TOPIC 17 EQUILIBRIUM

↳ is a state in
17.1
THE EQUILIBRIUM LAW which RateofFran
Reactin is equals the Rete

of Beckard Ran By: Merinda Sautel

Alameda Int’l Jr/Sr High School
Lakewood, CO
[email protected]
 In other wordy, Here is net
ESSENTIAL IDEA
no

in concentration ofReactant
charge
The position of equilibrium can be quantified by
the equilibrium
andlaw.the product constant for
The equilibrium
a particular reaction only depends on the
sonten
Nettet-Bad temperature.
will mis
Retin
equ
so in
NATURE OF SCIENCE (1.8 and 1.9) D
Agate
c

perfect
- +
i -
Employing quantitative reasoning – experimentally
2

determined rate expressionsReatant Product

for forward and backward
reactions can be deduced directly from the stoichiometric
equations and allow Le Chatelier’s principle to be applied.
is also coll
- This kind of
equilibrines
Dynamic equin
 provesOF
THEORY KNOWLEDGE
Dynamic many
The equilibrium law can be deduced by assuming that

a
ofBelame
state
the order of the forward reaction and backward reaction
matches the coefficients in the chemical equation. What

process
is the role of deductive reasoning in science?
Between Continuing
We can use mathematics successfully to model
equilibrium systems. Is this because we create
mathematics to mirror reality or because the reality is
intrinsically-
mathematical?
A -
B
product
-

Reactant
Many problems in science can only be solved when
assumptions are made which simplify the mathematics.
What is the role of intuition in problem solving?
 can
or
ESSENTIAL
we
say IDEA
into Productby is

Reactant
the
is
it
converting
The position of equilibrium can be quantified
equilibrium law. The equilibrium constant for
a particular reaction only depends ondirectin
forward the
with Rate of
the temperature.

8
I
NATURE OF SCIENCE (1.8 and 1.9) in

simultaneously B
Employing quantitative reasoning
is Coverting
– experimentally
determined rate expressions for forward and backward
want fill the
So allow
equations and her if
reactions can be deduced directly
I from theIstoichiometric
Le Chatelier’s principle to be applied.

Rection
Information in
 A
B
A homogeneous system is one in which
all substances are in the same phase for
example all gases or all solutions.

B - C
A t -
--
-°

q
statt
g q
S
S
S
l l
l
 A hetrogeneous system is one in which
substance present is in more than one
APPLICATION/SKILLS
phase

C
B
-

A t
Solution of homogeneous
-

equilibrium
sate S problems g
R using the

expression for Kc.

These
state
all
will
sam
note Vetrogenat
in
0
S

l
⑨
g
eq
 UNDERSTANDING/KEY IDEA
7.1.B

The equilibrium law describes how

the equilibrium constant (Kc) can
be determined for a particular
chemical reaction.
Equilibrium Constant Kc
For the reaction:

jA + kB lC + mD
[C ]l [ D]m
K=
[ A] j [ B]k
Where Kc is the equilibrium constant, and
is unitless. The only thing that can change
Kc for a reaction is a change in
temperature.
 APPLICATION/SKILLS

Be able to deduce the equilibrium

constant (Kc) from an equation for
a homogeneous reaction.
 Writing an Equilibrium Expression
Write the equilibrium expression for the reaction:

2NO2(g) 2NO(g) + O2(g)

Remember that concentrations are written with square brackets [ ]. Kc is calculated
using molar concentrations. Solids and liquids are not included in the K expression.

Kc = ???
2
[ NO] [O2 ]
K= 2
[ NO2 ]
 Heterogeneous Equilibria
The position of a heterogeneous equilibrium does not depend on the amounts of
pure solids or liquids present. Liquids and solids are never a part of the K
expression.

Write the equilibrium expression for the reaction:

PCl5(s) PCl3(l) + Cl2(g) K [Product)
=

M
↑

red guid
Pure Pure ∴ K = [Cl2 ]
solid liquid
 UNDERSTANDING/KEY IDEA
7.1.C

The magnitude of the equilibrium

constant indicates the extent of a
reaction at equilibrium and is
temperature dependent.
Remember the Equilibrium Constant Kc

i
jA + kB lC + mD

patiete
nt
[C ]l [ D]m
isK= a
[ A] j [ B]k
Where Kc is the equilibrium constant, and
is unitless. The only thing that can change
Kc for a reaction is a change in
temperature.
Remember the Equilibrium Constant Kc

jA + kB lC + mD
[C ]l [ D]m
K=
[ A] j [ B]k
Where Kc is the equilibrium constant, and
is unitless. The only thing that can change
Kc for a reaction is a change in
temperature.
Remember the Equilibrium Constant Kc

jA + kB lC + mD
[C ]l [ D]m
K=
[ A] j [ B]k
Where Kc is the equilibrium constant, and
is unitless. The only thing that can change
Kc for a reaction is a change in
temperature.
 Solving for Equilibrium Constant

for this
Consider
a Given Concentration
Reacting
reaction at some temperature:

H2O(g) + CO(g) H2(g) + CO2(g) K = 2.0

Assume you start with 8 moles of H2O and 6 moles of CO in a 1 dm3

container. How many moles of H2O, CO, H2, and CO2 are present at
equilibrium?

How solve?
Here, we I
learn about “ICE” – the most important problem solving
technique in solving all equilibrium problems.
alright.
follow my
Just approach is ICE Fech
the technique name
 what mering
ICE TABLES in
of
Only molar concentrations are used in ICE
tables.

ICE stands for

“Initial” concentrations, I indus
“Change” in concentrations, and Imoes
“Equilibrium” concentrations./mo

meaningof
Case few
now what is the
exuable
we will
study by a
FirstFam
ICE TABLES
Only molar concentrations are used in ICE
tables.

ICE stands for

“Initial” concentrations,
“Change” in concentrations, and
“Equilibrium” concentrations.
 Solving for Equilibrium
Concentration
H2O(g) + CO(g) H2(g) + CO2(g) K = 2.0

Step #1: We write the K expression for the reaction. Always use
concentrations in ICE tables.

[ H 2 ][CO2 ]
2.0 =
[ H 2O][CO]
 Solving for Equilibrium Concentration
Step #2: We make an ICE table using the initial concentrations. The “change”
comes from the coefficients.

initially
H2O(g) + CO(g) H2(g) + CO2(g) is no
were

Initial:
-8 6 0 ) d. God 0

in
6

an
-x 8
Change: 0
-x +x +x

Equilibrium: 8-x 6-x x x

+x

Re

e
6 -

is
 Solving for Equilibrium Concentration
Step #2: We make an ICE table using the initial concentrations. The “change”
comes from the coefficients.

H2O(g) + CO(g) H2(g) + CO2(g)

Initial: 8 6 0 0

Change: -x -x +x +x

Equilibrium: 8-x 6-x x x

-
 you went I
2 e
Solving -

for Equilibriumnoi ->

Concentration
site this egh
Step #2:(8 x)x(6
We make
x)
an ICE table using the initial concentrations. The
-

comes from the coefficients.

-

“change”

variable
-

more
2(8 n) + (6 -

n)
=
x

left cial
-

H2O(g) + CO(g) H2(g) + CO2(g) ↳

(68 u) -n6
(16-2n)
Initial:

simplify
+ - 0
=
0- 0

Change: -x -x +x +x
-

46-16x -12x 2n -n 0
=

Equilibrium: 8-x 6-x x x

-Passage of
=
96 -28x n
+ 0

-28x+96
"
0
=

squaduti c
 Solving for Equilibrium
- z8x q6 Concentration
0 + =

I into our equilibrium expression, and

Step #3: We plug equilibrium concentrations
solve for x

-
W
H2O(g) + CO(g) H2(g) + CO2(g)

x
~
-
4x - (4x +
96 0
=

↑X 96
Equilibrium: 8-x 6-x x x

-A -3
x(x n) - -
24(u ) -
0
=

24
( x)( x) 14

E
Here 2.0 = any
factor out
(8 − x)(6 − x)
(1 4)
-
(x- 24)
x t0

x = 4-
n 4
wante
4 0
=

e
3
=
-

M
2 i
=
n -
n
 given sign
96 for Equilibrium Concentration
Solving t ~

Step #3: We plug equilibrium concentrations into our equilibrium expression,een

and
-x
solve for x 96
4
= ↑

I 96

48
Ewowhi
H2O(g) + CO(g)
=

is
H2(g) + CO2(g)

2
Equilibrium: 8-x 6-x x x
an
96
3 32:
Ree
( x)( x) -
↑ zu2.0e
= fati I
96

- 16 (8 − x )(62− x ) 48

⑧ 12 x=4 3
32

z
Y
 Solving for Equilibrium Concentration
Step #3: We plug equilibrium concentrations into our equilibrium expression, and
solve for x
Linen
H2O(g) + CO(g) H2(g) + CO2(g) K 2.0
=

Equilibrium: 8-x 6-x x x

( x)( x)
2.0 =
(8 − x)(6 − x)
x=4
 Solving for Equilibrium Concentration
Step #3: We plug equilibrium concentrations into our equilibrium expression, and
solve for x

H2O(g) + CO(g) H2(g) + CO2(g)

Equilibrium: 8-x 6-x x x

( x)( x)
2.0 =
(8 − x)(6 − x)
x=4
 Solving
A mixture for Equilibrium
of 2 moles Concentration
H2O and 2 moles of CO is
Stepallowed toequilibrium
#3: We plug come to equilibrium.
concentrations Calculate
into our the
equilibrium expression, and
equilibrium
solve for x concentration of all the chemical species.
Given Kc = 4
H2O(g) + CO(g) H2(g) + CO2(g)

Equilibrium: 420(9)8-x cog)

+

6-x - Un(g)
x
+Co2s)
x

( x)( x)

ze
2.0 =

x=4
inee (8 − x)(6 − x)
 2

ADDITIONAL COMMENTS
(2-n)
4 =

• Many equilibrium ICE tables have to be

solved using the quadratic
2 equation.

• 4(2 -

will not bex)

You n)x(z -
expected
=
x
to use
calculations involving the quadratic
-

equation.
4m)x(2- x) =x
(8 -

• When Kc is very small (10-3 or smaller),

you will be making an assumption that the
change in concentration of the reactants is
basically zero. -

...
 30 16x + 16
ADDITIONAL
-
COMMENTS
=
0

• Many equilibrium ICE tables have to be 16

3 x
solved using the quadratic equation.
-
• You will not be expected to use
Y
4 4
calculations involving the quadratic

•
equation. I
When Kc is very small (10-3 or smaller),
- 4
you will be making an assumption that the
change in concentration of the reactants is
basically zero.
 ADDITIONAL COMMENTS
• Many equilibrium ICE tables have to be
solved using the quadratic equation.
• You will not be expected to use
calculations involving the quadratic
equation.
• When Kc is very small (10-3 or smaller),
you will be making an assumption that the
change in concentration of the reactants is
basically zero.
 UNDERSTANDING/KEY IDEA
17.1.A

Le Chatelier’s principle for changes

in concentration can be explained
by the equilibrium law.
 LeChatelier’s Principle
When a system at equilibrium is placed under stress,
the system will undergo a change in such a way as
to relieve that stress.
Translated: The system undergoes a temporary shift in order to restore equilibrium.
1. When you add a substance or heat, the system shifts to the opposite side.
2. When you take out a substance or heat, the system shifts to the side of the take
out.
When you increase pressure, the system shifts to the side with the least
number of gaseous molecules.
 KINETICS AND EQUILIBRIUM
• The equilibrium constant is the ratio of the rate
constants of the forward and backward
reactions.
• If “k” for the forward reaction is greater than “k”
for the backward reaction, then the reaction is
product favored and proceeds toward
completion. K is large.
• If “k” for the backward reaction is greater than
“k” for the forward reaction, then the reaction
has barely taken place. K is small.
• Using the relationship between k, the rate
constant, and K, the equilibrium constant,
we can add to our interpretation of how
equilibrium responds to changing
conditions.
 CHANGING CONCENTRATION
• If you increase the concentration of the
reactant(s), you will increase the rate of
the forward reaction thus shifting
equilibrium to the right.
• If you increase the concentration of the
product(s), you will increase the rate of the
backward reaction thus shifting equilibrium
to the left.
• The value of the equilibrium constant, K,
stays constant since only temperature
affects K.
 ADDING A CATALYST
• Adding a catalyst increases the rate
constants, k, of both the forward and
reverse reactions by the same amount so
the equilibrium constant is not affected.
 CHANGING TEMPERATURE
• We know from kinetics and our studies of the
Arrhenius equation, k = Ae-Ea/RT, that as
temperature increases, the rate constant “k”
increases.
• From the potential energy diagrams, we know
that the activation energies of the forward and
backward reactions are different so their rate
constants would be different and are affected
differently by temperature.
• The ratio of the rate constants of the
forward and backward reactions is
temperature dependent.
• For an endothermic reaction, where Ea of
the forward reaction is greater than that of
the backward reaction, the increase in
temperature has a greater effect on
increasing “k” for the forward reaction so
Kc increases as temperature increases.
 HOW DO YOU PROVE IT?
• Take the time with your partner and prove
the previous statement using the potential
energy diagrams and the
Arrhenius equation k = Ae-Ea/RT.
 UNDERSTANDING/KEY IDEA
17.1.B

The position of equilibrium

corresponds to a maximum value
of entropy and a minimum value of
the Gibbs free energy.
• Different reactions have very different Kc
values reflecting a wide range of the
directions and extents of these reactions.
• Some reactions go almost all the way to
completion and others barely react at all.
• Gibbs free energy can help determine
these differences in reactions.
• ΔG◦ = negative
– Spontaneous
– Reaction proceeds in the forward direction
• ΔG◦ = positive
– Non-spontaneous
– Reaction proceeds in the backward direction
• ΔG◦ = zero
– Reaction is at equilibrium
• A reaction with a value of ΔG◦ that is large
and negative appears to occur
spontaneously and has an equilibrium
mixture with a high proportion of products.
• A reaction with a value of ΔG◦ that is large
and positive appears to be non-
spontaneous and has an equilibrium
mixture with a high proportion of reactants.
 ΔG neg ΔG neg

ΔG pos ΔG pos
Non- Non-
spontaneous spontaneous

pixshark.com
The position of equilibrium corresponds to a
maximum value of entropy for the system.
In other words, any system has the highest
possible value of entropy when free energy
is at a minimum (equilibrium).
 UNDERSTANDING/KEY IDEA
17.1.C

The Gibb’s free energy change of a

reaction and the equilibrium constant
can both be used to measure the
position of an equilibrium reaction and
are related by the equation,
ΔG◦ = -RTlnK.
 APPLICATION/SKILLS

Understand the relationship

between ΔG and the equilibrium
constant.
 APPLICATION/SKILLS

Be able to do calculations with the

equation ΔG◦ = -RTlnK.
 Kc AND THERMO DATA
• We now have 2 terms which relate to the
position of equilibrium.
– Kc, the equilibrium constant
– ΔG◦, the change in free energy
• From the equation, ΔG◦ = -RTlnK, we can
deduce relationships between the two
values, Kc and ΔG◦.
ΔG◦ negative ln K positive K>1 mostly products

ΔG◦ positive ln K negative K<1 mostly reactants

ΔG◦ = 0 ln K = 0 K=1 mixture of both

The equation ΔG◦ = -RTlnK can be used to solve for either

Gibb’s free energy or the equilibrium constant.
It is useful in situations where the K is difficult to measure
directly such as if the reaction is too slow to reach equilibrium
or when the component amounts are too small to measure.
The value of Gibb’s free energy is the reason that different
reactions have such different values for K.
Remember that Gibb’s free energy is also dependent upon the
change in enthalpy and change in entropy ΔG◦ = ΔH – TΔS.