DR.

RONALD BROWN (RONNIE)

Subject Coordinator
ronaldb@uow.edu.au
42213039
18.G20

WEEK SEVEN:
Learning Outcomes:
Understand concepts:
a.) Characteristics of chemical
equilibrium including magnitude of K,
Le Châtelier’s Principle and catalyst
effects.
Demonstrate:
a.) Understanding of equilibrium constants by writing
expressions for Kc and Kp and interconverting.
b.) Prediction of reaction direction using Q.
c.) Calculation of K including using ICE tables.

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CHEM103 So Far

how we talk • The Language of Chemistry

about matter • Quantity in Chemistry
what matter IS: structure and • Matter on the Molecular Scale
properties • Matter on the Macroscale (I and II)
• Thermochemistry (how hot)
we are here • Chemical Equilibrium (how far)
how matter BEHAVES: • Acid-Base Equilibrium
chemical reactions • Electrochemistry
The IMPLICATIONS of this • Equilibria and the Environment
(applications and • Chemical Kinetics (how fast)
considerations) • Industrial Organics
• Review of Content

2
Some Reactions Can Go Forwards AND Backwards
For a chemical reaction forming a product and also re-forming reactant/s (i.e.
going forwards and backwards), equilibrium occurs when the forward and
reverse reaction have the same RATE.
N2O4 (g) ⇌ 2 NO2 (g)

The concentration of
reactants and products
are CONSTANT at
equilibrium (formed and
consumed at the same
rate).

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We Can Describe Equilibria More Formally
For the reaction: aA + bB ⇌ cC + dD
Products.
[C]! [D]" normalize to
reference concentration
The equilibrium expression is: K! = Reactants. so units ‘cancel’
[A]#[B]$ ! #
Equilibrium constant, [𝐶] [𝐷]
Kc is dimensionless. C [concentration] 𝑐" 𝑐"
is for concentration. K! = $ %
[𝐴] [𝐵]
C0 = reference concentration = 1 mol L-1 𝑐" 𝑐"

Question: write the equilibrium expression for each of the following reactions:

N2 (g) + 3 H2 (g) ⇌ 2 NH3 (g) 2 NO (g) + Cl2 (g) ⇌ 2 NOCl (g)

%
𝑁𝐻" 𝑚𝑜𝑙𝐿#$
1 𝑚𝑜𝑙𝐿#$ [NOCl]%
K! = " K! =
[𝑁%]𝑚𝑜𝑙𝐿#$ 𝐻% 𝑚𝑜𝑙𝐿#$ [NOCl]%[Cl%]
1 𝑚𝑜𝑙𝐿#$ 1 𝑚𝑜𝑙𝐿#$

[𝑁𝐻"]%
= 4
[𝑁%][𝐻%]"
We Can Relate Equilibrium to Pressure for Gases
Since concentration is proportional to pressure for gases in closed systems,
the equilibrium expression can also be written as follows: normalize to
Products. reference pressure

P&! P'"
so units ‘cancel’

K% = Reactants. 𝑃) !
𝑃* #
P(#P)$ 𝑝" 𝑝"
Here, P is for pressure and K& = $ %
equilibrium constant, Kp is
p0 = reference pressure
𝑃+ 𝑃,
still dimensionless. P = partial pressure 𝑝" 𝑝"
= 100 kPa (1 bar)

We can convert between Kc and Kp using the ideal gas equation:

PV = nRT
Concentration.
n
P= RT (moles product gas)
V – (moles reactant gas)

reference concentration
∆(
c " RT
∆( K& = K!
K & = K ! RT p"
reference pressure

Units don’t ‘cancel out’ Units ‘cancel out’ 5

We Can Relate Equilibrium to Pressure for Gases
Question: In the synthesis of ammonia from nitrogen and hydrogen (The Haber
Process):
N2 (g) + 3 H2 (g) ⇌ 2 NH3 (g)

Kc = 9.60 at 300 °C. Calculate Kp for this reaction at the same temperature.
–/
)
c RT
∆+ 1 molL,- RT
K' = K( K ' = 9.60 x
p) 100 kPa
/
Δn = (moles of product gas) 100 kPa
= 9.60 x
– (moles of reactant gas) 1 molL,- RT
=–2 100 kPa /
Dimensionless. = 9.60 x
1 molL,- × 8.3145LkPaK ,- mol,- × 573K

= 4.23×10,0

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Equilibrium Can Be Reached From Either Direction

N2O4 (g) ⇌ 2 NO2 (g)

reversed reversed

[NO- ]-
K! =
[N- O. ]

No matter what the initial concentrations of species

are, the system equilibrates to the same ratio of
species, giving the same value of Kc for each case.

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K Value Tells Us HOW FAR A Reaction Proceeds

If K >> 1, the reaction is product-

favored; product predominates at
equilibrium.

[C]! [D]" 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠

K! = i.e.
[A]#[B]$ 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

If K << 1, the reaction is reactant-

favored; reactant predominates at
equilibrium.

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There Are Rules For Manipulating K
The equilibrium constant of the reverse reaction is the reciprocal of the
equilibrium constant of the forward reaction.
Forward: N2O4 (g) ⇌ 2 NO2 (g) Reverse: 2 NO2 (g) ⇌ N2O4 (g)
[NO- ]- [N- O. ] 1
K! = = 0.212 at 100 °C K! = = = 4.72 at 100 °C
[N- O. ] [NO- ]- 0.212
The equilibrium constant of a reaction that has been multiplied by a number is
the equilibrium constant raised to the power of that number.
x2
N2O4 (g) ⇌ 2 NO2 (g) 2 N2O4 (g) ⇌ 4 NO2 (g)
[NO- ]- [782 ]3
K! = = 0.212 K6 = = 0.2129 = 0.0449
[N- O. ] [72 83 ]2

The equilibrium constant for a net reaction made up of the sum of two or
more steps is the product of the equilibrium constants for the individual steps.

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There Are Rules For Manipulating K
Question: how does the magnitude of the equilibrium constant Kp change from
the first to the second of the following reactions?
1.) 2 HI (g) ⇌ H2 (g) + I2 (g) 2.) 6 HI (g) ⇌ 3 H2 (g) + 3 I2 (g)

𝑃3 𝑃4
𝑃 " 𝑃 "
K& =
𝑃34 -
𝑃"
(P/)(P1 ) (P/)0 (P1 )0
K& = K& =
(P/1 )- (P/1 )2

Equation 2. ) has (K &)0

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Heterogenous Equilibria
The Concentrations of Solids and Liquids Are Essentially Constant.
Both can be obtained by dividing density by molar mass, and both are constant
at constant temperature.
More importantly, the “value” for pure solids and liquids is defined as 1 so they
play no direct role and do not appear in the equilibrium expression.

PbCl2 (s) ⇌ Pb2+ (aq) + 2 Cl– (aq)

Sometimes called Ksp Kc = [Pb2+][Cl–]2

(solubility product).

Question: write the equilibrium expression for the evaporation of water in terms
of partial pressures, Kp:
Product.
Reactant (liquid). H2O (l) ⇌ H2O (g)
! #
𝑃) 𝑃* Products.
𝑃3&5
𝑝" 𝑝" K& =
K& = $ % Reactants. 𝑃"
𝑃+ 𝑃,
𝑝" 𝑝"
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Heterogenous Equilibria
Question: what is the correct equilibrium expression for this reaction?
Reactant (solid). Product (liquid).
P4 (S) + 6 Cl2 (g) ⇌ 4 PCl3 (l)

Products.
[C]! [D]"
K! = Reactants.
[A]#[B]$
Recall: The equilibrium constant of the reverse reaction is the reciprocal
of the equilibrium constant of the forward reaction.

1
K! =
[ClS]T

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We Can Use an ICE Table for Equilibrium Calculations
Question: a closed system initially containing 1.000 x 10-3 M H2 and 2.000 x 10-3 M
I2 at 448 °C is allowed to reach equilibrium. During equilibrium, the concentration
of HI is found to be 1.87 x 10-3 M. Calculate Kc at 448 °C for this reaction:
H2 (g) + I2 (g) ⇌ 2 HI (g)
[H2] (M) [I2] (M) [HI] (M)
Initial 1.000 x 10-3 2.000 x 10-3 0
Change
Equilibrium 1.87 x 10-3

[H2] (M) [I2] (M) [HI] (M)

Initial 1.000 x 10-3 2.000 x 10-3 0
Change – 0.935 x 10-3 – 0.935 x 10-3 + 1.87 x 10-3
Equilibrium 0.065 x 10-3 1.065 x 10-3 1.87 x 10-3
C0 (so K is dimensionless). %
1.87×10#"𝑚𝑜𝑙𝐿#$
[HI]% 1 𝑚𝑜𝑙 𝐿#$
K! = = = 51
[𝐻%][𝐼%] 0.065×10#"𝑚𝑜𝑙𝐿#$ 1.065×10#"𝑚𝑜𝑙𝐿#$
1 𝑚𝑜𝑙 𝐿#$ 1 𝑚𝑜𝑙 𝐿#$
13
Reaction Quotient Predicts How Equilibrium Occurs
The reaction quotient (Q) is found by substituting the concentrations of
reactants and products NOT AT EQUILIBRIUM into the equilibrium expression.
Value of Q tells us whether a reaction will proceed forwards or backwards to
reach equilibrium.

Q=K

Q<K Q>K
Too much reactant: Too much product:
reaction shifts right reaction shifts left
(forwards) to form more (reverse) to form more
products to reach reactants to reach
equilibrium. equilibrium.

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Equilibrium Counteracts Changes to Conditions
Le Châtelier’s Principle states that “If a system at equilibrium is disturbed by a
change in temperature, pressure, or the concentration of one of the components,
the system will shift its equilibrium position so as to counteract the effect of the
disturbance.”
The Haber Process is one of the most industrially significant chemical
reactions, particularly for industries such as agriculture (synthetic nitrogen-rich
fertilisers). If H2 is added to the system, N2 will be consumed and the
two reagents will form more NH3 to re-establish equilibrium.

N2 (g) + 3 H2 (g) ⇌ 2 NH3 (g)

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Equilibrium Counteracts Changes to Conditions

The reaction apparatus used

in The Haber Process contains
an outlet to remove NH3
product from the system, to
continually push the
equilibrium in the forwards
direction to produce more
product.

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Equilibrium Counteracts Changes to Conditions

2 NO2 (g) ⇌ N2O4 (g)

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Equilibrium Counteracts Changes to Conditions
Co(H2O)62+ (aq) + 4 Cl– (aq) ⇌ CoCl42– (aq) + 6 H2O (l)
The forward reaction is endothermic (absorbs heat).
– An increase in temperature will shift the equilibrium to the RIGHT to
absorb the heat, forming more products and increasing K value.
The opposite would occur for an exothermic reaction.

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Catalysts Increase the Rate of BOTH Reactions
A catalyst can facilitate a chemical reaction and leaves the reaction in the
same form it entered.
⚙ Catalysts speed up chemical reactions: equilibrium will be achieved faster,
but the composition of that equilibrium is the same.
– eg. in The Haber Process, an iron-based catalyst can be used to provide a
surface for ammonia formation.

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