k > 500 nm, the first positive N 2 system. The kinetics of reaction (7.1.17) at
M = He, p He < 20 Torr is termolecular; at M = He, N 2 , p He = 0.3−1 Torr, p N 2 %
0:1 Torr, it is intermediate between bi - and termolecular, and at M = N 2 , p N 2 [ 0:1
Torr is bimolecular (see [4], p. 96, [5], p. 155 and references);
2N
4 S
À Á !
ðMÞ
N 2 A
3 R
þ
g ; v A
! N 2 X
1 R
þ
g
þ hv
ð7:1:18Þ
k = 230–350 nm, the Vegard-Kaplan bands. Reaction (7.1.18) is the first-order
one for [N(
4 S)] and [N 2 ]], at [N
4 S] > 10
12 cm
−3 and p N 2 \0:13 Torr. For [N
(
4 S)] = (10
12
−10
13 ) cm
−3 , p N 2 [ 100 Torr it is first-order reaction relative to [N
(
4 S)] and zero-order relative to [N 2 ]
(see [4], p. 96, [5], p. 155, and references).
The complete characteristic of a chemiluminescent reaction is the spectral distribution of the chemiluminescence rate constant k chl (k).
8. The spectral distribution of the rate constant of chemiluminescence reactions
with:
unimolecular kinetics:
k
I
chl ðkÞ ¼ I chl ðkÞ=½A photon=species Á s Á nm
ð7:1:19Þ
hereinafter, I chl (k) (photon/cm
3
ÁsÁnm) is the intensity of chemiluminescence emitted
at 1 cm
3 of the reaction zone and 1 s in a solid angle of 4p sr in the spectral range
Dk = 1 nm; species A is a reagent (molecule, radical), to the concentration of
which the rate of the chemiluminescent reaction is proportional;
kinetics intermediate between bi- and uninomolecular:
k
I
chl ðk; ½MÞ ¼ I chl ðkÞ=½A photon=species Á s Á nm:
ð7:1:20Þ
Here the rate constant of chemiluminescence of the first order k
I
chl (k, [M]) does
not depend linearly on [M];
with bimolecular kinetics:
k
II
chl ðkÞ ¼ I ch ðkÞ=½A Á ½B photon Á cm
3
=species
2
Á s Á nm
ð7:1:21Þ
with kinetics intermediate between bi- and termolecular:
k
II
chl ðk; ½MÞ ¼ I chl ðkÞ=½A Á ½B photon Á cm
3
=species
2
Á s Á nm
ð7:1:22Þ
with termolecular kinetics:
k
III
chl ðk; ½MÞ ¼ I ch ðkÞ=½A Á ½B Á ½M photon Á cm
6
=species
3
Á s Á nm
ð7:1:23Þ
7.1 Types of Chemiluminescent Processes. Rate Constants. Definitions
269
M = He, p He < 20 Torr is termolecular; at M = He, N 2 , p He = 0.3−1 Torr, p N 2 %
0:1 Torr, it is intermediate between bi - and termolecular, and at M = N 2 , p N 2 [ 0:1
Torr is bimolecular (see [4], p. 96, [5], p. 155 and references);
2N
4 S
À Á !
ðMÞ
N 2 A
3 R
þ
g ; v A
! N 2 X
1 R
þ
g
þ hv
ð7:1:18Þ
k = 230–350 nm, the Vegard-Kaplan bands. Reaction (7.1.18) is the first-order
one for [N(
4 S)] and [N 2 ]], at [N
4 S] > 10
12 cm
−3 and p N 2 \0:13 Torr. For [N
(
4 S)] = (10
12
−10
13 ) cm
−3 , p N 2 [ 100 Torr it is first-order reaction relative to [N
(
4 S)] and zero-order relative to [N 2 ]
(see [4], p. 96, [5], p. 155, and references).
The complete characteristic of a chemiluminescent reaction is the spectral distribution of the chemiluminescence rate constant k chl (k).
8. The spectral distribution of the rate constant of chemiluminescence reactions
with:
unimolecular kinetics:
k
I
chl ðkÞ ¼ I chl ðkÞ=½A photon=species Á s Á nm
ð7:1:19Þ
hereinafter, I chl (k) (photon/cm
3
ÁsÁnm) is the intensity of chemiluminescence emitted
at 1 cm
3 of the reaction zone and 1 s in a solid angle of 4p sr in the spectral range
Dk = 1 nm; species A is a reagent (molecule, radical), to the concentration of
which the rate of the chemiluminescent reaction is proportional;
kinetics intermediate between bi- and uninomolecular:
k
I
chl ðk; ½MÞ ¼ I chl ðkÞ=½A photon=species Á s Á nm:
ð7:1:20Þ
Here the rate constant of chemiluminescence of the first order k
I
chl (k, [M]) does
not depend linearly on [M];
with bimolecular kinetics:
k
II
chl ðkÞ ¼ I ch ðkÞ=½A Á ½B photon Á cm
3
=species
2
Á s Á nm
ð7:1:21Þ
with kinetics intermediate between bi- and termolecular:
k
II
chl ðk; ½MÞ ¼ I chl ðkÞ=½A Á ½B photon Á cm
3
=species
2
Á s Á nm
ð7:1:22Þ
with termolecular kinetics:
k
III
chl ðk; ½MÞ ¼ I ch ðkÞ=½A Á ½B Á ½M photon Á cm
6
=species
3
Á s Á nm
ð7:1:23Þ
7.1 Types of Chemiluminescent Processes. Rate Constants. Definitions
269