Le Chtelier's

Principle

Tabl e of Cont ents
1. 1. Introduction
2. 2. Concentration Changes
1. 2.1. Increasing a concentration
2. 2.2. Decreasing a concentration
3. 3. Pressure Changes
1. 3.1. Increasing the pressure
2. 3.2. Decreasing the pressure
3. 3.3. What happens if there are the same number of molecules on both
sides of the equilibrium reaction?
4. 3.4. Summary
4. 4. Temperature Changes
1. 4.1. Increasing the temperature
2. 4.2. Decreasing the temperature?
3. 4.3. Summary
5. 5. Catalysts
6. 6. Outside Links
7. 7. Problems
8. 8. References
9. 9. Contributors
Le Chtelier's principle states that if a dynamic equilibrium is disturbed by
changing the conditions, the position of equilibrium shifts to counteract the
change to reestablish an equilibrium. If a chemical reaction is at equilibrium
and experiences a change in pressure, temperature, or concentration of
products or reactants, the equilibrium shifts in the opposite direction to
offset the change. This page covers changes to the position of equilibrium
due to such changes and discusses briefly why catalysts have no effect on
the equilibrium position.
Introduction
An action that changes the temperature, pressure, or concentrations of
reactants in a system at equilibrium stimulates a response that partially
offsets the change while a new equilibrium condition is established (2).
Hence, Le Chtelier's principle states that any change to a system at
equilibrium will adjust to compensate for that change. In 1884 the French
chemist and engineer Henry-Louis Le Chtelier proposed one of the central
concepts of chemical equilibria, which describes what happens to a system
when something briefly removes it from a state of equilibrium.
It is important to understand that Le Chtelier's principle is only a useful
guide to identify what happens when the conditions are changed in a
reaction in dynamic equilibrium; it does not give reasons for the changes at
the molecular level (e.g., timescale of change and underlying reaction
mechanism).
Concentration Changes
Le Chtelier's principle states that if the system is changed in a way that
increases the concentration of one of the reacting species, it must favor the
reaction in which that species is consumed. In other words, if there is an
increase in products, the reaction quotient, Qc, is increased, making it
greater than the equilibrium constant, Kc. Consider an equilibrium
established between four substances, A, B, C, and D:
A+2BC+D
Increasing a concentration
What happens if conditions are altered by increasing the concentration of
A?
According to Le Chtelier, the position of equilibrium will move in such a
way as to counteract the change. In this case, the equilibrium position will
move so that the concentration of A decreases again by reacting it with B to
form more C and D. The equilibrium moves to the right (indicated by the
green arrow below).

In a practical sense, this is a useful way of converting the maximum
possible amount of B into C and D; this is advantageous if, for example, B
is a relatively expensive material whereas A is cheap and plentiful.
Decreasing a concentration
In the opposite case in which the concentration of A is decreased,
according to Le Chtelier, the position of equilibrium will move so that the
concentration of A increases again. More C and D will react to replace the
A that has been removed. The position of equilibrium moves to the left.

This is essentially what happens if one of the products is removed as soon
as it is formed. If, for example, C is removed in this way, the position of
equilibrium would move to the right to replace it. If it is continually removed,
the equilibrium position shifts further and further to the right, effectively
creating a one-way, irreversible reaction.
Pressure Changes
This only applies to reactions involving gases, although not necessarily all
species in the reaction need to be in the gas phase. A general
homogeneous gaseous reaction is given below:
A(g)+2B(g)C(g)+D(g)
Increasing the pressure
According to Le Chtelier, if the pressure is increased, the position of
equilibrium will move so that the pressure is reduced again. Pressure is
caused by gas molecules hitting the sides of their container. The more
molecules in the container, the higher the pressure will be. The system can
reduce the pressure by reacting in such a way as to produce fewer
molecules.
In this case, there are three moles on the left-hand side of the equation, but
only two on the right. By forming more C and D, the system causes the
pressure to reduce. Increasing the pressure on a gas reaction shifts the
position of equilibrium towards the side with fewer moles of gas molecules.

Example 1: Haber Process Equilibrium
N2+3H22NH3
If this mixture is transferred from a 1.5 L flask to a 5 L flask, in which direction does a net change occur to return to equilibrium? Because the volume is
increased (and therefore the pressure reduced), the shift occurs in the direction that produces more moles of gas. To restore equilibrium the shift needs to
occur to the left, in the direction of the reverse reaction.
Decreasing the pressure
The equilibrium will move in such a way that the pressure increases again.
It can do that by producing more gaseous molecules. In this case, the
position of equilibrium will move towards the left-hand side of the reaction.

What happens if there are the
same number of molecules
on both sides of the
equilibrium reaction?
In this case, increasing the pressure has no effect on the position of the
equilibrium. Because there are equal numbers of molecules on both sides,
the equilibrium cannot move in any way that will reduce the pressure again.
Again, this is not a rigorous explanation of why the position of equilibrium
moves in the ways described. A mathematical treatment of the explanation
can be found on this page.
Summary
Three ways to change the pressure of an equilibrium mixture are: 1. Add or
remove a gaseous reactant or product, 2. Add an inert gas to the constant-
volume reaction mixture, or 3. Change the volume of the system.
1. Adding products makes Qc greater than Kc. This creates a net change in
the reverse direction, toward reactants. The opposite occurs when adding
more reactants.
2. Adding an inert gas into a gas-phase equilibrium at constant volume does
not result in a shift. This is because the addition of a non-reactive gas does
not change the partial pressures of the other gases in the container. While
the total pressure of the system increases, the total pressure does not have
any effect on the equilibrium constant.
3. When the volume of a mixture is reduced, a net change occurs in the
direction that produces fewer moles of gas. When volume is increased the
change occurs in the direction that produces more moles of gas.
Temperature Changes
To understand how temperature changes affect equilibrium conditions, the
sign of the reaction enthalpy must be known. Assume that the forward
reaction is exothermic (heat is evolved):

In this reaction, 250 kJ is evolved (indicated by the negative sign) when 1
mole of A reacts completely with 2 moles of B. For reversible reactions, the
enthalpy value is always given as if the reaction was one-way in the
forward direction. The back reaction (the conversion of C and D into A and
B) would be endothermic, absorbing the same amount of heat.


The main effect of temperature on equilibrium is in changing the value of
the equilibrium constant.
Warning: It is not uncommon that textbooks and instructors to consider
heat as a independent "species" in a reaction. While this is
rigorously incorrect because one cannot "add or remove heat" to a
reaction as with species, it serves as a convenient mechanism to predict
the shift of reactions with changing temperature. For example, if heat is a
"reactant" (H>0), then the reaction favors the formation of products at
elevated temperature. Similarly, if heat is a "product" (H<0), then the
reaction favors the formation of reactants. A more accurate, and hence
preferred, description is discussed below.
Increasing the temperature
If the temperature is increased, then the position of equilibrium will move so
that the temperature is reduced again. Suppose the system is in equilibrium
at 300C, and the temperature is increased 500C. To cool down, it needs
to absorb the extra heat added. In the case, the back reaction is that in
which heat is absorbed. The position of equilibrium therefore moves to the
left. The new equilibrium mixture contains more A and B, and less C and D.

If the goal is to maximize the amounts of C and D formed, increasing the
temperature on a reversible reaction in which the forward reaction is
exothermic is a poor approach.
Decreasing the temperature?
The equilibrium will move in such a way that the temperature increases
again. Suppose the system is in equilibrium at 500C and the temperature
is reduced to 400C. The reaction will tend to heat itself up again to return
to the original temperature by favoring the exothermic reaction. The
position of equilibrium will move to the right with more A and B converted
into C and D at the lower temperature:



Example 2:
Consider the formation of water
O2+2H22H2OH=125.7kJ
1. What side of the reaction is favored? Because the heat is a product of the reaction,
the reactants are favored.
2. Would the conversion of O2 and H2 to H2O be favored with heat as a product or as a
reactant? Heat as a product would shift the reaction forward, creating H2O.
The more heat added to the reaction, the more H2O created.
Summary
Increasing the temperature of a system in dynamic equilibrium favors the
endothermic reaction. The system counteracts the change by absorbing the
extra heat.
Decreasing the temperature of a system in dynamic equilibrium favors the
exothermic reaction. The system counteracts the change by producing
more heat.

4. Hubungan Kesetimbangan Reaksi dengan Suhu
Nilai konstanta kesetimbangan bergantung pada suhu.
Kebergantungan tersebut dapat ditentukan melalui
persamaan-persamaan fundamental termodinamika dengan
cara mengukur besaran H baik secara kualitatif maupun
secara kuantitatif.
G = H -
TS (1.15)
Dari persamaan (5) dan (6) :
-RT ln K = H - TS
ln K = -H/RT + S/R

Catalysts
Adding a catalyst makes absolutely no difference to the position of
equilibrium, and Le Chtelier's principle does not apply. This is because a
catalyst speeds up the forward and back reaction to the same extent and
adding a catalyst does not affect the relative rates of the two reactions, it
cannot affect the position of equilibrium.
However, catalysts have some application to equilibrium systems. For a
dynamic equilibrium to be set up, the rates of the forward reaction and the
back reaction must be equal. This does not happen instantly and for very
slow reactions, it may take years! A catalyst speeds up the rate at which a
reaction reaches dynamic equilibrium.
Example 3
You might try imagining how long it would take to establish a dynamic equilibrium if you took the visual model on the introductory page and reduced
the chances of the colors changing by a factor of 1000 - from 3 in 6 to 3 in 6000 and from 1 in 6 to 1 in 6000. Starting with blue squares, by the end of
the time taken for the examples on that page, you would most probably still have entirely blue squares. Eventually, though, you would end up with the
same sort of patterns as before - containing 25% blue and 75% orange squares.
Outside Links
Huddle, Benjamin P. "Conceptual Questions" on LeChatelier's Principle." J.
Chem. Educ.1998 75 1175.
Thomsen, Volker B. E. " Le Chtelier's Principle in the Sciences." J. Chem.
Educ. 2000 77 173.
Problems
1. Varying Concentration
What will happen to the equilibrium when more 2SO
2
(g) is added to the
following system?
2SO2(g)+O2(g)2SO3(g)
Solution:
Adding more reactants shifts the equilibrium in the direction of the products;
therefore, the equilibrium shifts to the right.
Overall, the concentration of 2SO2 from initial equilibrium to final
equilibrium will increase because only a portion of the added amount
of 2SO2 will be consumed.
The concentration of O2 will decrease because as the equilibrium is
reestablished, O2 is consumed with the 2SO2 to create more 2SO3. The
concentration of 2SO3 will be greater because none of it is lost and more
is being generated.
2. Varying Pressure
What will happen to the equilibrium when the volume of the system is
decreased?
2SO2(g)+O2(g)2SO3(g)
Solution:
Decreasing the volume leads to an increase in pressure which will cause
the equilibrium to shift towards the side with fewer moles. In this example
there are 3 moles on the reactant side and 2 moles on the product side, so
the new equilibrium will shift towards the products (to the right).
3. Varying Temperature
What will happen to the equilibrium when the temperature of the system is
decreased?
N2(g)+O2(g)2NO(g)H=180.5kJ
Solution
Because H is positive, the reaction is endothermic in the forward
direction. Removing heat from the system forces the equilibrium to shift
towards the exothermic reaction, so the reverse reaction will occur and
more reactants will be produced.
References
1. Pauling, L., College Chemistry, 3rd ed., Freeman, San Francisco, CA,
1964.
2. Petrucci, R., Harwood, W., Herring, F., Madura, J., General Chemistry, 9th
ed., Pearson, New Jersey, 1993.
3. http://www.jce.divched.org/Journal/I...2N08/p1190.pdf





Le Chatelier's Principle
In 1884 the French chemist and engineer Henry-Louis Le Chatelier proposed one of
the central concepts of chemical equilibria.Le Chatelier's principle can be stated as
follows: A change in one of the variables that describe a system at equilibrium
produces a shift in the position of the equilibrium that counteracts the effect of
this change.
Le Chatelier's principle describes what happens to a system when something
momentarily takes it away from equilibrium. This section focuses on three ways in
which we can change the conditions of a chemical reaction at equilibrium:
(1) changing the concentration of one of the components of the reaction
(2) changing the pressure on the system
(3) changing the temperature at which the reaction is run.


Changes in Concentration
To illustrate what happens when we change the concentration of one of the reactants
or products of a reaction at equilibrium, let's consider the following system at 500
o
C.
N
2
(g) + 3 H
2
(g) 2 NH
3
(g) K
c
= 0.040
Initial: 0.100 M 0.100 M 0
Equilibrium: 0.100 - C 0.100 - 3 C 2 C
We obtain the following results when we solve this problem.
[NH
3
] = 2 C 0.0020 M
[N
2
] = 0.100 - C 0.099 M
[H
2
] = 0.100 - 3 C 0.097 M
The fact that C is small compared with the initial concentrations of N
2
and H
2
makes
this calculation relatively easy to do. But it implies that very little ammonia is actually
produced in the reaction. According to this calculation, only 1% of the nitrogen
present initially is converted into ammonia.
What would happen if we add enough N
2
to increase the initial concentration by a
factor of 10? The reaction can't be at equilibrium any more because there is far too
much N
2
in the system. Adding an excess of one of the reactants therefore places a
stress on the system. The system responds by minimizing the effect of this stress
by shifting the equilibrium toward the products. The reaction comes back to
equilibrium when the concentrations of the three components reach the following
values.
[NH
3
] = 2 C 0.0055 M
[N
2
] = 1.00 - C 1.00 M
[H
2
] = 0.10 - 3 C 0.092 M
By comparing the new equilibrium concentrations with those obtained before excess
N
2
was added to the system, we can see the magnitude of the effect of adding the
excess N
2
.
Before After
[NH
3
] 0.0094 M [NH
3
] 0.026 M
[N
2
] 0.095 M [N
2
] 0.99 M
[H
2
] 0.29 M [H
2
] 0.26 M
Increasing the amount of N
2
in the system by a factor of 10 leads to an increase in the
amount of NH
3
at equilibrium by a factor of about 3. Adding an excess of one of the
products would have the opposite effect; it would shift the equilibrium toward the
reactants.


Changes in Pressure
The effect of changing the pressure on a gas-phase reaction depends on the
stoichiometry of the reaction. We can demonstrate this by looking at the result of
compressing the following reaction at equilibrium.
N
2
(g) + 3 H
2
(g) 2 NH
3
(g)
Let's start with a system that initially contains 2.5 atm of N
2
and 7.5 atm of H
2
at
500
o
C, where K
p
is 1.4 x 10
-5
, allow the reaction to come to equilibrium, and then
compress the system by a factor of 10. When this is done, we get the following
results.
Before Compression After Compression
P
NH3
= 0.12 atm P
NH3
= 8.4 atm
P
N2
= 2.4 atm P
N2
= 21 atm
P
H2
= 7.3 atm P
H2
= 62 atm
Before the system was compressed, the partial pressure of NH
3
was only about 1% of
the total pressure. After the system is compressed, the partial pressure of NH
3
is
almost 10% of the total.
These data provide another example of Le Chatelier's principle. A reaction at
equilibrium was subjected to a stress an increase in the total pressure on the
system. The reaction then shifted in the direction that minimized the effect of this
stress. The reaction shifted toward the products because this reduces the number of
particles in the gas, thereby decreasing the total pressure on the system, as shown in
the figure below.

N
2
(g) + 3 H
2
(g) 2 NH
3
(g)


Changes in Temperature
Changes in the concentrations of the reactants or products of a reaction shift the
position of the equilibrium, but do not change the equilibrium constant for the
reaction.
Similarly, a change in the pressure on a gas-phase reaction shifts the position of the
equilibrium without changing the magnitude of the equilibrium constant. Changes in
the temperature of the system, however, affect the position of the equilibrium by
changing the magnitude of the equilibrium constant for the reaction.
Chemical reactions either give off heat to their surroundings or absorb heat from their
surroundings. If we consider heat to be one of the reactants or products of a reaction,
we can understand the effect of changes in temperature on the equilibrium. Increasing
the temperature of a reaction that gives off heat is the same as adding more of one of
the products of the reaction. It places a stress on the reaction, which must be alleviated
by converting some of the products back to reactants.
The reaction in which NO
2
dimerizes to form N
2
O
4
provides an example of the effect
of changes in temperature on the equilibrium constant for a reaction. This reaction is
exothermic.
2 NO
2
(g) N
2
O
4
(g) H
o
= -57.20 kJ
Thus, raising the temperature of this system is equivalent to adding excess product to
the system. The equilibrium constant therefore decreases with increasing temperature.
Practice Problem 7:
Predict the effect of the following changes on the reaction in which SO
3
decomposes to form
SO
2
and O
2
.
2 SO
3
(g) 2 SO
2
(g) + O
2
(g) H
o
= 197.78 kJ
(a) Increasing the temperature of the reaction.
(b) Increasing the pressure on the reaction.
(c) Adding more O
2
when the reaction is at equilibrium.
(d) Removing O
2
from the system when the reaction is at equilibrium.
Henri Louis Le Chatelier (1884) berhasil menyimpulkan
pengaruh faktor luar tehadap kesetimbangan dalam suatu azas
yang dikenal dengan azas Le Chatelier sebagai berikut:
Bila terhadap suatu kesetimbangan dilakukan suatu tindakan
(aksi), maka sistem itu akan mengadakan reaksi yang
cenderung mengurangi pengaruh aksi tersebut.
Secara singkat, azas Le Chatelier dapat dinyatakan sebagai:
Reaksi = Aksi
Artinya : Bila pada sistem kesetimbangan dinamik terdapat
gangguan dari luar sehingga kesetimbangan dalam keadaan
terganggu atau rusak maka sistem akan berubah sedemikian
rupa sehingga gangguan itu berkurang dan bila mungkin akan
kembali ke keadaan setimbang lagi. Cara sistem bereaksi
adalah dengan melakukan pergeseran ke kiri atau ke kanan.