V = v - v' = kc1c2 ... - k'c1c'2 ...;

this states the fundamental law of chemical kinetics.

The equilibrium equation is simply a special case of this more general

one, and results when the total velocity is written zero, just as in

analytical mechanics the equilibrium conditions follow at once by

specialization of the general equations of motion.

No difficulty presents itself in the generalization of the previous

equations for the reaction which proceeds after the scheme

n1A1 + n2A2 + ... = n'1A'1 + n'2A'2 + ...,

where n1, n2, ..., n'1, n'2, ... denote the numbers of molecules of the

separate substances which take part in the reaction, and are therefore

whole, mostly small, numbers (generally one or two, seldom three or

more). Here as before, v and v' are to be regarded as proportional to

the number of collisions at one point of all molecules necessary to the

respective reaction, but now n1 molecules of A1, n2 molecules of A2,

&c., must collide for the reaction to advance from left to right in the

sense of the equation; and similarly n'1 molecules of A'1, n'2 molecules

of A'2, &c., must collide for the reaction to proceed in the opposite

direction. If we consider the path of a single, arbitrarily chosen

molecule over a certain time, then the number of its collisions with

other similar molecules will be proportional to the concentration C of

that kind of molecule to which it belongs. The number of encounters

between two molecules of the kind in question, during the same time,

will be in general C times as many, i.e. the number of encounters of two

of the same molecules is proportional to the square of the concentration

C; and generally, the number of encounters of n molecules of one kind

must be regarded as proportional to the nth power of C, i.e. C^n.

The number of collisions of n1 molecules of A1, n2 molecules of A2 ...

is accordingly proportional to C1^{n1}C2^{n2} ..., and the

reaction-velocity corresponding to it is therefore

v = kC1^{n1}C2^{n2} ...,

and similarly the opposed reaction-velocity is

v' = k'C'1^{n'1}C'2^{n'2} ...;

the resultant reaction-velocity, being the difference of these two

partial velocities, is therefore

Encyclopaedia Britannica, 11th Edition, "Châtelet" to "Chicago" Volume 6, Slice 1 · 第 10 / 67 题