E. W.

Lund
University of Oslo

Oslo, Norway

Guldberg and Waage and the

Law of Mass Action

Last year, the hundredth anniversary of

the first publication by Guldberg and Waage dealing
with "The Law of Mass Action" was celebrated in their
native country (1). While the importance of this and
their later publication of 1867 is generally appreciated
by writers on the history of chemistry, the usual presentation of Guldberg and Waage's work, commonly found
in textbooks, was criticized in an article in the Textin 1956 (2). In
book Errors series of THB JOURNAL
that article, however, important parts of Guldberg
and Waage's work were not given an adequate treatment, in the present author's opinion. I therefore
feel that readers might profit from a further examination
of excerpts from the original papers, in assessing the
significance of Guldberg and Waage's contributions to
knowledge of both equilibrium and reaction rates.
In their first publication (S), presented to the
Christiania (now Oslo) Academy of Science and Letters
on March 11, 1864, Guldberg and Waage introduced
the concept of a reaction sequence. They distinguished
clearly between simple and composite reactions and
considered a composite reaction to consist of several
simple ones in a sequence. The remainder of their
treatment is limited to simple substitution reactions.
Throughout their work, Guldberg and Waage applied
the concept of "chemical force" which at that time was
considered to be the clue to the solution of the problem
of chemical affinity. Briefly, their arguments run as
follows: When a compound is formed in a chemical reaction, a strong chemical force is assumed to be acting.
Very often, however, one must conclude that two
opposing forces are active at the same time under given
conditions. This was particularly assumed to be the

548 / Journal of Chemical Education

case in reactions for which the direction may be reversed by changing temperature or relative concentrations. By careful selection of experimental conditions a state of equilibrium can be attained a t which
the two opposing forces balance.
It is evident that Guldberg and Waage's work was influenced by the investigations of Berthelot and St. Gilles
in 1861-63 (4) dealing with the formation and ddecomposition of esters. Guldberg and Waage's own
experimental work was primarily concerned with heterogeneous equilibria in systems containing sulfates and
carbonates of barium and potassium. In such cases
they find the same kind of situation as reported by
Berthelot and St. Gilles in their experiments, namely
that in a reaction of the kind A B = A'
B' there
is a limiting situation where all four substances are
present a t the same time. Guldberg and Waage considered this to be a state of equilibrium at which two
opposing forces were of equal magnitude. A few direct
quotations indicate their starting point and their
conclusion in the form of a general law.

In order to study the chemical force we have chosen the conditions where the formation and decomposition are taking place
at the same time. In this case, the forces which produce the
formation of the two molecules and those which decompose these
molecules in regenerating the original molecules, are acting s t the
same time and give rise to a. state of equilibrium.
When two molecules A and B with masses M and N tend to
form the two new molecules A' and B' by a substitution of their
elements, the total volume being V , the force which tends to
produce this substitution may be expressed by u ( M / V ) " ( N / V ) b
where a , a, and b are specific coefficients far the species
Let
us suppose that one has 8. system of four substances A, B, A',
and B' with masses p, q, p', and q' respeotively. When the state

...

of equilibrium is attained, the quantity z of A and of B is transformed into A' and B' and the masses are p - I , q - z, p',+ z ,
and q'
z . The force which tends to form A'
B' w111 he
a [ ( p - z ) / V I S [ ( q- z ) / V I b , and that which tends to form A
B will be a ' [ ( p '
z)/VI"[(qf
z ) / V ] b ' . These two forces
are equal and one ohtsina the equation

Thus with this statement a mathematical formulation

of the condition for chemical equilihrium was given for
the first time. It is clear however, that the authors
failed to realize that the powers to which a concentration had to be raised should be integers deducible from
the chemical equation. They considered the powers
to be parameters which had to be determined by experiment.
The quotations given above are taken from the puhlication in the French weekly periodical Les Mondes in
the issue of May 19, 1864 (6). I n their first publication
of March, Guldberg and Waage formulated two laws
for the force, one of Mass Action and one of Volume
Action. As shown above, the two laws were combined
into one of concentration action two mouths later.
I n the summer of 1864 Guldberg and Waage also
presented papers dealing with the influence of time on
chemical reactions. They proposed the idea that the
driving force is proportional to the rate of the reaction.
Again they considered the substitution reaction A
B = A'
B' and treated two cases mathematically.

Let Us assume that the new bodies A'and B' do not react. Let
I, and o be the number of molecules of A and B. v the veloeitv. t

where k is a constant depending on the nature of the bodies, the

volume, the temperature, and the solvent.
Then, let us consider the more general case where the new substances A' and B' react and give the origind bodies A and B.
The force which tends to produce A
B ia equal to oza'9' and,
b' = n, one has the velocity
pntting a'

v = d x / d t = k [ ( p - x)]'[(q

- x)]b - a x "

I n this case s state of equilibrium is attained far a. certain value

of 2 .

For this value of x, the net velocity is equal to zero.

The authors then showed how it is possible to carry
out an approximate integration of their rate equation.
They applied the formula to a few reactions, i.e., some
of the esterificatious reported by Berthelot and St.
Gilles and the reaction between barium peroxide and
hydrochloric acid for which experimental values had
been given by Brodie in 1863 (7).
I n the case of the ester formation they found that an
increase of the amount of acid makes the reaction go
faster, whereas an increase in the amount of alcohol
slows it down. They applied their formulae to various
cases (diierent kinds of alcohols and of acids and different temperatures). Very probably, this different
influence of acid and alcohol on the rate of reaction was
the main reason why they introduced the powers to he
determined experimentally in their equilibrium and
rate equations.
I n a second paper (8)written in French and presented
as an official publication of Oslo University in 1867,
Guldberg and Waage made a change in the formulation.
They gave a detailed discussion of their view on the

forces acting in a chemical system. From this discussion it follows that they considered forces to he
acting between all pairs of molecules present. Most
important were the "affinity forces" between the chemically reacting species. I n addition, weaker "secondary forces" were assumed to he acting between any
other pnir of molecules present. These latter forces
might rr:tard or accelerate the reaction.
Again they considered a system containing four substances A, B, A', and B' in a dynamical chemical
equilibrium with the equation A
B = A'
B'.
This time the concentrations (which they called "active
masses") were denoted by the letters p, q, p', and q',
respectively.
In order to simplify matters the authors introduced
the concept af an ideal reaction-in which the secondary
forces might be neglected. From their experiments
they considered themselves in the position to conclude
that the affinity force between A and B was proportional to the product of the concentrations, i.e., equal
to kpq, where k is a constant ("aflinity coefficient").
The opposite force, causing regeneration of A and B,
will be k'p'q' where k' is the affinity coefficient for that
reaction. This force is in equilibrium with the first
force, and consequently kpq = k'p'q'.
A few direct quotations may be appropriate to show
their further treatment.

After hwing determined the active masses of p, q, p', and q'

one can find the ratio between the coefficients k and k'. On the
other hand. havine found the ouatient k'lk.
, , one can ealeulate
in advance the result of the rertctians for an arbitrary initial state
of the four substances.
Let us denote by P , Q, P', and Q' the absolute quantities of
the four bodies A, B, A', and B' before the reaction starts and
let z be the number of atoms of A and B which are transformed
into A' and B'. Let us sumose that the total volume is constant
during the reaction and eq%S to V . One then obtains
p = (P - z)/V
z)/V
p' = ( P '

q = (Q - z ) / V
q' = (Q'
z)/V

After having introduced these values into the equation and

multiplied by Veone finds
(P

- z ) ( Q - 2) = ( k ' / k ) ( P ' + XI(&' + z )

With the aid of this equation, one easily determines the value of z .
When the two bodies A and A' have constant active masses
during the reaction and when the values of these masses are
equal, the formula reduces t o

This is the situation, a t least approximately, when A and A'

are solids while B and B' artre liquids.

They applied this formula to the reaction between

barium sulfate and potassium carbonate and found
very good agreement between observed and calculated
values. (Today we know this occurred because the
amount of solutes chosen were such that the solutions
had approximately the same ionic strength.)
Extensive applications were also made to esterification reactions. For these reactions they found that the
secondary forces could not be neglected. Therefore in
the case of the reaction between acetic acid and ethyl
alcohol, the equilihrium equation is
pq = 0.2372 p'q'

- 0.01843 pp' - 0.00626 pp'

0.0372 p'q

+ 0.00723 9.9'

Here p, q, p', and q' denote the concentrations of acetic

Volume 42, Number 10, Odober 1965

549

acid, ethyl alcohol, ethyl acetate, and water respectively. The last four terms on the right hand side
express the action of secondary forces. They clearly
are of minor importance.
In the same paper of 1867, Guldberg and Waage also
considered reaction rate in the new formulation and
gave observed and calculated values in a number of
cases.
We know today that some of the ideas of Guldberg
and Waage have been abandoned, for instance the
vague concept of "chemical force." This was, however, at the time a frequently used idea in the theory
of chemical affinity. Furthermore, it was perhaps
unfortunate that they based the theories so much on
heterogeneous equilibria. Their treatment of this
case was not quite correct because they considered the
active masses of BaSOPand of BaC03 to be equal.
On the other hand, they introduced useful ideas about
the concept of a reaction sequence and the influence of
"foreign" substances on reaction rate and equilibrium.
Of far greater importance, however, was their formulation of a general equilibrium equation, namely kpq =
k'p'q'. Their motivation for this equation was based
on general arguments in terms of forces and they
checked their hypotheses by experimental data, both
on reaction rates and on equilibrium.
The essential content of their work was made generally known due to the application of the equilibrium
equation by the Danish thermochemist Julius Thomsen
in a paper of 1869 (9). August Horstmann quoted the
same formula in 1873 and considered it to be in correspondence with his own theory of dissociation (10).
Horstmann also used Guldberg and Waage's experimental results in the case of the equilihrium between
BaSOa, BaC03, K2SOa, and K2C03. He found the
ratio between the concentration of KsSOa and K&O,
to he constant and independent of the relative amounts
of BaSOa and BaCOa present. This result, he admits,
was already suggested by Guldberg and Waage.
As a supplement to this account of Guldherg and
Waage's work, it seems appropriate to make a brief
note on other papers which represent two important
steps in the further development of the field. In 1877
van't Hoff gave a treatment (11) of the kinetics of
ester formation, based on the data of Berthelot and
St. Gilles. He assumed that the rate of a reaction is
proportional to the product of the numbers (P and Q )
of the interacting molecules and inversely proportional
to the total volume, i.e.
From this assumption he arrived at the simple equilibrium equation pq = '/rp'q' (here written in Guldberg
and Waage's notation). In spite of a somewhat incorrect rate law the equilihrium equation is correct
because there are two reactants on both sides.

550 / Journal of Chemical Educafion

In the same year Horstmann published a paper (12)

dealing with thermal dissociation of a solid into two
gaseous products. From thermodynamic arguments he
derived an equilihrium equation of the form pzm X
pan = d. Here p, and pa are the partial pressures of the
gaseous products, m and n are the number of moles
formed per mole of solid, and d is a function of temperature only. As far as it has been possible to determine,
this is the first appearance of the powers in an equilibrium equation as being equal to the coefficients in the
chemical equations.
Some of the publications in the 1870's must have
given Guldberg and Waage the impression that their
papers of 1864 and 1867 had not been generally known.
They must have felt the need to write about their ideas
in a more widely circulated journal, because such an
article appeared in Journal fur Praktische Chenzie in
1879 (15). In this last paper, molecular kinetics and
energy considerations were taken into account. The
authors stated that the molecules of a certain compound
may be in different states of energy and that only a
certain fraction of the molecules is in such a state that a
collision can initiate a reaction. The reaction rate is
proportional not only to these fractions of the active
masses, hut also to the active masses themselves.
Ideas along the same line had, however, been puhlished by Pfaundler in 1867 and 1874 (14, 15). This
last paper by Pfaundler and that by Horstmann in
1873 are especially interesting because they represent
the first applications of the second law of thermodynamics to chemical equilibrium. As is well known, this
approach in the hands of J. Willard Gihhs has provided
the most powerful tool in solving the problem of chemical affinity.
Literature Cited
(1) "The Law of Mass Action" (a. centenary volume), Det
Norske Videnskaps-Akademi i Oslo, Oslo, 1964.
E. A,, J. CHEM.EDUC.,33,544 (1956).
(2) GUGGENAEIM,
(3) G U ~ B E R GC., M., AND WAAGE,P., "Avhandl. Nomke
Videnskws-Akademi Oslo." Mat. Natorv. Kl., 1864,
p. 35.
(4) BERTHELOT,
M., AND PEAN DE SAINT-GILLES,L., Ann.
Chim. Phys. (3), 65, 385, (1862); 66, 5 (1862); 68, 225
ilRRR>.
GULDBERQ,
C. M., AND WAAGE,P., Les Mondes, 12, 107113 (1864).
Ibid., 12,627-32 (1864).
BBODIE,B.C.,Ann. Phya. Chem. 120,294(1863).
C. M., AND WAAGE,P., etude^ S L I 1.8
~ Affinitks
GULDBERG,
ehimique," Christiania, 1867; Ostwald's Klassiker, 104.
J., Ann. Phys. Chem., 138,65 (1869).
THOMSEN,
H O R S ~ A N A,,
N , Ann. Chem. & Phann., 170, 192 (1873);
Ostwald'sKh~iker,137.
J. H., Ber., 10,669 (1877).
YAN'THOFF,
HORSTMANN,
A,, Vwhand. NaturhistMed. Ver. Heidelberg,
1 (5), 465 (1877); Ostwald's Klassiker, 137.
GULDBERG,
C. M., AND WAAGE,P., J . Prakt. Chm., 127,
69 (1879); Ostwald's Klassiker, 104.
PFAUNDLER,
L., Ann. Phys. Chem., 131,55 (1867).
L., Ann. Phys. Chem., Jubelband, 182 (1874).
PFAUNDLER,
\----,-