is the principal channel of the interaction. The chemical compositions do not
change in them. Energies and the states of colliding partners vary in these processes. Therefore, they cannot be called as reactions. The ‘unreactive process’ term
is used in [2] (see p. 30, e.g.) for the processes in which chemical composition does
not change. The kinetic descriptions of reaction (2.1.1a) and processes of an O(
1 D)
atom electronic deactivations (2.1.2, 2.1.3) are the same, as the reader will see.
Below, the term process is used for the definition of chemical reactions and
process leading to the formationes in which chemical compositions do not change.
The reader sees that the term process is more comprehensive than the term reaction.
Let us consider a process of collision of m 1 species A 1 with m 2 species A 2 and so
on leading to the formation of m
0
1 species, A
0
1 , m
0
2 species A
0
2 , and so on. The m 1 ,
v
0
1 ¼ 1; 2; 3. . . numbers called stoichiometric coefficients are directly proportional
to the numbers of moles of the corresponding reagents.
v 1 A 1 þ v 2 A 2 þ . . . ¼ v
0
1 A
0
1 þ v
0
2 A
0
2 þ . . .
ð2:1:4Þ
or
X
i
v i A i ¼
X
k
v
0
k A
0
k
ð2:1:5Þ
The (2.1.4, 2.1.5) are called stoichiometric equations.
If m 1 = 1, 2 and 3, the process has first, second and third order regarding A 1 ,
respectively. For the reaction (2.1.1a), for example, the stoichiometric equations is:
Oð
1 DÞ þ H 2 O e
X
1
A 1
À
Á ¼ 2OH X
2 P; v X ; J X
À
Á ;
ð2:1:1bÞ
and the reaction has first order regarding the O(
1 D) and H 2 O(
$
X
1
A 1 ).
An another example is
Cl 2 þ 2Na ¼ 2NaCl:
ð2:1:6aÞ
It is obvious, that the stoichiometric equation (2.1.6a) does not describe the real
reaction mechanism. It states that to produce NaCl molecule it is necessary one Cl 2
molecule and two Na atoms, and two NaCl molecules are produced as a result. In
other words, a stoichiometric equation is an ‘account’ equation.
One should note that the equal signs and arrows are used in the stoichiometric
equations and processes, respectively. Below, concentrations of reactants (initial
products) and process products (final products) are denoted as [A i ] and [A
0
k ],
respectively.
The rate of a gas-phase process (a chemical reaction, in particular) is determined by the changes of reactant (or reaction product) concentrations with time.
Reactant product states are taken into account in this definition. According to
IUPAC Compendium of Chemical Terminology [1], ‘for the general chemical
reaction:
6
2 General Kinetic Rules for Chemical Reactions, Collisional …
change in them. Energies and the states of colliding partners vary in these processes. Therefore, they cannot be called as reactions. The ‘unreactive process’ term
is used in [2] (see p. 30, e.g.) for the processes in which chemical composition does
not change. The kinetic descriptions of reaction (2.1.1a) and processes of an O(
1 D)
atom electronic deactivations (2.1.2, 2.1.3) are the same, as the reader will see.
Below, the term process is used for the definition of chemical reactions and
process leading to the formationes in which chemical compositions do not change.
The reader sees that the term process is more comprehensive than the term reaction.
Let us consider a process of collision of m 1 species A 1 with m 2 species A 2 and so
on leading to the formation of m
0
1 species, A
0
1 , m
0
2 species A
0
2 , and so on. The m 1 ,
v
0
1 ¼ 1; 2; 3. . . numbers called stoichiometric coefficients are directly proportional
to the numbers of moles of the corresponding reagents.
v 1 A 1 þ v 2 A 2 þ . . . ¼ v
0
1 A
0
1 þ v
0
2 A
0
2 þ . . .
ð2:1:4Þ
or
X
i
v i A i ¼
X
k
v
0
k A
0
k
ð2:1:5Þ
The (2.1.4, 2.1.5) are called stoichiometric equations.
If m 1 = 1, 2 and 3, the process has first, second and third order regarding A 1 ,
respectively. For the reaction (2.1.1a), for example, the stoichiometric equations is:
Oð
1 DÞ þ H 2 O e
X
1
A 1
À
Á ¼ 2OH X
2 P; v X ; J X
À
Á ;
ð2:1:1bÞ
and the reaction has first order regarding the O(
1 D) and H 2 O(
$
X
1
A 1 ).
An another example is
Cl 2 þ 2Na ¼ 2NaCl:
ð2:1:6aÞ
It is obvious, that the stoichiometric equation (2.1.6a) does not describe the real
reaction mechanism. It states that to produce NaCl molecule it is necessary one Cl 2
molecule and two Na atoms, and two NaCl molecules are produced as a result. In
other words, a stoichiometric equation is an ‘account’ equation.
One should note that the equal signs and arrows are used in the stoichiometric
equations and processes, respectively. Below, concentrations of reactants (initial
products) and process products (final products) are denoted as [A i ] and [A
0
k ],
respectively.
The rate of a gas-phase process (a chemical reaction, in particular) is determined by the changes of reactant (or reaction product) concentrations with time.
Reactant product states are taken into account in this definition. According to
IUPAC Compendium of Chemical Terminology [1], ‘for the general chemical
reaction:
6
2 General Kinetic Rules for Chemical Reactions, Collisional …