Chemistry for Everyone
LeChteliers Principle in the Sciences
Volker B. E. Thomsen
Spectro Analytical Instruments, 160 Authority Drive, Fitchburg, MA 01420
Conceived by a chemist for chemical equilibria,
LeChteliers principle is actually a very general statement
about systems in equilibrium and their behavior when sub-
jected to external force or stress. It seems strange, therefore,
that one almost never finds mention of his name or law in
other sciences. In fact, several analogous principles do exist.
They simply appear under different names and address the
concept of equilibrium within different contexts.
In this note we examine some of the interesting forms
taken by this chemical principle in the fields of physics,
geology, biology, and economics. The discussion is presented
to provide additional insight into the nature of LeChteliers
principle along with analogies useful in its teaching.
LeChteliers Law
Henri Louis LeChtelier (18501936), a French chem-
ist, noted the effect of disturbances on equilibrium states in
chemical systems in 1884 and first published his principle
in 1888: For a system in equilibrium, external changes will
be accompanied by changes in the state of the system which
will act to reduce the magnitude of the initial change. The
changes referred to here may be in concentration, pressure,
or temperature. Examples can be found in most introduc-
tory texts.
The temperature and pressure dependence may be pre-
dicted quantitatively by the equations for the change in the
Gibbs free energy (1, 2),
d(G )/dP = V (1)
and
d(G )/dT = S (2)
It is understood that the temperature is held constant in the
first equation and pressure in the second.
Some comments on the origin of these statements are
important for the discussion that follows. Starting with the
first law of thermodynamics, dU = dQ + dW, and substituting
the expression for the work, dW = P dV, we get
dU = dQ PdV
Now the second law comes into play with the addition of
the entropy variable, defined as dS = dQ/T for a reversible
process. This leads us to
dU = TdS P dV
Other thermodynamic variables such as the free energy are
defined in terms of the variables in this equation.
The Gibbs free energy is a thermodynamic state variable
with the units of energy, defined as G U + PV TS. The
alternate form, G = U + PV TS, shows the way to eqs 1 easiest to see by assuming the opposite and noting that it
and 2 above. Consequently, we may note that LeChteliers
principle is a result of both the principle of conservation of
energy and the second law of thermodynamics.
The vant Hoff law of equilibrium is a special case of
this principle. Jacobus Henricus vant Hoff (18521911), a
JChemEd.chem.wisc.edu Vol. 77 No. 2 February 2000 Journal of Chemical Education
Dutch theoretical chemist, was the first recipient of the Nobel
Prize for chemistry in 1901. His law of equilibrium states that
when the temperature of a system is raised, the reaction goes
in the direction that absorbs heat. This is clearly an application
of the LeChtelier principle. However, since the times of
discovery or publication are similar, at least one source (3)
has suggested the name HoffLeChtelier law.
The vant Hoff equation for the variation of the equilib-
rium constant (K ) with temperature (T ) is
d(ln K )/dT = H/RT 2 (3)
where H the enthalpy of reaction and R is the universal gas
constant.
LeChteliers principle, stated in the most general terms,
is: If system in a state of equilibrium is subjected to an external
force, action, or stress that disturbs this equilibrium, then
the equilibrium is shifted in a direction such that the effect
of the applied force is reduced. In other words, a change takes
place within the system, opposing the action of the force and
tending to restore the initial state of equilibrium.
Lenzs Law in Physics
Heinrich Friedrich Emil Lenz (18041865) was a
German physicist who did most of his work in Russia. His
law indicating the direction of electromagnetically induced
currents was published in 1834.
We start with a coil of wire connected to a galvanometer.
Move a magnet toward this coil and a current will be registered
by the galvanometer. Stop the motion and the current ceases.
Remove the magnet and a current in the opposite direction
is observed. In general, an (instantaneous) voltage is induced
in a circuit that is equal to the rate of change of magnetic
flux through the circuit. This is a statement of Faradays law:
V = N (/t) (4)
where V is the induced voltage, N is the number of turns in
the coil, is the magnetic flux, and t is time.
In magnetic induction, Lenzs law states that the direction
of current produced by the induced voltage (emf ) is such as
to counter the original change. The polarity of the induced
emf is such that it produces a current whose magnetic field
opposes the change in the magnetic flux through the loop.
That is, the induced current tends to maintain the original flux
through the circuit (4 ). This statement is certainly similar
to that of LeChteliers principle.
Algebraically, Lenzs law amounts to the minus sign in
Faradays law. It should also be noted that this law is a direct
consequence of conservation of energy (4, 5). (This is perhaps
violates conservation of energy.)
Lenzs law may be characterized as an example of elec-
tromagnetic equilibrium, as opposed to the thermodynamic
equilibrium of LeChteliers principle. Since the entropy does
not enter into this law of physics, it must remain an analogy.
173
 Chemistry for Everyone
A Geological Application
The geological principle of isostatic uplift, sometimes
called isostatic rebound, also shows definite similarities to
LeChteliers principle. The basic idea of isostasy is that the
crustal masses of the earths surface layer float upon the
semiplastic mantle, much like ice cubes in a tub of water.
We can equate large ice cubes with mountains and small ones
with plains. If material is added to the small ice cube it floats
lower in the water. On the other hand, if matter is removed
from the large ice cube it will rise in the water.
There exists a gravitational equilibrium in the earths
crust. If this equilibrium is disturbed, then there occurs a
compensatory movement in the crust. For example, owing
to erosion, mountains become lighter and rise, whereas the
areas of deposition of the eroded material become heavier
and sink. If the Greenland ice cap were to melt, the crust
would rise until a new isostatic balance is achieved (6 ).
The British geophysicist John Henry Pratt (18091871)
and the astronomer Sir George Biddell Airy (18011892)
introduced this concept in 1855, although the two differed
in their consideration of the density of the various crustal
blocks (7).
This principle is also analogous to LeChteliers principle,
but it is an example of mechanical rather than thermody-
namic equilibrium. It is a consequence solely of conservation
of energy, in this case gravitational potential energy.
Biological Applications
We find an analogy to LeChteliers principle in the
biological sciences appearing under the name homeostasis:
Homeostasis...is the term generally applied to the tendency
for biological systems to resist change and to remain in a state
of equilibrium (8). The similarity with LeChteliers principle
is made even clearer in the following excerpt: Homeostasis
is said to be shown by a (physiological) system if, given a
moderate disturbance that tends to displace the system from
its normal values, its parts so react and interact that the harmful
effects of the disturbance are much diminished (9). This
concept of homeostasis finds application at various levels of
biological organization.
An example from the ecology of population distributions
is provided by the following excerpt from Odums classic text
on the subject (10): Lotka (1925) has shown on theoretical
grounds that a population tends to develop a stable age
distribution, that is, a more or less constant proportion of
individuals of different ages, and that if this stable situation
is disrupted by temporary changes in the environment or by
temporary influx from or egress to another population, the
age distribution will tend to return to the previous situation
upon restoration of normal conditions. More permanent
changes, of course, would result in development of a new
stable distribution.
Examples of homeostatic regulation at the physiological
level include the maintenance of body temperature
(homeothermy) and the bodys acidbase balance. All these
examples of regulatory phenomenaare correlated with the
general maintenance of a so-called steady state, or HOMEO-
STASIS, in the body. The internal environment is maintained
in a relatively constant condition by a complex series of
174 Journal of Chemical Education Vol. 77 No. 2 February 2000 JChemEd.chem.wisc.edu
Figure 1. Equilibrium and steady state.
mechanisms such as those for preventing marked changes in
the volume or composition of the blood, in the temperature
of the body, in the normal sugar and salt content of the blood,
and so on (11).
Is homeostasis the biological equivalent of LeChteliers
principle, or simply another analogy like the previous two
examples (Lenzs law and isostasy)? While the above quotations
show a clear similarity to this principle, they also raise some
flags. Note the use of the term equilibrium in the first
quotation of this section and steady state in the last. Also,
the term regulation surfaces.
The concept of equilibrium is not applicable to biological
systems, except at the molecular level. At all higher levels of
organization, cell, organ, organism, and community, there is a
constant flow of energy and matter maintaining a steady state.
The confusion of these two terms equilibrium and steady
state is not really surprising, as in common (dictionary) usage
the term equilibrium is usually defined as a state of balance,
which may be used to describe both conditions. (Note that we
have a similar problem with the terms precision and accu-
racy.) Figure 1, adapted from ref 12, shows the difference
between an equilibrium condition and a steady state. On the
left we find an equilibrium between fresh water and salt water.
The water is also in equilibrium with the air above it in the
closed container. A steady-state geological analogue is shown on
the right. Note the feedback loop from the ocean to the lake.
One of the few nonchemical references to LeChteliers
principle discovered was in the field of biology (13). The editor
of this volume states in his introduction that LeChteliers
principle is not applicable: Events in the inorganic world
to which man-made machines do not belongthough
governed by laws are not conspicuously regulated, claims
to the contrary like LeChteliers (1888) principle notwith-
standing. Although in agreement with the inapplicability of
LeChteliers principle, it should be noted that the geological
example of Figure 1 shows regulation through feedback in the
inorganic world. In fact, one might conclude that regulation
is a steady-state phenomenon, required as a necessary (but
not sufficient) condition. (Steady-state heat transfer along a
rod is an example without feedback.)
There is another theoretical approach to LeChteliers
principle, based on non-equilibrium or irreversible thermo-
dynamics (14 ), which ties this all together. In the section
entitled Stationary States and Biological Systems, this ref-
erence mentions LeChteliers principle explicitly and shows
that it is a special case of the entropy production condition,

Figure 2. Supply and demand curves.
valid only for the equilibrium situation: It is a fact, however,
that the increase of flux is always attended by a diminution of
the force conjugate to it, that the flux Jm will tend to nullify
the perturbation Xm, and thus restore the unperturbed
stationary state. This conclusion was first formulated by
LeChtelier (1888) for thermostatic equilibrium (k = 0); the
extension of his principle to k = 1 was made by Prigogine
(1947) and to stationary states of higher order by de Groot
(1951). The more general case is that of a steady-state system,
with application to biological systems (15, 16 ).
Therefore, while the biological concept of homeostasis
provides another interesting analogy to LeChteliers principle,
we must conclude that it is not identical. In fact, because of
its steady-state nature, it would seem to be more general.
Economics and LeChteliers Principle
The Law of Supply and Demand has been called
LeChteliers principle applied to economics (17). And indeed,
when we examine a statement of this law, the analogy becomes
apparent.
The supply of and demand for a particular commodity
establish its market price. The market is said to be in equi-
librium when the price remains constant. A disturbance of
the market equilibrium due to a change in supply or demand
will result in a shift of the equilibrium to a new price level in
a direction such as to offset the disturbance.
In modern economic theory there is no supply or de-
mand; rather, there are supply and demand curves. In Figure 2
the amount of commodity available (y-axis) is graphed versus
the price per unit quantity (x-axis) (18). The supply curve
has a positive slope, whereas the slope of the demand curve
is negative. The intersection of the two curves establishes the
equilibrium market price. With a shift in the demand curve
to the right, for example, a shift in the equilibrium occurs
such that the new market price is greater than before, tending
to counteract the increased demand.
This is a regulatory mechanism in a steady-state system,
similar to the concept of homeostasis already discussed. The
use of the term equilibrium is inappropriate, though perhaps
understandable (see comments above), and should be replaced
in the discussion above with steady state. Therefore, this law
would also seem to be more general than LeChteliers principle.
Nevertheless, this example from the field of economics can
provide a useful analogy in introductory chemistry classes.
JChemEd.chem.wisc.edu Vol. 77 No. 2 February 2000 Journal of Chemical Education
Chemistry for Everyone
Conclusions
LeChteliers principle is a very general statement and
we find analogies in various fields of scientific endeavor that
may well be pedagogically useful in introductory chemistry
classes. Each of the four examples presented above shows an
obvious similarity to the statement of this principle. In fact, at
first glance, they all appear identical. A closer look, however,
reveals that Lenzs law in physics and the geological principle
of isostatic uplift both depend only on conservation of energy
and thus might be considered more restrictive (less general)
than the thermodynamic principle of LeChtelier. The bio-
logical concept of homeostasis and the economic law of supply
and demand are examples of steady-state systems regulated
by feedback mechanisms. They too must also be regarded
as analogies, albeit of a higher order, with LeChteliers
principle as the special case.
It may, however, be more appropriate to consider all these
principles, laws, and concepts as principles of stability
within the applicable context of mechanical, electromagnetic,
or thermodynamic equilibrium, or the non-equilibrium
steady-state systems discussed above. In each case we find
mechanisms in place that serve to maintain the equilibrium
or steady-state conditionthat is, the state of balance.
Viewed in this way, any characterization as less general or
more general disappears in favor of the context of application
of the principle: All show that regulation occurs broadly in
the natural universe.
Finally, it is also important from a pedagogical viewpoint
to identify LeChteliers principle as a consequence of the
more general law of conservation of energy and the second
law of thermodynamics. Only in this way can the attention
of the student be diverted from the many individual laws to
the few truly important general principles of science.
Acknowledgment
I am indebted to the anonymous reviewer who pointed
out several flaws in the initial manuscript and generously pro-
vided suggestions to improve the revision.
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Chemistry for Everyone
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