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CHEMICAL REACTIONS O F T H E THIRD ORDER*

BY FRANK E. E. GERMANS

The general form of stoichiometric equations for reactions of the third


order may be represented by
A + +
B C j R i + + +
Rz RB (1)
A special case of a third order reaction may be represented by
3A e R i + + +
Rz RS (2)
which states that three molecules of A react in such a way as to give the
products on the right side of the equilibrium equation.
According to the principle of the mass action law, we may write in the
first case
d(a - x) d(b - x) - d(c - X)
- ____ = k(a - x) (b - x) (c - x) (3)
dt dt dt
or dx,idt = k(a - x) (b - x) (c - x) (4)
in which a, b and c represent the initial concentration in mols per liter of
A, B and C respectively present in the solution a t zero time. z therefore
represents the mols per liter of each compound, A, B and C, which hnve
disappeared at time t.
In the same way, we may write for the second case
d(a - x) - dx -
(ka - x ) ~
dt dt
This is also the form assumed in the first case, if the initial concentrations
of A, B and C are equal. If, however, a f b = c, that is, if the initial concen-
trations of B and C are identical, but different from A, we have
dx,/dt = k(a - x) (b - x ) ~ (6)
Up to this point the discussion is equally valid whether we speak in terms
of mols or equivalents per liter.
Suppose now we have a third order reaction of the form
A + 2 B e R i + +
Rz (7)
If we are using equivalents per liter as the measure of concentrations, then
we have
dx/dt = k(a - x) (b - x)' (8)
which is identical to (6). If, however, we are expressing our concentration
in terms of mols per liter, it is obvious from the equation that two mols
of B disappear for every mol of A that disappears. We must, therefore,
now write
dx/dt = k(a - x / 2 ) (b - x ) ~ (9)

* Contribution from the Department of Chemistry of the University of Colorado by


Frank E. E. Germann.
CHEMICAL REACTIONS O F THE THIRD ORDER I749

A particular case of an actual reaction which was first carefully studied by


Noyesl is represented by the equilibrium
SnClz 2FeC13 + e zFeC1’ +
SnC14 (10)
Since Xoyes expressed concentrations in terms of equivalents] he made use
of equation (8), which on integration yielded
k = - . -I 1

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)

pressing all concentrations, since there is less danger of confusion. As a re-


sult, many errors have crept into treatises on chemistry] and as a necessary
consequence, into the research work of the unsuspecting. Thus we find2 in
Getman’s “Outlines of Theoretical Chemistry” the statement] “The fol-
lowing table gives the results obtained with 0.025 molar solutions of ferric
chloride and stannous chloride.” As a matter of fact the table is a copy of
Table 6 of Noyes taken from page 551 of the article referred to above, except
for the fact that Noyes expressly labels his concentrations as “ 0 . 0 2 5 normal”
in place of “0.025 molar” as given.
I n connection with the same reaction,$ Taylol-l states specifically that
concentrations are expressed in mols per liter and goes on to state (referring
to the equation of the form of equation ( I ) ) “If the initial concentrations
of A and B are equal, or if the stoichiometric equation has the form 2A C =+
one or more resultants] we have
dx/dt = k (a - x ) (c
~ - x)
whence
k = - . I- 1

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

was under consideration.


This eiror n'as pointed out and critically examined by Wegscheider: Z.
physik. C'heni., 3 5 , 580 (1900); but no formula for k was given which can be
readily compared with equations (1 7 ) or ( I 8).