)(1

/ .

)(2
:

/ .

:

) (.
)
(
) (Pt
) ( :
Pt
H 2 + O 2
H 2O + heat

)

(.
)
(
.
.

)(3
:

/ .

.

.

.
.

.

.

) ).(-

) : (-

)(4
:

/ .

:
: ) (rate of reaction

.
:

)(how does a chemical reaction occur

.
:

( ): (extremely fast reactions

)
( :
) (
)(10-7 s

NaCl + AgNO3
) AgCl(s) + NaNO3 (aq

:
N 2 O 4
2NO 2

)(5
:

/ .

.
( ): (Moderately slow reactions

.

): (450 C

450 C
)2HI(g
) H 2 (g) + I 2 (g

) (
.
+

H
CH 3COOH + C 2 H 5OH
CH 3COOC 2 H 5 + H 2 O

( ): (Very slow reactions

) ( G
. :



.

)(6
:

/ .

.

.
.

":
".


.
:
) .(mol L-1
) .(mol L-1 s-1
).(atm s-1

) ( G

)(7
:

/ .

) ( G
:
:
G = - 79 kJ/mol

)C(diamond) + O2 (g
) CO 2 (g

) ( G
.
:
G = - 742.2 kJ/mol

)4Fe(s) + 3O2 (g
) 2Fe2 O3 (s

) ( G

.
)(

.
.


.

)(8
:

/ .

:
( .
( .
(
.
(
.

:
.
.
.
.

.
:

.

)(9
:

/ .

.
.


.
.
-

.

.
:

:

) 2NH3 (g
)N 2 (g) + 3H 2 (g

)(10
:

/ .

) (200 C
.
) ( ) (450 C
.


.

)(.




.

)(11
:

/ .

)(Kinetic Chemistry

) (

.

.
:
:

.
:
.
:

) (Wihelmy ) 1850(

)(12
:

/ .

)(Beithelot and Gills

)1862(.
)(Wage and Guibrege

) (law of mass action

.
:

) (closed system
:



.
) (closed system

.

) (flow system

)(13
:

/ .

) (
.

)(14
:

/ .

)(Stoichimetry



.

:
)N 2 (g) + 3H 2 (g
) 2NH3 (g

) (2 mol
) (3 mol .
:
2KMnO4 + 16 HCl
2KCl + 2MnCl2 + 8 H 2 O + 5Cl2

.

.
:
:
2N 2 O
2N 2 + O 2

)(15
:

/ .

:
:
N 2 O
O: + N 2

.
O: + N 2 O
N 2 + O2

:
N 2 O
O: + N 2
O: + N 2 O
N 2 + O2

2N 2 O
2N 2 + O 2

.

.
:
:
CH3CHO
CH 4 + CO

)(16
:

/ .

.
CH 3CHO
CH 3 + CHO

.
:
CH 3CHO
CH 3 + CHO
CH 3 + CH 3CHO
CH 4 + CH 3CO
CH 3CO
CH3 + CO
CH 3 + CH 3
C2 H 6

:
2N 2 O5
4NO2 + O2

:
) (

N 2 O5
2NO 2 + O

N 2 O5 + O
2NO 2 + O 2

.
:
]Rate = k [N2O5
) (k .

)(17
:

/ .

.
:

)(18
:

/ .

:
:
- )(Homogeneous Reactions

) (
.
:

)( :

) 2NH3 (g
)N 2 (g) + 3H 2 (g

)(
:

) CH3COOH(L) + C2 H5OH(L
)CH3COOC2 H5 (L) + H 2 O(L

)
(:

) CH3COOC 2 H 5 (L) + H 2 O(L

)CH3COOH + CH 3CH 2OH(L

)(19
:

/ .

) 2HBr(g
)H 2 (g) + Br2 (g

- )(Heterogeneous Reactions

)
( )
( .
:
MnO2
)2H 2 O(A
) 2H 2 O(A) + O 2 (g

)C(s) + O 2 (g
) CO 2 (g
)2HCl(A) + Mn(s
) MnCl2 (s) + H 2 (g
)2HCl(A) + Na 2 CO3 (s
) 2NaCl(s) + CO 2 (g) + H 2 O(A

: :
- ) ( :

) ( .
:

)(20
:

/ .

:
)C(s) + O 2 (g
) CO 2 (g
)2HCl(A) + Na 2 CO3 (s
) 2NaCl(s) + CO 2 (g) + H 2 O(A

- ) ( :

) (

) ( .

)
( .

:
)ZZX 2NH 3 (g
N 2 (g) + 3H 2 (g) YZZ
)ZZX CH3COOH(L) + C2 H 5OH(L
CH 3COOC2 H 5 (L) + H 2 O(L) YZZ
)ZZX 2HBr(g
H 2 (g) + Br2 (g) YZZ
)ZZX 2HI(g
H 2 (g) + I 2 (g) YZZ
)ZZX PCl3 (g) + Cl2 (g
PCl5 (g) YZZ

)(21
:

/ .

:
( ): (closed system

) (static system
:
) (liquid phase
) (flask ).(closed calorimeter

) (reaction vessel .
( ): (open system

) .(flow system
:
) (catalyst
) (biological system
) (nutrients
).(surroundings
) (
) (
) (rate of reaction

)(22
:

/ .

.
.

) ( ) (
) ( .



) (reaction zone
.
:

) (surface catalysis

) (chemical kinetic theory
.
)
( ) (isothermal
) (independent variable
)(non-isothermal

)(23
:

/ .

) ( )(adiabatic systems

)reactions

(exothermic

) (flame reactions ) (explosions

) (heat of reaction .

)(24
:

/ .

.
) (90 km/h
) (90 km


.
.
:

.
:

.


.

)(25
:

/ .

:
:



 

products

reactants

).(-

) : (- :



 

products

reactants

) ( .
.


.

)(26
:

/ .

:
:
)H 2 (g) + I2 (g
) 2HI(g

) (I2
) (H2 ).(HI
).(-

) : (- :
)H 2 (g) + I 2 (g
) 2HI(g

.


.

)(27
:

/ .

.
:
:
)2N 2 O5 (g
) 4NO2 (g) + O2 (g

) (N2O5
) (0.16 M
) (N2O5 ) (
) (- :
) : (- ) (N2O5

)(

][N2O5
mol/L

] [ N 2 O5
t

0
1
2
3
4

0.16
0.113
0.080
0.056
0.040

mol/L min.
0.047
0.033
0.024
0.016

mol/L min
0.060
0.039
0.028
0.020
0.014

)(28
:

/ .

) (average rate

.
=

] [ N 2O5

] [ N 2 O5
t

average rate = -

) (t ] [ .
) (N2O5
) (0.160 M

) (0.113 M

( 0.113 - 0.160 ) = 0.047 mol/L min

) (1 - 0

] [ N 2 O5
t

average rate = -

) ) 4NO 2 (g) + O 2 (g

] [ N 2 O5
= average rate
t

) ( 2N O (g
5

) . ( t

)(29
:

/ .
:

) ( t
) (instantaneous rate
. )(-
).(-

) : (- ) (N2O5

) ( ) (-
) (t = 0
) (t = 0

)(30
:

/ .

) (initial rate
.
:
= 0.060 mol L-1min -1

) ( 0.1 - 0.16
1-0

initial rate = -

:
= 0.019 mol L-1min -1

) ( 0.3 - 0.07
4.1 - 2

instaneous rate = -

.
) (N2O5 ) (O2 ) (NO2
) (NO2 ) (O2 :
] [ NO5
t
] [O2
t

= average rate
= average rate

] [ N 2 O5
= average rate
t

)(31
:

/ .

.
.
.

) ) 4NO 2 (g) + O 2 (g
) ( 2N 2O5 (g

) (N2O5 ) (NO2 ) (O2

) (N2O5
) (NO2
:
] [O2
] 1 [ NO 2
=
= 2

2 t
t

] [ N 2 O5
t

average rate = -

:
] 1 [ N 2 O5 ] 1 [ NO 2 ] [ O 2

=
=
t
t
2
4 t

average rate = -

] 1 [ N 2 O5 ] 1 [ NO 2 ] [ O 2
average rate = -

=
=
2
t
t
4 t

.
:

)(32
:

/ .
aA + bB
qQ + rR

:
]1 [A
] 1 [ B] 1 [ Q ] 1 [ R
==
=
a t
b t
q t
r t

average rate = -

) (average rate
)) (instantaneous rate
(
).(-

) : (- )
(
.

) ( )
) ( d[A]/dt

)(33
:

/ .

) . ( [A]/t
.

) ( [A]/t ) ( t :
]d [A
dt

] [A

limit

t
t
0

) ( d[A]/dt .

.
.

.

]1 [A
] 1 [ B] 1 [ Q ] 1 [ R
==
=
= average rate
a t
b t
q t
r t

]1 d [A
] 1 d [ B] 1 d [ Q ] 1 d [ R
==
=
a dt
b dt
q dt
r dt

instantaneous rate = -

]1 d [A
] 1 d [ B] 1 d [ Q ] 1 d [ R
==
=
= instantaneous rate
a dt
b dt
q dt
r dt

)(34
:

/ .

:
:
aA + bB
cC + dD

:
): (A
): (B

] [A
t
] [ B
t

rA = -

rB = -

): (C

] [ C
t

= rC

): (D

] [ D
t

= rD

:
]1 [A
]1 [ B
]1 [ C] 1 [ D
rate = -
=-
=
=

a t
b t C t d t

.



.

)(35
:

/ .

:
1
1
1
1
) )r(A) ) = ( r(B) ) = ( r(C) ) + ( r(D
(
a
b
c
d

= rate

:
1
1
)r(A) = r(B
a
b
b
)r(B) = r(A
a

:
:
2A
Q + R

:
]d[R
dt

= rR

]d[Q
,
dt

rQ = +

]d[A
,
dt

rA = -

) (t ] [



) (R ) (Q )(A
:

)(36
:

/ .
]1 d[A] d[Q] d[R
=

=
2 dt
dt
dt

:
2H 2 + O 2
2H 2 O

:
] d[H 2
] d[O 2 ] d[H 2 O
= - 2
=
dt
dt
dt

] 1 d[H 2
]d[O 2 ] 1 d[H 2 O
=

=
2 dt
dt
2 dt

.


.
:
aA + bB
qQ + rR + ...

) (r :

)(37
:

/ .
]1 d[A
]1 d[B] 1 d[Q] 1 d[R

=-
=
=

a dt
b dt q dt r dt

r=-

]1 d[A
]1 d[B] 1 d[Q] 1 d[R
==
=
= r
a dt
b dt
q dt
r dt

:
(concentration) (time)-1

:
mol dm-3 s-1 = mol L-1 s-1 = M s-1
).(1 dm3 = 1 L


:
.
) (conductivity
.
) (angle of optical rotation
.


.

)(38
:

/ .

]1 d[A
]1 d[B] 1 d[Q] 1 d[R
==
=

a dt
b dt
q dt
r dt

= . r

) (tangent
) (-
( 2A
) Q + R
) (A ).(Q
) (-
) (initial rates
(rQ)i (rA)i


) (instantaneous rates

)(39
:

/ .

) (rQ) (rA
.

) : (- ) (A ) (Q

) ( 2A Q + R

)(40
:

/ .

.

.

.

) ([A2] [A]1 ) (t2 t1
) ( :
] [ A 2 ] - [ A1
t 2 - t1

) ( :
]d[A
dt

A - A
] [ 2 ] [ 1

t 2 - t1

] d[A

dt

.
) (-
.

)(41
:

/ .

) (
)] ([ A1 ] > [ A 2 d[A] < 0
dt

] [ A 2 ] - [ A1
]d[A
=

, =
dt
t 2 - t1

) (
)] ([ A 2 ] > [ A1

] [ A 2 ] - [ A1
=

t 2 - t1

] d[A

> 0

dt

]d[A

dt

) : (- .

)(42
:

/ .

)(
) (H2O2
.
( .
( ) (H2O2
.
:
140
0.45

20
0.15

] [O2 ] [ H 2O] [ H 2O2

,
,
t
t
t

)(s
][O2

) (20 s

).(140 s

( :

2H 2 O 2
2H 2 O + O 2

)(43
:

/ .
( ) 2H 2O + O2
( 2H 2O2

:
] [ H 2O] [ H 2O
] [O2

=
= 2

t t

=
) (20 s ) (140 s :
) [ O 2 ] ( 0.45 - 0.15
= rO2
) = ( 2.5 10-3 mol L-1 s -1
=
)(140 - 20
t

:
] [ H 2O
] [O2
-3
-1 -1
3

= 2
= 2 ( 2.5 10 ) = 5 10 mol L s
t
t
] [ H 2O2
] [O2
-3
-1 -1
3
= 2
= 2 ( 2.5 10 ) = 5 10 mol L s
t
t

)(
) (NH3 ) (N2 ) (H2 :
2NH3
3H 2 + N 2

(
:
)(H2) (N2
( )(.

)(44
:

/ .

(
] d[NH 3
dt
] d[H 2
=
dt
] d[H 2
=
dt

= rNH3rH2
rN 2

( :
] 1 d[NH 3 ] 1 d[H 2 ] d[H 2
=

=
2 dt 3 dt
dt

r=-

)(
) (
) (NO
): (3.5 10-2 Ms-1
(

( .
( .

(

:

)(45
:

/ .
)4NH3 (g) + 5O2 (g
) 4NO(g) + 6H 2 O(g

:
] 1 d[NH 3
]1 d[O 2 ] 1 d[NO] 1 d[H 2 O
==
=
4 dt
5 dt
4 dt
6 dt

r=-

( :

] 1 d[NH 3
]1 d[O 2 ] 1 d[NO] 1 d[H 2O
==
=

4 dt
5 dt
4 dt
6 dt

= r

:
] 1 d[NH 3
] 1 d[O 2
=
4 dt
5 dt
] d[O 2 ] (1/ 4 ) d[NH 3
=
dt
(1/ 5) dt
] d[O 2 ] 5 d[NH 3
=
dt
4 dt
d[O 2 ] 5
) = (3.5 10-2
dt
4
] d[O 2
= 4.38 10-2 M s -1
dt

( :

] 1 d[NH 3
]1 d[O 2 ] 1 d[NO] 1 d[H 2O

==
=
= r
4 dt
5 dt
4 dt
6 dt

) (NH3 ) (NO ):(1/4

]1 d[NH 3 ] 1 d[NO
=
4 dt
4 dt

)(46
:

/ .

) (NO :
]d[NO
= 3.5 10-2 Ms -1
dt

( :

] 1 d[NH 3
]1 d[O 2 ] 1 d[NO] 1 d[H 2 O

==
=
= r
4 dt
5 dt
4 dt
6 dt

] 1 d[NH3
]1 d[H 2 O
=
4 dt
6 dt
] d[H 2 O] 1/ 4 d[NH 3
=

dt
1/ 6 dt
] d[H 2 O] 6 d[NH 3
=
dt
4 dt
d[H 2 O] 6
= 3.5 10-2 = 5.25 10-2 Ms -1
dt
4

)(

:
)NO2 (g) + CO(g
) NO(g) + CO2 (g

:
] d[NO 2
] d[CO] d[NO] d[CO 2
==
=
dt
dt
dt
dt

rate = -

)(


:
1
)O 2 (g
) H 2 O(g
2

H 2 (g) +

)(47
:

/ .

:
( = -

] [H2
t

( = -

] [O2
t

( =

rate = -

rate = -

] [ H 2O
t

= rate

:
]1 [ O2 ] [ H 2O

=
t
(1/2 ) t

=-

] [ O2 ] [ H 2O
=-2
=
t
t

] [H2
t
] [H2
t

= raterate = -

)(

:
)1) H 2 (g) + I2 (g
) 2HI(g
)2) 4NH 3 (g) + 3O 2 (g
) 2N 2 (g) + 6H 2 O(g

)(48
:

/ .

)H 2 (g) + I2 (g
( 2HI(g) :

:
)= (H2
)= (I2
)= (HI

] [H2
t

] [ I2
t

] [ HI
t

:
] 1 [ HI

2 t

] [ I2
t

=-

] [H2
t

rate = -

.
(

) )(g) + 6H 2 O(g

) ( 4NH (g) + 3O (g
2N
2

:
)= (NH3
)= (O2
)= (N2

] [ NH 3
t

] [ O2
t

] [ N2
t

)= (H2O

] [ H 2O
t

)(49
:

/ .
] 1 [ NH 3
]1 [O2 ] 1 [ N 2 ] 1 [ H 2O
==
=
4 t
3 t
2 t
6 t

rate = -

)(

:
1) NO + O3
NO2 + O 2
2) 4NH3 + 5O 2
4NO + 6H 2 O
I 2
HI

] [O2

] [ NO 2

1
2

H2 +

] [ O3

=-

1
2

)3

] [ NO

1) rate = -

t
t
t
t
] 1 [ NH 3
] 1 [ O 2 ] 1 [ NO ] 1 [ H 2 O
2) rate = -
=-
=
=

5 t 4 t 6 t
4 t

] [H2
] [ I 2 ] [ HI
3) rate = - 2
= - 2
=
t
t
t

] [ ]

[d

)(
A + 2B
C :

) (A :
0.41
360

0.45
180

0.5
0

[A], M
)T (min.

( ) (A )(180 min.

)(50
:

/ .

( ) (A )(180 min
)(360 min.
( )( )(
( ) (B )(A
).(0 180 min

( ) (A ) (t = 0 ):(t = 180 min.

10- 4 mol L-1min -1

( 0.45 - 0.5) = 2.78

) (180 - 0

=-

] [A
t

rate = -

( ) (A ) (t = 180 min
): (t = 360 min

] [A
( 0.41 - 0.45) = 2.22 10- 4 mol L-1min -1
=t
) ( 360 - 180

rate = -

( )( ) (2.22 10 - 4
)( ) (2.78 10 - 4

.
( ) (B ) (A
): (0 180 min

)(51
:

/ .
]1 [ B
2 t

=-

] [A

t
1
rA = rB
2
2
rB = rA
1
rB = 2 2.77 10- 4
rB = 5.54 10- 4 mol L-1min -1

)(
:

)CO(g) + NO2 (g
) CO 2 (g) + NO(g

[CO] = [NO2] = 0.1 mol/L

) (25 s
[CO] = [NO2] = 0.025 mol/L :
25
0.025
0.025

0
0.1
0.1

Time , s
][CO
][NO2

( ][NO2
( ][CO2
( ][NO2
( ][CO2
( )( )(

( ]: [NO2

)(52
:

/ .
[ NO 2 ] = [ NO 2 ]f - [ NO 2 ]i

[ NO 2 ] = 0.025 - 0.1 = - 0.075 mol/L

( ]: [CO2
[ CO 2 ] = [ CO 2 ]f - [ CO 2 ]i

[ CO 2 ] = 0.075 - 0 = 0.075 mol/L

( ][NO2
10-3 mol L-1s-1

( - 0.075) = 3
) ( 25 - 0

=-

] [ NO2
t

rate = -

( ][CO2
10-3 mol L-1s-1

( 0.075) = 3
) ( 25 - 0

] [ CO 2
t

rate = -

( )( )( )(NO2
) .(CO2
.
.
= CO ) = (NO2
) = (CO2 ) (NO :
] [ NO
t

] [ CO 2
t

] [ NO 2

=-

] [ CO

t
t
= rNO2 = rCO2 = rNO

rCO

)(53
:

/ .

= rNO2 = rCO2 = rNO

(r

CO

.
)(
:
)2N 2O5 (g
) 4NO 2 (g) + O2 (g

) (N2O5 :
)(0.048 mol L-1 s-1
:
( )(NO2
( ).(O2

(r ) = (r ) = r

O2

NO2

1
4

N 2 O5

1
2

( ): (NO2
r

1
4 NO2

1
2 N 2 O5

rNO2 = 42 rN2O5
) (0.048

4
2

= rNO2

rNO2 = 0.096 mol/L s

)(54
:

/ .

( ): (O2
= rO2

1
2 N 2 O5

rO2 = 12 0.048
rO2 = 0.024 mol/Ls

)(
:
)N 2 (g) + 3H 2 (g
) 2NH3 (g

(
( ) (H2 ) (- 0.6 mol/L
).(NH3

( :
] 1 [ H 2 ] 1 [ NH 3
=
3 t
2 t

=-

] [ N2
t

rate = -

( ( N (g) + 3H (g) 2NH (g) ) :

3

) (NH3 ) (H2
) (- 0.6 mol/L :

)(55
:

/ .
] 1 [ H 2 ] 1 [ NH 3
-
=

3 t 2 t
] 1 [ H 2 ] 1 [ NH 3
-
=

3 t 2 t
1
1
)] - ( [ H 2 ]) = ( [ NH 3
3
2
2
)] [ NH 3 ] = ( [ H 2
3
2
) [ NH 3 ] = ( - 0.6
3
[ NH 3 ] = 0.4 mol/L

)(
)N 2 O4 (g
2NO 2 (g) :

) (NO2 ) (0.05 molar ) (0.06 molar

).(20 s
( ).(NO2
( ) (NO2 .
( .
( ).(N2O4

( ): (NO2
[ NO2 ] = [ NO2 ]f - [ NO2 ]i

[ NO2 ] = 0.06 0.05 = 0.01 molar

)(56
:

/ .

( ) (NO2 :
10-4 molar s-1

( 0.06 - 0.05) molar = 5

20 s
( 0.06 - 0.05) molar = 3 102 molar min -1
=
( 20 /60 ) min

] [ NO 2
t
] [ NO 2
t

= rate
= rate

(
) ) 2NO2 (g
) ( N 2O4 (g :
] 1 [ NO 2

2 t

] [ N 2O4
t

rate = -

( ) (N2O4
) ) 2NO 2 (g
) ( N 2O4 (g :

] [ N 2O4
] 1 [ NO 2

= 2 t
t
1
] ( [ NO2 ]) = - [ N 2O4
2
1
)] - [ N 2 O 4 ] = ( [ NO 2
2
1
)] - [ N 2 O 4 ] = ( [ NO 2
2
1
) - [ N 2 O 4 ] = ( 0.06 - 0.05
2
) [ N 2O 4 ] = ( 5 103 molar

)(57
:

/ .

)(
)C2 H 4 (g) + 3O2 (g
2CO2 (g) + 2H 2 O(g) :

(
( ) (O2 ) (0.6 mol/L s
).(C2H4
( )(CO2
( ).(H2O

( :
)+ 3O 2 (g
) ) 2CO 2 (g) + 2H 2 O(g

)( C H (g
4

] 1 [ O 2 ] 1 [ CO 2 ] 1 [ H 2 O

=
=

3 t 2 t 2 t

=-

] [ C2 H 4
t

rate = -

(
:
]1 [ O 2 ] 1 [ CO 2 ] 1 [ H 2 O
=
=
t
3 t
2 t
2 t
1
1
1
rateC2 H4 = rO2 = r CO2 = rH2O
3
2
2
=-

] [ C2 H 4

): (C2H4

rate = -

)(58
:

/ .

1
rO
3 2
1
= rateC2 H 4
0.6 = 0.2 mol/L.s
3
= rateC2 H 4

( ): (CO2
1
rH O
2 2

CO 2

1
1
rO2 = r
3
2

= rate C2 H4

1
1
rO2 = r CO2
3
2
1/ 3
= rCO2
rO
1/ 2 2
2
rCO2 = rO2
3
2
rCO2 = 0.6 = 0.4 mol/L.s
3

( ): (H2O
1
rH O
2 2

CO 2

1
1
rO2 = r
3
2

= rateC2 H4

1
1
rO2 = rH2O
3
2
1/ 3
= rH2O
rO
1/ 2 2
2
rH2O = rO2
3
2
rH2O = 0.6 = 0.4 mol/L s
3

)(
)4NH3 (g) + 3O 2 (g
2N 2 (g) + 6H 2 O(g) :

) (1.4 mol/L s :

)(59
:

/ .

(
( O2
( NH3

2N 2 (g) + 6H 2 O(g) ) :
) ( 4NH3 (g) + 3O 2 (g :
] 1 [ NH 3
]1 [O2 ] 1 [ N 2 ] 1 [ H 2O
==
=
t
3 t
2 t
6 t
4
1
1
1
1
rate = rNH3 = rO2 = rN2 = rH2O
4
3
2
6
rate = -

(
1
1
rN 2 = rH 2O
2
6
6
6
rH 2O = rN 2 = 1.4 = 4.2 mol/Ls
2
2

( ): (O2
1
1
rN2 = rO2
2
3
3
3
rO2 = rN2 = 1.4 = 2.1 mol/Ls
2
2

( )(NH3
1
1
rN2 = rNH3
2
4
4
4
rNH3 = rN2 = 1.4= 2.8 mol/Ls
2
2
3.

)(60
:

/ .

)(
:

)N 2 (g) + 3H 2 (g
) 2NH3 (g

) (0.3 mol/L s
.

) :

)(g
) 2NH3 (g

( N (g) + 3H :

1
1
rH2 = rNH3
3
2

= rN2

:

1
1
rH2 = rNH3
3
2
0.3

) ( 12
) ( 13

= rH2

3
0.3
2
rH2 = 0.45 mol/Ls
= rH2

1
rNH
2 3
1
rN2 = 0.3
2
rN2 = 0.15 mol/L s
= rN2

)(
:
)CO(g) + NO 2 (g
) CO 2 (g) + NO(g

:
[NO2] mol/L
0.067
0.05

)Time (s
10
20

)(61
:

/ .

: NO2
] [ NO 2
0.05 0.067
3
rate = -
=
= 1.7 10 mol/L s
20 10
t

)(
:
)N 2 O 4 (g
) 2NO 2 (g

:
[N2O4] mol/L
0.07
0.05

)Time (s
10
20

[NO2] mol/L
0.06
0.1

( ) (N2O4 )(10 20 s
( ) (NO2 ).(10 20 s

( ) (N2O4 ): (10 20 s
)N 2 O 4 (g
) 2NO 2 (g
0.05 0.07
3
=
= 2 10 mol/Ls
20 10

] [ N 2O4
t

rN2O4 = -

( ) (NO2 ).(10 20 s
0.1 0.06
3
=
= 4 10 mol/Ls
20 10

] [ NO 2
t

= rNO2

)(62
:

/ .

) (NO2
) (N2O4
) ) 2NO 2 (g
) ( N 2O4 (g

) (NO2 ): (N2O4
)N 2 O 4 (g
) 2NO 2 (g
] [ N 2O4
] 1 [ NO 2
=2 t
t
] [ N 2O4
] [ NO 2
= 2
t
t

: :
)N 2 O 4 (g
) 2NO 2 (g
] 1 [ NO 2
t
2 t
0.05 0.07 1 0.1 0.06
-3
rate =
=
= 2 10 mol/L.s
20 10 2 20 10
=

] [ N 2O4

rate = -

)(
)N 2 (g) + 3H 2 (g
2 NH3 (g) :

( .
( ) (H2
) (N2 ).(0.3 mol/Ls
( ) (H2 ) (- 0.6 mol/L s
)(NH3

)(63
:

/ .

(
) ( N (g) + 3H (g:
) ) 2 NH (g
3

] [ N 2 ] 1 [ H 2 ] 1 [ NH3
==
t
3 t
2 t

rate = -

:
1
1
rH 2 = rNH3
3
2

= rate = rN2

( ) (H2 )(N2
) (0.3 mol/Ls :
1
r
) 3 ( N2
= 3 0.3 = 0.9 mol/L s

= ) rate( H2
rH2

( ) (NH3 ) (H2
) (- 0.6 mol/L s :

)(64
:

/ .
] 1 [ H 2 ] 1 [ NH 3
=
3 t
2 t
1
1
] - [ H 2 ] = [ NH 3
3
2
1/3
[ NH 3 ] = -
] [H2
1/2

2
] [ NH 3 ] = [ H 2
3
2
[ NH 3 ] = - ( - 0.6 ) = 0.4 mol/L
3
-

)(
) (Li ) (HCl
) (0.075 mol/L ) (9 min )(0.0534 mol/L
( )(mol/L min
( )(mol/L s

( ): (mol/L min
= 4 10-5 mol/L min

) ( 0.0534 - 0.075
9

= -

] [ HCl
t

rate = -

( ): (mol/L s
= 4 10-5 mol/L min

) ( 0.0534 - 0.075
9 60

= -

] [ HCl
t

rate = -

)(65
:

/ .

)(
) (2.7 g
) (3 min
) (1.35 g )) (mol/L s
= .(27

:
m
2.7
=
= 0.1mol
Aw 27

= n Al

:
m 1.35
=
= 0.05 mol
Aw
27

= n Al

:
[ Al] = 0.05 0.1 = 0.05 mol

:
)(- 0.05
= 2.78 104 mol/L s
3 60

=-

] [ Al
t

rate = -

)(

:

)(66
:

/ .
N 2 + 3H 2
2NH3
2H 2 + O2
2H 2 O
NO + O3
NO 2 + O 2
2N 2O5
4NO 2 + O 2

2H 2 + O 2
2H 2O

N 2 + 3H 2
2NH3

] [O2
] 1 [H2
]1 [ H 2O
] [ N2
] 1 [H2
] 1 [ NH 3

= -
=
= rate = -
=

2 t
t
2
t
t
3 t
2 t

rate = -

1
1
rH2 = rO2 = rH2O
2
2

1
1
rH 2 = rNH3
3
2
NO + O3
NO 2 + O 2
= rN 2

] [ O3 ] [ NO2 ] [ O2
= -
=
=

t t t

2N 2 O5
4NO 2 + O 2

][ NO
t

rate = -

] 1 [ N2O5 ] 1 [ NO2 ] [ O2

=
=

2 t 4 t t

rNO = rO3 = rNO2 = rO2

1
1
rN 2O5 = rNO2 = rO2
2
4

rate = -

)(
) ( :
( -
A
B

(
(
(
(

] d [A

dt

)(67
:

/ .

( - :
2ICl + H 2
I 2 + 2HCl

:
]1 [ ICl
2 t

a) rate = -

] b) rate = - [ ICl] - [ H 2
2

]c) rate = [ I 2 ] + [ HCl

{}

]d) rate = [ ICl] + [ H 2 ] + [ I 2 ] + [ HCl

( - :

) B

( A :

] -t/ [ A

- [ B] /t

- [ A ] /t

( - :

) 4C

[ A ] /t

( A + 2B

:
( ) (C ) (4 ).(B
( ) (C )(B
( ) (B )(A
( ) (A ) (4 ).(C
CH 4 + 2O 2
( - CO 2 + 2H 2 O :

) (0.4 mol/L s ) (H2O :

( 0.4

( 0.2

( 0.8

( 0.08

)(68
:

/ .

( - :

) (10 20 s ) (mol/L s

( 0.0025

( 0.005

( 0.0075

( 0.015

(- ) (-
) (mol/L s ) (0.05 mol/L :
( 0.015

( 0.0025

( 0.005

( 0.0075

( -
:
( .
(
( .
(

)(69
:

/ .

( :
2NO + F2
2NO2 F

F2 ) (0.2 mol/L s
) (NO2F ): (mol/L s
( 0.1

( 0.2

( 0.4

( 0.04

)(70
:

/ .

)( )(Measurement of Reaction Rate

.

.
) (
)(

.
:





.

....

)(71
:

/ .

.
:

:



.

)(72
:

/ .

) (ethyl acetate
.
:
CH 3CH 2 OH + CH 3COOH
 
acetic acid

ethyle alcohol

H
CH 3CH 2 COOCH 3 + H 2O


ethyl acetate

.


)(
.



.
) (N2O5
:
) 2 N 2O5 (in CCl4
) 4 NO 2 (in CCl4 ) + O 2 (g

)(73
:

/ .

) (manometer ).(-

) : (- ) (N2O5

) (N2O5 ) (NO2
) (O2
) (O2 .

:
( )(electrical conductivity
( )(refractive index
( )(spectroscopy

)(74
:

/ .

( )(mass spectroscopy
( )(chromatography

.


.

.


:
2NH3
N 2 + 3H 2

) 2 ( ) (2NH3
) 4 ) .(3H2 + N2
) (2.00 atm ) (25 % ) 1/4 (
) .(2.50 atm

)(75
:

/ .

) (50 % ) (3.00 atm

).(-
)(-

)(atm
0
25
50

)(atm
2.00
1.50
1.00

)(atm
0
0.25
0.50

)(atm
0
0.75
1.50

)(atm
2.00
2.50
3.00

:
N 2 + 3H 2
2NH3

) (NH3, H2, N2
(0, 3, 1) : ) (25 %
) (N2 ) (H2 )(3.50 atm
) (50 %
) (3.00 atm ).(-
)(-

)(atm
0
25
50

)(atm

)(atm

)(atm

)(atm

3.00
2.25
1.50

1.00
0.75
0.50

0
0.50
1.00

4.00
3.50
3.00

)(76
:

/ .

.

.






.

.
CH3 Br + H 2 O
CH3OH + HBr

) (NaOH ) (HBr
) (CH3Br .

)(77
:

/ .

) (OH-
) (OH-
): (HCl
CH3Br + OH -
CH3OH + Br -

) (HCl ) (OH-
) (OH-
CH3Br .
.
. :
( ) (
:
CH3COOH + C2 H5OH
CH3COOC2 H5 + H 2O

.
( :
CH3COOC 2 H 5 + H 2O
CH 3COOH + C 2 H 5OH

)) (
(
.
( :
CH3COOC2 H5 + OH -
CH 3COO- + C2 H5OH

)(78
:

/ .

.
) ( )(OH-
).(HCl


.

.

) (10-12


.

.
" "t
.

)(79
:

/ .
)( :
- .
- .
- .
- .
- .

)(80
:

/ .

)(

:






:
.

.

:
:


.
: :
)N 2 (g) + 3H 2 (g
) 2NH3 (g

)(81
:

/ .

:
:

) (
.
: :
)2H 2 O 2 (L
) 2H 2 O(L) + O 2 (g

) (


.



.

:
(
( .
(

)(82
:

/ .

(
( .
( .
( ) ( )
(inhibitors
( .

:
Dependence of Reaction Rate on Nature of Reactants



)
(
.

:
.
.

)(83
:

/ .

.

.

) (Na )(Zn
) (Sn
) (HCl

. .


.


.


.

)(84
:

/ .

.
) ( :
) (NaCl
) (.

)(.
) (Fe2+ ) ( MnO -4
) ( C2O2-4 ) : ( MnO -4
5Fe 2+ + MnO-4 + 8H +
5Fe3+ + Mn 2+ + 4H 2 O
5C2 O 2-4 + 2MnO-4 + 16H +
10CO 2 + 2Mn 2+ + 8H 2O

) ( C O .
24

.
:
2Na + 2H 2 O
2NaOH + H 2
Mg(OH) 2 + H 2
Mg + 2H 2 O

)(85
:

/ .

.

.
) (K2SO4
Ba(NO3)2
.

) (BaSO4 :
)Ba(NO3 ) 2 (aq) + K 2SO 4 (aq
) 2KNO3 (aq) + BaSO4 (s

:
H 2 + F2
2HF :

2H 2 + O2
2H 2 O

.

.

)(86
:

/ .

) . ( G = -


.

) (H2 ) (O2 ) (H2O

) (436 kJ/mol ) (H-H
) (498.3 kJ ) (O-O
.
) (F-F )) (157 kJ/mol
.(O-O
) (H2 )(O2
.
.
.
.
( :

)(87
:

/ .
1) H + + OH -
H2O
2) 2Fe + O 2
2FeO
3) CH 3COOH + CH 3OH
CH 3COOCH 3 + H 2 O

( .
( :
1) H 2 + Cl 2
2HCl
2) H 2 + Br2
2HBr
3) 3H 2 + N 2
2NH 3

(
.
Br2 ) ( Cl2
.

)(88
:

/ .

- ) (
) (

.
:

.
) (HCl
) (Na2CO3
.
.
)(


.
) (

.

)(89
:

/ .
( : .

(

.
( :
( )(0.2 M
( ).(0.2 M
:

.
-




.
) (phase
)(Homogeneous

)(90
:

/ .

).(Heterogeneous
-





.

" "
" :
)(
.



.

)(91
:

/ .

.
:


.


.
( : .

:
)ZZX 2NH 3 (g
N 2 (g) + 3H 2 (g) YZZ

)(92
:

/ .

) (k ).(-

) : (- .

.


.

.
. ) (T1

.

)(93
:

/ .

.Ea ) (T2

.
).(-

) : (-
.
.

) (-
) (T1 ) (T2 ) (T2
.
.
.

)(94
:

/ .

)(Activation Energy

.
) (activation energy ) (Ea .

.

.


) (energy barrier of activation
.
).(-

)(95
:

/ .

) : (- .

) (A
) (D ) (B

) (activated state ) (transition state

. ) (AB
) (Ea1 :
) (A

) (B
.
.

)(96
:

/ .

)(ABD
) (A ) (D

) (Ea1

) D

( A ) (EB

).(EA

E a1 = E B - E A
) (Ea2

) A

(D

:
Ea 2 = EB - ED

) (Ea2, Ea1 :
) E = ( E a1 - E a 2
E = E D - E A

) ( E
) ( H
.
)(-

) > ED

( EA

)(97
:

/ .

) : (- .

:
H = E D - E A

) ( E D > E A ) ( H
.

) (40 ) (200
/ ) (625 /
.

)(98
:

/ .

) (H2) (Cl2


)(.

)(

) (Cl
.
)Cl2 (g
) 2Cl(g
)2Cl(g) + H 2 (g
) 2HCl(g
) ) 2HCl(g
) ( 2Cl(g) + H 2 (g

.
.

) (Br2 ) (H2

)(99
:

/ .

.


.


.


.


.

)(100
:

/ .

The Arrhenius Equation

) (1889


:

k = A e-Ea /RT
) (ln :

lnk = ln A e-Ea /RT

Ea
RT

lnk = lnA -

:
) : (Ea .
) : (R ).(R = 8.314 J/mol K
) (T .
) : (A ) (collision frequency
) (frequency factor
.

)(101
:

/ .
Ea

ln k = lnA - RT

Ea

ln k = lnA
RT

) (A .

.

.

Ea

lnk = lnA - RT

Ea

lnk
=
lnA

RT

) (y = a x + b

:
Ea 1

R T

lnk = lnA -

) (ln k ) (1/T
) (-Ea/RT
) (ln A ).(A

)(102
:

/ .

) (T1, T2
) (k1, k2 :
1

T1

Ea
R

lnk1 = lnA -

Ea 1

R T2

lnk 2 = lnA -

:
Ea 1

R T2
E 1
lnk1 = lnA - a
R T1
lnk 2 = lnA -

1
Ea 1
lnA +

R T1
T2
E 1 E 1
lnk 2 lnk1 = - a + a
R T2
R T1
Ea
R

1

T2

lnk 2 lnk1 = lnA -

1 Ea
T1 R
E 1 1
lnk 2 lnk1 = a
R T1 T2
Ea
R

= lnk 2 lnk1

:
k E T -T
ln 2 = a 2 1
k1 R T2 T1

)(103
:

/ .

)(

.
)CH 3CHO(g
) CH 4 (g) + CO(g

.
810
0.789

790
0.343

760
0.105

700
0.011

730
0.035

)T (K
K (mol-1 L s-1

1

T

Ea
R

lnk = lnA -

).(-Ea/R
810
0.789
- 0.240

790
0.343
- 1.070

760
0.105
- 2.250

1.32 10-3 1.27 10-3 1.23 10-3

730
0.035
- 3.35

1.37 10-3

)T (K
700
-1
-1
k (mol L s
0.011
ln k
- 4.51
-1
1.43 10-3
) 1/T (K

).(-

)(104
:

/ .

) )(-

:
)- 4.00 - ( - 0.45
= - 2.09 104 K
-3
-3
) (1.41 10 - 1.24 10

= slope

) (- Ea/R ) (Ea
:
Ea
R
) E a = - ( slope R

slope = -

) E a = - ( - 2.09 104 8.314

E a = 173762.6 J/mol
E a = 173.76 kJ/mol

)(105
:

/ .

)(

) (298 K ) (k1 = 3.46 10-2 s-1
) (k2 ) (350 K
).(Ea = 50.2 kJ/mol

k E T -T
ln 2 = a 2 1
k1 R T2 T1
3
k2

50.2 10 350 - 298

ln
=

-2
8.314 350 298
3.46 10
k2

ln
= 3.0
-2
3.46
10

k2
= e3.0
-2
3.46 10
k2
= 20.085
3.46 10-2
k 2 = 0.695

)(
) (k :
2HI
H 2 + I2

:
427

1.21 10-3

-4

410
5.53 10

-5

374
8.96 10

-5

342
1.24 10

-6

302
1.1810

)T (C
)K (mol-1 L s-1

)(106
:

/ .

(
( ).(400 C

(
) (575 K, 615 K
:
k E T -T
ln 2 = a 2 1
k1 R T2 T1
1.24 10-5
E a 615 - 575
ln
=

-6
1.18 10 8.314 615 575
1.13 10-4 E a
= 2.3522
8.314
-4
1.13 10 E a = 2.3522 8.314
2.3522 8.314
1.13 10-4
E a = 173063.6354 J
= Ea

E a = 173.064 kJ

( ) (400 C = 673 K
:

)(107
:

/ .
k E T -T
ln 2 = a 2 1
k1 R T2 T1
1.21 10-3 173063.6354 700 - 673
ln
=

k
8.314
700 673

1
ln (1.21 10-3 ) ln k1 = 1.19302

) ln k1 = 1.19302 ln (1.21 10-3

) ln k1 = 1.19302 (6.717135
ln k1 = 7.910155
ln k1 = 7.910155
k1 = 3.670 10- 4

)(
:
2ICl + H 2
I 2 + 2HCl

) (230 C ) (240 C )(0.163 L mol-1 s-1

) (0.348 L mol-1 s-1 .
( ) (Ea .
( ).(A

)(108
:

/ .

(
k E T -T
ln 2 = a 2 1
k1 R T2 T1
E a 513 - 503
0.348
ln
=

0.163 8.314 513 503

0.75845 = 4.661 10-6 E a
0.75845
4.661 10-6
E a = 162723.0807 J
= Ea

E a = 162.7231 kJ
162.7231
= 39.230 kCal
4.148

= Ea

( ) (A :
1

T
162723.0807 1
ln ( 0.348 ) = lnA

8.314
513
1.05555 = lnA - 38.1524
lnA = 1.05555 + 38.1524
Ea
R

lnk = lnA -

lnA = 37.09685
A = 1.2911 1016 mol-1 L s -1

)(109
:

/ .

)(

) (27 C ).(37 C

k E T -T
ln 2 = a 2 1
k1 R T2 T1
E 310 - 300
2
ln = a

1 8.314 310 300

0.69315 = 1.2933 10-5 E a
0.69315
1.2933 10-5
E a = 53595.45349 J
= Ea

E a = 53.595 kJ

)(
:
)2HI(g
) H 2 (g) + I2 (g

) (182 kJ/mol
) (700 C ) (1.57 10-3 L mol-1 s-1
)(600 C

k = 1.19 10-4 mol-1 L s-1 :

)(110
:

/ .

)(
) (C2H5Cl ) (k
) (3.2 10-2 s-1 ) (550 C )(9.3 10-2 s-1

) (575 C
.

Ea = 59.0 kcal/mol :
)(
) (40 C
) .(20 C
.

Ea = 10.01 kcal/mol = 41.8 kJ/mol :

)(
) (25 k cal/mol
) (k ) (1.160 10-2 s-1
) .(349.5 K ).(A

A = 4.998 1013 s-1 :

)(111
:

/ .

-
Dependence of Reaction Rate on Concentration

) (
.

) (
.

. :
A
B + C

) (A ) (t1 [A]1 )(t2

) ([A]2 ) .(mol/L
) (A :
] [A
t

=-

[ A ]2 - [ A ]1
t 2 - t1

) (C, B
:
] [ C
t

] [ B
t

[C]2 - [C]1
t 2 - t1

[ B]2 - [ B]1
t 2 - t1

)(112
:

/ .

]) [A [ A ] =

) ([A]2 ) ([A]1
.
] [C
t

] [ B
t

)] ( [ A
t

.
:
)( :
AB
A + B

) : (-

)(113
:

/ .

) (-
) (AB
.
): (N2O5
)2N 2 O5 (g
) 4NO 2 (g) + O 2 (g

) .(N2O5


.
) (N2O5 )]([N2O5
.
) (0.160 M ) (0.80 M (0.80
) M ) (0.04 M
) (0.056 mol L-1 min-1 ) (0.028 mol L-1 min-1
) (0.028 mol L-1 min-1 ) (0.014 mol L-1 min-1
) (N2O5
).(-

)(114
:

/ .

) : (- ) (N2O5
.

) (.


).(rate law
) ) 4NO 2 (g) + O 2 (g
) ( 2N 2O5 (g :

] Rate = k [N 2 O5

)(N2O5
" "k
" "

)(115
:

/ .

.
.
(

( HCl ) (0.1 M ) (NaOH ).(0.1 M

( ) (HCl ) (0.2 M NaOH ).(0.1 M
: .
( : .

:
.

.
.

:
(
( .

)(116
:

/ .

" " :
"
".

.

) (a ) (A ) (b ) (B
) (c ) (C )(V
:
ZZX cC
aA + bB YZZ

) ( :

= k [A]a .[B]b

) ]( = k [A] .[B
b

)(117
:

/ .

.
)ZZX 2HI(g
H 2 (g) + I 2 (g) YZZ

.
.


.
)(
) (NO2
:
2NO 2
2NO + O 2

)(118
:

/ .

( ) (NO2
) (NO )(O2
( ) (NO2 )(4.0 10-13 mol L-1 s-1

) (NO ).(O2

( ) (NO2 :
] - [ NO 2
t

) (NO ) (O2 :
] [ NO ] [ O 2
,
t
t

( )(2NO2
) (2NO :
= 4.0 10-13 mol L-1s -1

] [ NO
t

] [ NO 2
t

) (NO ).(O2
) (NO
:
] 1 [ NO ] [ O 2

2 t t
] [ NO
] [O2
-13
-1 -1

= 2
= 4.0 10 mol L s
t
t
[ O 2 ] 1 [ NO ] 4 1013

=
=
= 2.0 10-13 mol L-1s -1
t
2 t
2

)(119
:

/ .

) (NO2 ) (NO
) (O2 :
O2

NO

NO 2

) ( 4.0 10 ) : ( 4.0 10 ) : ( 2.0 10

-13

-13

-13

) (2 : 2 : 1
) 2NO + O 2
. ( 2NO2

-

.
.
.

:
)ZZX 2HI(g
H 2 (g) + I 2 (g) YZZ

)(120
:

/ .

:
)ZZX 2NH3 (g
N 2 (g) + 3H 2 (g) YZZ

.


:
ZZX PCl3 + Cl2
PCl5 YZZ

)(121
:

/ .

-
) (
.

.
: .
- )(

).(catalyst


) (
)
- (
) (.

.

)(122
:

/ .

.

) (
.

)(H2O2

:
)2H 2O 2 (aq
) 2H 2 O(L) + O2 (g

) (MnO2

.




MnO2
)2H 2 O 2 (aq
) 2H 2O(L) + O 2 (g

)(123
:

/ .

)(KClO3
MnO2
)2KClO3 (s
) 2KCl + 3 O2 (g

.

)(-

) : (- ) ( H
.

)(124
:

/ .

(
:
3H 2 + N 2
2NH3

( .
( ) (MnO2
) (H2O2 :
MnO2
2H 2O 2
2H 2 O + O 2

( ) (Mn2+ ) (MnO4-
).(C2O42-

)(125
:

/ .

:
( ): (homogeneous catalysis
( ).(heterogeneous catalysis

:

.


) (SO3 )(H2SO4
):(SO2
)2SO 2 (g) + O2 (g
) 2SO3 (g

) (SO2 ) (O2 )(SO2

) (SO3

) (NO .
NO
)2SO 2 (g) + O 2 (g
)2SO3 (g

)(126
:

/ .

:
2NO + O 2
2NO 2
2NO 2 + 2SO 2
2NO + 2SO3
______________________________________
)2SO 2 (g) + O 2 (g
) 2SO3 (g

+ 2SO 2
) 2NO + 2SO3

( 2NO

:

) (phase
.
)MnO2 (s
)2H 2 O 2 (aq
) 2H 2O(L) + O 2 (g

)(127
:

/ .

) (adsorption
.

)(physisorption

) (physisorption
.
.
)(chemisorption

) (chemisorption
.

.


) (H2 ) (C2H4
.

)(128
:

/ .
Pt
CH 2 =CH 2 + H 2
CH3 -CH3

).(-

) : (-

)(129
:

/ .

)( :
.
)( :



.
)( :

.

.
)( :

.
)(.

)(130
:

/ .

:
- ) (Haber's process :
:
Fe
)N 2 (g) + 3H 2 (g
) 2NH3 (g

.
( ) (Ostwald Process )(HNO3

) (NH3 ) (O2
)(platinum-rhodium catalyst
): (800 C
Pt, Rh
)4NH 3 (g) + 5O 2 (g
) 4NO(g) + 6H 2 O(g
800 C

) (NO) (nitric oxide

) ( ) nitrogen
: (NO2) (dioxide
)NO(g) + O2 (g
) 2NO2 (g

)(131
:

/ .

) (NO2) (nitrogen dioxide

)(Nitrous acid) (HNO2
):(HNO3
)2NO 2 (g) + H 2O(L
) HNO2 (aq) + HNO3 (aq

:
)3HNO 2 (aq
) HNO3 (aq) + H 2 O (L) + 2NO(g

) (NO) (nitrogen dioxide

) ) HNO3 (aq) + H 2O (L) + 2NO(g

)( 3HNO (aq
2

)(NO2) (nitrogen dioxide

.
(

) (pollution
) (CO )(NO
.
) (Pt ) (Pd
) (transition metal oxide ) (CuO )(Cu2O3
) (CO2 ).(N2

)(132
:

/ .

:
(
) (
.
.
(

.
:
) (S
.
:

.




.
( :

)(133
:

/ .
( :
O3 + O
2O 2

:
1) O3 + NO
NO 2 + O 2
2) NO 2 + O
NO+O 2

) (NO
) (.
( :
2SO 2 + O 2
2SO3

:
1) 2NO + O 2
2NO 2
2) 2NO2 + 2SO 2
2SO3 + 2NO

) (NO
) (.

)(134
:

/ .

-

. : .
( :
(
.
( .
(
.
(
.
( .
( ) (C2H4
) (C2H6 .
(
. .
(
.
) (Ea . ) . ( E
( ) (NO
.

.

)(135
:

/ .

)(Law of Mass Action

)(
.

"
)(
)(".

:
ZZX cC + dD
aA + bB YZZ

) (rf :
]rf [ A ] [ B
a

]rf = k f [ A ] [ B
a

) (kf .
) (C ) (D
) (rb :
] rb [ C] [ D
c

] rb = k b [ C] [ D

) (kb .

)(136
:

/ .

)( :
rf = rb
] k f [ A ] [ B] = k b [ C ] [ D
c

:
] k f [ A ] [ B] = k b [ C ] [ D
c

k
kf
a
b
c
d
] [ A ] [ B] = b [ C ] [ D
kb
kb

] [ C] [ D
]k f [ A ] [ B
=
k b [ A ]a [ B]b [ A ]a [ B]b
d

]k f [ C] [ D
=
k b [ A ]a [ B]b
d

) (kf/kb
" "Kc
"."Kc
:
]k [ C] [ D
= Kc = f
k b [ A ]a [ B]b
d

)(137
:

/ .

) ( .
).(mol L-1 s-1
:
:
A + B
C + D
][X

][Y

] [X ] [Y
.

) (V :
( .
]d[X
dt

V=-

( :
]d[Y
dt

=V

) C + D
( A + B

)(138
:

/ .
]d[X
dt

r=-

]d[Y
dt

=r
]d[X
]d[X

=, r = V
dt
dt

]d[Y
]d[Y

=, r
= V

dt
dt

. :
aA + bB
cC + dD

" "A
" "B " "A
" "B " "C ") "D
C D
( " "A " "B

).(-

)(139
:

/ .

) : (-

) ( aA + bB cC + dD
) (A ) (B
) (C ) (D :

) (A

]d [A
dt

) (B

]d [ B
dt
]d [ C
= rate
dt
]d [ D
= rate
dt

) (C
) (D

rate = -

rate =

( :

)(140
:

/ .

:
(

) ( aA + bB cC + dD

:
] rate = d [C] rate = - d [ B] rate = - d [ A
dt

dt

dt

]d [ D
= rate

dt

) (stoichimetry
) (a, b, c

.
( )
(

) ( aA + bB cD + dD
) (

].[B], [A

): (-

)(141
:

/ .

) : (- .

) ( A ) ( t )(t1, t2
) (t3, t4



) cC + dD
( aA + bB :
y

]rate = k A [ B
x

: k ) (x ) (y
. ] [A ] [B
) (A) (B.

)(142
:

/ .

(
.
:
:
A + 2B
3C + 5 D

) (A
) (B ) (C ) (D :
] 1 d [ B] 1 d [ C ] 1 d [ D
=
=
2 dt
3 dt
5 dt

=-

]rate = k A [ B

]d [A
dt

( ) (A ) (3.5 10-2 ) (2.85 10-2

) (23 min .
( ) (k :
) (3 10-7 s-1 ) (0.1 mol L-1
:

( mol L-1 s-1

( mol ml-1 s-1

( mol L-1 s-1

)(143
:

/ .

:


.

) (autoinhibition
).(autocatalysis


:
( ) (retarder or inhibitor
).(negative catalysis
( ) (accelerator
).(positive catalysis

).(rate law

)(144
:

/ .

) (overall reaction
.
) : (-


Experimentally determined rate law
)(at constant temperature

Overall reaction

]d[HI
} = 2 {k[H 2 ][I 2 ] - k ' [HI]2
dt
]d[HBr
2k [H 2 ].[Br2 ]1/2
=r
=
dt
] 1 + k ' [ HBr ] /[Br2
=r

d[Cl- ] k OCl I
=r
=
dt
OH -
]d[(CH 3 ) 2 CO
=r = k 4 [ (CH 3 ) 2 CO ] OH -
dt

H 2 + I 2
2HI
H 2 + Br2
2HBr
-

OH -

OCl + I
OI + Cl
-

1.
2.
3.

4. (CH 3 )2CO + 3Br2 + H 2O

-

OH

CH 3COOH + CHBr3 + 3HBr

) (-



.

)(145
:

/ .

.

+ Br2
) 2HBr

(H

) 2HI

+ Cl-

OH
+ H 2 O
CH 3COOH + CHBr3 + 3HBr

( OCl + I OI

OH -

( H 2 + I2

( (CH ) CO + 3Br
3 2

) (ki ) (k'i
.
) (-
(

:

H 2 + I 2
2HI,

H + Br
2HBr
2
2

OH
+ H 2 O
CH 3COOH + CHBr3 + 3HBr

+ Br2
) 2HBr

( (CH ) CO + 3Br

3 2

( H .

)(146
:

/ .

+ I 2
2HI, H 2 + Br2
2HBr

( H

]d[HI

'
2
r
=
=
2
k[H
][I
]
k
][HI
{
},
2
2

dt

]d[HBr
2k [H 2 ].[Br2 ]1/2

] r = dt = 1 + k ' [ HBr ] /[Br

2

:
OH
OCl- + I-

OI- + Cl

OH CH ) CO + 3Br + H O

CH
COOH
+
CHBr
+
3HBr

3 2
2
2
3
3

d[Cl- ] k OCl I
= r

=
,
dt
OH -

r = - d[(CH 3 ) 2 CO] = k [ (CH ) CO ] OH -

3 2

dt

:
]d[(CH3 ) 2CO

= k [ (CH3 ) 2 CO] OH -
= rdt

)(147
:

/ .

) (Br2
.
(


:

d[Cl- ] k OCl I
= r

=
,
dt
OH -

r = - d[(CH 3 ) 2 CO] = k [ (CH ) CO ] OH -

3 2

dt

:
OH
OCl- + I-
OI- + Cl- ,

k
OCl
I
] d[Cl

=
= r

dt
OH -

OH
(CH3 )2 CO + 3Br2 + H 2 O
CH3COOH + CHBr3 + 3HBr,

r = - d[(CH3 ) 2 CO] = k (CH ) CO OH -

]

[4
3 2
dt

)(148
:

/ .

) ) (-


.

)(149
:

/ .

)(Order of Reaction

.
.


) (N2O5 ) (NO2 )(25 C
2N 2 O5
4NO 2 + O 2
0.040
1.4 10-6

0.080
2.8 10-6

0.020
0.70 10-6

-1

) [N2O5] (mol L
)Rate (mol L-1 s-1

2NO2
2NO + O2
0.040
3.0 10-13

0.080
12.0 10-13

0.020
0.75 10-13

][NO2
)Rate (mol L-1 s-1

) (N2O5
) (NO2
.

.
:
] rate [ N 2 O5 ] , rate [ NO 2

)(150
:

/ .

k :
] rate = k [ N 2 O5
] rate = k [ NO2

.
.
.


) (k
. .
) (k .

:
H 2 + I 2
2HI

) (400 C
I2 H2
:
] rate = k [ H 2 ][ I 2

)(151
:

/ .

) (H2 ) (I2
) (H2

.
)(HI
)( ) (H2 ) (I2 : [HI]2
2HI
H 2 + I2

:
2HI
H 2 + I2
]rate = k [ HI

)(
) (HI ) (8.0 10-6 mol L-1 s-1
) (HI ) (0.040 M
) (0.010 M HI

HI :
] rate = k [ HI

) (0.040 M :

)(152
:

/ .
] rate = k [ HI

2
2

) 8.0 10-6 = k ( 0.040

8.0 10-6 mol L-1s -1

mol2 L-2

) ( 0.040

=k

k = 5 10-3 L mol-1s -1

): ([HI] = 0.010 M
]rate = k [ HI

rate = ( 5 10-3 ) (0.010) 2

rate = 5 10-7 mol L-1s-1

:
) rate at ([HI] = 0.010
5 10-7
1
=
=
-6
rate at ([HI] = 0.040 ) 8.0 10
16

)(153
:

/ .

]rate = k A [ B
x

) (y), (x ) (A ) (B
3
.
:
A
B
] rate [ A

] rate = k [ A

) (x = 0
.
) (x = 1 .
) (x = 2 .
) (x = 3 .
) (x = 1/2 .

)(154
:

/ .

.
x
y
) ] ( rate = k A [ B ) (n

): (x, y
n=x+y
) (x ) (A ) (y
) .(B ) (k
.

) (
.

.

.

. :

)(155
:

/ .
dc1
) = f (c1 ,c 2 ...................,c n
dt

:
dc A
= K' caA c Bb .........c nN
dt

) ( aA + bB dD
] - d [ A :
dt

) ([ A ] = a, [ B] = b ) (D ) (t x
) (t ): (A
] d [a - x
dt

rate = -

: D
dx
dt

rate = -

)(156
:

/ .

:
:
2N 2O5
4NO 2 + O2

:
] d[N 2 O5
] = k [N 2 O5
dt

.
:
2NO 2
NO + O 2

:
] d[NO 2
= k [NO 2 ]2
dt

.

:
( C2 H 5 )4 NBr
( C2 H5 )3 N + C2 H5 Br

:
]d[C 2 H 5 Br
] = k [ C 2 H 5 Br ][ (C 2 H 5 )3 N
dt

)(157
:

/ .

): (720 K
CH3CHO
CH 4 + CO

:
]d[CH 3CHO
3/ 2
] = k [ CH 3CHO
dt

) .(3/2


.


.
) (k
) (pseudo order

:
+

H
C12 H 22 O11 + H 2 O + H +
C6 H12 O 6 + C6 H12 O 6

:
= k [ C12 H 22 O11 ][ H 2 O ] H +

] d [ C12 H 22 O11
dt

rate = -

)(158
:

/ .

] [ C12 H 22O11 ] [H+

] [H2O
.

] d [ C12 H 22 O11
= k [ C12 H 22 O11 ][ H 2 O ] H +
= ratedt

. . ] [H+
] [H2O
): (pseudo-first order
] = k [ C12 H 22 O11

] d [ C12 H 22 O11
dt

rate = -

) NO + O 2

) 4NO 2 + O 2

( 2N O
2

( 2NO

.
) (- .

)(159
:

/ .
) : (- .

0
1/2
1
3/2
2
2
3
3
3

dx
dx
= k(a - x)0
=k
dt
dt
dx
= k (a - x)1 2
dt
dx
)= k (a - x
dt
dx
= k (a - x)3/2
dt
dx
= k (a - x) 2
dt
dx
) = k(a - x) ( b - x
dt
dx
= k (a - x)3
dt
dx
2
) = k (a - x) ( b - x
dt
dx
) = k (a - x)2 ( b - x
dt

.




:
aA + bB + dD
qQ + rR +...

)(160
:

/ .

:
]1 [ A ] 1 d [Q

=
] = k [A] [ B] [ D
a dt
q dt

r=-

) (overall order of reaction

:
n=++

) (exponents

), ,

]1 [ A ] 1 d [Q

r
=
=
=
k
][A
B
D
[
]
[
]

a dt
q dt

) (A
) (B ) (D .
) (n :

.

)(161
:

/ .

).(Molecularity

)
... (
) (elementary reaction
.

.
)(
) (k :

]1 [ A ] 1 d [Q

=
] = k [A] [ B] [ D
= ra dt
q dt

) (rate constant
) (specific rate constant
:

)(162
:

/ .

(concentration)(1 n)(time)-1

:
(concentration)(1 n)(time)-1

( mol dm ) s
(
) = mol( ) ( dm

-1

s -1

) 1-n

) (1-n

-3

1-n

-3

n -1) -1

(dm3

(= mol

) 1-n

:
s-1
s -1

) (1 - n

) (1 - n

) (L
-1

) ( mol L
-1

(= mol

)1 - n

= mol(1 - n ) L( n - 1)s -1

:
1 -1) -1

s = s -1

(mol( ) dm3
1-1

mol(1-2) dm3( 2 -1)s -1 = mol-1 dm3 s -1

.

]1 [ A ] 1 d [Q
y
z
=
] = k [A]x [ B] [ D
= ra dt
q dt

) (r

)(163
:

/ .

]1 [ A ] 1 d [Q
y
z
=
] = k [A]x [ B] [ D
a dt
q dt

), y , z

= .r

( x

) (a, b, d

), y b , z d...

(x a

]1 d [Q
b
z
] = k [A]x [ B] [ D
q dt

= ] . r = - 1 [ A
a dt

) ( ) (- :

]d[HI

'
2
r = dt = 2 {k[H 2 ][I 2 ] - k [HI] } ,

]d[HBr
2k [H 2 ].[Br2 ]1/2

] r = dt = 1 + k ' [ HBr ] /[Br

2

)(164
:

/ .

d[Cl- ] k OCl I
= r

=
,
dt
OH -

r = - d[(CH 3 ) 2 CO] = k [ (CH ) CO ] OH -

3 2

dt

d[Cl- ] k OCl I
= r

=

dt
OH -

) (OCl

) (I- )(OH-

+ Cl-

( OCl + I OI
OH -

) (OH-
) ( n = x + y + z ): (n
n=x+y+z
n=1+1-1=1

OH
+ H 2 O
CH 3COOH + CHBr3 + 3HBr

( (CH ) CO + 3Br

]d[(CH 3 ) 2 CO

= k [ (CH 3 ) 2 CO ] OH -
= rdt

3 2

) (CH3COCH3 ) (OH-
:
n=1+1+0+0=2

)(165
:

/ .

)(166
:

/ .

)(rate constant
) (k

.
.

) (k


) (1 M
.

( .
( :

.


) (k .

)(167
:

/ .

)(Order of the Reaction

.
:
:
aA + bB
qQ + rR

:
y

] rate = k [ A ] [ b
x

) (x ) (order of reaction )(A

) (y ) .(B
) (overall reaction order
) (n :
n=x+y
) (x ) (y
.

)(168
:

/ .

) (a ) (b .

:
( )(Zero-order Reactions
( (First- Order Reactions) :
( (Second- Order Reactions) :
- (Third Order Reactions) :

.

) ( aA + bB qQ + rR
) (x = 0 ) (y = 1
) (A
) (A ) (B
:
]rate = k [ A ] [ b ] = k [ B
1

.
) (x = 1 ) (y = 1 :

)(169
:

/ .
]rate = k [ A ][ B

).(second order reaction

)(170
:

/ .

( ) (k :
) (k
:
A
B
] rate (mol L-1 s -1 ) = k [ A

) rate (mol L-1 s-1

][A

=k

) rate (mol L-1 s-1

=k
1
-1 -1
) k = ( mol L s

:
dx
= k (a - x)0
dt
dx mol L-1
= k
=
= mol L-1s -1
dt
s

:
dC
0
)= k (C
dt
dC mol L-1
=k=
= mol L-1s -1
dt
s
-

)(171
:

/ .

) (mol/L s
).(mol/L min.
( ) (k :
) (k :
A
B
] rate (mol L-1 s-1 ) = k [ A
) rate (mol L -1 s-1
=k
) [ A ] (mol L-1
k = s -1

:
dx
= k(a - x)1
dt
dx
mol L-1s 1
dt
=k
=
= s -1
-1
)(a - x
mol L

) (s-1
).(min-1
( ) (k :
A
B
] rate (mol L-1 s-1 ) = k [ A

) rate (mol L-1 s-1

) (mol 2 L-2

][A

=k

k = L mol-1 s -1

)(172
:

/ .

:
dx
= k(a - x) 2
dt
dx
mol L-1s -1
dt
= k = 2
= mol-1 L-1 s -1
2
-2
)(a - x
mol L

) (L/ mol s
).(L/ mol min
( ) (k :
B
A
] rate (mol L-1 s-1 ) = k [ A

) rate (mol L-1 s-1

) (mol 32 L-32

][A

=k

k = L2 mol-2 s -1

) (L2/ mol2 s
).(L2/ mol2 min

)(173
:

/ .

( ) (k :
B
A
] rate (mol L-1 s-1 ) = k [ A

) rate (mol L-1 s -1

) (mol 43 L- 43

][A

=k

k = L3 mol-3 s -1

) (L3/ mol3 s
).(L3/ mol3 min
( ) (k ): (1/2
A
B
] rate (mol L-1 s -1 ) = k [ A

1/ 2

) rate (mol L-1 s-1

) (mol1/2 L- 1/2

][A

1/2

=k

k = mol1/2 L-1/2 s -1

) (1/2
) (mol1/2/L1/2 s
).(mol1/2/L1/2 min.

)(174
:

/ .

( ) (k ): (3/2
A
B
] rate (mol L-1 s -1 ) = k [ A

3/ 2

) rate (mol L -1 s -1
) (mol3/2 L- 3/2

][A

3/2

=k

k = L1/2 mol- 1/2 s -1

) (3/2
) (L1/2/mol1/2 s
).(L1/2/mol1/2 min.

" "k " "n :
-1

) ( concentration ) . ( time
1-n

) (
.
.
) (- .

)(175
:

/ .
) : (-

0
1
2
3
4
1/2
3/2

k
mol L-1 s-1
M s-1
s-1
mol-1 L s-1
M-1 s-1
mol-2 L2 s-1
M-2 s-1
mol-3 L3 s-1
M-3 s-1
mol1/2 L-1/2 s-1
M1/2s-1
mol-1/2 L1/2 s-1
M-1/2 s-1

)(176
:

/ .

)(Determining the Rate Law

.

) (initial rate

) (concentration initial


.
).(-


. .

)(177
:

/ .

) : (-
.

)(178
:

/ .
) : (-

] k [ N 2 O5

2N 2 O5
4NO 2 + O 2

] k [ H 2O2

2H 2 O 2
2H 2 + O 2

] k [SO 2 Cl2

SO 2 Cl2
SO 2 + Cl2

]k [ C2 H 5Cl

C2 H 5Cl
C2 H 4 + HCl

] k [ NO ][ O3

] k [ NO 2

] k [ NO 2 ][ CO
] k [ H 2 ][ I 2
] k [ C 2 H 4 Br2 ][ KI

NO + O3
NO 2 + O 2
2NO 2
2NO + O 2
NO 2 + CO
NO + CO 2
H 2 + I 2
2HI
C2 H 4 Br2 + 3KI
C 2 H 4 + 2KBr + KI3

[CH3COOC2 H5 ] OH -

CH 3COOC 2 H 5 + OH -
CH 3COO- + C2 H 5OH

] k [ NO ] [ O 2

2NO + O 2
2NO 2

] k [ NO ] [ Cl2

2NO + Cl2
2NOCl

] k [ NO ] [ Br2

2NO + Br2
2NOBr

] k [ NO ] [ H 2

2NO + 2H 2
N 2 + 2H 2O

] k [ CO ][ Cl2

CO + Cl 2
COCl2

] k [ COCl2 ][ Cl2

COCl2
CO + Cl2

3/2
1/2

)(179
:

/ .

)(
) (NO ) (H2
:
2NO + 2H 2
N 2 + 2H 2 O

:
3
0.40
0.20
6.40 10-3

2
0.20
0.40
1.28 10-2

1
0.20
0.20
3.2 10-3

Exp.
][H2
][NO
rate mol L-1 s-1

: ): (NO

:
y

] rate = k [ NO] .[ H 2
x

) (1, 2 )(NO
) (0.20 ) (0.40 ) (H2 ) (0.20 :

)(180
:

/ .
y

] rate = k [ NO] .[ H 2
x

)6.40 10-3 = k (0.40) x (0.20) y ......................(1

)3.2 10-3 = k (0.20) x (0.20) y ..........................(2

) (1 ) (2 :
6.40 10-3 k (0.40) x (0.20) y
=
3.2 10-3
k (0.20) x (0.20) y
x

0.40
=2

0.20
x

)2 = ( 2

) log ( 2 ) = log ( 2

) log ( 2 ) = x log ( 2
) log ( 2
) log ( 2

=x

x=1

).(NO

:
) (NO ) (0.20 ) (0.40
) (H2 ) (0.20
) (3.2 x 10-3 )(6.40 x 10-3
6.40 10-3

= 2

-3
3.2 10

).(NO

)(181
:

/ .

: ): (H2

:
y

] rate = k [ NO] .[ H 2
x

) (1, 3 ) (H2
) (0.20 ) (0.40 ) (NO ) (0.20 :
y

] rate = k [ NO] .[ H 2
x

)6.40 10-3 = k (0.20) x (0.40) y ......................(1

)3.20 10-3 = k (0.20) x (0.20) y ..........................(2

) (1 ) (2 :
y

] rate = k [ NO] .[ H 2
x

)6.40 10-3 = k (0.20) x (0.40) y ......................(1

)3.20 10-3 = k (0.20) x (0.20) y ..........................(2
6.40 10-3
k (0.20) x (0.40) y
=
3.20 10-3
k (0.20) x (0.20) y
y

0.40
=2

0.20

) log 2 = log ( 2

) log 2 = y log ( 2
) log ( 2
) log ( 2

=y

y=1

)(182
:

/ .

).(H2

:
) (0.20 ) (0.40
) (NO ) (6.40 x 10-3
): (1.28 x 10-2
1.28 x 102

=
2

-3
6.40 10

)(H2

) (H2, NO :
1+1=2
:
]rate = k [H2] . [NO
)(

:
2NO 2
2NO + O 2

)(rate = 1.4 10-3 mol L-1 s-1

) (NO2 ) .(0.500 M

)(183
:

/ .

) (NO2 (0.250) M
(0.125) M .

)(0.500 M
:
rate = k [NO 2 ]2
2

s-1

) 1.4 10-3 = k ( 0.500

1.4 10 ) mol L
(
=k
-3

-1

mol2 L-2

) ( 0.500

k = 0.0056 L mol-1 s -1

] rate = k [NO 2

0.250 M

) rate = 0.0056 ( 0.250

rate = 3.5 10-4 mol L-1 s -1

rate = k [NO 2 ]2

0.125 M

) rate = 0.0056 ( 0.125

rate = 8.75 10-5 mol L-1 s -1

)(184
:

/ .

)(
:
2 NO + Cl2
2 NOCl

:
3
0.760
0.760
4.0 10-2

2
0.380
0.760
1.0 10-2

Exp.
)[NO] (mol L-1
)[Cl2] (mol L-1
)rate (mol L-1 s-1

1
0.380
0.380
5.0 10-3

: ): (NO

:
y

] rate = k [ NO] .[ Cl2

x

) (2, 3 )(NO
) (0.380 ) (0.760 ) (Cl2 ) (0.760 :
y

] rate = k [ NO] .[ Cl2

x

)4.0 10-2 = k ( 0.760 ) . ( 0.760 ) ..............................(1

y

)1.0 10-2 = k ( 0.380 ) . ( 0.760 ) ..............................(2

y

) ( ) ( :

)(185
:

/ .
y

] rate = k [ NO] .[ Cl2

x

)4.0 10-2 = k ( 0.760 ) . ( 0.760 ) ..............................(1

y

)1.0 10-2 = k ( 0.380 ) . ( 0.760 ) ..............................(2

x

) 4.0 10-2 k ( 0.760 ) . ( 0.760

=
1.0 10-2 k ( 0.380 ) x . ( 0.760 ) y
y

0.760
=4

0.380

0.760
log 4 = log

0.380
0.760
log 4= x log

0.380
) log 4 = x log ( 2
log 4
log 2
x=2
=x

).(NO

:
) (NO ) (0.380 ) (0.760
) (Cl2 ) (0.760
) (1.0 x 10-2 )(4.0 x 10-2
4.0 10-2

=
4

-2
1.0 10

).(NO

)(186
:

/ .

: ): (Cl2

:
y

] rate = k [ NO] .[ Cl2

x

) (2, 3 ) (Cl2
) (0.380 ) (0.760 ) (NO ) (0.380 :
y

] rate = k [ NO] .[ Cl2

x

)1.0 10-2 = k ( 0.380 ) . ( 0.760 ) ..............................(1

x

)5.0 10-3 = k ( 0.380 ) . ( 0.380 ) ..............................(2

x

) ( ) ( :
) 1.0 10-2 k ( 0.380 ) . ( 0.760
=
5.0 10-3 k ( 0.380 ) x . ( 0.380 ) y
y

0.760
=2

0.380

0.760
log 2 = log

0.380
y

) log 2 = log ( 2

) log 2 = y log ( 2
) log ( 2
) log ( 2

=y

y=1

) (Cl2

)(187
:

/ .

) (Cl2 ) (0.380 ) (0.760
)) (NO (0.380
) (5.0 x 10-3 ): (1.0 x 10-2
1.0 10-2

=
2

-3
5.0 10

)(Cl2

) (Cl2, NO :
1+2=3
) 2 NOCl
( 2 NO + Cl2

:
]rate = k [NO]2 . [Cl2
)(
2N 2O5
4NO 2 + O 2

)] (rate = k [N2O5 )([N2O5] = 0.040 M
)(rate = 1.4 10-6 mol L-1 s-1

)(188
:

/ .

] rate = k [N 2 O5
) 1.4 10-6 = k ( 0.040
1.4 10 ) mol L s
(
=k
-6

-1 -1

( 0.040 ) mol L-1

k = 3.5 x 10-5 s -1

)(

): (rate = k [NO2]2
2NO2
2NO + O2

) ([NO2] = 0.040 M
).(rate = 3 10-13 mol L s-1

rate = k [NO2 ]2
2

) 3 x 10-13 = k ( 0.040

( 3 x 10 ) mol L s
=k

-1 -1

mol2 L-2

-13

) ( 0.040

k = 1.875 10-10 L mol-1 s -1s -1

)(189
:

/ .

)(
) (CH3CHO
:
)CH3CHO(g
) CH 4 (g) + CO(g

:
4

0.4

0.3

0.2

0.1

1.400

0.760

0.340

0.085

Exp.

][CH3CHO
mol/L

rate mol/L

) ) CH 4 (g) + CO(g

) ( CH3CHO(g :

] rate = k [ CH3CHO

) (
:
x

] rate = k [ CH 3CHO
x
x

)0.085 = k ( 0.1

) 0.340 = k ( 0.2

)(190
:

/ .
) k ( 0.2
0.340
=
x
0.085
)k ( 0.1

0.2
=4

0.1
x

)4 = ( 2

) log 4 = log ( 2
log 4 = x log 2
log 4
=x
log 2
x=2

:
]rate = k [ CH3CHO

) (3 :
] rate = k [ CH 3CHO

rate

][CH3CHO

0.760
2

)( 0.3

=k
=k

k = 8.4 mol-1 L s -1

)(191
:

/ .

)(
( :
-

OH
)I - (aq) + ClO - (aq
) IO - (aq) + Cl- (aq

:
4
0.010
0.010
0.020
3.05 10-4

2
3
0.020
0.010
0.010
0.020
0.010
0.010
-4
12.20 10 12.20 10-4

1
0.010
0.010
0.010
6.10 10-4

Exp.

][I-
] [ClO-
]mol/L [OH-

)rate (mol/L s

( .
(
(

:
z

rate = k I- ClO- OH -

) (x, y, z

:
: ) (x ) (I-
): (1, 2

)(192
:

/ .
z

rate = k I- ClO - OH -
6.10 10-4 = k (0.010) x (0.010) y (0.010) z
12.20 10-4 = k (0.20) x (0.010) y (0.010) z

:
12.20 10-4 k (0.020) x (0.010) y (0.010) z
=
6.10 10-4
k (0.010) x (0.010) y (0.010) z
x

0.20
=2

0.010
2 = 2x
x=1

) (I- ).(x = 1
: ) (y ) (ClO-
): (1, 3
z

rate = k I- ClO- OH -
6.10 10-4 = k (0.010) x (0.010) y (0.010) z
12.20 10-4 = k (0.01) x (0.020) y (0.010) z

:
12.20 10-4
k (0.010) x (0.020) y (0.010) z
=
6.10 10-4
k (0.010) x (0.010) y (0.010) z
y

0.020
= 2

0.010
2 = 2y
y=1

) (ClO- ).(y = 1

)(193
:

/ .

: ) (z ) (OH-
): (1, 4
y

rate = k I- ClO- OH -
6.10 10-4 = k (0.010) x (0.010) y (0.010) z
3.05 10-4 = k (0.02) x (0.010) y (0.010) z

:
3.05 10-4
k (0.010) x (0.010) y (0.020) z
=
6.10 10-4
k (0.010) x (0.010) y (0.010) z
0.020
= 0.5
z
0.010
0.5 = 2z
log 2z = log 0.5
log 0.5
log 2
z=-1
=z

) (- 1
.
( :
n=x+y+z
n=1+11=1
.

)(194
:

/ .

( :
I- ClO-
rate = k
OH -

(
): (3
I- ClO -
rate = k
OH -
rate OH -
I- ClO -

=k

) (12.20 10 ) ( 0.010
=k
-4

) ( 0.010 )( 0.020

k = 0.061 s -1

)(
:
N 2 + 3H 2
2NH 3

. ) (k
).(rate = 0.3 mol/L s

] rate = k [ N 2 ] [ H 2

)0.3 mol/Ls = k (1) (1

k = 0.3 mol L-1s -1

)(195
:

/ .

)(
:
A + B
C

) (A ) (B
.

]rate = k [ A ][ B

.
)(
:
A
B

:
]rate = k [A
A .

1 = A =1

)(196
:

/ .

)(
:
H 2 + I2
2HI

:
] rate = k [ H 2 ][ I 2

) (H2 ) (1 ) (I2
) (1 ).(2
)(
2NO + Br2
2NOBr :

:
] rate = k [ NO ] [ Br2
2

Br2

NO

2+1=3

)(197
:

/ .

)(
:
H 2 O2 + 3I- + H +
I3- + 2H 2 O

:
rate = k [ H 2 O 2 ] I-

H+

I-

H 2O2

1+1=2

)(
:
2Br - + H 2 O2 + 2H +
Br2 + 2H 2 O

( .
(
( .

)(198
:

/ .

( :
+
] [ H 2O2
] [ Br2 ] 1 [ H 2 O
1 Br
1 H
= rate===
=
2 t
t
2 t
t
2 t

( :
rate = k Br - [ H 2 O 2 ] H +

( :
1+1+1=3
)(
:
A
B

).(A

:
x

] rate = k [ A

] 2 rate = k 2 [ A

)(199
:

/ .

:
x

k ( 2 ) A
2 rate
=
x
rate
k A
2 = 2x
x=1
x

) (A
:
] rate = k [ A

)(
:
CH3Cl + H 2 O
CH3OH + HCl

) (CH3Cl
) (H2O.
( CH3Cl, H2O
(
( [CH3Cl] = [H2O] = 0.2 mol/L
).(1.5 mol/L s

)(200
:

/ .
y

] rate = k [CH 3Cl]x [ H 2 O

CH3Cl
CH3Cl :
y
y

] rate = k [CH 3Cl]x [ H 2 O

]2 rate = k ( 2[CH3Cl]) [ H 2 O
x

:
y

] k ( 2[CH 3Cl]) [ H 2 O
2 rate
=
y
rate
] k [CH 3Cl]x [ H 2 O
x

k ( 2 ) ([CH 3 Cl]) H 2 O
2 rate
=
y
rate
k [CH 3Cl]x H 2 O
x

=2

)( 2

x=1

H2O
:

] k [CH 3Cl]x 2 [ H 2 O
y

] k [CH 3Cl]x [ H 2 O

4 rate
=
rate

k[CH 3Cl]x ( 2 ) H 2 O
4 rate
=
y
rate
k [CH 3Cl]x H 2 O
y

=4

)( 2

y=2

)(201
:

/ .

) (CH3Cl
) .(H2O ).(1 + 2 = 3
( ) ( :
]rate = k [CH3Cl][ H 2 O

( :
]rate = k [CH3Cl][ H 2 O

1.5 mol/L s = k (0.2) (0.2) 2

1.5 mol L-1 s -1
=k
(0.2) (0.2) 2 mol3 L-3
k = 187.5 L2 /mol2 s

)(
:
A
B

) (A ) (0.2 mol/L
) (0.04 mol/L. s
:
(
(
(
(

)(202
:

/ .

rate = k = 0.04 mol/L s

] 1) rate = k [ A

rate
0.04 mol L-1 s -1
=k
=
= 0.2 s -1
-1
0.2 mol L
][A

] 2) rate = k [ A

= 1 mol-1 L s-1
= 5 mol-2 L2 s -1

0.04 mol L-1 s -1

mol2 L-2

) ( 0.2

0.04 mol L-1 s -1

-3

mol L

) ( 0.2

=
=

rate

][A

rate

][A

= 3) rate = k [ A ] k
2

= rate = k [ A ] k
3

)4

)(

) (A, B :
) (4 10-6 mol L-1 min-1 ) (0.2 mol/L
.

)(1 + 1 = 2
:
]rate = k [ A ] .[ B
rate
][ A ][ B

=k

4 10-6 mol L-1min -1

( 0.2 0.2 ) mol2 L2

=k

k = 1 10-4 mol-1L min -1

)(203
:

/ .

)(
:
CH3CHO
CH 4 + CO

) (0.18 mol L-1 s-1

)(0.1 mol L-1
(
( .

( :
]rate = k [ CH3CHO

( :
]rate = k [ CH 3CHO

rate

][CH3CHO

0.18 mol L-1 s -1

mol2 L-2

) ( 0.1

=k
=k

k = 18 mol-1 L s -1

)(
:
2N 2 O3
4NO + O2

)(204
:

/ .

:
2
0.2
8 10-2

3
0.05
2 10-2

Exp.
[N2O3] mol/L
rate mol/L s

1
0.1
4 10-2

(
(
( k
( [N2O3] = 0.5 mol/L .

( :
x

] rate = k [ N 2 O3

)( rate )1 = k [ N 2O3 ]1 4 10-2 = k ( 0.1

x
x
) ( rate )2 = k [ N 2O3 ]2 8 10-2 = k ( 0.2
x
) k ( 0.2
8 10-2
=
x
4 10-2
)k ( 0.1
x
)2 = ( 2
x
) log 2 = log ( 2
) log 2 = x log ( 2
x

log 2
log 2
x=1
=x

.
( :

] rate = k [ N 2 O3

)(205
:

/ .

( :

] rate = k [ N 2 O3
rate
] [ N 2 O3

=k

( 4 10 ) mol L s
=k
-2

-1 -1

( 0.1) mol L-1

k = 0.4 s -1

( [N2O3] = 0.5 mol/L

] rate = k [ N 2 O3
) rate = 0.4 ( 0.5
rate = 0.2 mol/L s

)(
:
2NO + 2H 2
N 2 + 2H 2 O

:
3
15 10-3
10 10-3
3.6 10-4

2
15 10-3
2.5 10-3
9 10-5

1
5 10-3
2.5 10-3
3 10-5

Exp.
][NO
][H2
)Rate (Ms-1

)(206
:

/ .
y

] rate = k [ NO] [ H 2
x

) (NO :
y
y

) 9 10-5 = k (15 10-3 ) . ( 2.5 103

x

] rate = k [ NO ] .[ H 2

) 3 10-5 = k ( 5 10-3 ) . ( 2.5 103

x

) k (15 10-3 ) . ( 2.5 103

x

9 10
=
x
y
3 10-5
) k ( 5 10-3 ) . ( 2.5 103
x

-5

15 10-3
=3
-3
5 10
x
x

)3 = ( 3

)log 3 = log ( 3

)log 3 = x log ( 3
log 3
log 3
x=1

=x

) (NO .

)(207
:

/ .

) (H2 ) (2 ): (3
y
y

) 3.6 10- 4 = k (15 10-3 ) . (10 10-3

] rate = k [ NO ] .[ H 2

) 9 10- 5 = k (15 10-3 ) . ( 2.5 10-3

x

) k (15 10-3 ) . (10 10-3

x

-4

3.6 10
=
x
y
9 10- 5
) k (15 10-3 ) . ( 2.5 10-3
y

10 103
=4
3
2.5 10
y
y

)4 = ( 4

) log 4 = log ( 4

log 4 = y log 4
log 4
log 4
y=1
=y

:
1+1=2
:
] rate = k [ NO ] .[ H 2

) (k
): (1

)(208
:

/ .
y

] rate = k [ NO] .[ H 2
x

) 3 10-5 = k ( 5 10-3 )( 2.5 10-3

3 10-5 mol L-1 s -1
=k
( 5 10-3 )( 2.5 10-3 ) mol2 L-2
k = 2.4 mol-1 L s -1
k = 2.4 M -1 s -1

)(
:
3
0.4
0.12
8 10-3

1
0.2
0.12
2 10-3

2
0.2
0.24
4 10-3

Exp.
][A
][B
rate mol L-1 s-1

( ) (A ) (B.
( .k
.

:
y

]rate = k [ A ] .[ B
x

) (A
) (B ): (1, 3

)(209
:

/ .
y

]rate = k [ A ] .[ B
x

)8 x10-3 = k (0.12) x . (0.4) y ..............................(1

)2 x 10-3 = k (0.12) x . (0.2) y ..............................(2
8 x10-3
k (0.4) x . (0.4) y
=
2 x 10-3 k (0.2) x . (0.2) y
x

0.4
=4

0.2
x

)4 = ( 2

log 4 = log (2) x

)log 4 = x log (2
)log (4
)log (2
x=2
=x

).(A
) (B :
) (B
) (A ): (1, 2

)(210
:

/ .
y

]rate = k [ A ] .[ B
x

)4 x10-3 = k (0.2) x . (0.24) y ..............................(1

)2 x 10-3 = k (0.2) x . (0.12) y ..............................(2
4 x 10-3 k (0.2) x . (0.24) y
=
2 x 10-3 k (0.2) x . (0.12) y
y

0.24
=2

0.12
y

)2 = ( 2

log 2 = log (2) y

)log 2 = y log (2
)log (2
=y
)log (2
y=1

).(B
:
2+1=3
:
]rate = k [ A ] .[ B
2

)(211
:

/ .
]rate = k [ A ] .[ B
2

) 2 10-3 = k ( 0.2 ) . ( 0.12

2

s-1

( 2 10 ) mol L
-3

-1

mol3 L-3

=k

) ( 0.2 ) . ( 0.12
2

k = 0.417 mol-2 L2 s -1
k = 0.417 M -2 s -1

)(
:
A + 2B + C
D

:
4
0.1
0.2
0.2
0.114

2
0.1
0.2
0.1
0.028

3
0.2
0.1
0.1
0.057

1
0.1
0.1
0.1
0.028

Exp.
][A
][B
][C
rate mol/L s

) D

( A + 2B + C :

]rate = k [ A ] .[ B] .[ C

)(212
:

/ .

) (A )(B, C
]rate = k [ A ] .[ B] .[ C

)(A

)0.057 = k ( 0.2 ) ( 0.1) . ( 0.1

y

)0.028 = k ( 0.1) ( 0.1) . ( 0.1

x

) 0.057 k ( 0.2 ) ( 0.1 ) . ( 0.1

=
0.028 k ( 0.1) x ( 0.1 ) y . ( 0.1 )z
y

0.2
= 2.036

0.1
x

) 2.036 = ( 2

) log 2.036 = log ( 2

) log 2.036 = x log ( 2

log 2.036
) log ( 2

=x

x = 1.026

)(A

) (B )(A, C
]rate = k [ A ] .[ B] .[ C

)(B

)0.028 = k ( 0.1) ( 0.2 ) . ( 0.1

)0.028 = k ( 0.1) ( 0.1) . ( 0.1

x

) 0.028 k ( 0.1 ) ( 0.2 ) . ( 0.1

=
0.028 k ( 0.1 )x ( 0.1) y . ( 0.1 )z

0.2
=1

0.1
y

)1 = ( 2

) log 1 = log ( 2

) log 1 = y log ( 2
log 1
) log ( 2

=y

y=0

).(B

)(213
:

/ .

) (C )(A, B

]rate = k [ A ] .[ B] .[ C

)(C

) 0.114 = k ( 0.1) ( 0.2 ) . ( 0.2

)0.028 = k ( 0.1) ( 0.2 ) . ( 0.1

x

) 0.114 k ( 0.1) ( 0.2 ) . ( 0.2

=
0.028 k ( 0.1) x ( 0.2 ) y . ( 0.1)z

) k ( 0.1 ) ( 0.2 ) . ( 0.2

y

)k ( 0.1 ) ( 0.2 ) . ( 0.1

x

0.2
= 4.071

0.1
z

= 4.071

) 4.071 = ( 2

) log 4.071 = log ( 2

) log 4.071 = z log ( 2

log 4.071
) log ( 2

=z

z  2
)(C

:
1+0+2=3
:
]rate = k [ A ] .[ B] [ C

]rate = k [ A ] .[ C

) (1 :

)(214
:

/ .
]rate = k [ A ] .[ B] [ C

0.028 = k (0.1) (0.1)0 (0.1)2

0.028 = k (0.1) (0.1) 2
0.028
=k
(0.1) (0.1) 2
0.028 mol L-1 s -1
=k
(0.1) (0.1) 2 mol3 L-3
k = 28 mol-2 L2 s -1
k = 28 M -2 s -1

)(
:
)2NO(g) + O2 (g
) 2NO2 (g

) (25 C
:

Initial rate
)(mol dm-3 s-1
7 10-6
14 10-6
21 10-6
84 10-6
189 10-6

Initial concentration
)(mol dm-3
NO
O2
0.001
0.001
0.001
0.002
0.001
0.003
0.002
0.003
0.003
0.003

( .
( .

Experiment
1
2
3
4
5

)(215
:

/ .

:
)2NO(g) + O2 (g
) 2NO2 (g

:
y

] Rate = k [ NO ] [ O 2
x

) ( :
Initial rate
)(mol dm-3 s-1
7 10-6
14 10-6

Initial concentration
)(mol dm-3
NO
O2
0.001
0.001
0.001
0.002

Experiment
1
2

) (0.001 M

) (0.002 M ) (NO

:
y

] Rate = k [ NO ] [ O 2
x

) 7 10- 6 = k (1 10-3 ) (1 10-3

x

) 14 10-6 = k (1 10-3 ) ( 2 10-3

y

)(216
:

/ .
) k (1 10 -3 ) ( 2 10-3
14 10-6
=
x
y
7 10-6
) k (1 10 -3 ) (1 10-3
x

2 10-3
=2
-3
1 10

2 10-3
log 2 = log
-3
1 10
2 10-3
log 2 = y log
-3
1 10
log 2
2 10-3
log
-3
1 10

=y

y=1

.
) (3 ): (4
Initial rate
)(mol dm-3 s-1
21 10-6
84 10-6

Initial concentration
)(mol dm-3
NO
O2
0.001
0.003
0.002
0.003

Experiment
3
4

) (NO
:
y

] Rate = k [ NO ] [ O 2
x

) 21 10- 6 = k (1 10-3 ) ( 3 10-3

x

) 84 10- 6 = k ( 2 10-3 ) ( 3 10-3

x

)(217
:

/ .

:
y

) ( 3 10
) ) ( 3 10

] Rate = k [ NO ] [ O 2
x

) k ( 2 10-3

-3 y

-3 y

84 10
=
21 10-6
k (1 10-3
x

-6

2 10-3
=4
-3
1 10

2 10-3
log 4 = log
-3
1 10
2 10-3
log 4 = x log
-3
1 10
log 4
2 10-3
log
-3
1 10

=x

x=2

) (A .
:
y

] Rate = k [ NO ] [ O 2
x

] Rate = k [ NO ] [ O 2

( :
) (k
.
) (1 :

)(218
:

/ .
] rate = k [ NO ] [ O 2

) (1 10

-3

) 7 10-6 = k (1 10-3
7 10-6

=k

) (1 10 ) (1 10
k = 7 10 ( dm ) mol s
-3 2

-3

3 2

-2 -1

( :
n=2+1=3

)(
:
A + B + C
D

:
]rate = k [ A ] [ C
2

]rate = k [ A ] [ C
2

A
2

B
0

C
1

: B
.

)(219
:

/ .

)(

:
] 1) rate = k [ A

]2) rate = k [ A ] [ B
0

]3) rate = k [ A ] [ B

] rate = k [ A

)(B
)(A
0

]rate = k [ A ] [ B

]rate = k [ A ] [ B

)(

)( .
H 2 + I2
1) 2HI
2NO 2
2) 2NO + O 2
CO + Cl 2
3) COCl2

2HI
H 2 + I2
2NO + O 2
2NO 2
COCl 2
CO + Cl2

rate = [HI]2
]rate = [NO]2[O2
]rate = [COCl2

2
3
1

)(220
:

/ .

)(
:
SO 2Cl 2
SO 2 + Cl2

(
( .

SO 2 Cl2
SO 2 + Cl2

]rate = k [SO2Cl2

-1 -1

rate
mol L s
=
= s -1
[SO2Cl2 ] mol L-1

=k

)(
:
A
B

) (A ) (0.2 mol L-1

) (rate = 0.04 mol L-1 s-1
:
(
(
(
(

)(221
:

/ .

] rate = k [ A

k = 0.04 mol L-1s -1

] rate = k [ A

rate 0.04 mol L-1s-1

=
= 0.2 s -1
-1
[ A ] 0.2 mol L

=k

] rate = k [ A

= 1 mol-1 L s -1

= 5 mol-2 L2 s -1

0.04 mol L-1s -1

) ( 0.2 mol L

-1 2

rate

][A

=k

] rate = k [ A

0.04 mol L-1s -1

) ( 0.2 mol L

-1 3

rate

][A

=k

)(
:
A
B

:
rate = k [A]x

)(222
:

/ .
x

)]2rate = k ( 2[A

:
x

)]k ( 2[A
2 rate
=
rate
k [A]x

k ( 2 ) [A]x
2 rate
=
rate
k [A]x
x

2 = 2x
log 2 = x log 2
log 2
=x
log 2
x =1

) (A
:
] rate = k [ A

.
)(
:
A
B

)(A

)(223
:

/ .

:
rate = k [A]x

) (A
:
x

)]4 rate = k ( 2[A

:
x

)]k ( 2[A
4 rate
=
rate
k [A]x

k ( 2 ) [A]x
4 rate
=
rate
k [A]x
x

x
x

)4 = ( 2

) log 4 = log ( 2

) log 4 = x log ( 2
log 4
=2
log 2

=x

) (A .


.

)(224
:

/ .

)(
:
A
B

).(A

:
rate = k [A]x

) (A
:
x

)]8 rate = k ( 2[A

:
x

)]k ( 2[A
8 rate
=
rate
k [A]x
2 x [A]x
=8
[A]x
8 = 2x
log 8 = log 2x
log 8 = x log 2
log 8
=x
log 2
x =3

)(225
:

/ .

) (A .


.
)(
:
A + 2B
3C + 2D

)(A
) (B
.
( )(A, B
( .
( ) (2.4 10-3 M/s )(A
) (0.1 M ) (B ) (0.2 M
.
( ) (A )(0.02 M
) (B ).(0.03 M

)(226
:

/ .

) ( A + 2B 3C + 2D

rate = k [A]x [B]y

) (A
:
2 rate = k ( 2[A]) [B]y
x

) (A
) ( 2 rate = k ( 2[A])x [B]y ) : ( rate = k [A]x [B]y
k ( 2[A]) [B]y
2 rate
=
rate
k [A]x [B]y
x

k ( 2 ) [A]x [B]y
2 rate
=
rate
k [A]x [B]y
x

x
x

)2 = ( 2

) log 2 = log ( 2

log 2 = x log 2
log 2
=x
=1
log 2

) (A .
) (B :
rate = k [A]x [B]y

)(227
:

/ .

) (B
:
y

)]9 rate = k [A]x ( 3[B

) )](9 rate = k [A] ( 3[B

y

) ]( rate = k [A] [B
y

:
y

)]k [A]x ( 3[B

9 rate
=
rate
k [A]x [B]y

k [A]x ( 3) [B]y
9 rate
=
rate
k [A]x [B]y
y

)9 = ( 3

log 9 = log 3y
log 9 = y log 3
log 9
log 3
y=2
=y

) (B .
:
n=x+y
n=1+2=3
( :
rate = k [A] [B]2

( :
) (rate = 2.4 10-3 Ms-1 ): ([A] = 0.1 M, [B] = 0.2 M

)(228
:

/ .
rate = k [A][B]2
rate
[A][B]2
2.4 10-3 mol L-1 s -1

) (0.1 mol L-1 ) ( 0.2 mol L-1

=k
=k

k = 0.6 L2 mol-2 s -1

( ) ([A] = 0.02 M, [B] = 0.03 :

rate = k [A] [B]2
2

) rate = ( 0.6 L2 mol-2s -1 ) ( 0.02 mol L-1 ) ( 0.03 mol L-1

rate = 1.08 10-5 mol L-1 s -1

)(
:
2A + 3 B
A 2 B3

) (A
) (A, B
.
.

:
): (A
:

)(229
:

/ .

rate = k [A]x [B]y

) (A
:
3 rate = k ( 3[A]) [B]y
x

) ](3 rate = k (3[A]) [B

y

) ]( rate = k [A] [B
y

:
k ( 3[A]) [B]y
3 rate
=
rate
k [A]x [B]y
x

k ( 3) [A]x [B]y
3 rate
=
rate
k [A]x [B]y
x

3 = 3x
log 3 = log 3x
log 3
log 3
x=1
=x

) (A .
) (B :
A :

rate = k [A][B]y
) (A, B

:

)(230
:

/ .

) 8 rate = k ( 2[A]) ( 2[B]y

)) ](8 rate = k ( 2[A]) ( 2[B

y

) ]( rate = k [A][B
y

:
) k ( 2[A]) ( 2[B]y
8 rate
=
rate
k [A][B]y
k ( 2 ) [A] ( 2 ) [B]y
8 rate
=
rate
k [A][B]y
y

) 8 = ( 2 )( 2
8
2

)( 2

=4

)( 2

log ( 2 ) = log 4
y

y log 2 = log 4
log 4
=y
log 2
y=2

) (B
:
rate = k [A][B]2

)(231
:

/ .

)(
:
2NO + Cl2
2NOCl

) (Cl2
) (Cl2, NO
.
.

): (Cl2
:

rate = k [NO]x [Cl2 ]y

) (Cl2
:
y

)] 2rate = k [NO]x ( 2[Cl2

) )] ( 2rate = k [NO] ( 2[Cl ) ] ( rate = k [NO] [Cl

y

)(232
:

/ .

) )] ( 2rate = k [NO] ( 2[Cl

y

) ] ( rate = k [NO] [Cl

x

x
)] 2 rate k [NO] . ( 2[Cl 2
=
rate
k [NO]x . [Cl2 ]y

x
y
] 2 rate k [NO] . ( 2 ) [Cl2
=
rate
k [NO]x . [Cl 2 ]y
y

y
y

)2 = ( 2

) log 2 = log ( 2

) log 2 = y log ( 2
log 2
) log ( 2

=y

y=1

).(Cl2
: ): (NO
) ) (Cl2 :
] rate = k [NO]x [Cl2

) (Cl2, NO
:
)] 8 rate = k ( 2[NO]) ( 2[Cl2
x

))] (8 rate = k ( 2[NO]) ( 2[Cl

x

)] ( rate = k [NO]x [Cl2

)(233
:

/ .
)] 8 rate k ( 2[NO]) ( 2[Cl2
=
rate
] k [NO]x [Cl2
x

x
8 rate k ( 2 ) [NO] ( 2 ) Cl2
=
rate
] k [NO]x [Cl2
x

)8 = 2 ( 2
8
2

)( 2

=4

)( 2

log ( 2 ) = log 4
x

x log ( 2 ) = log 4
log 4
) log ( 2

=x

x=2

).(NO
:
n=x+y
n=2=1=3
:
] rate = k [NO]2 . [Cl2

)(
:
CH 3Cl + H 2 O
CH 3OH + HCl

)(234
:

/ .

) (CH3Cl
) (H2O.
( )(CH3Cl, H2O
( .
( ) (1.5 mol/L s :
([H2O] = 0.2 mol/L , [CH3Cl] = 0.2 mol/L
.

:
rate = k [CH3Cl]x [H 2 O]y

) (CH3Cl )(rate
:
2 rate = k ( 2[CH3Cl]) [H 2 O]y
x

) ]( 2 rate = k ( 2[CH Cl]) [H O

) ]( rate = k [CH Cl] [H O

x

(235)
:

. /
k ( 2[CH 3Cl]) [H 2 O]y
2 rate
=
rate
k [CH 3Cl]x [H 2 O]y
x

k ( 2 ) ([CH 3Cl] ) [H 2 O] y
2 rate
=
rate
k [CH 3Cl] x [H 2 O] y
x

2 = ( 2)

log 2 = log ( 2 )

log 2 = x log ( 2 )
x=

log 2
log ( 2 )

x =1

( H2O)
:

( rate = k [CH Cl] [H O] )

x

( 2 rate = k [CH Cl] ( 2[H O] ) )

x

( rate = k [CH Cl] [H O] )

x

( 2 rate = k [CH Cl] ( 2[H O] ))

x

:
k [CH 3Cl]x ( 2[H 2 O]y )
4 rate
=
rate
k [CH 3Cl]x [H 2 O]y
k [CH 3Cl] x ( 2 ) [H 2 O] y
4 rate
=
rate
k [CH 3Cl] x [H 2 O] y
y

( 2) = 4
y
log ( 2 ) = log 4
y

y log 2 = log 4
log 4
y=
log 2
y=2

)(236
:

/ .

) CH 3OH + HCl

( CH Cl + H O :
3

rate = k [CH3Cl][H 2 O]2

( :
: (rate = 1.5 mol/L s) ([H2O] = 0.2 mol/L , [CH3Cl] = 0.2 mol/L
rate = k [CH 3Cl][H 2 O]2
1.5 mol L-1s-1 = k (0.2 mol L-1 )(0.2 mol L-1 ) 2
1.5 mol L-1s -1
=k
(0.2 mol L-1 ) (0.2 mol L-1 ) 2
k = 187.5 L2 mol-2s-1

)(
:
)2N 2 O5 (g
) 4NO2 (g) + O2 (g

:
3
4 10-4
3.6 10-2

2
3 10-4
2.7 10-2

(
(
( k

1
2 10-4
1.8 10-2

EXP.
[N2O5] mol/L
Rate mol/L s

)(237
:

/ .
rate = k [N 2 O5 ]x

:
1.8 10-2 = k [2 10-4 ]x
3.6 10-2 = k [4 10-4 ]x

:
x

) 1.8 10-2 = k ( 2 10-4

) 3.6 10-2 = k ( 4 10-4

) k ( 4 10-4
3.6 10-2
=
x
1.8 10-2
) k ( 2 10-4
x

4 10-4
3.6 10-2
=
-4
1.8 10-2
2 10
2x = 2
log 2x = log 2
x log 2 = log 2
log 2
log 2
x=1
=x

.
( :
rate = k [N 2 O5 ]x
] rate = k [N 2 O5

( : k

)(238
:

/ .

k
) (N2O5 :
] rate = k [N 2 O5
) 2.7 10-2 = k (3 10-4
2.7 10-2 mol L-1 s -1
3 10-4 mol L-1
k = 90 s -1
=k

.
)(
:
)2NOCl(g
) 2NO(g) + Cl2 (g

:
3
0.6
1.44 10-8

2
0.4
6.4 10-9

1
0.2
1.6 10-9

Exp.
[NOCl] molL-1
Rate mol L-1 s-1

( .
( .
( k
( ) (NOCl ) (0.5 mol L-1

( ) (0.4 ) (0.49
.

)(239
:

/ .

:
]rate = k [ NOCl

:
x

) 1.6 10-9 = k ( 0.2

) 6.4 10-9 = k ( 0.4

) 6.4 10-9 k ( 0.4

=
1.6 10-9 k ( 0.2 ) x
x

0.4
=4

0.2
x

)4 = ( 2

=4

)( 2

x log 2 = log 4
log 4
log 2
x=2
=x

( :
]rate = k [ NOCl

( ): (k
) (NOCl
:

)(240
:

/ .
]rate = k [ NOCl

rate

][ NOCl

1.44 10-8
2

) ( 0.6

=k
=k

k = 4 10-8

( : [NOCl] = 0.5 mol/L

]rate = k [ NOCl

2
2

) rate = 4 10-8 ( 0.5

rate = 1 10-8

( ) (0.4 ) (0.49 0.4

)(6.4 10-9 mol L-1 s-1
) (0.49 :
]rate = k [ NOCl

2
2

) rate = 4 10-8 ( 0.49

rate = 9.604 10-9 mol L-1s -1

) (0.49
) (0.4 :

( 9.604 10 ) mol L s
( 6.4 10 ) mol L s

-1 -1

= 1.5

-1

-9

-1

-9

) (0.4 ).(0.49

)(241
:

/ .

)(
:
2NO + Cl2
2NOCl

:
3
1.44
0.2
0.2

1
0.18
0.1
0.1

2
0.36
0.1
0.2

Exp
rate mol/L min
][NO
][Cl2

( ) (NO ) (Cl2 .
(
( )(k
( [NO] = [Cl2] = 0.5 mol/L :

( :
rate = k [NO]x [Cl2 ]y

:
y

)0.18 = k ( 0.1) ( 0.1

x

] [NO
]: [Cl2
y

) 0.36 = k ( 0.1) ( 0.2

x

)(242
:

/ .

) ( 0.2

) ( 0.36 = k ( 0.1 ) )( 0.18 = k ( 0.1) ( 0.1

x

) k ( 0.1 ) ( 0.2
0.36
=
x
y
0.18
)k ( 0.1 ) ( 0.1

0.2
=2

0.1
y

)2 = ( 2

log ( 2 ) = log 2
y

y log 2 = log 2
log 2
=y
log 2
y=1

).(Cl2

) ( rate = k [NO]x [Cl2 ]y ).(NO
) k ( 0.2 ) ( 0.2
1.44
=
y
x
0.36
) k ( 0.1) ( 0.2

0.2
=4

0.1
x

)4 = ( 2

log ( 2 ) = log 4
x

x log 2 = log 4
log 4
=x
log 2
x=2

).(NO

)(243
:

/ .

:
n=2+1=3
( :
] rate = k [NO]2 [Cl2

(
) ( :
] rate = k [NO]2 [Cl2
)0.18 = k ( 0.1) (0.1
2

0.18
)(0.1

)( 0.1

=k

k = 180 L2 mol-2 min -1

.
)(
:
2NO + 2H 2
N 2 + 2H 2 O

:
3
3.6 10-5
15 10-3
10 10-3

2
9 10-5
15 10-3
2.5 10-3

1
3 10-5
5 10-3
2.5 10-3

Exp
rate M s-1
][NO
][H2

)(244
:

/ .

) N 2 + 2H 2 O

( 2NO + 2H :
rate = k [NO]x [H 2 ]y

) (x, y
:
) (x )(NO

) (y )(H2
y

rate = k [NO]x [H 2 ]y

] rate = k [NO] [H 2

3 10-5 = k (5 10-3 ) x (2.5 10-3 ) y

9 10-5 = k (15 10-3 ) x (2.5 10-3 ) y

9 10-5 = k (15 10-3 ) x (2.5 10-3 ) y

3.6 10-4 = k (15 10-3 ) x (10 10-3 ) y

-3 x
-3 y
) 9 10-5 k (15 10 ) (2.5 10
=
3 10-5
k (5 10-3 ) x (2.5 10-3 ) y

k (15 10-3 ) x (10 10-3 ) y

3.6 10-4
=
9 10-5
k (15 10-3 ) x (2.5 10-3 ) y

15 10-3
=3
-3
5 10
x

)3 = ( 3
x =1

10 10-3
=4
-3
2.5 10
x

)4 = ( 4
y =1

:
x+y=1+1=2

:
] rate = k [NO][H 2

)] ( rate = k [NO][H 2
:

)(245
:

/ .
] rate = k [NO][H 2

) 3 10-5 = k ( 5 10-3 )( 2.5 10-3

3 10-5
=k
) ( 5 10-3 )( 2.5 10-3
k = 2.4 M -2 s -1

)(
:
A + 2B + C
D

:
4
0.112
0.1
0.2
0.2

3
0.057
0.2
0.1
0.1

2
0.028
0.1
0.2
0.1

1
0.028
0.1
0.1
0.1

Exp.
rate M s-1
][A
][B
][C

) D

( A + 2B + C :
rate = k [A]x [B]y [C]z

) (x, y, z

:

)(246
:

/ .

: ) (x ): (A
) (1 ) (3 ] [B][C

rate = k [A]x [B]y [C]z

0.028 = k(0.1) x (0.1) y (0.1)z
z

)0.057 = k ( 0.2 ) ( 0.1) ( 0.1

x

) k ( 0.2 ) ( 0.1 ) ( 0.1

0.057
=
0.028
k(0.1) x (0.1) y (0.1) z
y

0.2
=2

0.1
2 = 2x
x =1

: ) (y ): (B
) (1 ) (2 ] [C][A

rate = k [A]x [B]y [D]z

0.028 = k(0.1) x (0.1) y (0.1) z
z

)0.028 = k ( 0.1) ( 0.2 ) ( 0.1

x

) 0.028 k ( 0.1 ) ( 0.2 ) ( 0.1

=
0.028 k(0.1) x (0.1) y (0.1) z

0.2
=1

0.1
1 = 2y
2y = 1

log 2 y = log1
y log 2 = 0
0
=y
log 2
y=0

)(247
:

/ .

: z
) (C ) (2 ) (4 :
rate = k [A]x [B]y [C]z
0.028 = k(0.1) x (0.2) y (0.1) z
z

) 0.112 = k ( 0.1) ( 0.2 ) ( 0.2

x

) k ( 0.1 ) ( 0.2 ) ( 0.2

0.112
=
0.028
k(0.1) x (0.2) y (0.1) z

0.2
=4

0.1
4 = 2z

log 4 = log 2z
z log 2 = log 4
log 4
=z
log 2
z=2

:
x+y+z
1+0+2=3

:
rate = k [A]x [B]y [C]z
rate = k [A][B]0 [C]2
rate = k [A][C]2

)(248
:

/ .
rate = k [A][C]2
0.028 = k (0.1)(0.1) 2
0.028 mol L-1 s -1
=k
(0.1)(0.1) 2 mol3 L-3
k = 28 L2 mol-2s -1
k = 28 M -2s -1

).(
)(
:
A + B
C

:
3
9.2 10-4
2.7 10-2
6.4 10-2

2
9.2 10-4
5.4 10-2
6.4 10-2

1
2.3 10-4
5.4 10-2
3.2 10-2

Exp
rate M s-1
[A] M
[B] M

k .

:
) (A ) (B ) (2
)(2

)(249
:

/ .

:
]rate = k [ B

) (k :
]rate = k [ B

rate

][ B

2.3 10-4 mol L-1s-1

mol2 L-2

) ( 3.2 10

-2 2

=k
=k

k = 0.225 L mol-1 s -1
k = 0.225 M -1 s -1

)(
:
2
0.2
0.2
0.4
20

1
0.2
0.4
0.4
80

)(B

: B .

Exp.
][A
][B
][C
rate

)(250
:

/ .

)(
:
2NO + Cl2
2NOCl
3
0.6
0.3
2.8 10-3

2
0.3
0.3
1.4 10-3

1
0.3
0.15
7 10-4

Exp.
[NO] M
[Cl2], M
Rate, M/s

)(k

:
rate = k [NO] [Cl2] :
k = 0.015 M-1 s-1 :
)(
) (A, B :
3
0.4
0.12
8 10-3

2
0.2
0.24
4 10-3

1
0.2
0.12
2 10-3

Exp.
][A
][B
Rate mol/Ls

(
( ) (k .

)(251
:

/ .

:
) (A ) (2 ) (B (1
3
rate = k [A]2[B] :
k = 0.416 mol-2 L2 s-1
)(
:
F2 + 2ClO2
2FClO 2

:
3
0.2
0.01
2.4 10-3

2
0.1
0.04
4.8 10-3

1
0.1
0.01
1.2 10-3

k = 0.12 M-1 s-1 :

Exp.
][F2
][ClO2
)Rate (Ms-1

)(252
:

/ .

)(
:
2NO + O 2
2NO 2
3
0.0125
0.0506
0.056

2
0.025
0.0253
0.112

1
0.0125
0.0253
0.028

Exp.
][NO
][O2
Rate mol/L s

(
( ) (k .

( ) (NO )(2
) (O2 )(1
)(3
( k = [NO]2[O2]:
k = 7083 mol-2 L2 s-1 :

)(253
:

/ .

)(
:
2NO + Cl2
2NOCl
3
0.6
0.3
2.8 10-3

2
0.3
0.3
1.4 10-3

1
0.3
0.15
7 10-4

Exp.
[NO], M
[Cl2], M
Rate, M/s

) (k
.

rate = k [NO]2[Cl2] :
k = 0.0156 M-1 s-1 :
)(

:
1. RCl + OH -
ROH + Cl]k [RCl
]d[ROH
= ' 1dt
k1[Cl ] + 1
2.CH 3COCH 3 + 3Br2 + OH -
CH 3COO - + CHBr3 + 3HBr
] d[CH 3COCH 3
] = k[CH 3COCH 3 ][OH -
dt
3. 2NO + Cl2
2NOCl
-

] d[Cl2
] = k [NO]2 [Cl2
dt

)(254
:

/ .

)(
:
)Br2 (g) + 2NO(g
) 2NOBr(g

) (Br2 )(NO

).(0.050 L2 mol-2 s-1
( .
( :
[NO] = 0.050 mol/L, [Br2] = 0.10 mol/L

:
(
( rate = 1.25 10-5 mol L-1 s-1
)(
:
2NOCl
2NO + Cl2

) (27 C :
0.90
3.24 10-8

0.60
1.44 10-8

0.30
3.6 10-9

[NOCl] mol/L
mol/L s

)(255
:

/ .

(
(
( ) (NOCl ) (0.3 M ) (0.45 M
.

:
( rate = k [NOCl]2
( k = 4 10-8 L mol-1 s-1
( 2.25
)(

) ( D(g) products
) (0.030 mol L-1 min-1 ) (D
) (0.150 mol/L ) (k :
(
(
( .

)(256
:

/ .

:
( k = 0.03 mol L-1 mo-1
( k = 0.20 min-1
( k = 1.3 mol-1 L min-1
)(
:
2Br - + 2H + + H 2O 2
Br2 + 2H 2O

rate = k [Br-][H+][H2O2] :

)(257
:

/ .

( :
( :
(
(
(
( .
( :

2ICl + H 2
I 2 + 2HCl

:
( ] rate = k [ ICl] [ H
( ] rate = [ ICl] [ H

(
( ] rate = k [ ICl] [ H
]rate = k [ I2 ][ HCl

( :
H 2 O2 + 2H + + 2I-
I 2 + 2H 2O

:
z

rate = k [ H 2 O2 ] H + I-
y

:
( )(x + y + z
( ) (k .

( .
( ).(x = 1, y = 2, z = 2

( :
( mol L-1 s-1

( mol L s-2

( L mol-1 s-1

( L mol s-1

)(258
:

/ .

( ) (k = 8.5 L mol-1 s-1

:
(

( .

( :
rate = k [A] [B]2
) (A ) (0.3 mol/L ) (B
)mol/L

(0.1

) (1 x 10-4 mol/Ls :
( 3

( 0.3

( 0.03

( 30

( :
(
(

(
(

( :
(

( (

( ) (A, B )(4 10-6 M min-1

) (0.2 M
:
( 1 10-4 M min-1
( 3 10-4 M . min

( 4 10-4 M-2 min-1

( 1 10-4 M-1 min-1

( ) (2
:
( 3

( 6

( 9

)(259
:

/ .

( ) (80 C :
)2N 2 O5 (g
) 4NO2 (g) + O2 (g
0.056
0.4

0.021
0.15

0.035
0.25

[N2O5] mol/L
)rate (mol/L s-1

:
(

( :
)2NO(g) + Cl2 (g
) 2NOCl(g
3
0.2
0.2
1.44

1
0.1
0.1
0.18

2
0.1
0.2
0.36

Exp.
][NO
][Cl2
rate M/min

:
( ]rate = k [NO]2 [Cl2
( rate = k [NO]2 [Cl2]2

( :
( ]rate = k [A]2 [B
( ]rate = k [C

( ]rate = k [NO] [Cl2

( rate = k [NO] [Cl2]2
2A + B
C

( ]rate = k [A] [B
( .

( 8
) (X ) (X :
( 2

( 3

( 4

( 8

)(260
:

/ .

( :

A + B
C

) (A ) (B
:
( L/mol s

( mol3/L3 s

( L3/mol3 s

( L2/mol2 s

)(261
:

/ .

)( Reaction Mechanisms


. :
4NH 3 + 5 O 2
4NO + 6H 2O

) (9 (4) ) (5
. )(9
) (10
.

.


.

.

)
(

)(262
:

/ .

)
( .
) ()(elementary reaction
.
.
:
k1
ZZZ
X
A + B YZZ
Z products
k -1

:
k1
ZZZ
X
A + B YZZ
ZC
k -1
k2
C + A
CA
k3
CA + B
CB + A
k4
CB
products

) (k4, k3, k2, k-1, k1 .

CB CA C :
.




.

)(263
:

/ .
ZZX 2HBr
H 2 + Br2 YZZ

.
:
:
A 2 + 2B
2AB

)(A2
) (B :
] rate = k [ A 2 ][ B] = k [ A 2
0

) (A2
) (B
:
)(slow

A 2
2A

A + B
) AB (fast

) )(slow

2A
( A 2

.


:

)(264
:

/ .
A 2
2A

)(slow

2A + B
A2B

)(fast

A 2 B + B
) 2AB (fast

.
) 2AB
( A 2 + 2B

) (B, A2 :
]rate = k [ A 2 ][ B

:
)(slow

A 2 + B
A2B

)(fast

A 2 B
2AB

)(slow

A 2 + B
AB + A

)(fast

A + B
AB

A2
).(B

)(265
:

/ .

Elementary Reaction


.

.
)NO2 (g) + CO(g
) NO(g) + CO 2 (g

.
) .(500 K
] [NO2
]: [CO
]rate = k [ NO2 ] [ CO

] rate = k [ NO2

) (NO2
)(NO2
) (2NO2
) (NO2

)(266
:

/ .

) (NO ) (O2 ) (CO ) (O2

): (CO2
)(slow

2NO 2
2NO + O 2

)(fast

O 2 + 2CO
2CO 2

_____________________________
2NO 2 + 2CO
2NO + 2CO 2

) (2 :
NO2 + CO
NO + CO2

)(
) (CO ) (O2 ) (CO2
) .(500 K

.
.

) (500 K
) (NO2 ) (NO ) (NO3
) (NO3 ) (CO ) (CO2 ) (NO2 :
)(slow

NO 2 + NO 2
NO3 + NO

)(fast

NO3 + CO
NO 2 + CO 2

______________________________
)NO 2 (g) + CO(g
) NO(g) + CO 2 (g

)(267
:

/ .

NO3
.
.
.
) (NO2

)(NO3

) (NO

) (intermediate compound

. ) (CO ) (CO2
).(NO2

) (complex reaction



.


:

)(268
:

/ .
2H 2 + O 2
2H 2 O

:
1. H 2 + O 2
H + HO 2
2. H + O 2
O + OH
3. O + H 2
H + OH
4. H 2 + HO 2
H 2 O + OH
5. H 2 + OH
H 2O + H
6. H + OH
H 2O

) (
) (HO2, OH, O, H
.
.

.

.

)(269
:

/ .

( :

)( .
.

.

.
( :

.
) (ditertiary butyl peroxide ) (O-O
.
)
( .
) (HI )(
H 2 + I H = - 134 kJ mol-1
(1) H + HI
(2) I + HI
I 2 + H H = 146 kJ mol-1

)(270
:

/ .

) (146 kJ .
) (2 ).(1

:
H = 386 kJ mol-1

C2 H 5 + O:
C2 H5O

)(1

H = 85 kJ mol-1

CH 3CHO + H
C2 H 5O

)(2

H = 51 kJ mol-1

CH 3 + CH 2O
C2 H 5O

)(3

H = 122 kJ mol-1

C2 H 4 + OH
C2 HO

)(4

) (3
.
(
"

".
:
:
6CH 3 + 2CO
( CH3 )3 COOC(CH3 )3

)(271
:

/ .

( )( :


.
.
)
(.
MO
)2NH 3 (g
)N 2 (g) + 3H 2 (g
MnO 2
)2H 2 O 2 (L
) 2H 2 O(L) + O 2 (g

:
:
)2O3 (g
) 3O 2 (g

.
:
] = k 2 [ O3

] d [ O3
dt

:
] k [ O3

] [O2

] d [ O3
dt

)(272
:

/ .

:
k1
ZZZ
X
O3 YZZ
Z O2 + O
k
-1

k2
O + O3
2O 2

k2

2O 2

(O + O

:
] K [ O3

] [O2

= ][O

K ) .(k1/k--1
k
) ( O + O3 2O 2
2

.
" "O3 :
] k 2 K [ O3

] [O2

= ] = K 2 [ O ][ O3

] d [ O3
dt

:
Ka = k 2K

.
.

)(273
:

/ .

) (Molecularity ).(order
)(Molecularity



.

).(rate determining step
:
) (
.

) ( :
) ( .

.
.

)(274
:

/ .

:


) (
.


.
.
:

) (
)( .
.

.
) (
.

.

)(275
:

/ .

:
) (NO ): (O3

NO + O3
NO 2 + O 2
) (NO ) (O3
) (NO ) (O .
.

) (
.

.

:
)2O3 (g
) 3O2 (g

:
ZZX O 2 + O
O3 YZZ

O3 + O
2O 2

.
) (Unimolecular

)(276
:

/ .

.
) (bimolecular
.
:
.

.


:
- Unimolecular Reactions

:
A
B

)( :
A
B + C

:
)ZZX 2I(g
I 2 (g) YZZ

)(277
:

/ .

:
A
Product

:
] = k [A

)(k

) (1/time = time -1 ] [A
.

).(mol/dm3 = mol /L
:

CH 3CH=CH 2

)(1

(2) CH 3 NC
CH 3CN

2CH3

(3) C2 H 6

2C2 H 4

)(4

C2 H 4 + H

(5) C2 H 5

.
:
Rn + 24 He

86
222

Ra

88
226

) (Ra ) (Rn
.

)(278
:

/ .

-
.
:
dC Ra
= k C Ra
dt

.
)
( :

- : Bimolecular Reactions :

:
) ( :
A + B
AB
2A
A2

:
A + B
C + D
2A
C + D

)(279
:

/ .

:
)HI(g) + HI(g
) H 2 (g) + I 2 (g

:
)H 2 (g) + I2 (g
) 2HI(g

:
A + A
product

:
A + B
product

:
= k [A] [A] = k [A]2
] = k [A] [B

:
(1) CH3 + C2 H 5
C3 H 8
(2) CH3 + CH 3
C2 H 6
(3) C2 H 4 + HI
C2 H5 I
(4) H + H 2
H 2 + H
(5) O3 + NO
O 2 + NO 2

)(280
:

/ .

- Trimolecular Reactions


:
A + A + A
product
A + A + B
product
A + B + C
product

.
) (NO
:
ZZX N 2O + H 2O
2NO + H 2 YZZ

:
] = k [NO]2 . [H 2

:
2NO 2
(1) 2N + O 2
2NOCl
(2) 2NO + Cl2
2HI
(3) 2I- + H 2
H 2 + Ar
(4) H + H +Ar

)(281
:

/ .

.

.

:
CH 3 + CH 3
C2 H 6
C2 H 6 + M
CH3 + CH 3 + M

M
.

)(282
:

/ .

.

ZZX CH 3COOH + C2 H 5OH
CH 3COOC2 H 5 + H 2 O YZZ

) + (.

.
:

:

C4 H9 OH
C4 H8 + H 2 O

.
:
+

H
CH 3COCH 3 + I 2
CH 3COCH 2 I + HI

)(283
:

/ .

:
2Fe 2+ + H 2 O 2
2Fe3+ + 2OH -

:
] = k Fe2+ [ H 2 O 2

d Fe3+
dt

)(284
:

/ .

Rate Law for Elementary Reactions


.

.

.
.

.
:
) 3O 2 (g
)2O3 (g
ZZX O 2 + O
O3 YZZ
O3 + O
2O 2

+O

ZZX O
( O YZZ
3

] rate = k1 [ O3

+ O
) 2O 2

: (O

)(285
:

/ .

]rate = k 2 [ O3 ][ O

.
) (free radicals )(C2H5
:
2C2 H 5
C4 H10

:
] rate = k [ C2 H5

)(286
:

/ .

The Rate Law and the Mechanism

) (rate determining step

.



:
k1
)NO 2 (g) + NO 2 (g
) NO3 (g) + NO(g) (slow

)(fast

k2
)NO3 (g) + CO(g
) NO 2 (g) +CO 2 (g

______________________________________________
k
)NO 2 (g) + CO(g
) NO(g) + CO 2 (g

)(287
:

/ .

) (
:
] rate = k1 [ NO 2

2
) ] ( rate = k1 [ NO 2

) (NO2 ) (NO
) .(225 C

k
) ) NO(g) + CO 2 (g
) ( NO2 (g) + CO(g

) (CO ).(NO2

) (intermediate
.


:
)Cl2 (g) + CHCl3 (g
) HCl(g) + CCl4 (g

] rate = k [ CHCl3 ][ Cl2

1/2

)(288
:

/ .
1/2
) ] ( rate = k [ CHCl3 ][ Cl2

) (CHCl3 ) (Cl2

) ) HCl(g) + CCl4 (g
). ( Cl2 (g) + CHCl3 (g

:
k

1
ZZZ
X
Cl 2 (g) YZZ
)Z 2Cl(g
k

)(fast

-1

)(slow

k2
)Cl(g) + CHCl3 (g
) HCl(g) + CCl3 (g

)(fast

k3
)Cl(g) + CCl3 (g
) CCl4 (g

k
) ) HCl(g) + CCl3 (g
) ( Cl(g) + CHCl3 (g
2

.
]rate = k 2 [ CHCl3 ][ Cl

).(Cl2

)(289
:

/ .

.

.
) (Cl2
).(Cl
) (Cl )(Cl2
:
) )ZZX 2Cl(g
( Cl (g) YZZ
2

:
) )ZZX Cl (g
( 2Cl(g) YZZ
2

) )( Cl(g) + CHCl (g) HCl(g) + CCl (g

k2

. )(forward
) (reverse ) )ZZX 2Cl(g
( Cl (g) YZZ
2

.
. :
rate1 = rate-1
]k1 [ Cl2 ] = k -1 [ Cl

-2
1/2

] [Cl] = 1 [Cl2
k -1

)(290
:

/ .

1/2

] [Cl] = 1 [Cl2
k -1

)]( rate = k [CHCl ][Cl

3

:
1/2

] [Cl] = 1 [Cl2
k -1

]rate = k 2 [ CHCl3 ][ Cl
1/2

] rate = k 2 [ CHCl3 ] 1 [ Cl2

k -1

] rate = k [ CHCl3 ][ Cl2

1/2

) (k
(k = k2 (k1/k-1)1/2

.


.



.

)(291
:

/ .

.


.
)(
:
)2NO(g) + 2H 2 (g
) N 2 (g) + 2H 2 O(g

:
)(slow

2NO + H 2
N 2O + H 2O

)(fast

N 2 O + H 2
N2 + H2O

____________________________________________
) (

2NO + 2H 2
N 2 + 2H 2 O

( .
( .

)(292
:

/ .

)(
:
)N 2O(g) + CO(g
) CO 2 (g) + NO(g

:
)(slow

NO 2 + NO 2
NO3 + NO

)(fast

NO3 + CO
NO 2 + CO 2

.
)(
:
2NO + Br2
2NOBr

:
)(slow

NO + Br2
NOBr2

)(fast

2NOBr
NOBr2 + NO

.
)(
:
)Cl2 (aq) + H 2S(aq
) S(s) + 2HCl(aq

:
]rate = k [ Cl2 ][ H 2S

)(293
:

/ .

:
(
)(slow

Cl2
Cl+ + Cl-

)(fast

Cl- + H 2S
HCl + HS-

)(fast

Cl+ + HS-
HCl + S

__________________________________________________
) (

)Cl2 (aq) + H 2S(aq

) S(s) + 2HCl(aq

(
)(slow

Cl 2 + H 2S
HCl + Cl + + HS Cl + + HS-
HCl + S

)(fast

________________________________________________
Cl 2 + H 2S
2HCl + S

) (

(
)(slow

Cl2
Cl + Cl

)(fast

Cl + H 2S
HCl + HS

)(fast

HS + Cl
HCl + S

__________________________________________________
) (

)Cl2 (aq) + H 2S(aq

) 2HCl(aq) + S(s

)(294
:

/ .

)(
) (SO2Cl2 ) (SO2 )(Cl2
.
( .
(

)(slow

SO 2 Cl + Cl
SO 2 Cl 2

1.

)(fast

SO 2 + Cl 2
SO 2 Cl + Cl

2.

_________________________________
SO 2 + Cl2
SO 2 Cl2