Equilibrium

Chapter 7/17
 7.1 Equilibrium

Essential ideas: Many reactions are reversible. These reactions will reach a state
Of equilibrium when the rates of the forward reactionand reverse reaction are
equal.The position of the equilibrium can be controlled by changing the
conditions.
Equilibrium state: This occurs when the rate is the same going in
both directions in a reaction, so there is no net movement in
either direction.

Physical systems: This is when there is no chemical change in a

reaction but a physical one such as phase of state changes. The
book uses an example of Br that is liquid at ambient temperature
but can easily evaporate into a vapor. If this occurs in a closed
container the process cycles between the 2 phases.
Enclosed terrariums are in equilibrium. This terrarium
has been closed for 40 years.
Chemical systems: This occurs when a substance
dissociates into its constituents such as HI H2 + I2
Equilibrium is dynamic: The reaction has not stopped but forward and
backward rate occur at same rate

Equilibrium is achieved in a closed system where there is no exchange of

matter with surroundings, so reactants and products can reactant and
recombine with each other.

The concentrations of the reactants and products remain constant at

equilibrium because they are being produced and destroyed at an equal rate.

At equilibrium there is no change in macroscopic properties such as color and

density.

Equilibrium can be reaches in either direction from reactants or products.

The equilibrium constant Kc can be predicted from the stoichiometry. This
constant, k, is only true for the temperature being tested! The equation
must be balanced.
The magnitude of k can tell us which direction the
reaction is favored since the product(s) are in the
numerator and the reactants are in the denominator
If you take the concentration of the products and reactants
when the reaction is NOT in equilibrium you can obtain a
value called the
Reaction quotient Q
Overview of how changing conditions will affect equilibrium:

1. Lowering temperature favors product formation and exothermic reactions

2. Raising temperatures favors the reactants & endothermic reactions
3. Catalyst favors the product but not the amount, just faster
4. Decreasing pressure will favor side with more molecules (they can spread
out and be less stressed by electrostatic forces)
5. Increasing pressure favors side with less molecules
6. K is only affected by temperature!
7. Increasing temperature increases the value of Kc for an endothermic
reaction and decreases the value of Kc for an exothermic reaction
What happens when equilibrium is disrupted by
Changes in temperature
Changes in pressure
Changes in concentration
Addition of a catalyst

?? ? ??

Remember La Chateliers
Principle?
Effect of catalyst on equilibrium
IB loves the Haber Process. Be sure to read the history of this in your
book as it was used in WWI to make explosives. Fritz Haber was a Polish
Jew who moved to Germany and worked with Carl Bosch to develop this
process. It was also used to produce poisonous gas. Haber was expelled
from Germany in 1933 due to his Jewish heritage.
Summary of what improves the Haber process:

1. Remove ammonia as it is formed so the reaction is driven

towards the products

2. Favors high pressure as there are less molecules formed in the

product

3.Favors low temperature as it is exothermic

4. Use finely-divided iron powder as a catalyst (more surface

area), and also some Al & Mg.
 The production of methanol:
CO(g) + 2H2(g) CH3OH(g) (H = -90 kJ mol-1)

Catalyst: Cu-ZnO-Al2O3(alumina)
Conditions: 250 C, 50 - 100 atm
 17.1 The equilibrium law

Essential Idea: The position of equilibrium can be quantified by the equilibrium

la. The equilibrium constant for a particular reaction only depends on the
temperature.
How do you calculate Kc from [initial] & [equilibrium]?

1. Balance equation
2. List the 3 equations and label as initial, change, & equilibrium states
3. Use a sign for a [decrease] & + [increase]
4. All changes must be in same ratio as coefficients in balanced equation
5. Equilibrium=[initial] =+/- [change]
 Examples:
Example #1: Given this equation:
H2 + I2 2 HI
Calculate all three equilibrium concentrations when [H2]o = [I2]o = 0.200 M and Kc = 64.0.
(A subscript of 0 =initial

Solution: The solution technique involves the use of what is most often called an ICEbox. Here is an empty
one:

[H2] [I2] [HI]

Initial

Change

Equilibrium
Now fill in the [initial] which just uses the values given in the problem. The
change will be filled in with x as the values are unknown. Since the
[reactant] will decrease, use x and the [product] will increase use a +x but
make it twice since the coefficients must match. We do not know how much
of the reactants is being used but we do know that the molar ratios are the
same.

[H2] [I2] [HI]

Initial 0.200 0.200 0

Change -x -x +2x

Equilibrium
 Now we have to add in the equilibrium row. We still dont know the actual
concentrations but we can mathematically put in the change. Now plug the
original equation into the equilibrium equation.

[H2] [I2] [HI]

Initial 0.200 0.200 0

Change -x -x +2x

Equilibrium 0.200-x 0.200-x 2x

H2 + I2 2 HI
and the equilibrium expression is:

Kc = [HI]2 / ([H2] [I2])

Now plug in the [equilibrium]

64.0 = (2x)2 / ((0.200 - x) (0.200 - x))

Solve the equation:

Take the square root of each side
8.00 = (2x) / (0.200 - x)
8(0.200 - x) = 2x
1.6 x- 8 x= 2x
1.6=10x
1.6/10= x
X=0.160M
Now, go back to the chart and plug in the values:

[H2] = 0.200 - 0.160 = 0.040 M

[I2] = 0.200 - 0.160 = 0.040 M
[HI] = 2 (0.160) = 0.320 M

You can check your work by plugging it into the equilibrium equation:

x = (0.320)2 / ((0.040) (0.040))

Since x = 64.0. we know that the problem was correctly solved.

Example #2: Given this equation:

PCl3 + Cl2 PCl5

Calculate all three equilibrium concentrations when Kc = 16.0 and [PCl5]o =
1.00 M.
PCl3 Cl2 PCl5

initial 0 0 1.0

change +x +x -x

equilibrium x x 1.0-x
Kc = [PCl5] / ([PCl3] [Cl2])
Substituting gives:

16.0 = (1.00 - x) / (x2)

Rearrange to get:
16x2 + x - 1 = 0 which can be solved by using the quadratic equation

Using the quadratic formula, which is x = (- b square root[b2 - 4ac]) /

2a, we obtain:

x = (- 1 + square root[12 - (4) (16) (-1)]) / 32

After suitable calculations, we find x = 0.221.

We dropped the negative value because the concentration value cannot

be negative
Now plug this value into the equation:

Kc = [1.0-0.221]/ [0.221][0.221] =0.779/0.0488=15.963= 16 so answer

is correct!
Example #3: Given this equation:

COCl2 CO + Cl2
Calculate all three equilibrium concentrations when Kc = 0.680 with [CO]o =
0.500 and [Cl2]o = 1.00 M. Below, I filled in the ICE box for these [initial]

[COCl2] [CO] [Cl2]

Initial 0 0.500 1.00

Change
Equilibrium
Since the products will form Cobalt (II) chloride, put a +x in its box, then a
x in the carbon monoxide and chloride. Fill in the equilibrium row as before.

[COCl2] [CO] [Cl2]

Initial 0 0.500 1.00

Change +x -x -x
Equilibrium x 0.500-x 1.00 - x
The equilibrium expression is:

Kc = ([CO] [Cl2]) / [COCl2]

Substituting into the expression gives:

0.680 = ((0.5 - x) (1 - x)) / x

0.680 = [0.5-1.5 x+x2 ] x

0.680x = 0.5-1.5 x+x2
2.18 x=0.5+x2 rearrange to put into quadratic form
X2 -2.18 +0.5 =0
x = ( 2.18 square root[(2.18)2 - (4) (1) (0.5)] ) / 2

Then, [2.18 +/- 1.66] /2

X=1.92 or 0.26

Since the starting [0.5] the answer has to be 0.26.

Kc = ([CO] [Cl2]) / [COCl2]
Substituting into the expression gives:

0.680 = ((0.5 0.26) (1 0.26)) / 0.26

[0.24 x 0.74]/ 0.26
0.1776/0.26
0.680 =0.680

Answer checks!
Free energy & equilibrium

How can we know which reactions will go to completion and reach equilibrium?
We have to look at Gibbs free energy and look at the energy in an equation.
When Q<k, reaction
proceeds to the right
towards the products.

When Q>k, the

reaction proceeds to
the left towards the
reactants.

When Q=K, the

reaction is at
equilibrium and there
is no net direction.
Kc can be calculated from thermodynamic data. R is the gas constant 8.31 J
K-1 mol-1 and the natural log of Kelvin Temperature is used
Calculate the equilibrium constant at 298K for the dissociation of
dinitrogen tetroxide

equilibrium equation

N2O4(g) 2NO 2(g)

Equilibrium equation N2O4(g) 2NO 2(g)

Hf,298K/kJ mol1 +9.7 2 x +33.9

S298K/J mol1K1 304 2 x 240

 Hsys,298K = Hf,products Hf,reactants = (2 x +33.9) (+9.7) = +58.1 kJ mol1

Ssys,298K = Sproducts Sreactants = (2 x 240) (304) = 176 J mol1K1

Gsys,298K = Hsys TSsys = (+58.1) (298 x 176/1000) = +5.652 kJ mol1

Gsys = RT ln(Kp) = RT ln{(pNO22)/(pNO2)}

substituting: 5.652 x 1000 = 8.314 x 298 ln(Kp)ln(Kp) = 5652/(8.314 x 298) = 2.281
Kp = pNO22/pNO2 = exp(2.281) = e(2.281) = 0.102 atm

One data book value quoted is 0.115 atm, so not too bad!