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Chemical Equilibrium
-In doing stoichiometric calculations, we assume that reactions proceed to completion
(when one of the reactants is totally consumed)
-Many reactions do proceed to completion. On the other hand, there are many chemical
reactions that stop far short of completion and tend to have to go back and forth from
consuming reactants to form products and from consuming products to form back the
reactants
-Such reactions are said to move to the right to form products (forward reaction) or to
move to the left to form the reactants (reverse reaction)
-The forward and reverse reactions will both have specific rates at which they occur
-When the rates of the forward and reverse reactions become equal, chemical
equilibrium is then reached
-Chemical Equilibrium is the state reached by a reaction mixture when the rates of
forward and reverse reactions have become equal.
The Equilibrium Condition
-Equilibrium is not static, but is a highly dynamic state.
-At the macro level everything appears to have stopped but at the molecular level, there
is activity.
-The concentration of products builds as the reaction proceeds. There will come a time,
in some reactions, where the products will collide and thus react and reform the
reactants.
-When both the forward and reverse reaction occur at the same rate there is no change in
concentration reactants and products and the reaction is said to be at equilibrium.
-A double arrow (
) is used to show that a reaction can occur in either direction.
Example: consider the following reaction
CO (g) + 3H2 (g)
-This is a gaseous reaction in which carbon monoxide and hydrogen react to form
methane and steam. It consists of forward and reverse reactions as presented above.
-Suppose we place 1mol of CO and 3 moles of H2 into a 10-L closed vessel at 1200K
(927oC)
rate of reaction of CO and H2 depends on the concentrations of CO and H2.
before the reaction occurs, the reactants are present at their maximum
concentrations
mC + nD
-where A, B, C, and D represent chemical species and j, k, m, and n are their coefficients
in the balanced equation.
-Since the concentration of the products and reactants remains constant at equilibrium,
we can set up a mass action expression: Which is the concentration of the products
(raised to the power of their coefficients) divided by the concentration of the reactants
(raised to the power of their coefficients)
[C]m [D]n
K=
[A]j [B]k
This mass action expression can then be used to find a constant for the reaction at a
given temperature. This constant is known as the equilibrium expression (Kc or Keq) .
To change this into an equilibrium expression, set it equal to Kc.
[C]m [D]n
Kc = j
[A] [B]k
Solution
a)
Kc =
b)
Kc =
Practice Example:
N2 (g) + 3H2 (g)
Forward reaction
Kc =
Reverse reaction
Kc =
Forward reaction
Kc =
Reverse reaction
Kc =
2NH3 (g)
Practice example:
Solution:
a)
write the balanced equation for the Haber process at 127oC:
Therefore, using the law of mass action we can write the expression for K:
Kc =
=
=
b)
=
K'c =
c)
K"c =
then,
K" = K1/2 = (
) =
2NH3
CNH 2
3
Kc =
=
3
[N2] [H2]
( CN ) ( C H 3 )
2
Kp =
( PN ) ( PH 3 )
2
- Fot the units of Kc, when the powers of the numerator are cancelled by that of the
denominator, Kc will have no units. However, when the powers are different and do not
cancel out, Kc will have units and Kc will not equal Kp.
Heterogeneous Equilibria
-Homogeneous equilibria - where all reactants and products are all in the same phase
(ex. all gaseous).
-Heterogeneous equilibria - where all reactants and products are not in the same phase.
-These equilibria do not depend on the amounts of pure solids or liquids present (ie.
pure solids and liquids are not included in the equilibrium expression).
-Therefore, the concentrations of liquid or solids are considered to be constant
Example:
CaCO3 (s)
Kp = PCO
-When reactants and products are mixed in a given reaction, it becomes very useful to
know whether the mixture is at equilibrium, or it will shift right or left.
-One key point for predicting the direction of the reaction is to see which of the products
or reactants has a concentration of zero. The system will shift in the direction that
produces the missing component
-If all the initial concentrations (reactants and products) are not zero, it becomes more
difficult to determine the direction of the reaction for reaching equilibrium
-In such cases, for predicting the direction of a particular reaction, we use the reaction
quotient, Qc, which is an expression that has the same form as the equilibrium
constant expression (Kc) but whose concentration values are not necessarily those
at equilibrium.
Example:
CO (g) + 3H2 (g)
Q2]ci3=[CO]
[H
Qc =
(0.0200) (0.0200)3
= 6.25
Kc = 3.92
(at 1200K)
Therefore, the Qc must decrease from 6.25 to 3.92 in order to reach equilibrium.
One way to decrease it, is to decrease the numerator (concentrations of products)
and to increase the denominator (concentrations of the reactants)
The numerator is the right side of the reaction, and to decrease it, the reaction should
proceed to the left.
Similarly, the denominator is the left side of the reaction, and to increase it or make
more of, the reaction should also proceed to the left.
Therefore, this reaction, under the given conditions will proceed to the left
In General:
If Qc Kc, the reaction will go to the left
If Qc Kc, the reaction will go to the right
If Qc = Kc, the reaction mixture is at equilibrium
Practice example:
A 50.0-L reaction vessel contains 1.00 mol N2, 3.00 mol H2, and 0.500 mol NH3. Will
more ammonia, NH3, be formed or will it dissociate when the mixture goes to
equilibrium at 400oC? ( Kc= 0.500 at 400oC )
N2 (g) + 3H2 (g)
2NH3 (g)
Solution:
With the given conditions we must figure out the direction of the reaction in order for
the mixture to reach equilibrium.
Therefore, we must first figure out _____ so we can compare it to Kc
In order to figure out ______ we must find the concentrations of each component
We are given the _____ of each component and the ______ in which the reaction occurs
Hence, we have:
[N2] = (
[H2] = (
[NH3] = (
)/(
)/(
)/(
)=
)=
M
M
)=
]i
i
[ Qc ]=i[
Qc =
Kc = 0.500
Given:
Kc = 1.15 x 102
[HF]i = [H2]i = [F2]i = (3.000 mol) / (1.500 L) = 2.000 M
Find:
2 HF (g)
Kc =
[H2] [F2]
(2.000)2
10
[H2]i Q
[F2c]=
i
=
(2.000) (2.0000)
= 1.000
Therefore, Qc << Kc thus, the reaction will shift to the right to reach equilibrium
b)
(Concentrations)
H2 (g)
F2 (g)
2 HF (g)
Starting
2.000 M
2.000 M
2.000 M
Change
-x
-x
+ 2x
Equilibrium
2.000 x
2.000 x
2.000 + 2x
To solve for x, we then substitute the values at equilibrium in the equilibrium expression
Perfect square
of Kc:
[HF]2
= 1.15 x 102 =
Kc =
[H2] [F2]
(2.000 + 2x)2
(2.000 + 2x)2
=
(2.000 x) (2.000 x)
(2.000 x)2
The right side of this equation is a perfect square, so taking the square root of both sides
will give:
(2.000 + 2x)
2
1.15 x 10 =
which gives x = 1.528
(2.000 - x)
Subsitituting x = 1.528 into the equilibrium equations of each component, we get:
[H2] = [F2] = 2.000 x = 2.000 1.528 = 0.472 M
[HF] = 2.000 + 2x = 2.000 + (2)(1.528) = 5.056 M
Therefore, the equilibrium concentrations of all species are:
0.472 M H2
0.472 M F2
5.056 M HF
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Given:
Kc = 1.15 x 102
[HF]i = 0
[H2]i = (3.000 mol) / (3.000 L) = 1.000 M
[F2]i = (6.000 mol) / (3.000 L) = 2.000 M
Find:
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H2 (g)
F2 (g)
2 HF (g)
Starting
Change
Equilibrium
To solve for x, we then substitute the values at equilibrium in the equilibrium expression
of Kc:
Kc =
this will give us:
where
b2 - 4ac
x=
13
2a
if we plug in the above values into the equation, we will get two possible values for x;
x = 2.14 mol/L and x = 0.968 mol/L
using either of these values for [H2] = 1.000 x, we find that x=2.14 gives us a negative
value for the concentration which is physically impossible to have! Therefore, the
correct value of x to be used is 0.968 mol/L.
Therefore,
Subsitituting x = 0.968 into the equilibrium equations of each component, we get:
[H2] =
[F2] =
[HF] =
Therefore, the equilibrium concentrations of all species are:
M H2
M F2
M HF
Treating Systems that Have Small Equilibrium Constants
-Under certain conditions, we are able to make simplifications (assumptions) that
greatly reduces the mathematical difficulties
-Equilibrium constants that have small values will often tell us that there will be
relatively small changes in order to reach equilibrium. In other words, there is a
relatively small change in the concentrations of the reaction components
-Lets consider an example in order to clarify this point:
Example:
Gaseous NOCl decomposes to form the gases NO and Cl2 at 35oC. at this temperature
the equilibrium constant is 1.6 x 10-5 mol/l. in an experiment in which 1.0 mol of NOCl
is placed in a 2.0 L flask, what are the equilibrium concentrations of all the species?
1) The balanced reaction is:
2NOCl(g)
2NO(g) + Cl2(g)
[NO]2 [Cl2]
Kc =
[NOCl]2
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[NO]i = 0
[Cl2]i = 0
[NOCl]i = (1.0 mol) / (2.0 L) = 0.50 M
4) Since there are initially no products, the reaction will shift to the right in order to
produce the missing components
5)
(Concentrations)
2 NOCl (g)
2NO(g) + Cl2(g)
Starting
0.5 M
0M
0M
Change
-2x
+2x
+x
0.5 2x
2x
Equilibrium
6) substitute the above equilibrium values into the equilibrium expression in step 2)
[NO]2 [Cl2]
(2x)2 (x)
= 1.6 x 10-5 mol/L =
Kc =
[NOCl]2
(0.5 2x)2
To solve this, it will obviously need multiplying, and collecting terms that result in an
equation that requires complicated calculations and is time consuming
This can be avoided by assuming that since Kc is so small (1.6 x 10-5 mol/L), the system
will shift to the right but not that far. This means that the change in concentration (which
is the 'x' terms) will be relatively small. And consequently, the x term could be omitted
when subtracting or adding the x term.
Therefore, [NOCl] at equilibrium = 0.5 2x 0.5
Making this assumption allows us to simplify the equilibrium expression to be:
(2x)2 (x)
(2x)2 (x)
1.6 x 10-5 =
=
(0.5 2x)
4x3
=
(0.5)
(0.5)2
7) Now we must check the validity of this assumption by comparing the value of x with
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0.5 2x 0.5
0.5 2(1.0 x 10-2) = 0.48
Here we can see that the difference between 0.5 0.48 = 0.02 (4%) is relatively small
difference and will have relatively little effect on the outcome.
8) Now we can use the value for x = 1.0 x 10-2 mol/L to find the equilibrium
concentrations from step 5) :
[NO] = 2x = 2 (1.0 x 10-2 ) = 2.0 x 10-2 mol/L
[Cl2] = x = 1.0 x 10-2 mol/L
[NOCl] = (0.5 2x) = 0.48 mol/L 0.50 mol/L
9) Finally, it is always good to check if these concentrations, when used in the
equilibrium constant expression of K, will give the same value of K given in the
question ( K= 1.6 x 10-5 mol/L)
Check:
[NO]2 [Cl2]
Kc =
=
[NOCl]2
(0.5)2
Such problems, where K is relatively small, suggest that the equilibrium shifts to a
very small extent, allowing us to assume that 'x' is negligible compared to the
initial starting concentration.
(divide any given concentration by the value of K. If > 100, assumption of
removing 'x' will be valid)
Le Chteliers Principle: Changing the Reaction Conditions
-Obtaining the maximum amount of product from a reaction depends on the proper
selection of reaction conditions.
-By changing these conditions, we can increase or decrease the yield of the products.
-For gaseous reactions, there are three ways to alter their equilibrium composition and
possibly increase the yield.
1. Changing the concentrations by removing products or adding reactants to the
reaction vessel.
2. Changing the partial pressure of gaseous reactants and products by changing
the volume.
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Example:
Predict the direction of reaction when H2 is removed from a mixture (lowering its
concentration).
H2(g) + I2(g)
2HI(g)
When H2 is removed from the reaction mixture, lowering its concentration, the reaction
will proceed in the reverse direction (more HI dissociates to form H2 and I2) to partially
restore the H2 that has been removed.
Practice Example:
Consider the following equilibrium reaction:
CO(g) + 3H2(g)
CH4(g) + H2O(g)
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18
-A pressure change obtained by changing the volume can affect the yield of product in a
gaseous reaction if the reaction originally involves a change in total moles of gas
CO(g) + 3H2(g)
CH4(g) + H2O(g)
-The above reaction is an example of a change in moles of gas. When the reaction
proceeds in the forward direction, a total of 4 moles of reactant gases (1CO + 3H2)
become a total of 2 moles of product gases (1CH4 + H2O).
If we decrease the volume of the reaction by half its original volume, we expect that
the pressure will increase, since we are compressing the gases! The two terms are
inversely proportional to each other. (PV = constant, at a fixed temperature)
Example:
So for the above example, if the pressure is doubled, we expect the volume to be
decreased by half, and that the concentration is increased. The mixture is no longer at
equilibrium!
The direction of the reaction then, can be predicted by using Le Chateliers Principle.
Let us restate the principle: Le Chateliers Principle states that when a system
in chemical equilibrium is disturbed by a change of temperature, pressure, or
concentration, the system shifts in a way that tends to counteract this change to
reach equilibrium once again.
In general, if the pressure is increased (compressing the mixture = decreasing the
volume), the reaction will favor the direction that contains the fewer moles of gas.
Example:
CO(g) + Cl2(g)
COCl2(g)
If the pressure is increased for the above reaction by changing the volume, in which
direction does the reaction shift in order to reach equilibrium once again?
Solution:
on the left side we have a total of 2 moles of gas (1mol CO + 1mol Cl2)
on the right side we have a total of 1 mol of gas (1mol COCl2)
Therefore, if we increase the pressure, the direction of the reaction will
favor the side that has the fewer moles.
In this case, it shifts to the _________
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Ho= -206.2 kJ
The value of Ho shows that this reaction is exothermic. As products are formed,
considerable heat is released.
In this case, if we increase the temperature, we expect that the reaction shifts to the left
to counteract this increase.
In general, energy must be treated as a reactant or product!
For an endothermic reaction (Ho positive), if the temperature is increased, the
forward reaction is favored to produce more products. If the temperature is
decreased, the reverse reaction is favored to produce more reactants.
For an exothermic reaction (Ho negative), if the temperature is decreased, the
forward reaction is favored to produce more products. If the temperature is
increased, the reverse reaction is favored to produce more reactants.
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Example:
CO(g) + H2O(g)
Example:
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