Unit 9

Chemical Equilibrium
Blueprint question

How do we produce enough fertilizer

to keep up with increased food production
demands due to growing population?
http://www.chemicals-technology.com/projects/burrup_fert/burrup_fert6.html
Blueprint question
Ammonia production plants execute the following reaction, using
the Haber-Bosch method:
N2(g) + 3 H2(g)  2 NH3(g)

Can we increase the

equilibrium
concentration of
products, to help meet
increasing global
ammonia demand and
production?

http://www.roperld.com/science/minerals/ammonia.htm
Learning Objectives
After mastering this unit you will be able to:
– Describe the relationship between ΔG°, ΔGrxn, Q, and K,
and and apply this relationship to gain information about
chemical reactions.
– Differentiate between a reaction quotient and equilibrium
constant and describe the meaning of both.
– Evaluate the extent of a reaction based on values for K, Q
or ΔGrxn.
– Predict how a system at equilibrium will respond to
perturbations.
– Calculate equilibrium constants at different temperatures.
– Calculate the concentrations of species in a system at
equilibrium using K, or vice versa.
Chemical Equilibrium (Review)
An equilibrium represents two competing
reactions:
N2(g) + 3 H2(g)  2 NH3(g) Forward reaction
2 NH3(g)  N2(g) + 3 H2(g) Reverse reaction
N2(g) + 3 H2(g)  2 NH3(g) K = 5.8 x 105

Reactants side Products side

Chemical Equilibrium
Chemical reactions are dynamic systems in
which reactants are converted to products and
products are converted to reactants.
The meaning of K
K tells us the extent of a reaction:
1. Small K; negligible product formation:
N2(g) + O2(g)  2 NO(g) K = 10-30 at 1000K
2. Large K; reaction goes practically to
completion:
2 CO(g) + O2(g)  2 CO2(g) K = 2.2 x 1022 at 1000 K

3. Intermediate K; significant [products] &

[reactants]:
2BrCl(g)  Br2(g) + Cl2(g) K = 5, at 1000 K
ΔGrxn: Non-Standard Conditions
The relationship below is used to determine the spontaneity
of a reaction under non-standard conditions (any conditions).

In the course of a reaction the concentration of reactants and

products changes thereby changing ΔG.

∆𝐺𝑟𝑥𝑛 = ∆𝐺° + 𝑅𝑇ln𝑄

Free energy change Reaction quotient for

at standard state non-standard conditions
(1M, 1 atm, etc.) (Any concentration)
 ΔGrxn vs. ΔG°

Concentrations and pressures Concentrations at 1 M,

can take on any value pressures at 1 bar, pure
liquids and solids

If ΔGrxn is: the reaction is:

Less than 0 (negative) spontaneous in the fwd. direction
Equal to 0 at equilibrium
Greater than 0 (positive) spontaneous in the rev. direction

ΔG° tells you about the EQUILIBIRUM position. ΔGrxn tells

you which way a reaction will proceed to reach equilibrium.
ΔG° and K

∆𝐺𝑟𝑥𝑛 = ∆𝐺° + 𝑅𝑇ln𝑄

At equilibrium, ΔGrxn = 0, and Q = K

0 = ∆𝐺° + 𝑅𝑇ln𝑄
Rearranging…

∆𝐺° = −𝑅𝑇ln𝐾
There is a relationship between free
energy and equilibrium!
Calculating ΔG / ΔG°

∆𝐺𝑟𝑥𝑛 = ∆𝐺° + 𝑅𝑇ln𝑄

ΔGrxn tells us about the spontaneity of a process
under ANY conditions.
∆𝐺° = −𝑅𝑇ln𝐾
ΔG° tells us about the equilibrium position.
Our reference point! Combining these…
𝑄
∆𝐺𝑟𝑥𝑛 = 𝑅𝑇ln
𝐾
Exercise
Calculate K when ΔG° = 100 kJ/mol, 0 kJ/mol,
and -100 kJ/mol.

ΔG° (kJ/mol) K Significance

100 3.0 x 10-18 No reaction

Equilibrium,
0 1.0
calculation is necessary

Reaction goes to
-100 3.4 x 1017
completion
What does Q/K tell you?
A (g)  B (g)

Pure A Pure B

Equilibrium
Q=K

Comparing Q to K and tells you about the direction

of spontaneous change as the system moves
towards equilibrium.
Activity, concentration, and pressure
∆𝐺𝑟𝑥𝑛 = ∆𝐺° + 𝑅𝑇ln𝑄
Q must be dimensionless to take logarithm!
K and Q are calculated using the activity of each
component (dimensionless) instead of concentration
Activities (a) reflect the real availability or “effective
concentration” of a species in a real solution:
P 0 and M0 are standard
Gases: aX = 𝛾X PX/P0
Solutions: aX = 𝛾X [X]/M0 pressure and concentration
Solids: aX = 1 for CHEM 154 assume 𝛾 = 1
Liquids: aX = 1 (e.g. H2O in aqueous systems!)

𝛾 is the (dimensionless) activity coefficient

Review expression for Q or K

For the general reaction

r1R1 + r2R2 + … → p1P1 + p2P2 + …
The reaction quotient in terms of activities is

𝑝1 𝑝2
𝑎𝑃 𝑎𝑃 ⋯
𝑄= 1 2
𝑎𝑅𝑟1 𝑎𝑅𝑟2 ⋯
1 2

At equilibrium, this expression has the value K.

ΔG° and Temperature
ΔG° and K depend on temperature. For a given
reaction, changing temperature changes the
value of K.

∆𝐺° = −𝑅𝑇ln𝐾
∆𝐺°
−
𝐾= 𝑒 𝑅𝑇
van’t Hoff equation
Assuming ΔH° does not change with temperature,
the van't Hoff equation gives the equilibrium
constant at (absolute temperature) T2 given its
value at T1.

𝐾2 ∆𝐻° 1 1
ln =− −
𝐾1 𝑅 𝑇2 𝑇1
ΔG° and temperature

∆𝐻° 1 ∆𝑆°
ln 𝐾 = − +
𝑅 𝑇 𝑅
y = m x + b
Le Chatelier’s Principle
“When a system at equilibrium is stressed, it
responds by re-establishing equilibrium to
reduce the applied stress.”

Three common means for introducing such

stresses:
– Changes in concentration
– Changes in pressure
– Changes in temperature
Coupled Reactions

Important reactions can be non-spontaneous:

2 Fe2O3(s) 4 Fe(s) + 3 O2(g) G0 = +1487 kJ

To make this reaction happen, couple it with

another reaction that is spontaneous:

2CO(g) + O2(g) 2CO2(g) ΔG0 = -514.4 kJ

Coupled Reactions

2 Fe2O3(s) 4 Fe(s) + 3 O2(g)  G0 = +1487 kJ

3x 2 CO(g) + 3x O2(g) 3x 2CO2(g)  G0 = 3x -514.4 kJ

2 Fe2O3(s) + 6CO(g) 4 Fe(s) + 6 CO2  G0 = -56 kJ

Exercise: calculating equilibrium concentrations

Acrylic acid is used in the polymer industry in

the production of acrylates. Calculate the
concentration of reactants and products at
equilibrium formed from a 0.11 M solution of
acrylic acid.

CH2CHCOOH(aq) + H2O(l)  CH2CHCOO-(aq) + H3O+(aq)

K = 5.6 x 10-5
Solubility equilibria
Solubility: The ability of a compound to dissolve
in solution.
K for an ionic solid dissociating into
its constituent ions is called Ksp
Consider:
Ca(OH)2(s)  Ca2+(aq) + 2 OH-(aq) K = 7.9 x 10-6

When [Ca2+]x[OH-]2 > 7.9 x 10-6 the equilibrium

will shift to the left and Ca(OH)2 will precipitate.
Exercise
Calculate the solubility of Ca(OH)2.

Ca(OH)2(s)  Ca2+(aq) + 2 OH-(aq) K = 7.9 x 10-6

Common ion effect
Shift in equilibrium when one or more ions that
are part of the equilibrium are introduced from
an outside source.
Blueprint question

How do we produce enough fertilizer

to keep up with increased food production
demands due to growing population?
http://www.chemicals-technology.com/projects/burrup_fert/burrup_fert6.html
Blueprint question
Ammonia production plants execute the following reaction, using
the Haber-Bosch method:
N2 (g) + 3 H2 (g)  2 NH3 (g)

Can we increase the

equilibrium N2(g) + 3 H2(g)  2 NH3(g)
concentration of
products, to help meet
increasing global
ammonia demand and
production?

http://www.roperld.com/science/minerals/ammonia.htm
Blueprint question
Fertilizer production represents 1.2% of global energy
consumption (majority is producing NH3)

N2(g) + 3 H2(g)  2 NH3(g) K = 2.81 x 10-5 at 472 °C

• How can we affect equilibrium concentrations of products and

reactants?
• Le Chatelier’s Principle:
o Increase pressure ($$$)
o Remove products

• How can we increase the rate of reaction?

o Use of a catalyst…

http://large.stanford.edu/courses/2014/ph240/yuan2/
http://www.sas.upenn.edu/~mcnemar/apchem/CH15.pdf