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, 2008


1.

1.1

1.2

1.3.

2.

2.1

2.2

2.3

3.

3.1.

3.2.


, . . . . , , .

, , , , .


1.

1.1

1.         .

2.         . ?

3.         ? .

4.         .

5.         ?

6.         ? .

7.         .

8.         , .. .

9.         : ) ; ) .

10.      ?

11.      : , . .

12.      , . υ0= υf.

13.      .

14.      .

15.      .

16.      ?

17.      .

18.      , , : ) , ) .

19.      ? .

20.      .

21.      : ) g > f; ) f > g ; ) f = g.

22.      - .. .

23.      , . 20.

24.      ? ?

25.      : . .. () () .

26.      ?

27.      (p, T) (H2 O2). ? . ?

28.      : ; ?

29.      ?

30.      .

31.      : ?

32.      , f <g?

33.      ? .

34.      .

35.      .

1.2

1.1      . . H2 + Br2 → 2HBr (1906), HBr 501-575

d[HBr] l [H2][Br2]½

υ = =

dt 1+ m[HBr]/ [Br2]


l 蠠 m .

. , . . (1919)

1

Br2 → Br· + Br· -

2

Br· + H2 → HBr + H·

3 -

H· + Br· → HBr + Br·

4

H· + HBr → H2 + Br· -

5

Br· + Br· → Br2 - 蠠

( , Br· + Br· + → Br2 + , , .)

: , [H·] [Br·] , l m .

: HBr,


d[HBr]

υ = = k2[Br·][H2] + k3[H·][Br2 -k4[H·][HBr]

dt

H· Br·,

d[Br·]

= 2k1[Br2] - k2[Br·][H2] + k3[H·][Br2]

dt

- k4[H·][HBr] - 2k5 [Br·]2 = 0 (2)

d[H·]

= k2[Br·][H2] - k3[H·][Br2] k4[H·][HBr] = 0 (3)

dt

(2) (3),

k1[Br2] - k5 [Br·]2 = 0 (4)

k1

[Br·] = ()½[Br2]½ (5)

k5

(3) [H·] [Br·] (5)

k2[Br·][H2] k2(k1/ k5)½ [H2] [Br2]½

[H·] = =

k3[Br2] +k4[HBr] k3[Br2] +k4[HBr] (6)


(5) (6) , , , ( [H·]). (1) H· Br· - (5) (6), HBr

d[HBr]

= k2(k1/ k5)½ [H2] [Br2]½ + { k3[Br2] k4[HBr] }×

dt

k2(k1/ k5)½ [H2] [Br2]½ 2k2(k1/ k5)½ [H2] [Br2]

× = (7)

k3[Br2] +k4[HBr] 1+ k4[HBr]/ k3[Br2]

(7) ,

l =2k2(k1/ k5)½ m = k4/ k3

1.2      (CH3SOCH3) , , 11,5 · -1 .

k1

CH3SOCH3→·CH3+ SOCH3 (1)

k2

·CH3+CH3SOCH3→CH4 + ·CH2SOCH3 (2)


k3

·CH2SOCH3→CH2SO+·CH3 (3)

k4

·CH3+·CH2SOCH3→ (4)

1 = 16 · -1 , 2 = 2,4 · -1 , 3 = 4,8 · -1 , 4 ≈ 0. ·CH3 ·CH2SOCH3 , (4) (2), , .

: υ1, υ2, υ3, υ4.

υ2=k2[·CH3][CH3SOCH3]. (1)

·CH3 ·CH2SOCH3

d[·CH3]

(2) = υ1 - υ2 + υ3 - υ4 = 0

dt

(3) d[·CH2SOCH3]

= υ2 - υ3 - υ4 = 0

dt


(2) (3) , υ1 = 2υ4, ..

k1 [CH3SOCH3]

[·CH2SOCH3] = (4)

24[·CH3]

(3) ,

υ2=υ3+υ4≈υ3 (5)

, (4) ,

k1 [CH3SOCH3]

k2 [·CH3] [CH3SOCH3] =k3

2k4 [·CH3]

k1k3 [CH3SOCH3]

k2 [·CH3]2 [CH3SOCH3] =

2 k4

 

[·CH3]

k1k3

[·CH3] = ()½ (6)

2k2 k4

(6) (1)


k1k2 k3

υ= υ2 = ()½[CH3SOCH3] (7)

2 k4

, .

ki

Ea k1k2 k3

k = exp[- ] = ()½ (8)

RT 2 k4

,

Ea

ki = i,exp[- ](9)

RT

(8) (9) ( : )

= ½ (1 + 2 + 3 4) = ½(16+ 4,8 + 2,4)= 11,6 · -1 (10)


1.3*. () -

: - → 2R·(k1) R· +→R·( k2). R· , , υ2>>υ1. ƒ R· , .. R·, ƒ .

R·+→ R2·(kr)

R2·+→ R3·

Ri·+M→ Ri+1·, i=1,2,..,∞

, kr.

: : R̼·+ Rk·→ R̼+k·(kƒ), k 1 ∞ kƒ , k.

: ) υ2 k1, ƒ []

) , υr = k[M][A]1/2. k kr, kƒ, k1 ƒ;

) ƒ : 15,45 0, 2096 (), 14, 500 55 . 1,6826 , 0,042% . k1 1,2·10-4 -1 500. .

: ) , R· , .. R·

1                          d [R·]

                       = k1[A] (1)

2                          dt

d [R·] d [R·]

υ2 = = ƒ 2ƒ k1[A] (2)

dt dt

) R·

R·+ → R1·( k2) (3)

R1·+→ R2·( kr) (4)

(3) (4) R1·

d[R1·]

=2ƒ k1[A]- kr [R1·][M] (5)

dt

, R1· R1·+ Rk· → R1+k· (6)


d[R1·] k=∞

= - kƒ[R1·](∑ [Rk·]) (7)

dt k=1

, (7) (5),

d[R1·]

= 2ƒ k1[A]- kr [R1·][M]- kƒ[R1·](∑ [Rk·])=

dt =0 (8)

Ri·

d[Ri·]

= kr [Ri-1·][M] - kr [R1·][M] -

dt

-kƒ[R1·](∑ [Rk·])=0 (9)

(8) (9) , k=∞

2ƒ k1[A]- kr [R1·][M]- kƒ[R1·](∑ [Ri·])(∑ [Rk·])=0

k=1 (10)

, i→∞, [Ri·]→0 (10) k=∞

2ƒ k1[A] - kƒ[R1·](∑ [Ri·])(∑ [Rk·])=0 (11)

k=1

i k ,


k=∞

∑ [Ri·]= (∑ [Rk·]) (12)

i k=1

(11)

2ƒ k1[A]

( ∑ [Ri·])2= (13)

i kƒ

ࠠ d[M]

υ = - = 2ƒ k1[A]+ kr[M]( ∑ [Ri·]) (14)

dt i

, (13), 2ƒ k1[A]

υ= 2ƒ k1[A]+ kr[M]()1/2 (15)

, () , (15) :

υ= k[M][A]1/2, (16)

2ƒ k1

k= kr()1/2 (17)

;

)


k1 d[A]

→ 2R·; - = k1[A] (18)

dt

, m:

dm

- = k1m (19)

dt

(19)

m0 m =mo (1-e-k1t) (20)

k1t , . m0 m =mo k1t= 0,2096·1,2·10-4 ·55= 1,383 , m0- .

, , , m=1,6826·4,2·10-4= 0,707 .

m 0,707

ƒ = = = 0,51 (21)

m0 m 1,383

: , , .


1.3

1.         R2

R2 → 2R (1)

R + R2 → PB +R′ (2)

R′ → PA + R (3)

2R → PA + R (4)

, R2, PA, PB , R, R′ - . R2 .

d[R2] k1

: - = k1[R2] + k2()1/2[R2]3/2

dt k4

2.        

AH → A· + H· (1)

A· → B· + C (2)

AH + B· → A· + D (3)

A· + B· → P, (4)

A·, B·, H· - .

. , .

. .


d[AH] k1k3

: - = (k1+ )[ AH]),

dt 2 kk4

k1 8 k2k3

k= [1+ (1+ )1/2]

4k4 k1 k4

3.        

k1

A1 → R1 + A2 E1 = 320 · -1

k2

R1 + A1 → R1H + R2 E2 = 40 · -1

k3

R2 → R1 + A3 E3 140 · -1

k4

R1 + R2 → A4 E4 = 0,

, R1, R2, - , Ai .

,


d [A1] k1 k2 k3

Ai υ = - = ( )½ [A1]

dt 2k4

: = 250 ·-1

4.        

1

I → R· + R·

2

R· + M → P + R′·

3

R′· + N → Q + R·

4

R· + R· → Z

. .

. I, M, N .

: A. M+N = P+Q; . υ = k2(k1/ k4)1/2[M][I]1/2

5.         . . :


1

C2H6 → ·CH3 + ·CH3

2

·CH3 + C2H6 → CH4 + ·C2H5

3

·C2H5 → C2H4 + H·

4

H· + C2H6 → H2 + ·C2H5

5

H· + ·C2H5 → C2H6

. , , k1 ki.

. . , C2H6 C2D6: () 2 D2, (b) HD () 2, HD D2.

: . υ=( k1 k3 k4/ k5)1/2 [C2H6] . ()

6.         2 Br2

2

Br· + H2 → HBr + H·


3

H· + Br2 → HBr + Br·

76 4 · -1.

. 2 Br2 500 , Br· [·].

. Br· H· () [Br·], , Br2 , H·, , H·, .

: . 7·106 . [Br] ; [H]

7.        

CO + Cl2 → COCl2

,

d [COCl2]

= k [CO] [Cl2]3⁄2

dt

, ,

k1

Cl2 + M → 2Cl· + M


k2

CO + Cl· → ·COCl

k3

·COCl + Cl2 → COCl2 + Cl·

k4

COCl → CO + Cl·

k5

Cl· + Cl· + M → Cl2 + M

: k4>> k3 [Cl2],

k2k3

k= ( k1/ k5)1/2

k4

8*. (C2H5)2O → C2H6 + CH3CHO. 1. ,

k1

(C2H5)2O → ·CH3 + C2H5O·CH2 (1)

k2

·CH3 + (C2H5)2O → C2H6 + C2H5O·CH2 (2)


k3

C2H5O·CH2 → ·CH3 + CH3CHO (3)

k4

·CH3+ C2H5O·CH2 → (C2H5)2O (4)

d[CH3CHO]

: υ= = k[(C2H5)2O],

dt

k1k2k3

k= ()1/2

k4

9*. 2 + D2 → HD 0 1000 :

0, 4 8

τ½, 񅅅 192 135

. .

. :

H2 ↔ 2H

] ()

D2 ↔ 2D

H + D2 ↔ HD + D

] ()

D + H2 ↔ HD + H


H + D → HD

. . ) ?

: . n= 1,5. . υ=(PH2)1,5

10*. , 2O3 →3O2 Cl2 .

Cl2 + O3 → ClO· + ClO2· (1)

ClO2· + O3 → ClO3· + O2 (2)

ClO3· + O3 → ClO2· + 2O2 (3)

ClO3· + ClO3· → Cl2 + 3O2 (4)

ClO·, (1), .

. [ClO3·] [Cl2], [O3] ki.

. , 2, (4). ?

. .

. i .

: . [ClO3·]= (k1/2 k4)1/2[Cl2]1/2[O3]1/2.

. υ= { k1/2 k4}1/2 k3[Cl2]1/2[O3]3/2, Cl2-

. l≈ k3(1/ 2k1k4)1/2([O3]/[ Cl2])1/2 ;. = 3+0,5(1-4)


11*. H2 + NO2 = H2O + NO

k1

H2 + NO2 → H· + HONO

k2

H· + NO2 → OH· + NO

k3

OH· + H2 → H2O + H·

k4

OH· + NO2 → HNO3

,

d [H2O]

= k′ [H2]2

dt

, NO2, .

d [H2O]

: = k1k3/k4[H2]2,

dt


[NO2]

12*. Me3SiSiMe3 ( ) ( ). . 700 800

k1

Me3SiSiMe3 → 2Me3Si

k2

Me3Si + PhMe → Me3SiH + Ph·CH2

k3

Ph·CH2 + Me3SiSiMe3 ↔ PhMe + Me3SiSi(·CH2)Me2

k-3

k4

Me3SiSi(·CH2)Me2 → Me3Si·CH2SiMe2

k5

Me3Si·CH2SiMe2 + PhMe → Me3SiCH2Si(H)Me2 + Ph·CH2

k6

Ph·CH2 + Ph·CH2 → PhCH2CH2Ph

. , .

. , , k4 k-3 [PhMe].

d[B] k1 [A]3/2

: . = k3 k4()1/2

dt k6 k4+ k-3[PhMe]

. = 3+0,5(1-6)

13. HBr H2 Br2

k1

Br2 +M → 2Br· + M E1 = 192,9 · -1

k2

Br + H2 → HBr + H E2 = 73,6 · -1

k3

H + Br2 → HBr + Br E3 = 3,8 · -1

 

k4

H + HBr → H2 + Br E4 = 3,8 · -1

k5

2Br + M → Br2 + M E5 = 0,


. H2 + Br2 → 2HBr, HBr

d [HBr] k[H2] [Br2]½

υ= =

dt [HBr]

1+k′

[Br2]

k4

k = 2k2(k1⁄ k5 )½ k′ = . k′ 򠠠 k3

?

: = 170 ·-1; k′

14.* CH3CHO → CH4 + CO

k1

CH3CHO → ·CH3 + ·CHO

k2

·CHO → CO + H·

k3

H + CH3CHO → H2 + CH3C·O


k4

CH3C·O → ·CH3 + CO

k5

·CH3 + CH3CHO → CH4 + CH3C·O

k6

2 ·CH3 → C2H6

. CH3CHO .

. 3 , .. k1 ki?

d[CH3CHO] k1

: .υ=- = 2 k1[CH3CHO]+ k5()1/2[CH3CHO]3/2;

dt k6

d[CH4] k1 d[H2] d[C2H6]

= k5()1/2[CH3CHO]3/2; == k1[CH3CHO];

dt k6 dt dt

d[CO] k1

= k1[CH3CHO]+ k5()1/2[CH3CHO]3/2.

dt k6


d[CH3CHO] d[CH4] d[CO]

. k1ki , υ= - = = =

dt dt dt

= k5(k1/ k6)1/2[CH3CHO]3/2, ..

CH3CHO → CH4 + CO.

15. C2H6 + Cl2 → C2H5Cl + HCl (V, T=const) , Cl2 b C2H5.

Cl2→ 2Cl·(k1)

C2H6 + Cl· → · C2H5+ HCl(k2)

·C2H5 + Cl2→ C2H5Cl + Cl·( k3)

Cl· + Cl·→ Cl2 (k3)

Cl· ·C2H5, :

) l b ;

) , 575 : k1 / k4 = 5,30× 10-23 M, k2 = 4,19 · 1010 · -1· -1 , k3 = 5,27 · 109 · -1 × -1 .

: ) υ= k2(k1/ k4)1/2[C2H6][Cl2]1/2

) k= 0,305 1/2·-1/2·-1

16.* CH3OCH3


CH3OCH3 → ·CH3 + CH3O· (k1)

·CH3 + CH3OCH3 → CH4 + ·CH2OCH3 (k2)

·CH2OCH3 → + ·CH3 (k3)

CH3O· → ·+ (k4)

· + CH3OCH3 → ·CH2OCH3 + 2 (k5)

2 ·CH3 → C2H6

. [CH3OCH3] ki .

. (CH4 HCHO). ? ?

: .[ CH3O·]=( k1/ k4)1/2[CH3OCH3]; [·]=( k1/ k5);

[·CH3]=(k1/k6)[CH3OCH3]1/2;[·CH2OCH3]= k2/k3(k1/k6)1/2[CH3OCH3]3/2+

+ k1/k3[CH3OCH3];

d[CH3OCH3]

. υ= - =2k1[CH3OCH3]+ k2(k1/k6)1/2[CH3OCH3]3/2

dt

d[CH3OCH3] d[] d[CH4]

υ=- = = ,

dt dt dt ,

2k1[CH3OCH3] k2(k1/k6)1/2[CH3OCH3]3/2, .. (1)

.

17.* F2O (1- 100 ) (500 580 )

d [F2O]

- = k1[F2O]2 + kII[F2O]3⁄2

dt

. F2O

F2O + F2O → F·+FO· + F2O (k1)

F· + F2O → F2 + FO· (k2)

FO· + FO· → O2 + 2 F· (k3)

2 F· + F2O → F2+ F2O (k4)

, F2O .

. (2) (O-F) F2O

(4) ,

19350

kI = 7,8 · 1013 exp (- ) [·-1 ·-1];

T

16910

kII = 2,3·1010exp (- )[½·-½·-1];

T

= 540 .

0

ΔfHF2O, =24,4 ·-1, F-F= 156,9 ·-1,

EO-O= 498,3 ·-1..

d [F2O]

: ) - = k1[F2O]2+k2(k1/k4)1/2[F2O]3/2,

dt

k1= kI k2(k1/k4)1/2= kII; ) 2~57,2 ·-1, (-F)≈ 221 ·-1


2.

2.1

1.         .

2.         , , ?

3.         .

4.         - .

5.         ?

6.         -- .

7.         ?

8.         -.

9.         , .

10.      -. ?

: 1, 2


2010