Chemical Equilibrium..

Until now, weve treated reactions as though they can only go

in one direction.with all of the reactants turning into
products
Most reactions that we have witnessed appear this way

Are all reactions like this?

Is it possible to reverse a reaction after it is completed?
Can we turn CO2 and H2O back into gasoline and O2 after it
burns?
2 C8H18 + 25 O2 16 CO2 + 18 H2O
16 CO2 + 18 H2O 2 C8H18 + 25 O2 ?

Chemical equilibrium

Most chemical reactions are reversible!

Reactions will continue to occur until they finally
maintain a ratio of products versus reactants that
will not change
This ratio is called the Equilibrium Constant
Expression, or Keq, or Kc, and is equal to the final
product concentration over the final reactant
concentration
K = Products
Reactants

Lets take the following chemical reaction:

aA + bB <-------------> cC + dD
When a chemical reaction reached equilibria, the
Equilibrium Constant Expression, or Keq, is:
Keq = [C]c[D]d
[A]a[B]b

Chemical Equilibrium
(continued)
Keq = [C]c[D]d
[A]a[B]b

A, B, C, and D represent the concentration of each

chemical at the end of the reaction
This concentration is measured in Molarity, or M
Once the reaction reaches equilibrium, the concentrations
of these molecules WILL NOT CHANGE

Lets examine the following

reaction

N2O4(g) <-----------> 2 NO2(g) at 250C

This reaction is reversible

At equilibrium, the constant, or Keq, is equal to:

Keq = [NO2]2
[N2O4]1
BUT WHAT DOES THIS TELL US?

It tells us whether we have more products or

reactants at equilibrium!!!!
Looking at the same reaction:
N2O4(g) <-----------> 2 NO2(g) at 250C
If the concentration of N2O4(g) at equilibrium was .0445 M
and the concentration of NO2(g) was .0161 M, then:

Keq = [NO2]2 = [.0161]2 = .00582 = 582

[N2O4]
[.0445]
1 100,000
This is the same as:

5.82
1000

Is this a exothermic
or endothermic
reaction.and why?

Suppose we have this reaction:

CO(g) + H2O(g) <--------> H2(g) + CO2(g)

The Keq = 5.10 at 5270C.

1
This means that products are favored over reactants almost 5
to 1!!
Lets say we are at some point in time, NOT AT
EQUILIBRIUM and we measure the concentrations of each
of the molecules in the reaction

Is it possible to predict if a reaction

is at equilibrium?
CO(g) + H2O(g) <--------> H2(g) + CO2(g)

The Keq = 5.10 at 5270C.

The concentrations are [CO] = .15 M,

[H2O] = .25 M, [H2] = .42 M, and
[CO2] = .37 M.
Can you set up a ratio of concentrations?

DO IT NOW!!!!!

Does your ratio look like this?

Q=

1
1
[.42] [.37]

[.15]1[.25]1
This

is called the REACTION

QUOTIENT, OR Q
It is set up the same way as Keq, but it
is not Keq
Why is it not the same as Keq?

What does Q tell you???

The reaction quotient, or Q, tells you where you

are in the reaction. You compare it to your Keq!

Q = [.42]1[.37]1 = 4.14
[.15]1[.25]1
1
Q = 4.14, which is less than Keq = 5.10

Q = 4.14, which is less than Keq = 5.10

1
1

If Q < Keq, then the reaction will make more

products to reach equilibrium
If Q > Keq, then the reaction will turn products
back into reactants to reach equilibrium
It Q = Keq, then the reaction is..
AT EQUILIBRIUM!!!!!
That means it is possible for a reaction to reverse
itself and turn product back into reactant!

AT EQUILIBRIUM
- The forward reaction, where molecules A
and B are forming molecules C and D
A + B --------> C + D
- Occurs at the same rate as the reverse
reaction, the reaction where molecules C
and D are forming molecules A and B
C + D --------> A + B
That is how the ratio at equilibrium never changes!

Chemical Equilibrium does not

mean:

That there are equal

concentrations of
reactant and product
when the reaction
reaches equilibrium!
It simply means that
there is eventually a
ratio reached that will
not change!

Chemical Equilibrium..
Lets look at problem #12 in the homework.
The reaction of elemental hydrogen and fluorine to form
hydrofluoric acid has an equilibrium constant of 1.15 x 102 at a
certain temperature. In one experiment, 3.00 mol of all 3
components, including the product, was added to a 1.50-liter
flask. Calculate the equilibrium concentrations of all species.
Write the reaction:

H2 (g) + F2 (g) --------> 2 HF (g)

This is an odd problem, because there is actually some of the

product present before the reaction actually begins! This is not
common product isnt usually present until the reaction
happens!

Chemical Equilibrium..
We want to set up an ICE:

1 H2 (g) + 1 F2 (g) --------> 2 HF (g)

I

C
E

Remember, I mean initial, C means change, and E means end or

equilibrium!
And we use concentration not moles, or amount!
What are the initial concentrations of each chemical?

Chemical Equilibrium..
What does our ICE look like?

1 H2 (g) + 1 F2 (g) --------> 2 HF (g)

I

2M

2M

2M

-x

-x

+2x

2-x

Kc 115 =

2-x

[HF]2

[H2]1[F2]1

2 + 2x
[2 + 2x]2

[2-x]1[2-x]1

Remember, we insert the concentrations into our K at

equilibrium!
We want to solve for the amounts at equilibrium this is going
to require some algebra!

Chemical Equilibrium..
Kc 115 =
1

[HF]2

[H2]1[F2]1

[2 + 2x]2
[2-x][2-x]

We have to expand this..

115 = 4 + 8x + 4x2
1

4 - 4x + x2

460 460x + 115x2 = 4 + 8x + 4x2

Rearranging,
0 = 456 468x + 111x2 or 111x2 468x + 456 = 0
How do we solve this?

Chemical Equilibrium..
111x2 468x + 456 = 0
Use the quadratic formula!
You can use the program on your calculator to solve this

You can go to http://www.wolframalpha.com/ and enter in the

equation it will solve it for you!
What are the solutions for x?

X = 1.5284 and 2.6878

One of these solutions cant work.
Which one? Why?

Chemical Equilibrium..

H2 (g) + F2 (g) --------> 2 HF (g)

I

2M

2M

2M

-x

-x

+2x

E 2-x 2-x

2 + 2x

X = 1.5284 and 2.6878

It is impossible to lose 2.6878 when you only start with 2!

This is the non-real solution
So x = 1.5284
What are the amounts at equilibrium then?

Chemical Equilibrium..

H2 (g) + F2 (g) --------> 2 HF (g)

I

2M

2M

2M

-x

-x

+2x

E .4716

.4716

5.0568

Lets plug these values back into K to see if they equal 115/1!

Kc 115 =
1

[HF]2
[H2]1[F2]1

[5.0568]2
[.4716]1[.4716]1

114.975/1

We can set up a ratio of pressures instead of

concentrations too! THIS IS MORE CONVENIENT
FOR GASES, BECAUSE PRESSURE IS EASIER
TO MEASURE THAN CONCENTRATION!
This is called Kp
Lets look at number 24
Hydrogen gas and iodine vapor react to form hydrogen
iodide gas. The equilibrium constant, or Kc, is 1.00 x
102 at 250C. Suppose hydrogen at 5.0 x 10-1 atm,
iodine at 1.0 x 10-1 atm, and hydrogen iodide at 5.0 x
10-1atm are added to a 5.0 L flask. Calculate the
equilibrium pressures of all species.
What is the reaction?

Hydrogen gas and iodine vapor react to form hydrogen

iodide gas. The equilibrium constant, or Kc, is 1.00 x 102
at 250C. Suppose hydrogen at 5.0 x 10-1 atm, iodine at 1.0
x 10-1 atm, and hydrogen iodide at 5.0 x 10-1atm are added
to a 5.0 L flask. Calculate the equilibrium pressures of all
species.
H2 (g) + I2 (g) --------> 2 HI (g)
What would Kp look like?
Kp = [P HI]2
[P H2]1[P I2]1
Where P is the pressure, instead of concentration, of the gas!
But the problem gives us the Kc, and not the Kp are they the
same? No!

Kp = Kc (RT)Dn
What is delta n?
It is the moles of gas produced minus the moles of gas you
start with
In this reaction, you make 2 moles of HI, and start with one
mole of H2, and one mole of I2
So, Dn = 2 2 = 0
Kp = 100 [(.0821)(298)]0
Kp = 100
In this case, the Kp actually did equal the Kc!
So..

H2 (g) + I2 (g) --------> 2 HI (g)

I

.5 atm .1 atm

-x

E .5 x

.5 atm

-x

+2x

.1 x

.5 + 2x

Same exact setup as before but we are using pressures instead

of concentrations, so we use a Kp and not a Kc!
Kp = [.5+2x]2

= 100

[.5-x]1[.1-x]1
Can you do the algebra?

Remember, if concentrations are given, use

a Kc if pressures are given, use a Kp
To convert between them:
Kp = Kc(RT)Dn

Lets watch a computer

simulation of equilibrium in
action!

Le Chateliers Principle:

If a system at equilibrium is disturbed by a

change in temperature, pressure, or the
concentration of one of the molecules, the
system will shift its equilibrium position to
counteract the disturbance

WHAT DOES THAT MEAN.?

Fritz Haber was a German Scientist who utilized

LaChateliers Principle in making ammonia for
explosives in World War I:
N2(g) + 3H2(g) ------> 2 NH3(g)
Keq = 9.60
1
at 3000C and 200 atm
At equilibrium, products are
favored, but how do we get the
reaction to continue to make
NH3, or ammonia?

N2(g) + 3H2(g) <-----> 2 NH3(g)

By adding more N2(g) or H2(g), the reaction

would..?
Shift to the right and make more ammonia - but
this requires more reactant and more money!
By adding more NH3(g), the reaction would.?
Shift to the left and form more N2(g) and H2(g),
which is NOT what we want!

N2(g) + 3H2(g) <-----> 2 NH3(g)

By removing NH3(g)..
The reaction shifts to the right, N2(g) and H2(g)
hurrying to create equilibrium again and create
more NH3(g).
This causes even more NH3(g) to be produced,
driving the reaction to completion and producing
the maximum amount of ammonia!
The ammonia is removed by liquefying it at -330C
The reaction will always maintain its Keq = 9.60
1

Kc, or Keq, only applies to chemicals reacting in the

solid, liquid, or gaseous state. Kp only applies to
gases. They do not apply to aqueous solutions
(reactions that occur in water).

Ksp deals with aqueous reactions, or reactions

that occur in water!