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Chemical Equilibrium
Equilibrium
• Physical Equilibrium refers to the equilibrium between
two or more states of matter (solid, liquid and gas)
– A great example of physical equilibrium is shown by the
concept of vapor pressure
Chapter 13 2
1
Reversible Reactions
• Previously, we have assumed that reactants convert completely to
products. However, this is not always true.
• For some reactions, the reaction can proceed towards products (the
forward reaction) or towards reatants (the reverse reaction).
• The reactions are called reversible reactions.
Chemical Equilibrium
• Most reactions are ongoing, reversible processes; preceding in
both the forward direction to give products and in the reverse
direction to give the original reactants.
2
Chemical Equilibrium
Chapter 13 5
Chapter 13 6
3
Chemical Equilibrium and Reaction Rates
4
Homogeneous Equilibria
• A homogeneous equilibrium is a reaction where all of the
products and reactants are in the physical same state.
– The amounts are given as molarity (aqueous or gas) or partial
pressures (gas)
• What is the equilibrium constant expression for the
homogeneous equilibrium?
2 SO2(g) + O2(g) ⇆ 2 SO3(g)
[SO 3 ]2
KC =
[SO 2 ]2 [O 2 ]
Chapter 13 9
Heterogeneous Equilibria
• A heterogeneous equilibrium is a reaction where one of
the substances is in a different physical state.
C(s) + H2O(g) ⇆ CO(g) + H2(g)
[CO][H2]
KC =
[H2O]
• The concentrations of liquids and solids do not change,
and they are therefore omitted from equilibrium constant
expressions:
Chapter 13 10
5
Equilibrium Constant Expressions
What are the equilibrium
constant expressions for the
following reactions?
NH4NO3(s) ⇆ N2O(g) + 2 H2O(g)
Chapter 13 11
[HI]2 (1.07)2
Kc = = = 57.2
[H2][I2] (0.10)(0.20)
Chapter 13 12
6
Equilibrium Constant Expressions
• The following pictures represent mixtures of A molecules
(red) and B molecules (blue), which interconvert according
to the equation A ⇆ B.
– If Mixture (1) is at equilibrium, which of the other mixtures is also at
equilibrium?
Chapter 13 13
Equilibrium Constant Kp
• Because gas pressures are easily measured, equilibrium
expressions for gas-phase reactions are often written with partial
pressures rather than concentrations.
aA+bB ⇆ cC+dD
• We call this version of the equilibrium expression Kp
Kp =
(P ) (P )
C
c
D
d
(P ) (P )
A
a
B
b
Kp =
(P ) (P )
C
c
D
d
=
([C]RT ) ([D]RT )
c d
=
[C]c [D]d
x(RT )
( c + d )−( a + b )
(P ) (P )
A
a
B
b
([A]RT) ([B]RT)
a b
[A] [B]
a b
K p = K C (RT )
∆n
Chapter 13 14
7
Equilibrium Constant Expressions
• Write the Kp and Kc expressions for:
Chapter 13 15
Chapter 13 16
8
Using Equilibrium Constants
• The value of Kc or Kp can indicate whether products or
reactants are favored in a reaction.
QC =
[A]a [B]b
• The direction of the reaction can be predicted by
comparing Qc with Kc:
Qc > Kc System proceeds to form reactants.
Qc = Kc System is at equilibrium.
Qc < Kc System proceeds to form products
Chapter 13 18
9
Predicting the Direction of the Reaction
Chapter 13 19
Chapter 13 20
10
Using Kc to Calculate Concentrations
STEP 1
Write the Keq expression for the
equilibrium equation
STEP 2
Solve the Keq expression for the
unknown concentration.
STEP 3
Substitute the known values into the
rearranged Keq expression
STEP 4
Check answer by using the calculated
concentration in the Keq expression
Chapter 13 21
Chapter 13 22
11
Using Equilibrium Constants
• We can also use the equilibrium constant to calculate
equilibrium concentrations from initial concentrations.
• We use the Initial Change Equilibrium method (the
ICE table!).
H2 (g) + I2 (g) ⇆ 2HI (g)
Initial (M) 0.100 0.100 0
Change (M) -X -X + 2X
Equilibrium (M) 0.100 – X 0.100 – X 2X
Chapter 13 23
Using STEP 1
Write the balanced equation
Equilibrium for the reaction
Constants STEP 2
Under the balanced equation,
Set up your ICE table
concentrations. STEP 4
Solve the Kc expression for X. If you have
• We use the Initial Change made an assumption, make sure it is
valid. If it is not, you must use the
Equilibrium method (the ICE quadratic equation!
table!). STEP 5
A + B ⇆ 2C Go back to your ICE table and calculate
the Equilibrium concentrations using X
Initial 0.100 0.100 0
STEP 6
Change -X -X +2X Check answer by substituting your
calculated equilibrium concentrations
Equilibrium 0.100 - X 0.200 - X 2X into the Kc expression
Chapter 13 24
12
Using Equilibrium Constants: The Assumption
• Once you have prepared your ICE table, and plugged your equilibrium
concentrations into your Kc expression, you may not be able to solve for
x using simple algebra.
• If you cannot solve for x with simple algebra, there are two ways to
proceed:
– The “Assumption” (Sometimes works)
– The Quadratic Equation (Always works)
• The Assumption is that x <<< than [ ] so you can ignore subtracting or
adding it.
• If you make this assumption, you must check that you are correct once
you find x.
• For the assumption to be valid x < 3% of the number your are
comparing it to.
• If it is more than 3% you must go back and use the Quadratic Equation!
Chapter 13 25
13
Using Equilibrium Constants: The Quadratic
• If you find that your assumption is NOT valid (i.e. X >
3%) then you must go back and solve the Quadratic
Equation for X
• The expression must first be rearranged to:
ax 2 + bx + c = 0
• The values are substituted into the quadratic and solved
for a positive solution to x and pH. For additional info,
see Appendix A.4 on
− b ± b 2 − 4ac page A-9 in the back
x= of your text
Chapter 13
2a 27
X= (2.60 - X)
2a 0 = X 2 + 0.0580(X) − 0.151
a b c
14
Using Equilibrium Constants
• Calculate the equilibrium concentration of all species when 1.00
mol of sulfur dioxide and 2.00 mol of chlorine are sealed in a 100
L reactor. The temperature is raised to 400 K where the Kc=89.3.
SO2 (g) + Cl2 (g) ⇆ SO2Cl2 (g)
SO2 (g) + Cl2 (g) ⇆ SO2Cl2 (g)
Initial 0.0100 0.0200 0
Change -X +X +X
Equilibrium 0.0100 – X 0.0200 - X X
[SO 2 Cl 2 ] X
KC = =
[SO 2 ][Cl 2 ] (0.01 - X)(0.02 - X)
Chapter 13 29
Chapter 13 30
15
Le Châteleir’s: Effect of Concentration
• Let’s look at the following reaction: A⇆B + C
• When the concentration of A
is increased (A is added!),
the equilibrium must shift
towards the products
• This shift allows the system
to remove the extra A by
making more product
Increasing [CO]?
Increasing [H2]?
Decreasing [H2O]?
Decreasing [CO2]?
Chapter 13 32
16
Le Châteleir’s: Common Ion Effect
•When two dissolved solutes that contain the same ion
(cation or anion) that ion is termed a Common Ion
•The Common-Ion Effect is the shift in equilibrium caused
by increasing the concentration of one of the ions in solution.
Chapter 13 33
17
Le Châteleir’s: Effect of Pressure & Volume
• Consider the reaction: N2O4(g) ⇆ 2 NO2(g), taking
place in a cylinder with a volume = 1 L.
[NO2 ] = 2 mol/L = 2
[N2 O4 ] = 1 mol/L = 1
[NO2 ]2
K= =4
[N2 O4 ]
Chapter 13 35
[NO2 ] = 2 mol/0.5 = 4
[N2 O4 ] = 1 mol/0.5 = 2
[NO2 ]2
Q= =8
[N2 O4 ]
18
Le Châteleir’s: Effect of Pressure & Volume
Chapter 13 37
Chapter 13 38
19
Le Châteleir’s: Effect of Temperature
• Consider the reaction:
N2(g) + 3 H2(g) ⇆ 2 NH3(g) ∆Hrxn = -92.2 kJ
NO NH3 H2O O2
Chapter 13 40
20
Effect of a Catalyst
• If we add a catalyst to a reaction at equilibrium, what do you
think will happen?
• A catalyst decreases the
activation energy of the reaction
• This decrease effects results in
the increase of the rate of both
the forward and reverse reactions
equally
• However, the same ratios of
products and reactants are
attained.
Summary of Le Châtelier’s
Chapter 13 42
21
Link between Equilibrium and Kinetics
aA+bB ⇆
kf
k
cC+dD r
• When the system reaches equilibrium then the rate of the forward
reaction is equal to the rate of the reverse reaction:
22