Химическая кинетика. Наумов А.В. - 10 стр.

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ɩɨ ɮɨɪɦɭɥɟ ɬɢɩɚ (I.5), ɛɵɥɚ ɛɵ ɧɟɩɨɦɟɪɧɨ ɜɵɫɨɤɚ. Ⱥɪɪɟɧɢɭɫ ɩɪɟɞɩɨɥɨɠɢɥ,
ɱɬɨ ɪɟɚɤɰɢɨɧɧɵɦɢ ɹɜɥɹɸɬɫɹ ɬɨɥɶɤɨ ɬɟ ɫɬɨɥɤɧɨɜɟɧɢɹ, ɤɨɬɨɪɵɟ ɩɪɨɢɫɯɨɞɹɬ
ɫ ɷɧɟɪɝɢɟɣ, ɩɪɟɜɵɲɚɸɳɟɣ ɧɟɤɨɬɨɪɵɣ ɩɨɪɨɝ E
a
. ȼɫɟ ɫɬɨɥɤɧɨɜɟɧɢɹ ɫ ɷɧɟɪ-
ɝɢɟɣ E < E
a
ɨɤɚɡɵɜɚɸɬɫɹ ɧɟɷɮɮɟɤɬɢɜɧɵɦɢ: ɫɨɭɞɚɪɹɸɳɢɟɫɹ «ɦɟɞɥɟɧɧɵɟ»
ɱɚɫɬɢɰɵ ɧɟ ɪɟɚɝɢɪɭɸɬ. ɗɬɨɬ ɩɨɪɨɝ ɢ ɩɪɟɞɫɬɚɜɥɹɟɬ ɫɨɛɨɣ
ɷɧɟɪɝɢɸ ɚɤ-
ɬɢɜɚɰɢɢ
, ɚ ɫɬɨɥɤɧɨɜɟɧɢɹ ɫ ɭɫɥɨɜɢɟɦ E
· E
a
ɧɚɡɵɜɚɸɬ ɚɤɬɢɜɧɵɦɢ.
ɋɬɚɬɢɫɬɢɱɟɫɤɢɣ ɩɨɞɫɱɟɬ ɱɚɫɬɨɬɵ z
a
ɛɢɧɚɪɧɵɯ ɚɤɬɢɜɧɵɯ ɫɬɨɥɤɧɨɜɟɧɢɣ
ɜ ɢɞɟɚɥɶɧɨɦ ɝɚɡɟ, ɨɫɧɨɜɚɧɧɵɣ ɧɚ ɪ ɚ ɫ ɩ ɪ ɟɞɟɥɟɧɢɢ Ɇɚɤɫɜɟɥɥɚ
ɦɨɥɟɤɭɥ ɝɚɡɚ ɩɨ ɫɤɨɪɨɫɬɹɦ, ɩɨɤɚɡɵɜɚɟɬ, ɱɬɨ

1
2
22
12 1
8
()
*
a
E
RT
aA
ɤT
rrN e CC
S
SP
z
2
(I.15)
(ɫɦ. ɥɢɬɟɪɚɬɭɪɭ [2, 4, 5]). Ɂɞɟɫɶ r
1
ɢ r
2
ɪɚɞɢɭɫɵ ɫɬɚɥɤɢɜɚɸɳɢɯɫɹ ɱɚɫɬɢɰ;
P* – ɢɯ ɩɪɢɜɟɞɟɧɧɚɹ ɦɚɫɫɚ:
12
111
*
PPP
,
ɚ ɦɧɨɠɢɬɟɥɶ
V = S(r
1
+ r
2
)
2
ɧɚɡɵɜɚɟɬɫɹ ɫɟɱɟɧɢɟɦ ɫɨɭɞɚɪɟɧɢɹ. Ɉɧɨ ɩɪɟɞɫɬɚɜɥɹ-
ɟɬ ɫɨɛɨɣ ɫɟɱɟɧɢɟ ɰɢɥɢɧɞɪɚ, ɜ ɤɨɬɨɪɨɦ ɞɨɥɠɧɵ ɨɤɚɡɚɬɶɫɹ ɰɟɧɬɪɵ ɦɚɫɫ ɫɮɟɪɢ-
ɱɟɫɤɢɯ ɱɚɫɬɢɰ, ɱɬɨɛɵ ɫɥɭɱɢɥɨɫɶ ɫɨɭɞɚɪɟɧɢɟ. ɂɫɩɨɥɶɡɭɹ ɮɨɪɦɭɥɭ (I.5), ɤɨɬɨ-
ɪɚɹ ɞɥɹ ɱɚɫɬɨɬɵ
ɜɫɟɯ ɞɜɨɣɧɵɯ ɫɨɭɞɚɪɟɧɢɣ ɪɚɡɥɢɱɧɵɯ ɱɚɫɬɢɰ ɢɦɟɟɬ ɜɢɞ
*)

1
2
22
12 1
8
()
*
A
ɤT
rrN CC S
SP
z
2
,
ɩɨɥɭɱɢɦ:
a
E
RT
a
e
zz .
Ɍɟɦ ɫɚɦɵɦ ɦɧɨɠɢɬɟɥɶ e
E
a
/RT
ɩɪɟɞɫɬɚɜɥɹɟɬ ɫɨɛɨɣ ɞɨɥɸ ɚɤɬɢɜɧɵɯ ɫɬɨɥɤɧɨ-
ɜɟɧɢɣ ɫ ɷɧɟɪɝɢɟɣ E > E
a
.
Ʉɚɤ ɜɢɞɧɨ, ɩɨɫɥɟɞɧɟɟ ɭɪɚɜɧɟɧɢɟ ɫɨɜɩɚɞɚɟɬ ɩɨ ɮɨɪɦɟ ɫ ɭɪɚɜɧɟɧɢɟɦ Ⱥɪ-
ɪɟɧɢɭɫɚ. Ɉɬɥɢɱɢɟ ɫɨɫɬɨɢɬ ɜ ɬɨɦ, ɱɬɨ ɩɪɟɞɷɤɫɩɨɧɟɧɰɢɚɥɶɧɵɣ ɦɧɨɠɢɬɟɥɶ
ɡɚɜɢɫɢɬ ɨɬ ɬɟɦɩɟɪɚɬɭɪɵ. ɗɬɚ ɡɚɜɢɫɢɦɨɫɬɶ, ɜɩɪɨɱɟɦ, ɨɫɬɚɟɬɫɹ ɫɥɚɛɨɣ, ɩɪɨ-
ɩɨɪɰɢɨɧɚɥɶɧɨɣ T
1/2
, ɱɬɨ ɜ ɧɟɛɨɥɶɲɨɦ ɢɧɬɟɪɜɚɥɟ ɬɟɦɩɟɪɚɬɭɪ ɧɟɫɭɳɟɫɬɜɟɧ-
ɧɨ ɩɨ ɫɪɚɜɧɟɧɢɸ ɫ ɛɵɫɬɪɨɪɚɫɬɭɳɟɣ ɮɭɧɤɰɢɟɣ e
E
a
/RT
.
ɍɪɚɜɧɟɧɢɟ (I.15) – ɨɫɧɨɜɧɨɟ ɭɪɚɜɧɟɧɢɟ ɬɟɨɪɢɢ ɚɤɬɢɜɧɵɯ ɫɬɨɥɤɧɨɜɟ-
ɧɢɣɫɨɞɟɪɠɢɬ ɡɚɤɨɧ ɞɟɣɫɬɜɭɸɳɢɯ ɦɚɫɫ (ɩɪɨɩɨɪɰɢɨɧɚɥɶɧɨɫɬɶ C
1
C
2
). ȿɫɥɢ
ɭɱɟɫɬɶ, ɱɬɨ ɫɪɟɞɧɹɹ
ɨɬɧɨɫɢɬɟɥɶɧɚɹ ɫɤɨɪɨɫɬɶ ɱɚɫɬɢɰ ɢɞɟɚɥɶɧɨɝɨ ɝɚɡɚ
*)
Ɏɨɪɦɭɥɚ (I.5) ɩɨɥɭɱɚɟɬɫɹ, ɟɫɥɢ ɩɨɥɨɠɢɬɶ r
1
= r
2
, P
1
= P
2
ɢ C
1
= C
2
, ɚ ɬɚɤɠɟ ɭɱɟɫɬɶ, ɱɬɨ
ɩɪɢ ɨɬɨɠɞɟɫɬɜɥɟɧɢɢ ɱɚɫɬɢɰ (1 { 2) ɩɨɥɭɱɢɬɫɹ ɭɞɜɨɟɧɧɨɟ ɱɢɫɥɨ ɫɨɭɞɚɪɟɧɢɣ. Ɉɬɫɸɞɚɤɨ-
ɷɮɮɢɰɢɟɧɬ 2 ɜ (I.5).
19

1/2
8
*
ɤT
u
SP
,
ɬɨ ɟɦɭ ɦɨɠɧɨ ɩɪɢɞɚɬɶ ɮɨɪɦɭ
2
12
a
E
RT
aA
uNe CC
Vz .
ɉɪɨɢɡɜɟɞɟɧɢɟ z
0
= uV ɧɚɡɵɜɚɟɬɫɹ ɮɚɤɬɨɪɨɦ ɫɨɭɞɚɪɟɧɢɣ. Ɉɧ ɩɪɟɞɫɬɚɜɥɹɟɬ
ɫɨɛɨɣ ɱɚɫɬɨɬɭ ɜɫɬɪɟɱ ɞɜɭɯ ɞɚɧɧɵɯ ɱɚɫɬɢɰ 1 ɢ 2, ɞɜɢɠɭɳɢɯɫɹ ɜ ɟɞɢɧɢɰɟ
ɨɛɴɟɦɚ.
ɇɚɤɨɧɟɰ, ɧɭɠɧɨ ɩɪɢɧɹɬɶ ɜɨ ɜɧɢɦɚɧɢɟ, ɱɬɨ ɞɚɠɟ ɚɤɬɢɜɧɨɟ ɫɨɭɞɚɪɟɧɢɟ
ɧɟ ɜɫɟɝɞɚ ɪɟɚɤɰɢɨɧɧɨ ɷɮɮɟɤɬɢɜɧɨ. Ⱦɥɹ ɜɡɚɢɦɨɞɟɣɫɬɜɢɹ ɦɨɥɟɤɭɥ, ɨɛɥɚ-
ɞɚɸɳɢɯ ɧɟɤɨɬɨɪɵɦ ɩɪɨɫɬɪɚɧɫɬɜɟɧɧɵɦ ɫɬɪɨɟɧɢɟɦ, ɧɟɨɛɯɨɞɢɦɨ, ɱɬɨɛɵ ɢɯ
ɜɡɚɢɦɧɚɹ ɨɪɢɟɧɬɚɰɢɹ ɜ ɦɨɦɟɧɬ ɫɬɨɥɤɧɨɜɟɧɢɹ (ɢɥɢ, ɤɚɤ ɝɨɜɨɪɹɬ ɤɨɧɮɢɝɭɪɚ-
ɰɢɹ ɫɬɨɥɤɧɨɜɟɧɢɹ) ɛɵɥɚ ɩɨɞɯɨɞɹɳɟɣ. ɉɨɷɬɨɦɭ ɞɥɹ ɫɤɨɪɨɫɬɢ ɪɟɚɤɰɢɢ ɩɪɢ-
ɧɢɦɚɸɬ:
12
a
E
RT
a
ppeC
vz z C , ɢɥɢ
a
E
RT
pe
kz
ɞɥɹ ɤɨɧɫɬɚɧɬɵ ɫɤɨɪɨɫɬɢ. Ɇɧɨɠɢɬɟɥɶ p, ɩɨɤɚɡɵɜɚɸɳɢɣ ɞɨɥɸ ɷɮɮɟɤɬɢɜɧɵɯ
ɜ ɧɚɡɜɚɧɧɨɦ ɫɦɵɫɥɟ ɫɬɨɥɤɧɨɜɟɧɢɣ, ɧɚɡɵɜɚɟɬɫɹ ɩɪɨɫɬɪɚɧɫɬɜɟɧɧɵɦ ɢɥɢ
ɫɬɟɪɢɱɟɫɤɢɦ
*
)
ɮɚɤɬɨɪɨɦ.
9. Ɉɛɪɚɬɢɦɵɟ ɪɟɚɤɰɢɢ
Ⱦɨ ɫɢɯ ɩɨɪ ɪɚɫɫɦɚɬɪɢɜɚɥɢɫɶ ɪɟɚɤɰɢɢ, ɩɪɨɬɟɤɚɸɳɢɟ ɜ ɨɞɧɨɦ ɧɚɩɪɚɜɥɟ-
ɧɢɢ. ɗɬɨ ɹɜɥɹɟɬɫɹ ɩɪɢɛɥɢɠɟɧɢɟɦ ɢ ɨɩɪɚɜɞɚɧɨ ɜ ɬɨɣ ɢɥɢ ɢɧɨɣ ɫɬɟɩɟɧɢ ɞɥɹ
ɧɚɱɚɥɶɧɨɝɨ ɩɟɪɢɨɞɚ ɩɪɨɰɟɫɫɚ. ɉɭɫɬɶ ɢɦɟɟɬɫɹ ɩɪɨɫɬɚɹ ɪɟɚɤɰɢɹ ɫ ɭɪɚɜɧɟɧɢɟɦ
11
mn
ii j j
ij
A
B
¦Q ¦Q' , (I.16)
ɢ ɩɭɫɬɶ ɜ ɧɚɱɚɥɶɧɵɣ ɦɨɦɟɧɬ ɜɪɟɦɟɧɢ ɜ ɫɢɫɬɟɦɟ ɨɬɫɭɬɫɬɜɨɜɚɥɢ ɜɟɳɟɫɬɜɚ B
B
j
.
Ʉɚɤ ɬɨɥɶɤɨ ɜɟɳɟɫɬɜɚ B
j
B ɩɨɹɜɹɬɫɹ ɢ ɫɬɚɧɭɬ ɧɚɤɚɩɥɢɜɚɬɶɫɹ, ɜɨɡɧɢɤɧɟɬ ɢ ɫɬɚ-
ɧɟɬ ɪɚɡɜɢɜɚɬɶɫɹ ɜɫɬɪɟɱɧɵɣ ɩɪɨɰɟɫɫ ɩɪɟɜɪɚɳɟɧɢɹ, ɨɬɜɟɱɚɸɳɢɣ ɬɨɦɭ ɠɟ
ɫɬɟɯɢɨɦɟɬɪɢɱɟɫɤɨɦɭ ɭɪɚɜɧɟɧɢɸ, ɧɨ ɩɪɨɱɢɬɚɧɧɨɦɭ ɫɩɪɚɜɚ ɧɚɥɟɜɨ. ȼ ɷɬɨɦ
ɫɥɭɱɚɟ ɝɨɜɨɪɹɬ, ɱɬɨ ɪɟɚɤɰɢɹ ɹɜɥɹɟɬɫɹ ɨɛɪɚɬɢɦɨɣ ɢ, ɱɬɨɛɵ ɩɨɞɱɟɪɤɧɭɬɶ ɷɬɨ
ɨɛɫɬɨɹɬɟɥɶɫɬɜɨ, ɩɢɲɭɬ:
11
mn
ii j j
ij
A
B
¦Q ¦Q
'
&
.
ɉɪɢ ɬɚɤɨɦ ɩɨɥɨɠɟɧɢɢ ɞɟɥɚ ɫɤɨɪɨɫɬɶ ɪɟɚɤɰɢɢ ɦɵ ɩɨ-ɩɪɟɠɧɟɦɭ ɨɩɪɟɞɟ-
ɥɹɟɦ ɮɨɪɦɭɥɨɣ (I.4) ɢ ɫɥɟɞɢɦ ɡɚ ɪɚɡɜɢɬɢɟɦ ɩɪɨɰɟɫɫɚ ɩɨ ɨɞɧɨɦɭ ɢɡ ɤɨɦɩɨ-
*)
Ɉɬ ɝɪɟɱ. ıIJİȡȩȢɬɜɟɪɞɵɣ, ɜ ɩɟɪɟɧɨɫɧɨɦ ɫɦɵɫɥɟɩɪɨɫɬɪɚɧɫɬɜɟɧɧɵɣ, ɨɛɴɟɦɧɵɣ.
20
ɩɨ ɮɨɪɦɭɥɟ ɬɢɩɚ (I.5), ɛɵɥɚ ɛɵ ɧɟɩɨɦɟɪɧɨ ɜɵɫɨɤɚ. Ⱥɪɪɟɧɢɭɫ ɩɪɟɞɩɨɥɨɠɢɥ,                                                                                      8ɤT
                                                                                                                                                                        1/ 2

ɱɬɨ ɪɟɚɤɰɢɨɧɧɵɦɢ ɹɜɥɹɸɬɫɹ ɬɨɥɶɤɨ ɬɟ ɫɬɨɥɤɧɨɜɟɧɢɹ, ɤɨɬɨɪɵɟ ɩɪɨɢɫɯɨɞɹɬ                                                                             u                             ,
ɫ ɷɧɟɪɝɢɟɣ, ɩɪɟɜɵɲɚɸɳɟɣ ɧɟɤɨɬɨɪɵɣ ɩɨɪɨɝ Ea. ȼɫɟ ɫɬɨɥɤɧɨɜɟɧɢɹ ɫ ɷɧɟɪ-                                                                                        SP*
ɝɢɟɣ E < Ea ɨɤɚɡɵɜɚɸɬɫɹ ɧɟɷɮɮɟɤɬɢɜɧɵɦɢ: ɫɨɭɞɚɪɹɸɳɢɟɫɹ «ɦɟɞɥɟɧɧɵɟ»                                    ɬɨ ɟɦɭ ɦɨɠɧɨ ɩɪɢɞɚɬɶ ɮɨɪɦɭ
                                                                                                                                                                    Ea
ɱɚɫɬɢɰɵ ɧɟ ɪɟɚɝɢɪɭɸɬ. ɗɬɨɬ ɩɨɪɨɝ ɢ ɩɪɟɞɫɬɚɜɥɹɟɬ ɫɨɛɨɣ ɷ ɧ ɟ ɪ ɝ ɢ ɸ ɚ ɤ -                                                                                       
ɬ ɢ ɜ ɚ ɰ ɢ ɢ, ɚ ɫɬɨɥɤɧɨɜɟɧɢɹ ɫ ɭɫɥɨɜɢɟɦ E · Ea ɧɚɡɵɜɚɸɬ ɚɤɬɢɜɧɵɦɢ.                                                                       za         uVN A2 e       RT
                                                                                                                                                                          C1C2 .
    ɋɬɚɬɢɫɬɢɱɟɫɤɢɣ ɩɨɞɫɱɟɬ ɱɚɫɬɨɬɵ za ɛɢɧɚɪɧɵɯ ɚɤɬɢɜɧɵɯ ɫɬɨɥɤɧɨɜɟɧɢɣ                                 ɉɪɨɢɡɜɟɞɟɧɢɟ z0 = uV ɧɚɡɵɜɚɟɬɫɹ ɮɚɤɬɨɪɨɦ ɫɨɭɞɚɪɟɧɢɣ. Ɉɧ ɩɪɟɞɫɬɚɜɥɹɟɬ
ɜ ɢɞɟɚɥɶɧɨɦ ɝɚɡɟ, ɨɫɧɨɜɚɧɧɵɣ ɧɚ ɪ ɚ ɫ ɩ ɪ ɟ ɞ ɟ ɥ ɟ ɧ ɢ ɢ Ɇ ɚ ɤ ɫ ɜ ɟ ɥ ɥ ɚ                          ɫɨɛɨɣ ɱɚɫɬɨɬɭ ɜɫɬɪɟɱ ɞɜɭɯ ɞɚɧɧɵɯ ɱɚɫɬɢɰ 1 ɢ 2, ɞɜɢɠɭɳɢɯɫɹ ɜ ɟɞɢɧɢɰɟ
ɦɨɥɟɤɭɥ ɝɚɡɚ ɩɨ ɫɤɨɪɨɫɬɹɦ, ɩɨɤɚɡɵɜɚɟɬ, ɱɬɨ                                                           ɨɛɴɟɦɚ.
                                                                    1
                                                                                Ea                      ɇɚɤɨɧɟɰ, ɧɭɠɧɨ ɩɪɢɧɹɬɶ ɜɨ ɜɧɢɦɚɧɢɟ, ɱɬɨ ɞɚɠɟ ɚɤɬɢɜɧɨɟ ɫɨɭɞɚɪɟɧɢɟ
                                                       8ɤT          2       
                                                                                                     ɧɟ ɜɫɟɝɞɚ ɪɟɚɤɰɢɨɧɧɨ ɷɮɮɟɤɬɢɜɧɨ. Ⱦɥɹ ɜɡɚɢɦɨɞɟɣɫɬɜɢɹ ɦɨɥɟɤɭɥ, ɨɛɥɚ-
                         za                2
                                  S(r1  r2 ) N    2
                                                   A                    e       RT
                                                                                     C1C2   (I.15)
                                                       SP*                                           ɞɚɸɳɢɯ ɧɟɤɨɬɨɪɵɦ ɩɪɨɫɬɪɚɧɫɬɜɟɧɧɵɦ ɫɬɪɨɟɧɢɟɦ, ɧɟɨɛɯɨɞɢɦɨ, ɱɬɨɛɵ ɢɯ
(ɫɦ. ɥɢɬɟɪɚɬɭɪɭ [2, 4, 5]). Ɂɞɟɫɶ r1 ɢ r2 – ɪɚɞɢɭɫɵ ɫɬɚɥɤɢɜɚɸɳɢɯɫɹ ɱɚɫɬɢɰ;                           ɜɡɚɢɦɧɚɹ ɨɪɢɟɧɬɚɰɢɹ ɜ ɦɨɦɟɧɬ ɫɬɨɥɤɧɨɜɟɧɢɹ (ɢɥɢ, ɤɚɤ ɝɨɜɨɪɹɬ ɤɨɧɮɢɝɭɪɚ-
P* – ɢɯ ɩɪɢɜɟɞɟɧɧɚɹ ɦɚɫɫɚ:                                                                           ɰɢɹ ɫɬɨɥɤɧɨɜɟɧɢɹ) ɛɵɥɚ ɩɨɞɯɨɞɹɳɟɣ. ɉɨɷɬɨɦɭ ɞɥɹ ɫɤɨɪɨɫɬɢ ɪɟɚɤɰɢɢ ɩɪɢ-
                                                                                                     ɧɢɦɚɸɬ:
                                   1      1    1 ,
                                                                                                                                                  
                                                                                                                                                       Ea
                                                                                                                                                                                         
                                                                                                                                                                                             Ea
                                  P* P 1 P 2                                                                                v       pza   pze          RT
                                                                                                                                                            C1C2 , ɢɥɢ k           pze       RT

ɚ ɦɧɨɠɢɬɟɥɶ V = S(r1 + r2)2 ɧɚɡɵɜɚɟɬɫɹ ɫɟɱɟɧɢɟɦ ɫɨɭɞɚɪɟɧɢɹ. Ɉɧɨ ɩɪɟɞɫɬɚɜɥɹ-                          ɞɥɹ ɤɨɧɫɬɚɧɬɵ ɫɤɨɪɨɫɬɢ. Ɇɧɨɠɢɬɟɥɶ p, ɩɨɤɚɡɵɜɚɸɳɢɣ ɞɨɥɸ ɷɮɮɟɤɬɢɜɧɵɯ
ɟɬ ɫɨɛɨɣ ɫɟɱɟɧɢɟ ɰɢɥɢɧɞɪɚ, ɜ ɤɨɬɨɪɨɦ ɞɨɥɠɧɵ ɨɤɚɡɚɬɶɫɹ ɰɟɧɬɪɵ ɦɚɫɫ ɫɮɟɪɢ-                             ɜ ɧɚɡɜɚɧɧɨɦ ɫɦɵɫɥɟ ɫɬɨɥɤɧɨɜɟɧɢɣ, ɧɚɡɵɜɚɟɬɫɹ ɩɪɨɫɬɪɚɧɫɬɜɟɧɧɵɦ ɢɥɢ
ɱɟɫɤɢɯ ɱɚɫɬɢɰ, ɱɬɨɛɵ ɫɥɭɱɢɥɨɫɶ ɫɨɭɞɚɪɟɧɢɟ. ɂɫɩɨɥɶɡɭɹ ɮɨɪɦɭɥɭ (I.5), ɤɨɬɨ-                            ɫɬɟɪɢɱɟɫɤɢɦ * ) ɮɚɤɬɨɪɨɦ.
                                                                     *)
ɪɚɹ ɞɥɹ ɱɚɫɬɨɬɵ ɜɫɟɯ ɞɜɨɣɧɵɯ ɫɨɭɞɚɪɟɧɢɣ ɪɚɡɥɢɱɧɵɯ ɱɚɫɬɢɰ ɢɦɟɟɬ ɜɢɞ
                                                                        1
                                                                                                                                     9. Ɉɛɪɚɬɢɦɵɟ ɪɟɚɤɰɢɢ
                                                               8ɤT      2
                              z                2
                                    S(r1  r2 ) N      2
                                                       A                        C1C2 ,
                                                               SP*                                      Ⱦɨ ɫɢɯ ɩɨɪ ɪɚɫɫɦɚɬɪɢɜɚɥɢɫɶ ɪɟɚɤɰɢɢ, ɩɪɨɬɟɤɚɸɳɢɟ ɜ ɨɞɧɨɦ ɧɚɩɪɚɜɥɟ-
ɩɨɥɭɱɢɦ:                                                                                             ɧɢɢ. ɗɬɨ ɹɜɥɹɟɬɫɹ ɩɪɢɛɥɢɠɟɧɢɟɦ ɢ ɨɩɪɚɜɞɚɧɨ ɜ ɬɨɣ ɢɥɢ ɢɧɨɣ ɫɬɟɩɟɧɢ ɞɥɹ
                                                           
                                                               Ea                                    ɧɚɱɚɥɶɧɨɝɨ ɩɟɪɢɨɞɚ ɩɪɨɰɟɫɫɚ. ɉɭɫɬɶ ɢɦɟɟɬɫɹ ɩɪɨɫɬɚɹ ɪɟɚɤɰɢɹ ɫ ɭɪɚɜɧɟɧɢɟɦ
                                          za        ze
                                                     .         RT                                                                              m                    n
                              –Ea/RT                                                                                                           ¦ Qi Ai ' ¦ Q j B j ,                              (I.16)
Ɍɟɦ ɫɚɦɵɦ ɦɧɨɠɢɬɟɥɶ e                  ɩɪɟɞɫɬɚɜɥɹɟɬ ɫɨɛɨɣ ɞɨɥɸ ɚɤɬɢɜɧɵɯ ɫɬɨɥɤɧɨ-                                                               i 1                  j 1
ɜɟɧɢɣ ɫ ɷɧɟɪɝɢɟɣ E > Ea.                                                                             ɢ ɩɭɫɬɶ ɜ ɧɚɱɚɥɶɧɵɣ ɦɨɦɟɧɬ ɜɪɟɦɟɧɢ ɜ ɫɢɫɬɟɦɟ ɨɬɫɭɬɫɬɜɨɜɚɥɢ ɜɟɳɟɫɬɜɚ Bj.                          B




   Ʉɚɤ ɜɢɞɧɨ, ɩɨɫɥɟɞɧɟɟ ɭɪɚɜɧɟɧɢɟ ɫɨɜɩɚɞɚɟɬ ɩɨ ɮɨɪɦɟ ɫ ɭɪɚɜɧɟɧɢɟɦ Ⱥɪ-                                Ʉɚɤ ɬɨɥɶɤɨ ɜɟɳɟɫɬɜɚ Bj ɩɨɹɜɹɬɫɹ ɢ ɫɬɚɧɭɬ ɧɚɤɚɩɥɢɜɚɬɶɫɹ, ɜɨɡɧɢɤɧɟɬ ɢ ɫɬɚ-
                                                                                                                                B




ɪɟɧɢɭɫɚ. Ɉɬɥɢɱɢɟ ɫɨɫɬɨɢɬ ɜ ɬɨɦ, ɱɬɨ ɩɪɟɞɷɤɫɩɨɧɟɧɰɢɚɥɶɧɵɣ ɦɧɨɠɢɬɟɥɶ                                   ɧɟɬ ɪɚɡɜɢɜɚɬɶɫɹ ɜɫɬɪɟɱɧɵɣ ɩɪɨɰɟɫɫ ɩɪɟɜɪɚɳɟɧɢɹ, ɨɬɜɟɱɚɸɳɢɣ ɬɨɦɭ ɠɟ
ɡɚɜɢɫɢɬ ɨɬ ɬɟɦɩɟɪɚɬɭɪɵ. ɗɬɚ ɡɚɜɢɫɢɦɨɫɬɶ, ɜɩɪɨɱɟɦ, ɨɫɬɚɟɬɫɹ ɫɥɚɛɨɣ, ɩɪɨ-                              ɫɬɟɯɢɨɦɟɬɪɢɱɟɫɤɨɦɭ ɭɪɚɜɧɟɧɢɸ, ɧɨ ɩɪɨɱɢɬɚɧɧɨɦɭ ɫɩɪɚɜɚ ɧɚɥɟɜɨ. ȼ ɷɬɨɦ
ɩɨɪɰɢɨɧɚɥɶɧɨɣ T1/2, ɱɬɨ ɜ ɧɟɛɨɥɶɲɨɦ ɢɧɬɟɪɜɚɥɟ ɬɟɦɩɟɪɚɬɭɪ ɧɟɫɭɳɟɫɬɜɟɧ-                                ɫɥɭɱɚɟ ɝɨɜɨɪɹɬ, ɱɬɨ ɪɟɚɤɰɢɹ ɹɜɥɹɟɬɫɹ ɨɛɪɚɬɢɦɨɣ ɢ, ɱɬɨɛɵ ɩɨɞɱɟɪɤɧɭɬɶ ɷɬɨ
ɧɨ ɩɨ ɫɪɚɜɧɟɧɢɸ ɫ ɛɵɫɬɪɨɪɚɫɬɭɳɟɣ ɮɭɧɤɰɢɟɣ e–Ea/RT.                                                   ɨɛɫɬɨɹɬɟɥɶɫɬɜɨ, ɩɢɲɭɬ:
   ɍɪɚɜɧɟɧɢɟ (I.15) – ɨɫɧɨɜɧɨɟ ɭɪɚɜɧɟɧɢɟ ɬɟɨɪɢɢ ɚɤɬɢɜɧɵɯ ɫɬɨɥɤɧɨɜɟ-                                                                        m                    n

ɧɢɣ – ɫɨɞɟɪɠɢɬ ɡɚɤɨɧ ɞɟɣɫɬɜɭɸɳɢɯ ɦɚɫɫ (ɩɪɨɩɨɪɰɢɨɧɚɥɶɧɨɫɬɶ C1C2). ȿɫɥɢ                                                                              ' ¦ Q j Bj .
                                                                                                                                           ¦ Qi Ai &
                                                                                                                                           i 1                 j 1
ɭɱɟɫɬɶ, ɱɬɨ ɫɪɟɞɧɹɹ ɨɬɧɨɫɢɬɟɥɶɧɚɹ ɫɤɨɪɨɫɬɶ ɱɚɫɬɢɰ ɢɞɟɚɥɶɧɨɝɨ ɝɚɡɚ
                                                                                                        ɉɪɢ ɬɚɤɨɦ ɩɨɥɨɠɟɧɢɢ ɞɟɥɚ ɫɤɨɪɨɫɬɶ ɪɟɚɤɰɢɢ ɦɵ ɩɨ-ɩɪɟɠɧɟɦɭ ɨɩɪɟɞɟ-
                                                                                                     ɥɹɟɦ ɮɨɪɦɭɥɨɣ (I.4) ɢ ɫɥɟɞɢɦ ɡɚ ɪɚɡɜɢɬɢɟɦ ɩɪɨɰɟɫɫɚ ɩɨ ɨɞɧɨɦɭ ɢɡ ɤɨɦɩɨ-
    *)
     Ɏɨɪɦɭɥɚ (I.5) ɩɨɥɭɱɚɟɬɫɹ, ɟɫɥɢ ɩɨɥɨɠɢɬɶ r1 = r2, P1 = P2 ɢ C1 = C2, ɚ ɬɚɤɠɟ ɭɱɟɫɬɶ, ɱɬɨ
ɩɪɢ ɨɬɨɠɞɟɫɬɜɥɟɧɢɢ ɱɚɫɬɢɰ (1 { 2) ɩɨɥɭɱɢɬɫɹ ɭɞɜɨɟɧɧɨɟ ɱɢɫɥɨ ɫɨɭɞɚɪɟɧɢɣ. Ɉɬɫɸɞɚ – ɤɨ-                    *)
ɷɮɮɢɰɢɟɧɬ 2 ɜ (I.5).                                                                                         Ɉɬ ɝɪɟɱ. ıIJİȡȩȢ – ɬɜɟɪɞɵɣ, ɜ ɩɟɪɟɧɨɫɧɨɦ ɫɦɵɫɥɟ – ɩɪɨɫɬɪɚɧɫɬɜɟɧɧɵɣ, ɨɛɴɟɦɧɵɣ.

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