PAPER 2

ON THE REACTION VELOCITY OF THE

INVERSION OF CANE SUGAR BY ACIDSt

S. ARRHENIUS

[The so-called "Arrhenius law", which relates the rate constant £ of a

reaction to the absolute temperature Γ, is one of the most fundamental in
chemical kinetics. The relationship may be expressed as
k = Ae-ElRT (1)
where A and E are constants and R is the gas constant. Its general form
appears to have been first discovered empirically by J. J. Hood {Phil.
Mag. 6, 371 (1878); 20, 323 (1885)). Some significance was given to the
law by a thermodynamical argument due to J. H. van't Hoff, and this is
summarized by Arrhenius in the passage quoted below. In the latter part
of this passage Arrhenius gives further significance to the law by con-
sidering the matter from a statistical point of view.
Svante August Arrhenius (1859-1927) was a scientist of extraordinary
versatility. Born in Sweden, he studied at the Universities of Uppsala and
Stockholm, and in 1884 proposed in his doctoral dissertation that
electrolytes are dissociated in water; this theory was slow to gain
acceptance, but won him the 1903 Nobel Prize in Chemistry. He did not
work extensively on the theory of chemical kinetics; his discussion of
the "Arrhenius law", which is brief and to the point, represents his main
contribution in that field. He was a pioneer in the application of physico-
chemical methods to the study of biological systems, and wrote a book on
immunochemistry. He also published on cosmology, the causes of the ice
ages, and the origin of life.
The excerpt which follows is taken from pages 230 to 234 of his paper.]

IN HIS notable book Studies in Chemical Dynamics van't Hoff

gives a theoretically-based formulation of the influence of tem-
perature on the rate of reaction. Thus, in the case of an equilibrium
t An extract, translated from the German, from an article in Zeitschrift für
Physikalische Chemie, 4, 226 (1889).
31
32 CHEMICAL KINETICS

between four substances A, B, E and D (of which A and B can be

formed from E and D9 and vice versa) we have
=
k\ ^Α^Β ^2 CE^D (2)
in which equation CA, etc., signify the concentrations of the sub-
stances A, etc. This relationship also says that the amounts of E
and D produced in unit time from A and B are equal to the
amounts of A and B formed in the same time from E and D. That
is to say, the first quantity is represented by the term kx CACB
where k± is the rate constant (the specific reaction velocity): in the
same way k2 CECD represents the quantity of A and B newly
formed in unit time. For the system at equilibrium van't Hoff gives
^lognat fc i _ dlognatk2 q_
dT dT 2Γ 2 ^ ;

an equation that can be derived from the mechanical theory of

heat and van't Hoff 's law. In this equation T is the absolute
temperature and q the amount of heat (in calories) which is set
free when 1 gram-molecule each of A and B are converted into
E and D.
The two velocity constants for two reciprocal reactions are thus
related by this equation (3). "This equation", says van't Hoff,
"does not provide the desired relationship between the value of k
(the reaction velocity) and the temperature; it shows, however,
that this relationship has the following form:
d k
fo&iat A_ , B „ (4)
dT T2 K }

In equation (4) A and B are treated as constants. It is, however,

easily seen that B can be any function, F(T), of the temperature,
and equation (3) can only be obtained from (4) if the F(T) belong-
ing to the two reciprocal reactions are the same. I am of the
opinion, with regard to this, that there is no definite solution of
this problem, since F(T) can be anything at all.
It is not possible to proceed further without introducing a new
hypothesis, which is in a certain sense a paraphrase of the ob-
served facts. In order to reach such a hypothesis, which will be
 THE INVERSION OF CANE SUGAR BY ACIDS 33

used throughout, the following considerations must be taken into

account. The influence of temperature on the specific reaction
rate is very large in that, at ordinary temperatures, the rate
increases by 10 to 15 per cent for each one-degree rise in tempera-
ture. It cannot be assumed, therefore, that the increasing reaction
velocity comes from the increasing frequency of collisions of the
reacting molecules. According to the kinetic theory of gases, the
velocity of the gas molecules changes only by about 1/6 per cent
of its value for each one-degree rise in temperature and the
frequency of collisions increases in the same ratio. It is difficult to
say with certainty how large is the corresponding change in the
case of liquids, but it is suggested that it is similar to that in gases.
Even if the assumption that the velocity of the solute molecules
changes by 1/6 per cent per degree is not accepted, it must at
least be agreed that the difference between this value and the
observed 10 to 15 per cent per degree is much too large for it to be
assumed that the increase in the number of collisions of the react-
ing molecules is the reason for the increase in the reaction velocity
with the temperature. In the same way it can not very well be
assumed that the decrease of viscosity with increasing temperature
is the reason for the phenomenon under consideration, for the
viscosity decreases <*> by only some 2 per cent per degree. Apart
from this, the increase in reaction velocity differs in a very im-
portant way from the increase with temperature in most physical
quantities. Thus the change of these quantities is approximately
equal for an increase in temperature of 1°, even for very different
values of the temperature (e.g. 0° and 50°). On the other hand the
increase (in absolute value) per degree of the reaction velocity is
perhaps twice as large at 6° as at 0°, at 12° four times as large as
at 0°, at 30° perhaps thirty (25) times as large as at 0°, etc. This
fact indicates that the increase in reaction velocity with the
temperature cannot be explained in terms of the change in physical
properties of the reacting substances. There remains one way out.
A similar extraordinarily large change in specific reaction velocity
1
[The original paper says "increases" {nimmt zu) but this must be a
mistake.]
34 CHEMICAL KINETICS

(k) is to be found in another sphere. This is the change in rates of

reactions which are brought about by weak bases or acids, by the
addition of insignificant amounts of neutral salts (e.g. by addition
of NH4CI to NH3 acting upon ethyl acetate). In this case the facts
are explained thus : although the amount of the actual base (NH3)
or acid does not undergo a change on the addition of neutral salt
(NH4CI), by its addition there is a very rapid removal of free OH~
ions, which actually cause the reaction. Can it not be assumed that
the reaction velocity (for example the inversion of cane sugar) also
originates in this way, that the amounts of the actual reacting
substances rapidly increase with temperature? One actual reacting
substance is the H+ ion of the acid employed. The concentration
of this ion (for a constant amount of acid) changes only very little
with temperature for strong acids like HC1 (HN0 3 or HBr),
increasing (by something like 0-05 per cent per degree at 25°)
when the temperature rises. The explanation therefore can not lie
here. It must therefore be assumed, to be consistent, that the other
actual reacting substance is not cane sugar, since the amount of
sugar does not change with temperature, but is another hypo-
thetical substance which is regenerated from cane sugar as soon as
it is removed through the inversion.
This hypothetical substance, which we call "active cane sugar",
must rapidly increase in quantity with increasing temperature (by
about 12 per cent per degree) at the expense of the ordinary
"inactive" cane sugar. It must be formed from cane sugar at the
expense of heat (of q calories). It is further known that cane sugar
in solution at high temperatures has no important properties that
it does not possess at lower temperatures, as would probably be
the case if the absolute amount of the hypothetical active cane
sugar were increased considerably; it may therefore be assumed
that the absolute amount (although it increases by some 12 per
cent per degree) is still, at the highest temperatures employed,
exceedingly small in comparison with the amount of the "inactive
cane sugar". The amount of the latter is therefore independent of
temperature. Furthermore at constant temperature the reaction
velocity is approximately proportional to the amount of cane
 THE INVERSION OF CANE SUGAR BY ACIDS 35

sugar. Under these conditions (constant temperature), therefore,

the amount of "active cane sugar", Mfl, is approximately pro-
portional to the amount of inactive cane sugar, Mf. The equili-
brium condition is thus:
Me = jfc M, (5)
The form of this equation shows us that a molecule of "active
cane sugar" is formed from a molecule of inactive cane sugar
either by a displacement of the atoms or by addition of water. In
the equilibrium equation there is always on each side the product
of the amounts (concentrations) of the reacting substances. Since,
however, the amount of water is constant (the amount of cane
sugar varying) the water can also be active in the reaction without
its concentration appearing in the equation. Thus for the constant
k (or what is the same thing Mfl/M{) we have the equation
^lognatfc = JL (β)
dT 2Γ2 ;

which integrates to
T
kT =kT eqiTi - o>/2 T o r i.
■* 1 0l

If it is further assumed that the reaction velocity is proportional

only to the amounts of the reacting substances, a similar equation
can be written down for the reaction velocity corresponding to a
constant amount of reacting acid:
PTl = pToe«Ti-ToV2T0TK

We have given this equation above as equation (1) and have found
it to be in agreement with experiment.