Vous êtes sur la page 1sur 22

Chapter 13

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

• Chemical Equilibrium is achieved when two conditions


are met:
– The rates of the forward and reverse reactions are equal
– The concentrations of the reactants and products remain
constant

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.

• Strictly speaking, ALL reactions are reversible to some degree


Chapter 13 3

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.

• We indicate an equilibrium reaction with a double arrow:


forward reaction
Reactants reverse reaction Products
Chapter 13 4

2
Chemical Equilibrium

Chapter 13 5

Chemical Equilibrium and Reaction Rates


• In an equilibrium reaction, initially the rate of the forward
reaction is very fast.
• As more products are
formed, the rate of the
reverse reaction begins to
speed up.
• When the rates of the
forward and reverse
reactions are the same, the
system is at equilibrium.

Chapter 13 6

3
Chemical Equilibrium and Reaction Rates

• At Equilibrium, there is no further observable change


in the concentration of the reactants or products.
Chapter 13 7

Equilibrium Constant Expression (Kc)


• Consider the following general reaction:
aA+bB ⇆ cC+dD

• The constant, Kc, is the general equilibrium constant.


• The “c” indicates that the amounts of reactants and products are
concentrations (M)
• The value of Kc varies with temperature. So a given value of Kc is
valid only for a specific temperature.
Chapter 13 8

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)

CO(g) + H2(g) ⇆ CH3OH (l)

HCl(aq) + O2(g) ⇆ H2O(l) + Cl2(g)

Chapter 13 11

Using Equilibrium Expressions: Calculating Kc


• We can calculate the numerical value of Kc if we know the
equilibrium concentrations of all of the species in the
reaction.
• If the concentrations at equilibrium are [H2] = 0.10 M, [I2] =
0.20 M, and [HI] = 1.07 M, what is Kc?

H2(g) + I2(g) ⇆ 2 HI(g)

[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

• We can relate Kp to Kc by using the Ideal gas law (PV = nRT):

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:

2 N2O5(g) ⇆ 4 NO2(g) + O2(g)

• The equilibrium concentrations for the reaction between CO


and Cl2 to form carbonyl chloride (phosgene gas) at 74°C
are [CO] = 1.2 x 10–2 M, [Cl2] = 0.054 M, and [COCl2] =
0.14 M. Calculate Kc and Kp.
CO(g) + Cl2(g) ⇆ COCl2(g)

Chapter 13 15

Equilibrium Constant Expressions


• Methane (CH4) reacts with hydrogen sulfide to yield H2 and
carbon disulfide, a solvent used in manufacturing. What is
the value of Kp at 1000 K if the partial pressures in an
equilibrium mixture at 1000 K are 0.20 atm of CH4, 0.25
atm of H2S, 0.52 atm of CS2, and 0.10 atm of H2?

Chapter 13 16

8
Using Equilibrium Constants
• The value of Kc or Kp can indicate whether products or
reactants are favored in a reaction.

10-3 > K 10-3 < K < 103 K > 103


• The equilibrium constant (Kc) for the formation of nitrosyl
chloride, from nitric oxide and chlorine gas is 6.5 x 104 at
35°C. What is favored?
Chapter 13 17

Reaction Quotient (Qc)


• The Reaction Quotient (Qc) is determined by substituting
non-equilibrium concentrations into the equilibrium
expression
[ C] [ D ]
c d

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

Predicting the Direction of the Reaction


• The equilibrium constant (Kc) for the formation of nitrosyl
chloride, from nitric oxide and chlorine gas is 6.5 x 104 at
35°C.

2 NO(g) + Cl2(g) ⇆ 2 NOCl(g)


• In an experiment, 2.0 x 10–2 moles of NO, 8.3 x 10–3 moles
of Cl2, and 6.8 moles of NOCl are mixed in a 2.0-L flask. In
which direction will the system proceed to reach
equilibrium?

Chapter 13 20

10
Using Kc to Calculate Concentrations

Guide to Using Keq Value

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

Calculating Concentration Using Kc


• Ethanol can be produced by reacting ethylene (C2H4) with
water vapor. At 327°C, the Kc = 9.00 x 103.

C2H4 (g) + H2O (g) ⇆ C2H5OH (g)

• If an equilibrium mixture has concentrations of [C2H4] =


0.020 M and [H2O] = 0.015 M, what is the equilibrium
concentration of C2H5OH?

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

• Use Kc=57.0 to determine equilibrium concentrations.

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

• We can also use the equilibrium STEP 3


constant to calculate equilibrium Write the Kc expression and substitute
the equilibrium concentrations
concentrations from initial into the expression

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

Using Equilibrium Constants: The Assumption


• At a certain temperature, the decomposition of PCl5 (g) has an
equilibrium constant Kc = 5.8 x 10-2. Calculate the equilibrium
concentration of all species if the initial concentration of PCl5 is
2.60 M.
PCl5 (g) ⇆ Cl2 (g) + PCl3 (g)
PCl5 (g) ⇆ Cl2 (g) + PCl3 (g)
Initial 2.60 0 0
Change -X +X +X
Equilibrium 2.60 – X X X

[Cl 2 ][PCl 3 ] (X) 2 (X) 2 If you make the


KC = = ⇒ assumption, you must
[PCl 5 ] (2.60 - X) (2.60) show that it is valid!
Chapter 13 26
Assume X<<<2.60

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

Using Equilibrium Constants: The Quadratic


• For the example started on slide 26, our assumption was NOT valid so
we pull out the Quadratic Equation:
(X) 2
− b ± b − 4ac
2
5.80 x 10 =
-2

X= (2.60 - X)
2a 0 = X 2 + 0.0580(X) − 0.151
a b c

− 0.0580 ± (0.0580) 2 − 4(1)(−0.151)


X=
2(1)
X = 0.361 OR - 0.419
Chapter 13 Which answer makes sense? 28

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

Changing Equilibrium Conditions


• We know that at equilibrium, the concentrations of the reactants and the products
are not visibly changing.
• However, changes that occur in the reaction conditions will disturb the
equilibrium
• Le Châteleir’s principle states that when a reversible reaction at equilibrium is
“stressed” by a change in concentration, temperature, or volume (pressure),
the equilibrium must shift to relieve the stress.

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

• The concentration stress of an added reactant or product is relieved by


reaction in the direction that consumes the added substance (opposite
side).
• The concentration stress of a removed reactant or product is relieved by
reaction in the direction that replenishes the removed substance (same
side).
Chapter 13 31

Le Châteleir’s: Effect of Concentration


• Consider the effect of each of the following changes on the
equilibrium:

CO (g) + H2O (g) ⇆ CO2 (g) + H2 (g)

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

Le Châteleir’s: Effect of Pressure & Volume


• Changing the volume of a gas-state reaction has an effect on the pressure of the reaction
(Boyle’s Law!)
• PV = nRT tells us that increasing pressure or decreasing volume increases concentration.
• These changes will place stress on the reaction which must be relieved according to Le
Châtelier.
– If the Pressure increases, the reaction will shift to the side with the fewest moles of gas
– If the Pressure decreases, the reaction will shift to the side with the most moles of gas

CO(g) + 2H2(g) ⇆ CH3OH(g)


1 mole 2 moles 1 mole
3 moles
Low volume (high pressure) → products
High volume (low pressure) → reactants
Chapter 13 34

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

Le Châteleir’s: Effect of Pressure & Volume


• The Volume is then halved, which is equivalent to
doubling the pressure.

[NO2 ] = 2 mol/0.5 = 4
[N2 O4 ] = 1 mol/0.5 = 2
[NO2 ]2
Q= =8
[N2 O4 ]

• Since Q > K, the [product] is too high and the reaction


progresses in the reverse direction.
• Shifts towards the side with less moles of gas!
Chapter 13 36

18
Le Châteleir’s: Effect of Pressure & Volume

• Does the number of moles of products increase,


decrease, or remain the same when each of the
following equilibria is subjected to a decrease in
pressure by increasing the volume.
1. PCl5(g) ⇆ PCl3(g) + Cl2(g)

2. CaO(s) + CO2(g) ⇆ CaCO3(s)

3. 3 Fe(s) + 4 H2O(g) ⇆ Fe3O4(s) + 4 H2(g)

Chapter 13 37

Le Châteleir’s: Effect of Temperature


• Of the stresses we have talked about, only changing the temperature
results in a new Keq.
• The effect of a temperature change is dependent on whether the reaction
is endothermic (requires heat) or exothermic (gives off heat).
– Endothermic processes are favored when temperature increases.
– Exothermic processes are favored when temperature decreases.

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

• What is favored as the temperature increases,


Reactants or Products?
Chapter 13 39

Le Châteleir’s: Effect of Temperature


• In the first step of the Ostwald process for synthesis of nitric
acid, ammonia is oxidized to nitric oxide by the reaction:

4NH3(g) + 5O2(g) ⇆ 4NO(g) + 6H2O(g) ∆Hrxn = –905.6 kJ

• How do the equilibrium amounts of the following vary with an


increase in temperature:

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.

• Adding a catalyst has no effect on a system at equilibrium.


Chapter 13 41

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:

k f [A]a [B]b = k r [C]c [D]d


• Rearrangement leads to: And we know:
k f [C]c [D]d [C]c [D]d
= KC =
k r [A]a [B]b [A]a [B]b
kf
So….. = KC
Chapter 13 kr 43

22

Vous aimerez peut-être aussi