Le Chatelier's

principle

Le Chatelier's principle (UK: /lə ʃæˈtɛljeɪ/,

US: /ˈʃɑːtəljeɪ/), also called Chatelier's
principle or "The Equilibrium Law", can be
used to predict the effect of a change in
conditions on some chemical equilibria.
The principle is named after Henry Louis
Le Chatelier and sometimes Karl
Ferdinand Braun who discovered it
independently. It can be stated as:
 When any system at equilibrium
for a long period of time is
subjected to change in
concentration, temperature,
volume, or pressure, (1) the
system changes to a new
equilibrium and (2) this change
partly counteracts the applied
change.

It is common to treat the principle as a

more general observation,[1] such as
 When a settled system is
disturbed, it will adjust to
diminish the change that has
been made to it,

or, "roughly stated",[1]

Any change in status quo

prompts an opposing reaction in
the responding system.

The principle has a variety of names,

depending upon the discipline using it (see
homeostasis, a term commonly used in
biology).

In chemistry, the principle is used to

manipulate the outcomes of reversible
reactions, often to increase the yield of
reactions. In pharmacology, the binding of
ligands to the receptor may shift the
equilibrium according to Le Chatelier's
principle, thereby explaining the diverse
phenomena of receptor activation and
desensitization.[2] In economics, the
principle has been generalized to help
explain the price equilibrium of efficient
economic systems.
Phenomena in apparent contradiction to
Le Chatelier's principle can arise in
systems of simultaneous equilibrium: see
the article on the theory of response
reactions.

Status as a physical law

Le Chatelier's principle describes the
qualitative behavior of systems where
there is an externally induced,
instantaneous change in one parameter of
a system; it states that a behavioural shift
occurs in the system so as to oppose
(partly cancel) the parameter change. The
duration of adjustment depends on the
strength of the negative feedback to the
initial shock. Where a shock initially
induces positive feedback (such as
thermal runaway), the new equilibrium can
be far from the old one, and can take a
long time to reach. In some dynamic
systems, the end-state cannot be
determined from the shock. The principle
is typically used to describe closed
negative-feedback systems, but applies, in
general, to thermodynamically closed and
isolated systems in nature, since the
second law of thermodynamics ensures
that the disequilibrium caused by an
instantaneous shock must have a finite
half-life.[3] The principle has analogs
throughout the entire physical world.

The principle while well rooted in chemical

equilibrium and extended into economic
theory, can also be used in describing
mechanical systems in that the system
put under stress will respond in a way
such as to reduce or minimize that stress.
Moreover, the response will generally be
via the mechanism that most easily
relieves that stress. Shear pins and other
such sacrificial devices are design
elements that protect systems against
stress applied in undesired manners to
relieve it so as to prevent more extensive
damage to the entire system, a practical
engineering application of Le Chatelier's
principle.

Chemistry

Effect of change in concentration E…

Changing the concentration of a chemical

will shift the equilibrium to the side that
would reduce that change in
concentration. The chemical system will
attempt to partly oppose the change
affected to the original state of
equilibrium. In turn, the rate of reaction,
extent, and yield of products will be altered
corresponding to the impact on the
system.

This can be illustrated by the equilibrium

of carbon monoxide and hydrogen gas,
reacting to form methanol.

CO + 2 H2 ⇌ CH3OH

Suppose we were to increase the

concentration of CO in the system. Using
Le Chatelier's principle, we can predict that
the amount of methanol will increase,
decreasing the total change in CO. If we
are to add a species to the overall reaction,
the reaction will favor the side opposing
the addition of the species. Likewise, the
subtraction of a species would cause the
reaction to "fill the gap" and favor the side
where the species was reduced. This
observation is supported by the collision
theory. As the concentration of CO is
increased, the frequency of successful
collisions of that reactant would increase
also, allowing for an increase in forward
reaction, and generation of the product.
Even if the desired product is not
thermodynamically favored, the end-
product can be obtained if it is
continuously removed from the solution.

The effect of a change in concentration is

often exploited synthetically for
condensation reactions (i.e., reactions that
extrude water) that are equilibrium
processes (e.g., formation of an ester from
carboxylic acid and alcohol or an imine
from an amine and aldehyde). This can be
achieved by physically sequestering water,
by adding desiccants like anhydrous
magnesium sulfate or molecular sieves, or
by continuous removal of water by
distillation, often facilitated by a Dean-
Stark apparatus.

Effect of change in temperature E…

The reversible reaction N2O4(g) ⇌ 2NO2(g) is
endothermic, so the equilibrium position can be
shifted by changing the temperature.
When heat is added and the temperature increases,
the reaction shifts to the right and the flask turns
reddish brown due to an increase in NO2. This
demonstrates Le Chatelier's Principle: the
equilibrium shifts in the direction that consumes
energy.
When heat is removed and the temperature
decreases, the reaction shifts to the left and flask
turns colorless due to an increase in N2O4: again,
according to the Principle.
The effect of changing the temperature in
the equilibrium can be made clear by 1)
incorporating heat as either a reactant or a
product, and 2) assuming that an increase
in temperature increases the heat content
of a system. When the reaction is
exothermic (ΔH is negative, puts energy
out), heat is included as a product, and,
when the reaction is endothermic (ΔH is
positive, takes energy in), heat is included
as a reactant. Hence, whether increasing
or decreasing the temperature would favor
the forward or the reverse reaction can be
determined by applying the same principle
as with concentration changes.
Take, for example, the reversible reaction
of nitrogen gas with hydrogen gas to form
ammonia:

N2(g) + 3 H2(g) ⇌ 2 NH3(g)    ΔH = -92

kJ mol−1

Because this reaction is exothermic, it

produces heat:

N2(g) + 3 H2(g) ⇌ 2 NH3(g) + heat

If the temperature were increased, the heat

content of the system would increase, so
the system would consume some of that
heat by shifting the equilibrium to the left,
thereby producing less ammonia. More
ammonia would be produced if the
reaction were run at a lower temperature,
but a lower temperature also lowers the
rate of the process, so, in practice (the
Haber process) the temperature is set at a
compromise value that allows ammonia to
be made at a reasonable rate with an
equilibrium concentration that is not too
unfavorable.

In exothermic reactions, increase in

temperature decreases the equilibrium
constant, K, whereas, in endothermic
reactions, increase in temperature
increases the K value.
Le Chatelier's principle applied to changes
in concentration or pressure can be
understood by having K have a constant
value. The effect of temperature on
equilibria, however, involves a change in
the equilibrium constant. The dependence
of K on temperature is determined by the
sign of ΔH. The theoretical basis of this
dependence is given by the Van 't Hoff
equation.

Effect of change in pressure E…

The equilibrium concentrations of the

products and reactants do not directly
depend on the total pressure of the
system. They may depend on the partial
pressures of the products and reactants,
but if the number of moles of gaseous
reactants is equal to the number of moles
of gaseous products, pressure has no
effect on equilibrium.

Changing total pressure by adding an inert

gas at constant volume does not affect
the equilibrium concentrations (see Effect
of adding an inert gas below).

Changing total pressure by changing the

volume of the system changes the partial
pressures of the products and reactants
and can affect the equilibrium
concentrations (see §Effect of change in
volume below).

Effect of change in volume E…

Changing the volume of the system

changes the partial pressures of the
products and reactants and can affect the
equilibrium concentrations. With a
pressure increase due to a decrease in
volume, the side of the equilibrium with
fewer moles is more favorable[4] and with
a pressure decrease due to an increase in
volume, the side with more moles is more
favorable. There is no effect on a reaction
where the number of moles of gas is the
same on each side of the chemical
equation.

Considering the reaction of nitrogen gas

with hydrogen gas to form ammonia:

N2 + 3 H2 ⇌ 2 NH3     ΔH = -92kJ mol−1

4 moles 2 moles

Note the number of moles of gas on the

left-hand side and the number of moles of
gas on the right-hand side. When the
volume of the system is changed, the
partial pressures of the gases change. If
we were to decrease pressure by
increasing volume, the equilibrium of the
above reaction will shift to the left,
because the reactant side has a greater
number of moles than does the product
side. The system tries to counteract the
decrease in partial pressure of gas
molecules by shifting to the side that
exerts greater pressure. Similarly, if we
were to increase pressure by decreasing
volume, the equilibrium shifts to the right,
counteracting the pressure increase by
shifting to the side with fewer moles of
gas that exert less pressure. If the volume
is increased because there are more
moles of gas on the reactant side, this
change is more significant in the
denominator of the equilibrium constant
expression, causing a shift in equilibrium.
Effect of adding an inert gas E…

An inert gas (or noble gas), such as

helium, is one that does not react with
other elements or compounds. Adding an
inert gas into a gas-phase equilibrium at
constant volume does not result in a
shift.[4][5] This is because the addition of a
non-reactive gas does not change the
equilibrium equation, as the inert gas
appears on both sides of the chemical
reaction equation. For example, if A and B
react to form C and D, but X does not
participate in the reaction:
.
While it is true that the total pressure of
the system increases, the total pressure
does not have any effect on the
equilibrium constant; rather, it is a change
in partial pressures that will cause a shift
in the equilibrium. If, however, the volume
is allowed to increase in the process, the
partial pressures of all gases would be
decreased resulting in a shift towards the
side with the greater number of moles of
gas. The shift will never occur on the side
with fewer moles of gas. It is also known
as Le Chatelier's postulate.

Effect of a catalyst E…
A catalyst increases the rate of a reaction
without being consumed in the reaction.
The use of a catalyst does not affect the
position and composition of the
equilibrium of a reaction, because both the
forward and backward reactions are sped
up by the same factor.

For example, consider the Haber process

for the synthesis of ammonia (NH3):

N2 + 3 H2 ⇌ 2 NH3

In the above reaction, iron (Fe) and

molybdenum (Mo) will function as
catalysts if present. They will accelerate
any reactions, but they do not affect the
state of the equilibrium.

General statement of Le
Chatelier's principle
Le Chatelier's principle refers to states of
thermodynamic equilibrium. The latter are
stable against perturbations that satisfy
certain criteria; this is essential to the
definition of thermodynamic equilibrium.

For this, a state of thermodynamic

equilibrium is most conveniently described
through a fundamental relation that
specifies a cardinal function of state, of
the energy kind, or of the entropy kind, as a
function of state variables chosen to fit the
thermodynamic operations through which
a perturbation is to be applied.[6][7][8]

In theory, and, nearly, in some practical

scenarios, a body can be in a stationary
state with zero macroscopic flows and
rates of chemical reaction (for example,
when no suitable catalyst is present), yet
not in thermodynamic equilibrium,
because it is metastable or unstable; then
Le Chatelier's principle does not
necessarily apply.

General statements related to

Le Chatelier's principle
A body can also be in a stationary state
with non-zero rates of flow and chemical
reaction; sometimes the word 'equilibrium'
is used in reference to such states, though
by definition they are not thermodynamic
equilibria. Sometimes, it is proposed to
consider Le Chatelier's principle for such
states. For this exercise, rates of flow and
of chemical reaction must be considered.
Such rates are not supplied by equilibrium
thermodynamics. For such states, it has
turned out to be difficult or unfeasible to
make valid and very general statements
that echo Le Chatelier's principle.[9]
Prigogine & Defay demonstrate that such a
scenario may or may not exhibit
moderation, depending upon exactly what
conditions are imposed after the
perturbation.[10]

Applications in economics
In economics, a similar concept also
named after Le Chatelier was introduced
by U.S. economist Paul Samuelson in
1947. There the generalized Le Chatelier
principle is for a maximum condition of
economic equilibrium: Where all unknowns
of a function are independently variable,
auxiliary constraints—"just-binding" in
leaving initial equilibrium unchanged—
reduce the response to a parameter
change. Thus, factor-demand and
commodity-supply elasticities are
hypothesized to be lower in the short run
than in the long run because of the fixed-
cost constraint in the short run.[11]

Since the change of the value of an

objective function in a neighbourhood of
the maximum position is described by the
envelope theorem, Le Chatelier's principle
can be shown to be a corollary thereof.[12]

See also
Homeostasis
Common-ion effect
 Response reactions

References
1. Gall, John (2002). The Systems Bible
(3rd ed.). General Systemantics
Press. "The System always kicks
back"
2. "The Biophysical Basis for the
Graphical Representations" .
Retrieved 2009-05-04.
3. Kay, J. J. (February 2000) [1999].
"Application of the Second Law of
Thermodynamics and Le Chatelier's
Principle to the Developing
Ecosystem". In Muller, F. (ed.).
Handbook of Ecosystem Theories
and Management. Environmental &
Ecological (Math) Modeling. CRC
Press. ISBN 978-1-56670-253-9. "As
systems are moved away from
equilibrium, they will utilize all
available avenues to counter the
applied gradients... Le Chatelier's
principle is an example of this
equilibrium seeking principle."
For full details, see: "Ecosystems as
 Self-organizing Holarchic Open
Systems: Narratives and the Second
Law of Thermodynamics". 2000: 5.
CiteSeerX 10.1.1.11.856 .
4. Atkins (1993), p. 114.
5. onlinechemistry (2019-08-13). "Le
Chatelier's principle" . Online college
chemistry courses. Retrieved
2020-02-17.
6. Münster, A. (1970), pp. 173–174.
7. Callen, H.B. (1960/1985), Chapter 8,
pp. 203–214.
8. Bailyn, M. (1994), Chapter 8, Part A,
pp. 312–319.
 9. Prigogine, I., Defay, R. (1950/1954),
pp. 268–269.
10. Prigogine, I., Defay, R. (1950/1954), p.
265.
11. Samuelson, Paul A. (1983).
12. Silberberg, Eugene (1971). "The Le
Chatelier Principle as a Corollary to a
Generalized Envelope Theorem".
Journal of Economic Theory. 3 (2):
146–155. doi:10.1016/0022-
0531(71)90012-3 .

Bibliography of cited
references
Atkins, P.W. (1993). The Elements of
Physical Chemistry (3rd ed.). Oxford
University Press.
Bailyn, M. (1994). A Survey of
Thermodynamics, American Institute of
Physics Press, New York, ISBN 0-88318-
797-3.
Callen, H.B. (1960/1985).
Thermodynamics and an Introduction to
Thermostatistics, (1st edition 1960) 2nd
edition 1985, Wiley, New York, ISBN 0-
471-86256-8.
Münster, A. (1970), Classical
Thermodynamics, translated by E.S.
 Halberstadt, Wiley–Interscience,
London, ISBN 0-471-62430-6.
Prigogine, I., Defay, R. (1950/1954).
Chemical Thermodynamics, translated
by D.H. Everett, Longmans, Green & Co,
London.
Samuelson, Paul A (1983). Foundations
of Economic Analysis . Harvard
University Press. ISBN 0-674-31301-1.

Bibliography
Le Chatelier, H. and Boudouard O.
(1898), "Limits of Flammability of
Gaseous Mixtures", Bulletin de la
 Société Chimique de France (Paris), v.
19, pp. 483–488.
Hatta, Tatsuo (1987), "Le Chatelier
principle," The New Palgrave: A
Dictionary of Economics, v. 3, pp. 155–
57.
D.J. Evans, D.J. Searles and E. Mittag
(2001), "Fluctuation theorem for
Hamiltonian systems—Le Chatelier's
principle", Physical Review E, 63,
051105(4).

External links
YouTube video of Le Chatelier's principle
and pressure
Retrieved from
"https://en.wikipedia.org/w/index.php?
title=Le_Chatelier%27s_principle&oldid=943037699
"

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