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BY FRANK E. E. GERMANS
t (a - b)2 i ~
b(b - x) ---i
(a - b)x + a(b - x)
b(a - x)
The tendency a t the present time is to make use of mols per liter in ex-
(11)
t (c - a)’ i~
(c-a)x
a(a - x)
This is correct for the case of a = b, but not for the case of 2A +C = RI +
_-_- Obviously equation (12) in the case of concentrations expressed
in mols per liter, should be replaced by
dx/dt = k (a - x)’(c - x/2)
which is of the form of equation (9), and (13) should be replaced by the
integrated form of equation (14).
Although equations of the forms of (9) and (14) may have been used
and integrated in the past, they have successfully escaped the attention of
the writer. It may, therefore, be of interest t o develop this point more fully.
For integration, equation (8) may be writkn
dx
kJdt=J (a - x) (b - x)’
Similarly, equation (9) may be written
Soyes: Z. physik Chem., 16, 546 (1895).
Getman: 4th Edition, p. 433 (1927).
Taylor: “A Treatise on Physical Chemistry,” 2 , 872
Chapter written by Francis Owen Rice.
I750 FRAKK E. E. GERMANK
kJdt =/ dx
(a - x/2) (b - x ) ~
dx
(za - x) (b - x)'
(16)
I t is, therefore. obvious that if equation ( I I ) gives the value of k as derived
from equation (8),we have only to transform ( I 1) by introducing the factor
z in the numerator and replace a by 2a to obtain a value of k from equation
(9). Thus we have
k = 2 .I
(za - b) x
t ( 2 8 - b)' ( b(b - X)
+ In
za(b - x)
b(za - x)
Similarly the equation a t the bottom of page 8 7 2 in Taylor should read
In all other cases of ist, 2nd and 3rd order reactions, the equations de-
veloped for k are equally valid whether niols or equivalents are used. The
numerical value of k will naturally depend on the units chosen. K h e n Fork-
ing with orders higher than the third, the equations will, in general, be dif-
ferent for concentrations expressed in equivalents or in niols. S o attempt
has been made in the above to distinguish between different values of k by
means of different symbols.
Under the date of February 14,1928, Dr. F. 0. Rice called the attention
of the author t o an error of the above type in Bodenstein's article. (Z. physik.
Chem., 29, 6 7 7 (1899) ) in which the reaction
2 H, f 0 2 2 H,O