LeChateliers Principle

How does an equilibrium system react to change? Once a system reaches equilibrium, what happens if it gets
disrupted? What factors are there that affect and equilibrium system?

Have you ever tried to get a small child to do something? If youve never dealt with a child in the midst of
their Terrible 2s, their favorite word is NO. The funny thing is, it doesnt even really matter what it is you
are trying to get them to do; the answer will be NO. In fact, at the height of the Terrible 2s, a child will ac-
tively do the opposite of whatever it is you ask of them. If you say, Come here to the child, he runs away. If
you say, Dont touch that! to the child, she will certainly pick it up as soon as your back is turned. No mat-
ter what you do, the child tends to do the opposite. This, of course, leads to insane games of reverse psycholo-
gy in desperate attempts to have the child do the simplest tasks of eating, sleeping, dressing, etc. which is why
your parents look like they do now. It is because you went through (and in some cases are still going through)
this phase.

This is exactly what the concept of LeChateliers Principle in chemistry says: a change in factor that affects
an equilibrium system will cause the system to react in such a way as to reduce or counteract the change.
Basically, whatever you do to a system that is at equilibrium, it will try to undo it; it will do the opposite.
Lets take a look at an example of this:

If you dissolve cobalt (II) chloride in alcohol instead of water, you get a very interesting equilibrium system:

[CoCl4]-2 (alc) + 6 H2O (alc) <> [Co(H2O)6]+2 (alc) + 4 Cl-1 (alc)

Blue Pink

Please note that all of these species are dissolved in alcohol as the
solvent which is why we see (alc) instead of aqueous (aq). It is one
of the few times this year in an example that water is actually a so-
lute instead of a solvent!

Take a look at an example of this system. It is clear from this pic-

ture that the chemicals in the beaker are blue. This means that there
is far more of the:

[CoCl4]-2 ion present which is blue than the

[Co(H2O)6]+2 ion which is pink.

The system is currently at equilibrium as the color is not changing.

But what would happen in we disrupt this equilibrium by adding in
some H2O?

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Examine the Kc of the equation: As the amount of water increases,
it decreases the overall ratio be-
[Co(H2O)6]+2 *[Cl-1]4 cause water is in the denominator
Kc =
[CoCl4]-2 *[H2O]6

By adding in H2O to the system it makes the denominator bigger which makes the overall Kc ratio too small.
The system must shift so that the ratio of the products to the reactants gets bigger; the numerator must get big-
ger or the denominator must get smaller. How does this happen?

[CoCl4]-2 (alc) + 6 H2O (alc) <> [Co(H2O)6]+2 (alc) + 4 Cl-1 (alc)

Blue Pink

This can happen if the reaction shifts to the right side; there are more products and fewer reactants. If this oc-
curs, there will less of the blue [CoCl4]-2 substance and more of the pink [Co(H2O)6]+2 substance. What should
we see? We should see the blue color turn pink!

Take a look.
When water was added the solu-
tion turned pink just like ex-
pected. Now that equilibrium
has been re-established, can we
turn it back to blue? We can if
we add a substance that shifts the
reaction back to the left side.
Lets take a look again at the re-
action.

See this happen in video by going to this site. Click on the link marked LeChatelier 1.

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 [CoCl4]-2 (alc) + 6 H2O (alc) <> [Co(H2O)6]+2 (alc) + 4 Cl-1 (alc)

Blue Pink

What can we add so that the reaction shifts to the left? If we add Cl-1 ions then the ratio of products to reac-
tants will be too big.
[Co(H2O)6]+2 *[Cl-1]4
Kc = If you increase the Cl-1 ion, it
-2 6
[CoCl4] *[H2O] makes the numerator too big. The
reaction must go left to reduce it.

By making the numerator too big the reaction

is going to try to reduce the amount of Cl-1
ions added to the reaction by going to the left
side. This will make there be less of the pink
Co(H2O)6+2 and more of the blue CoCl4-2.
This should turn the solution back blue again.

If we summarize this result, in both cases

when we added a reactant to an equilibrium
system, the reaction shifted to the opposite
side of what we added.

It is just like that petulant two-year old we

discussed. Whatever you do the equilibrium
system, it will try to un-do.

(To see this in video, again to go this site and click on the LeChatelier video 2 link.)

Adding a species causes the equilibrium to shift to the

opposite side of the added species

Is that the only thing we can do? Of course not. Not only will a two-year old refuse to take something if given
to them (I once had my two-year old daughter refuse to eat chocolate cake Im not kidding) they will also
hold onto anything you try to take from them with a death grip. If you try to take something away, the child
will try to get it back. The same thing occurs in equilibrium systems.

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What would happen to this system if you added in some AgNO3? At first glance, it would appear that nothing
would happen as neither Ag+1 or NO3-1 are part of the equilibrium system. But remember from our solubility
rules that all chlorides (Cl-1) are soluble except Ag+1, Hg2+2, and Pb+2. By adding in Ag+1 to our system, the
Cl-1 ions will precipitate will them because AgCl is insoluble.
Ag+1 + Cl-1 > AgCl (s, ppt)

By doing this, what are we doing to the amount of Cl-1 distributed in the equilibrium system? We are reduc-
ing it, of course. The Ag+1 is precipitating out the Cl-1 ion as AgCl so the amount of free solvated Cl-1 ions
goes down.

How does the equilibrium system react? Remember LeChateliers principle says that whatever you do to the
system, it will try to un-do. If we take Cl-1 ions from the system, it will try to get them back. How does the
system make more Cl-1? By going to the right side where the Cl-1 is:

[CoCl4]-2 (alc) + 6 H2O (alc) <> [Co(H2O)6]+2 (alc) + 4 Cl-1 (alc)

Blue Pink

This should cause the system to form a precipitate (cloudy) and turn pink By making the amount of Cl-1 go
as it tries to make more Cl-1. down, the system will try to get it
See this in action by clicking here and watching LeChateliers video 3 back by going to the same side.

Notice the pink color

and the white precipitate
of AgCl that forms

Removing a species causes the equilibrium to shift to the

same side of the removed species

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LeChateliers Principle and Temperature
There is one last aspect to our Cobalt (II) chloride equation; temperature. What effect will temperature have
on the equilibrium system? Temperature is treated just like any other species; the only difference is that one
must figure out if the reaction is endothermic or exothermic. Remember that:

Endothermic: H = positive (+)

Exothermic: H = negative (-)
And
Endothermic equations position heat as a species on the left side of the equation
Heat + H2O (l) <> H2O (g) H = positive (+)
Exothermic equations position heat as a species on the right side of the equation
CH4 (g) + 2 O2 (g) > CO2 (g) + H2O (g) + Heat H = negative (-)

Thus, if you add heat (by raising the temperature or heating the system, for example) the effect will depend
upon whether the reaction is endothermic or exothermic; whether heat is on the left side of the equation or the
right side of the equation. What should happen to our Cobalt system?

If the reaction is endothermic (heat is on the left side):

Adding heat if the
Heat + [CoCl4]-2 (alc) + 6 H2O (alc) <> [Co(H2O)6]+2 (alc) + 4 Cl-1 (alc)
system is like this
Blue Pink
sends it to the right
and turns the sys-
Then by adding heat (increasing the temperature) it should shift the reaction to the right
tem pink
(adding makes it go to the opposite side) so the system should turn pink.

But if the system is exothermic (heat is on the right side): If heat is on this
[CoCl4]-2 (alc) + 6 H2O (alc) <> [Co(H2O)6]+2 (alc) + 4 Cl-1 (alc) + Heat side, then the reac-
Blue Pink tion should turn
blue when heated
Then by adding heat (increasing the temperature) the reaction should shift to the left as it goes back to
side or make the system turn blue. the left

Lets put two different test tubes; one pink and one blue in a beaker of hot water. After a few minutes, notice
that both of the tubes are now blue. This means that the reaction shifted to the left (blue side) so the reaction
must be exothermic (heat is on the right side; H = negative (-)). See LeChateliers video 4 here.

Room Temperature In Hot Water

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 LeChateliers Principle and solids and liquids
Examine the following equilibrium system:

Ca+2 (aq) + 2 HCO3-1 (aq) <> CaCO3 (s) + CO2 (g) + H2O (l)

Which way would the reaction shift (left or right) if we add more CaCO3 (s)? Your first instinct would be that
the reaction would go to the left because adding makes the reaction go to the opposite side. However, remem-
ber what LeChateliers Principle says: a change in any factor that affects the equilibrium system will cause the
system to react in such a way as to reduce or counteract the change. Examine the Kc equation for this system:
[CO2]
Kc =
[Ca+2] *[HCO3-1]2

Note that we ignored the CaCO3 because it is a solid and we ignored the H2O because it is a liquid. You only
count gases and aqueous species in the system. What effect will having more CaCO3 have on the K value?
None because CaCO3 is not included in the K calculations. So, what effect will adding more CaCO3 have on
the position of the equilibrium? None. It doesnt move.

Solids and liquid do not affect the position of the equilibrium

LeChateliers Principle and Catalysts

What effect do catalysts have on an equilibrium system? Remember the point of a catalyst; to provide an alter-
nate pathway by lowering the activation energy and thus increasing the rate of the reaction. Catalysts make the
reaction go faster. But remember that equilibrium reactions go both to the left and to the right. Which way
does the catalyst make go faster. The answer is simply; both. By lowering the activation energy it makes it
easier for the reaction to go from reactants to products as well as products to reactants. Thus, both the forward
and reverse reactions increase in rate and thus there is NO EFFECT on the position of the equilibrium.
Catalysts do not affect the position of the equilibrium

This is the activation This is the activation

energy of the forward energy of the reverse
reaction reaction

http://
monte.chem.ttu.edu/
group/tutorial/
br_sn2.html

A catalyst will lower the dotted horizontal line above, thus

lowering both the forward and reverse activation energies
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LeChateliers Principle and Gases
Because gases have a lot of space in between the individual particles, they can be compressed or expanded
which is why gases have a concentration. This does, however, lead us to a couple of circumstances that might
possibly affect the equilibrium system.

Gaseous Equilibrium Systems and Volume

Examine the following equilibrium system:
COCl2 (g) <> CO (g) + Cl2 (g) KP = 8

A system is made so that PCOCl2 = 1 atm, PCO = 2 atm, PCl2 = 4 atm. Is the system at equilibrium? In order to
check this, we must perform a Q calculation like we did before:

PCOPCl2 [2][4]
Kp = Q= =8 Yes, the system is at equi-
PCOCl2 [1]
librium because Q = K

What would happen if we were to compress the container the system is in (at constant temperature) so that the
volume is cut in half? Remember from Boyles Law that if the volume is cut in half, the pressure of the gas is
doubled. Thus, each of the pressures we have from before should double:

Pressure initially: PCOCl2 = 1 atm, PCO = 2 atm, PCl2 = 4 atm

Pressure under new conditions: PCOCl2 = 2 atm, PCO = 4 atm, PCl2 = 8 atm

Is the system still at equilibrium? Lets check by performing another Q equation:

PCOPCl2 [4][8]
Kp = Q= = 16 No! The system is NOT at
PCOCl2 [2]
equilibrium because Q K

What happened? Q is now too big. When Q is too big, the reaction goes to the left side so that Q gets smaller
until it equals K.

Think about it, though. We didnt really need to do this calculation if we remember that equilibrium systems
are like bratty kids; they want to un-do anything you do to the system. What did we do to the system? By low-
ering the volume, we increased the pressure on the system. How can the system relieve this pressure? By go-
ing to whichever side has the fewer moles of gases. In this case, the left side of the equation has only one mole
of gas; the right side has two moles of gas. There is less pressure on the left side so if the pressure increases,
the reaction shifts towards that side:

Right side has 2 moles of

Left side has only 1 mole of
COCl2 (g) <> CO (g) + Cl2 (g) gas. It has more pressure.
gas. It has less pressure.

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 Decreasing the volume increases the pressure.
The reaction shifts to the side with fewer moles of gas.

Increasing the volume decreases the pressure.

The reaction shifts to the side with more moles of gas.

If the moles of gas are the same on both sides, there is no effect from either
increasing or decreasing the volume of the container.

Example 1:
Which way will the following reaction shift (left, right, or no change) if the volume of the container is re-
duced at constant temperature?
N2 (g) + 3 H2 (g) <> 2 NH3 (g)

There are 4 moles of gas on the left and only 2 on the right. By decreasing the volume the pressure is in-
creased. The system will try to relieve that pressure by going to the side with fewer moles of gas. Thus, the
reaction shifts to the right.

Example 2
Which way will the following reaction shift (left, right, or no change) if the volume of the container is in-
creased at constant temperature?
CaO (s) + CO2 (g) <> CaCO3 (s)

There is 1 mole of gas on the left and 0 moles of gas on the right. By increasing the volume, the pressure of
the system decreases. The system can get that pressure back if it goes to the side with more moles of gas.
Thus, the system shifts to the left.

Example 3:
Which way will the following reaction shift (left, right, or no change) if the volume of the container is re-
duced at constant temperature?
H2 (g) + Cl2 (g) <> 2 HCl (g)

There are 2 moles of gas on the left and 2 on the right. By decreasing the volume the pressure is increased.
The system will try to relieve that pressure by going to the side with fewer moles of gas. However, because
there are equal moles of gas on each side, shifting the equilibrium will do no good so there is no change to
this system.

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Gaseous Equilibrium and Inert Gases
For the following equilibrium system:
2 CH4 (g) <> C2H2 (g) + 3 H2 (g) Kp = 32

Is the system at equilibrium if PCH4 = 4, PH2 = 2, and the PCH4 = 1?

Once again, do a Q test case:
PC2H2P3H2 [4][2]3
Kp = Q= = 32 Yes, the system is at equi-
P2CH4 [1]2
librium because Q = K

What will happen to the position of the equilibrium if 10 atm of Ne gas is pumped into the system with no
change of volume or temperature?

At first thought, it is obvious that adding in a bunch of Neon gas will increase the total pressure of the system
which might cause the reaction to shift in such a way as to reduce that new pressure. However, lets remem-
ber what Daltons Law of Partial Pressures says: the total pressure of a system is equal to the sum of the indi-
vidual partial pressures of each of the gases.

Thus, the total pressure of the system before the Neon gas was pumped in was:
Ptot = PCH4 + PC2H2 + PH2 = 4 + 2 + 1 = 7 atm total

After the Neon gas was added the total pressure of the system is:
Ptot = PCH4 + PC2H2 + PH2 + PNe = 4 + 2 + 1 + 10 = 17 atm total

The total pressure has indeed gone up. However, did you notice how the individual pressures of each of the
other species hasnt changed? The total pressure has been increased to 17 atm but what has happened to Q?
PC2H2P3H2 [4][2]3 The system is still in equilibrium because the
Kp = Q= = 32
P 2
CH4 [1]2 three species that are involved in the Kp equa-
tion didnt change. The addition of Ne gas
didnt affect them.

Thus, adding in an inert gas that is not involved in the system increases the total pressure but does not change
the position of the equilibrium.

Addition of an inert or non-participating gas to an equilibrium system does

not change the position of the equilibrium.

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 Summary
LeChateliers Principle: a change in factor that affects an equilibrium system will
cause the system to react in such a way as to reduce or counteract the change.

Addition of a participating gaseous or aqueous species shifts the reaction to the

opposite side of the equation the species is on

Removal of a participating gaseous or aqueous species shifts the reaction to the

same side of the equation the species is on

Endothermic reactions have heat on the left

Exothermic reactions have heat on the right
Heat is then treated like a participating species above

Solids and liquids and catalysts have no effect on the position of the equilibrium

Reducing the volume of a system will shift the reaction to the side with
fewer moles of gas

Increasing the volume of a system will shift the reaction to the side with
more moles of gas

Addition of a non-participating inert gas will increase the total pressure but will
not affect the position of the equilibrium

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