ɫɬɟɯɢɨ-
ɦɨɠɟɬ ɛɵɬɶ ɤɚɤ ɩɨɥɨɠɢɬɟɥɶɧɨɣ, ɬɚɤ ɢ ɨɬɪɢɰɚɬɟɥɶɧɨɣ. ɉɨɷɬɨɦɭ ɮɭɧɤɰɢɹ          ɦɟɬɪɢɱɟɫɤɢɯ ɤɨɷɮɮɢɰɢɟɧɬɨɜ 'Q.
K(T) ɦɨɠɟɬ ɛɵɬɶ ɤɚɤ ɜɨɡɪɚɫɬɚɸɳɟɣ, ɬɚɤ ɢ ɭɛɵɜɚɸɳɟɣ.
                                                                                ȼ ɢɬɨɝɟ ɦɨɠɧɨ ɧɚɡɜɚɬɶ ɫɥɟɞɭɸɳɢɟ ɡɚɤɨɧɨɦɟɪɧɨɫɬɢ.
    ɉɪɨɞɢɮɮɟɪɟɧɰɢɪɭɟɦ (I.24) ɩɨ ɬɟɦɩɟɪɚɬɭɪɟ:
                                              'H
                                                                                1. ɋɦɟɳɟɧɢɟ ɪɚɜɧɨɜɟɫɢɹ ɫɬɨɪɨɧɭ ɪɚɫɯɨɞɨɜɚɧɢɹ ɜɟɳɟɫɬɜɚ ɩɪɢ ɟɝɨ ɜɜɟ-
                            wK                        'H                   ɞɟɧɢɢ ɜ ɫɢɫɬɟɦɭ (ɜ ɨɬɤɪɵɬɨɣ ɫɢɫɬɟɦɟ).
                                     K 0e     RT
                                                   ˜        ,
                            wT                         RT 2                     2. ɋɦɟɳɟɧɢɟ ɪɚɜɧɨɜɟɫɢɹ ɜ ɫɬɨɪɨɧɭ ɩɨɝɥɨɳɟɧɢɹ ɬɟɩɥɨɬɵ ɩɪɢ ɭɜɟɥɢɱɟ-
ɢɧɚɱɟ                                                                       ɧɢɢ ɬɟɦɩɟɪɚɬɭɪɵ (ɜ ɡɚɤɪɵɬɨɣ ɫɢɫɬɟɦɟ).
                               w               'H                               3. ɋɦɟɳɟɧɢɟ ɪɚɜɧɨɜɟɫɢɹ ɜ ɫɬɨɪɨɧɭ ɭɦɟɧɶɲɟɧɢɹ ɨɛɴɟɦɚ ɩɪɢ ɭɜɟɥɢɱɟɧɢɢ
                                 ln K                              (I.25)   ɞɚɜɥɟɧɢɹ (ɜ ɡɚɤɪɵɬɨɣ ɫɢɫɬɟɦɟ).
                              wT               RT 2                             Ⱥɧɚɥɢɡɢɪɭɹ ɩɨɞɨɛɧɵɟ ɡɚɤɨɧɨɦɟɪɧɨɫɬɢ, Ʌɟ ɒɚɬɟɥɶɟ (H. L. Le Chatelier,
(ɫɪ. ɫ (I.14)). Ɇɵ ɢɫɩɨɥɶɡɭɟɦ ɡɞɟɫɶ ɫɢɦɜɨɥ ɱɚɫɬɧɨɣ ɩɪɨɢɡɜɨɞɧɨɣ ɩɨɬɨɦɭ,      1884) ɫɮɨɪɦɭɥɢɪɨɜɚɥ ɨɛɳɢɣ ɩɪɢɧɰɢɩ: ɜɨɡɞɟɣɫɬɜɢɟ, ɜɵɜɨɞɹɳɟɟ ɫɢɫɬɟɦɭ ɢɡ
ɱɬɨ ɛɭɞɟɦ ɢɫɫɥɟɞɨɜɚɬɶ ɡɚɜɢɫɢɦɨɫɬɶ ɤɨɧɫɬɚɧɬɵ ɧɟ ɬɨɥɶɤɨ ɨɬ ɬɟɦɩɟɪɚɬɭɪɵ,       ɪɚɜɧɨɜɟɫɢɹ, ɜɵɡɵɜɚɟɬ ɜ ɧɟɣ ɢɡɦɟɧɟɧɢɹ, ɩɪɢɜɨɞɹɳɢɟ ɤ ɨɫɥɚɛɥɟɧɢɸ ɷɬɨɝɨ
ɧɨ ɢ ɨɬ ɞɚɜɥɟɧɢɹ, ɬɚɤ ɱɬɨ K ɜɵɫɬɭɩɚɟɬ ɤɚɤ ɮɭɧɤɰɢɹ ɞɜɭɯ ɩɟɪɟɦɟɧɧɵɯ           ɜɨɡɞɟɣɫɬɜɢɹ. ɉɪɢɧɰɢɩ ɛɵɥ ɬɟɪɦɨɞɢɧɚɦɢɱɟɫɤɢ ɨɛɨɫɧɨɜɚɧ Ȼɪɚɭɧɨɦ
K(T, p). ɍɪɚɜɧɟɧɢɟ (I.25) ɢɡɜɟɫɬɧɨ ɤɚɤ ɭɪɚɜɧɟɧɢɟ ȼɚɧɬ-Ƚɨɮɮɚ (1884). ɂɡ      (C. Braun, 1887), ɩɨɷɬɨɦɭ ɧɨɫɢɬ ɧɚɡɜɚɧɢɟ ɩɪɢɧɰɢɩɚ Ʌɟ ɒɚɬɟɥɶɟ – Ȼɪɚɭɧɚ.
ɧɟɝɨ ɫɥɟɞɭɟɬ, ɱɬɨ                                                               ȼ ɡɚɤɥɸɱɟɧɢɟ ɨɬɦɟɬɢɦ, ɱɬɨ ɩɪɢɫɭɬɫɬɜɢɟ ɤɚɬɚɥɢɡɚɬɨɪɚ ɧɟ ɨɤɚɡɵɜɚɟɬ
              wK                                                            ɜɥɢɹɧɢɹ ɧɚ ɤɨɧɫɬɚɧɬɭ ɪɚɜɧɨɜɟɫɢɹ, ɯɨɬɹ ɫɭɳɟɫɬɜɟɧɧɨ ɢɡɦɟɧɹɟɬ ɤɨɧɫɬɚɧɬɵ
                 ! 0 , ɟɫɥɢ 'H > 0, ɬɨ ɟɫɬɶ ɬɟɩɥɨɬɚ ɩɨɝɥɨɳɚɟɬɫɹ,
              wT                                                            ɫɤɨɪɨɫɬɟɣ ɩɪɹɦɨɝɨ ɢ ɨɛɪɚɬɧɨɝɨ ɩɪɨɰɟɫɫɨɜ. Ⱦɟɥɨ ɜ ɬɨɦ, ɱɬɨ ɤɚɬɚɥɢɡɚɬɨɪ ɜ
              wK                                                            ɪɚɜɧɨɣ ɫɬɟɩɟɧɢ ɭɫɤɨɪɹɟɬ (ɢɧɝɢɛɢɬɨɪ – ɡɚɦɟɞɥɹɟɬ) ɷɬɢ ɩɪɨɰɟɫɫɵ, ɬɚɤ ɱɬɨ
                  0 , ɟɫɥɢ 'H < 0, ɬɨ ɟɫɬɶ ɬɟɩɥɨɬɚ ɜɵɞɟɥɹɟɬɫɹ              ɟɝɨ ɧɚɥɢɱɢɟ ɜɥɢɹɟɬ ɥɢɲɶ ɧɚ ɫɤɨɪɨɫɬɶ ɭɫɬɚɧɨɜɥɟɧɢɹ ɪɚɜɧɨɜɟɫɢɹ, ɚ ɧɟ ɧɚ ɟɝɨ
              wT                                                            ɩɨɥɨɠɟɧɢɟ.
ɩɪɢ ɩɪɨɯɨɞɟ ɪɟɚɤɰɢɢ ɫɥɟɜɚ ɧɚɩɪɚɜɨ ɫɨɝɥɚɫɧɨ ɨɪɢɟɧɬɢɪɨɜɚɧɧɨɣ ɡɚɩɢɫɢ ɫɬɟ-
ɯɢɨɦɟɬɪɢɱɟɫɤɨɝɨ ɭɪɚɜɧɟɧɢɹ. ȼ ɩɟɪɜɨɦ ɫɥɭɱɚɟ ɪɚɜɧɨɜɟɫɢɟ ɩɪɢ ɭɜɟɥɢɱɟɧɢɢ
ɬɟɦɩɟɪɚɬɭɪɵ ɫɦɟɳɚɟɬɫɹ ɜɩɪɚɜɨ, ɬɨ ɟɫɬɶ ɫɨɝɥɚɫɧɨ ɫɨɨɬɧɨɲɟɧɢɸ (I.22) ɜɟɳɟɫɬ-
ɜɚ Bj ɧɚɤɚɩɥɢɜɚɸɬɫɹ, ɚ ɜɟɳɟɫɬɜɚ Ai ɢɫɱɟɡɚɸɬ; ɜɨ ɜɬɨɪɨɦ – ɫɦɟɳɚɟɬɫɹ ɜɥɟɜɨ.
   B




    Ɇɨɠɧɨ ɩɨɤɚɡɚɬɶ, ɱɬɨ ɡɚɜɢɫɢɦɨɫɬɶ ɤɨɧɫɬɚɧɬɵ ɨɬ ɞɚɜɥɟɧɢɹ ɜɵɪɚɠɚɟɬɫɹ
ɭɪɚɜɧɟɧɢɟɦ, ɩɨɞɨɛɧɵɦ (I.25):
                                     25                                                                                   26

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