Equilibrium
Lesson 1
Dynamic
Equilibrium
Main
We Are Here
Main
Equilibrium
▶ In a ‘traditional’ reaction, all the reactants get
turned into products (assuming no excess)
▶ A state of equilibrium is reached when the rates of
the forward and reverse reactions are equal
‘TRADITIONAL’
REACTANTS
PRODUCTS
EQUILIBRIUM EQUILIBRIUM EQUILIBRIUM
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Writing Equilibrium Equations
▶ Equilibrium reactions are written using a double
arrow
▶ Each of the arrows only has a single-sided head
REACTANTS PRODUCTS
▶ The unit will make a lot of reference to the rate of
the:
▶ ‘forward reaction’ (reactants becoming products)
▶ ‘back reaction’ (products
Mainbecoming reactants)
Equilibrium and Solubility
▶ A saturated solution in a closed system will establish a dynamic equilibrium
if there is excess solid present
▶ The concentration of ions present in
the aqueous solution will increase
▶ Some aqueous ions will
recombine and precipitate out of
solution
▶ When the solution becomes saturated, the
rate of dissolving will equal the rate of
precipitation
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Dynamic Equilibrium
▶ The reaction hasn’t stopped, it is still going, but the rate
of the forward and back reactions are equal, so there is
no overall change.
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Dynamic Equilibrium
▶ The concentration of reactants
and products is constant
▶ They are NOT equal to each
other
▶ They are just not changing
▶ The rate of the forward reaction is
equal to the rate of the back
reaction
▶ At equilibrium these are not zero…
even though it looks like it on the
graph
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Characteristics of Equilibrium
1. Properties are constant at equilibrium (no color change or change
in density)
2. The rate of the forward reaction is equal to the rate of the
reverse reaction
3. There is no change in concentration of reactants and products
4. Equilibrium can only be obtained in a closed system
5. All species in the chemical equation are present in the
equilibrium reaction mixture
6. Equilibrium can be obtained from either direction
7. Changes such as temperature, pressure, or concentration of
reactants or products can affect the equilibrium
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Videos
Dynamic
Equilibrium
Bailing
Beakers
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The Equilibrium Law
▶ The equilibrium constant describes where the
position of equilibrium lies at a given temperature
▶ Can be used to maximize the yield of products and
the profitability of industry
▶ The Law of Chemical Equilibrium states that at a given
temperature the ratio of the concentration of products
to the concentration of reactants is constant
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Equilibrium Constant
wA + xB ⇌ yC
+ zD
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Changes in Reaction Equation
Change in Equilibrium Equilibrium Constant
Reaction Constant
Equation Expression
Reverse the reaction Inverse of 1
the Kc
expression
Halve the coefficients Square root of √Kc
the
expression
2
Double the coefficients Square the expression Kc
Sum equations Product of Kc=Kc1 x Kc2
Magnitude of the Equilibrium Constant
▶ If Kc is large, Kc>>1, at any given temperature,
products are favored over reactants
▶ If Kc is small, Kc<<1, at any given temperature,
the reaction is unfavorable
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Writing Equilibrium Constant Expressions
▶ For an aqueous reaction the concentration of
the solvent water does not appear in the
equilibrium constant expression
▶ For a non-aqueous solution, water must be included
in the equilibrium constant expression
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Reaction Quotient
▶ If a system has not reached equilibrium, the ratio of
concentration of product to reactants will not equal
Kc
▶ The ratio is the reaction quotient, Q, and it helps you
to determine the progress of the reaction
as it moves toward equilibrium
and the direction of the
reaction that is favored
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K c and Q
Q>Kc The concentration of products is greater than at
equilibrium and the reverse reaction is favored until
equilibrium is reached
Q<Kc The concentration of reactants is greater than at
equilibrium and the forward reaction is favored until
equilibrium is reached
Q=Kc The system is at equilibrium and the forward and
reverse reactions occur at equal rates
Lesson 2
Le Chatelier’s
Principle
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We Are Here
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Le Châ telier's Principle
▶ Useful tool for predicting the effect that changing
conditions will have on the equilibrium position
▶ “If a change is made to a system that is in
equilibrium, the balance between forward and reverse
reactions will shift to offset this change and return
the system to equilibrium.”
▶ Applies to:
▶ Concentration
▶ Pressure
▶ Temperature
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Changes in Concentration
▶ Decrease in [Reactant] or increase in [Product]
▶ Equilibrium shifts to the left
▶ This has the effect of increasing [Reactant] and decreasing
[Product]
▶ Increase in [Reactant] or decrease in [Product]
▶ Equilibrium shifts to the right
▶ This has the effect of decreasing [Reactant] and increasing
[Product]
▶ Equilibrium constant is not affected
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Changes in Pressure
▶ Increasing Pressure:
▶ Shifts equilibrium to the side with fewest gas molecules
▶ This has the effect of reducing the pressure increase
▶ Decreasing Pressure:
▶ Shifts equilibrium to the side with more gas molecules
▶ This has the effect of increasing the pressure
▶ Increase in pressure, decrease in volume and vice
versa
▶ Equilibrium constant is not affected
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Changes in Temperature
Type of Change in Equilibrium Equilibrium
Reaction Temperature Position Constant,
Kc
Exothermic Increase Moves to the Decreases
left, favoring
reactants
Decrease Moves to the Increases
right, favoring
products
Endothermic Increase Moves to the Increases
right, favoring
products
Decrease Moves to the Decreases
left, favoring
reactants
Catalysts
▶ Catalysts provide alternative pathways for a reaction
▶ In a forward reaction, a catalyst provides sufficient energy
to overcome the activation energy barrier and become
products
▶ In a reversible reaction, the lower activation energy has
the same effect on both the forward and reverse
reactions
▶ The position of the equilibrium will not change
▶ Equilibrium constant is not affected
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How is equilibrium around us?
CO₂(aq) ⇌ CO₂(g)
When you open the can, you no longer have a closed
system. The CO₂ molecules are free to escape into the
atmosphere.
This decreases the number of molecules returning to
the solution.The system is no longer at equilibrium.
You are decreasing the concentration of the product.
According to Le Châtelier's Principle, the system
responds by trying to replace the molecules that have
escaped.
These molecules then escape into the atmosphere.
The process continues until the pop goes flat. Main
Haber Process
▶ An artificial nitrogen fixation process and is the main
industrial procedure for the production of ammonia
today
▶ Before the development of the Haber process,
ammonia had been difficult to produce on an industrial
scale
▶ Although the Haber process is mainly used to produce
fertilizer today, during WWI, it provided Germany with
a source of ammonia for the production of explosives
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Haber Process
▶ The Haber process has been described as the most
important chemical reaction on Earth as it has
revolutionized global food production. However, it also
had a large impact on weaponry in both world wars .
▶ How does the social context of scientific work affect the
methods and findings of science? Should scientists be
held morally responsible for the applications of their
discoveries?
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Calculation of equilibrium
constants
Main
We Are Here
Main
Homologous Equilibrium Constants
When a mixture of 0.100 mol of NO, 0.051 mol of H2, and
0.100 mol of H 2 0 were placed in a 1.0dm3 flask at 300 K, the
following equilibrium was established:
2NO(g) + 2H2(g) ⇄ N2 + 2H2O
At equilibrium, the concentration of NO was found to be 0.062
mol dm-3. Determine the equilibrium constant, Kc, of the
reaction at this temperature
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ICE
2NO(g) + 2H2(g) ⇄ N2 +
2H2O
2NO 2H2 N2 2H2O
Initial (mol dm-3) 0.100 0.051 0.00 0.100
Change -X
(mol dm-3)
Equilibrium 0.062
(mol dm-3)
0.100-x=0.062 -x = 0.062-
-x = -0.038 0.100
x =0.038
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ICE
2NO(g) + 2H2(g) ⇄ N2 +
2H2O
2NO 2H2 N2 2H2O
Initial (mol dm-3) 0.100 0.051 0.00 0.100
Change -0.038 -0.038 +0.019 +0.038
(mol dm-3)
Equilibrium 0.062 0.013 0.019 0.138
(mol dm-3)
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Homologous Equilibrium Constants
2NO(g) + 2H2(g) ⇄ N2 +
2H2O
Kc = [N2]
[H2O][NO]
2
2
[H2]2 =[0.062]
[0.019][0.138]
2
[0.013]22
Kc = 5.6 x 102
IB does not require units for
Kc
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Calculating Equilibrium Concentrations
The Kc for the following reaction is 6.78 at a certain
temperature. The initial concentrations of NO and
SO3 were both 0.0300 mol dm-3. Calculate the
equilibrium concentration of each reactant and
product.
SO3(g) + NO(g) ⇄ NO2(g) + SO2(g)
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Calculating Equilibrium Concentrations
SO3(g) + NO(g) ⇄ NO2(g) +
SO2(g)
SO 3
NO NO 2
SO2
Initial (mol dm-3) 0.0300 0.0300 0.00 0.00
Change -x -x +x +x
(mol dm-3)
Equilibrium 0.0300-x 0.0300-x x x
(mol dm-3)
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Calculating Equilibrium Concentrations
SO3(g) + NO(g) ⇄ NO2(g) +
SO2(g)
Kc = [NO2] [SO2] = (x)
6.78= (x)
(0.0300-x)(0.0300-x)
[SO3] [NO]
(x)2
6.78= (0.0300-x)2
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Calculating Equilibrium Concentrations
Take the square root of both
sides: 2.60= x
0.0300-x
Solve for x:
0.078-2.60x =
x
0.078 = 3.60x
x = 0.0217
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Calculating Equilibrium Concentrations
SO3(g) + NO(g) ⇄ NO2(g) +
SO2(g)
SO 3
NO NO 2
SO2
Initial (mol dm-3) 0.0300 0.0300 0.00 0.00
Change -.0.0217 -0.0217 +0.0217 +0.0217
(mol dm-3)
Equilibrium 0.00830 0.00830 0.0217 0.0217
(mol dm-3)
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I.C.E.
ICE
Video
ICE
Tables
Main
Gibbs Free Energy
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Gibbs Free Energy
▶ Gibbs free energy describes the spontaneity
and temperature dependence of a reaction
▶ The free energy will change as reactants are converted
into products
▶ The reaction will be spontaneous in the direction that
results in a decrease in free energy (or in the direction
in which the free energy value becomes more
negative)
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Gibbs Free Energy
Equilibrium Constant Description Gibbs Free Energy Change
K=1 At equilibrium; neither ΔG = 0
reactants or products
favored
K>1 Products favored ΔG <0 (negative value)
K<1 Reactants favored ΔG > 0 (positive value)
▶ A negative ΔG indicates the reaction is spontaneous and the equilibrium
concentrations of the products are larger than the equilibrium
concentrations of the reactants.
Main
Gibbs Free Energy
ΔG = ΔH -TΔS
ΔGproducts-ΔGreactants = ΔG
ΔG = -RT lnK
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Example
Consider H2+I2 ⇄ 2HI. Given that the value of ΔG at 298K for this
reaction is
+1.3kJmol-1, calculate the value of the equilibrium constant.
ΔG=-RTlnK *R has units of JK-1 the value of ΔG must
ΔG=1300Jmol-1 be converted into Jmol-1
1300=-8.31 x 298 x
lnK
lnK=-1300 =-
Inverse
0.525 function for lnx is
e x
8.31 x 298
K=e-0.525
The equilibrium constant is less than 1, which implies that the position of
lies closer to reactants than products, which is also consistent with value of ΔG
equilibrium
K=0.59 positive
being
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