Rates & Equilibrium

The Rate Equation

Definitions
Order of Reaction

2
3
3

Concentration-Time Graphs
Shapes of Graphs
Determining the Order Using Concentration-Time Graphs

3
3
4

Rate-Concentration Graphs
Shapes of Graphs
Determining the Order Using The Initial Rate Method

6
6
7

The Rate Constant

Calculation and Units
The Effect of Temperature on k

8
8
9

The Rate Determining Step

Reactions Involving Different Molar Quantities

10
10

Equilibrium
The Equilibrium Constant Kc
The Units of Kc

11
11
11

The Effect of Changing Conditions on Kc

The Effect of Changing Concentration on Kc
The Effect of Changing Pressure on Kc
The Effect of A Catalyst on Kc
The Effect of Changing Temperature on Kc

12
12
12
12
13

Calculations Involving Kc
Kc From Equilibrium Constants
Kc From Initial Amounts
The Composition of a Reaction Mixture
Calculating the Amount of a Reactant Needed

14
14
14
15
16

The Rate Equation

The rate equation shows the relationship between the rate of a reaction and the initial
concentrations.

Rate is the chance in concentration per unit time.

[A] and [B] are the initial concentrations of the reactants. E.g.
A could be HCl and B NaOH.
a is the order of reaction with respect to A. This is determined
by experimentation.
b is the order of reaction with respect to B. This is determined
by experimentation.
a + b is the overall order of the reaction
k is the rate constant. K remains the same at a constant
temperature.

Definitions
Half Life the time taken for the concentration of a reactant to reduce by half.
Rate-determining step this step is the slowest step in the reaction and determines the
overall rate.
Order of Reaction the order with respect to a reactant is the power to which the
concentration of the reactant is raised in the rate equation.
Order of Reaction
The order is the power the initial concentration is raised to and can be determined
using either concentration time graphs or using rate concentration graphs.

Concentration-Time Graphs
Shapes of Graphs
2

When plotting concentration time graphs, different orders of reaction cause the graphs
to look different:

Zero Order

Concentration decreases
at a constant rate.

[A]

Half-life decreases with

time.
Time

First Order

In first order reactions the

half-life remains constant
i.e. it is the same amount
of time.

[A]

Time
Second Order

[A]

For second order

reactions, the half-life
increases, i.e. it decreases
with every half-life taken.

Time

This is a first order reaction as the measured half-life is constant.

Determining the Order Using Concentration-Time Graphs

Start with known concentrations of A and B. Have one reactant (e.g. B) in

excess so its concentration stays constant.
Determine the concentration of A at different times in the reaction.
Plot the concentration-time graph and match the shape with one of the above.

For example:

H+
Br2 + HCOOH 2HBr + CO2
Time/s

30

60

90

120

180

240

360

[Br2]
0.01 0.009 0.0081 0.0073 0.0066 0.0053 0.0044 0.0028
/moldm-3
The reaction of bromine with methanoic acid, catalysed by protons, can be followed
using a colorimeter to determine bromine concentration. As bromine is used up, the
orange colour fades and the readings can be compared to a graph of known
concentrations to find the actual bromine concentration.
A large excess of methanoic acid is used so the concentration is constant.

Reaction of Br2 & HCOOH

0.01
0.01
0.01
[Br2] moldm-3

0.01
0
0
0
0

30

60

90

120

180

240

360

480

600

Time/s

Using the line of best fit, find the half-lives. In this reaction, the half-lives are constant
at roughly 200, hence it is first order.
To find the initial rate, draw a tangent to the graph at t = 0 and find the gradient (the
change in y divided by the change in x). This is the initial rate. In this instance it is
3.1x10-5 moldm-3s-1

Rate-Concentration Graphs
Shapes of Graphs
The concentration of A
does not affect the rate of
reaction.
The rate is proportional to

First Order

Rate
Rate

Zero Order

[A]
[A]2

480

600

0.0020

0.0013

Second Order

Rate

a change in the
concentration.

Rate is proportional to a
change in the
concentration squared.

Rate

[A]
Drawn anther way:

[A]2
Determining the Order Using The Initial Rate Method
Respect to A:
Start with known concentrations of A and B.
Measure the rate of reaction by timing how long it takes for a measurable
change to occur.
Repeat the experiment changing the initial concentration of A but keeping the
initial concentration of B constant.
Experiment
1
2
3

[A]/moldm=3
0.5 x2
1.0
x2
2.0

[B]/moldm=3
3.0
3.0
3.0

Initial Rate/moldm-3s-1
0.18
x2
0.36
x2
0.72

As can be seen, when the [A] doubles, the rate doubles, therefore a change in the rate
is proportional to the change in concentration. Thus in the rate equation A is first
order.
Respect to B:
Start with known concentrations of A and B.
Measure the rate of reaction by timing how long it takes for a measurable
change to occur.
Repeat the experiment changing the initial concentration of B but keeping the
initial concentration of A constant.
Experiment
4
5
6

[A]/moldm=3
0.5
0.5
0.5

[B]/moldm=3
1.0
x2
2.0
4.0

Initial Rate/moldm-3s-1
0.02
x4
0.08
0.32
5

When [B] is doubled, the rate quadruples. This change in rate is proportional to the
change in the concentration squared and B is second order.
Hence the rate equation when A & B react together is:
Rate = k[A][B]2

The Rate Constant

The rate constant is always present in the rate equation and can be calculated by
rearranging the rate equation. Its units vary, so it is also important to be able to find
those.
Calculation and Units
Using the values from the previous page we know:
Experiment
1
2
3

[A]/moldm=3
0.5
1.0
2.0

[B]/moldm=3
3.0
3.0
3.0

Initial Rate/moldm-3s-1
0.18
0.36
0.72

Rate = k[A][B]2
Hence we get the equation:
0.18 = k(0.5)(3.0)2
Rearranged this gives:
k = 0.18
(9x0.5)
Thus k = 0.04

To calculate units we know:

moldm-3s-1 = k[moldm-3][ moldm-3]2
Rearranged gives:
moldm-3s-1
[moldm-3][ moldm-3]2
Thus k = mol-2dm6s=1
k=

Hence the units of k depend on the overall order of reaction

6

Overall Order

Rate Equation

Rate = k[A]

Rate = k[A][B]

Rate = k[A][B]2

Expression for k
k = rate
[A]
k = rate
[A][B]
k = rate
[A][B]2

Units of k
s=1
dm3mol-1 s=1
dm6mol-2s=1

The Effect of Temperature on k

The rate of reaction will always increase when temperature increases.

This is best illustrated using a Maxwell-Boltzmann distribution.

At higher temperatures, more molecules will have energy greater than or equal to the
activation energy, which results in more successful collisions.
If the concentrations of reactants are kept constant as temperature increases, k must
increase as the rate increases. The increase of k with temperature is exponential.
7

Temperature/K

The Rate Determining Step

Most reactions have what is called a reaction mechanism. This shows the series of
reactions that occur in a sequence of steps, the slowest of which controls the rate of
the reaction; this is known as the rate-determining step. The reactants that are
involved in the rate-determining step are present in the rate equation.
Any step that occurs after the rate-determining step will not affect the rate of the
reaction; hence the reactants involved will not appear in the rate equation.
For example:
The reaction between 2-chloro-2-methylpropane and KOH react as follows:
(CH3)CCl + OH- (CH3)COH + ClThe orders of the reactants are as follows:
[(CH3)CCl] First Order
[OH-] Zero Order
This means that the rate equation is as follows: rate = k[(CH3)CCl]
Therefore only (CH3)CCl can be present in the rate-determining step. There must be at
least two steps in the mechanism as OH- is not present in the first step. An example of
a mechanism could be:

Rate-Determining Step

This is a feasible mechanism as it corresponds to the rate equation and the overall
equation.
Reactions Involving Different Molar Quantities
Given the reaction:

2NO + O2 2NO2

And the rate equation:

Rate = k[NO]2
It shows you the rate-determining step has 2 moles of NO present due to the power of
two; thus a mechanism could be:
2NO N2O2
N2O2 + O2 2NO2

Equilibrium
When a system is in dynamic equilibrium it has
three main features:
The rate of the forward reaction equals the
rate of the backward reaction.
At equilibrium there is no net change in
the concentrations.
Equilibrium can only be reached in a
closed system.
The Equilibrium Constant Kc
Consider this reaction:

N2 + 3H2 2NH3
2

In this case Kc = [NH3]

[N2][H2]3

[N2], [H2] & [NH3] are the concentration of reactants and products at
equilibrium.
The powers [N2], [H2] & [NH3] are raised to represents the number of moles in
the balanced equation.

Kc is a constant value assuming the temperature stays constant. Its value tells us the
relative amounts of products and reactants at equilibrium:
A large Kc means the position of equilibrium is to the right.
A small Kc means the position of equilibrium is to the left.
The Units of Kc

As well as calculating Kc, the units must also be calculated as concentrations are in
moldm-3 and different powers and quantities of reactants and produces means its units
vary.
For example:
Equation

Kc

Units

Simplified Units

N2 + 3H2 2NH3

[NH3]2
[N2 ][H2]3

(moldm-3)2
(moldm-3)(moldm3)3

mol-2dm6

H2 + I2 2HI

[HI]2
[H2][I2]

(moldm-3)2
(moldm-3)(moldm3)

No Units

If a Kc expression has no units it is important to state that it has no units.

The Effect of Changing Conditions on Kc

The Effect of Changing Concentration on Kc
The value of Kc DOES NOT change when concentrations change. If the
concentrations change, the system will no longer be in equilibrium and hence will
shift to restore the Kc value.
Concentration of
Equilibrium shifts:
Reactant
Concentration
of
Equilibrium shifts:
Increases
Right
Product
Decreases
Left
Increases
Left
Decreases
Right
If the reactants
increase, more
products are produced to minimise the change of added reactants and vice versa.
For example:

2CrO42- + 2H+
Yellow

Concentration of H+
(reacants)

Cr2O72- + H2O
Orange

Equilibrium shifts:

Increases

Right

Decreases
(OH- added)

Left

Colour Change
Yellow > Orange
Orange > Yellow

The Effect of Changing Pressure on Kc

10

Kc DOES NOT change when the total pressure changes. When pressure is
increased/decreased, concentrations change, however the system will restore
equilibrium by shifting left or right.
Pressure

Equilibrium shifts

Explanation
Whilst
Fewer moles exert less
this
To the side with fewer
Increases
pressure, thus minimising
has no
moles
the increase
effect
More moles exert more
on Kc,
To the side with more
DecreasesEquilibrium
pressure, thus minimising
Temperatur
Explanation
Kc
an
moles
the decrease
e
shifts:
The reaction is exothermic so it shifts Decrease
Increases
Left
to absorb heat
s
The reaction is exothermic so it shifts
Decreases
Right
Increases
to release heat
increase in pressure will initially increase the forward and backward reactions
equally.
The Effect of A Catalyst on Kc
A catalyst increases the rate of the forward and backward reactions equally.
It has no effect on the Kc value.
It has no effect on the position of equilibrium or the yield.
The Effect of Changing Temperature on Kc
The way the system responds depends on if it is a exothermic or endothermic
reaction, however temperature changes do affect the value of Kc.

When the temperature is increased the system moves to absorb heat (the
endothermic reaction).
When the temperature is decreased the system moves to give out heat (the
exothermic reaction).

Exothermic

The forward reaction is exothermic

N2 (g) + 3H2 (g) 2NH3 (g) H = -92.4 KJmol-1

An increase in
temperature
The reverse reaction is endothermic
causes the system to shift left.

Endothermic
An increase in temperature causes the system to shift right.

11

The forward reaction is endothermic

[Co(H2O)6] (aq) + 4Cl- (aq) [CoCl4]2-(aq) + 6H2O(l) H = positive
The reverse reaction is exothermic

An increase in temperature increases the rate of forward and backward reactions but
to different extents.

Calculations Involving Kc
Kc From Equilibrium Constants
N2O4 NO2
Temperatur
e

Equilibrium
shifts:

Explanation

Kc

The reaction is endothermic so it shifts

to absorb heat
The reaction is endothermic so it shifts
Decreases
Left
to release heat
equilibrium. The amounts present at equilibrium are
14.70g NO2. The volume of the container is 200cm3.
Increases

Right

Moles at Equilibrium
Concentrations at
Equilibrium (moldm-3)

N2O4
3.6 = 0.0391
90
0.0391 = 0.1995
0.2

Kc =
Units of Kc

(moldm-3)2
moldm-3

Calculation

[1.6]2
[0.1955]

Increases

N2O4
and
NO2
are
at

Decrease
s
3.60g N2O4 and

NO2
14.7 = 0.320
46
0.32 = 1.6
0.2
[NO2]2
[N2O4]

13.1 moldm-3

Kc From Initial Amounts

1 mol ethanoic acid was added to 0.5 moles of ethanol and was left to reach
equilibrium. At equilibrium 0.58 mol of ethanoic acid was left.
CH3COOH + CH3CH2OH CH3COOCH2CH3 + H2O

12

Initial moles
Equilibrium
Moles
Concentration
s at
Equilibrium
moldm-3

CH3COOH
1
0.58

CH3CH2OH
0.5

0.42

0.58
V

0.08

CH3COOCH2CH3 H2O
0
0
+0.4
0.42 2
0.42

0.08
V

0.42
V

0.42
V

[CH3COOCH2CH3][ H2O]
[CH3CH2OH] [CH3COOH]

Kc Expression

Units of Kc

[moldm-3][ moldm-3]
[moldm-3][ moldm-3]

Calculation

[0.42][ 0.42]
[0.08] [0.58]

= 3.80 No units

In this instance, the Vs cancel out and Kc can be derived from moles.
The Composition of a Reaction Mixture
1 mole of ethanoic acid was added to one mole of ethanol. If Kc = 4 calculate the
number of moles of ethyl ethanoate and equilibrium.
CH3COOH + CH3CH2OH CH3COOCH2CH3 + H2O
Initial moles
Equilibrium
Moles
Concentration
s at
Equilibrium
moldm-3
Kc Expression

Units of Kc

CH3COOH
1
1-X
1-X
V

-X

CH3CH2OH
1
1-X

CH3COOCH2CH3 H2O
0
0
+X
X
X

1-X
V

X
V

X
V

[CH3COOCH2CH3][ H2O]
[CH3CH2OH] [CH3COOH]
[moldm-3][ moldm-3]
[moldm-3][ moldm-3]

Calculation
[X][ X] = 4
[1-X] [1-X]
X2 = 4(1-X)2

13

X2 = 4(X2 2X + 1)
X2 = 4X2 8X + 4
3X2 8X + 4
(3X - 2)(X-2)
Therefore X = 2/3 or X = 2
From the expression we have X = 2 or X = 2/3. X must be 2/3 as
otherwise you would have negative moles. So the number of moles
of ethyl ethanoate at equilibrium is 2/3.

Result

Calculating the Amount of a Reactant Needed

CH3COCH3 + HCN CH3C(CN)(OH)CH3
If Kc = 30 dm mol calculate the number of moles of HCN required to produce one
mole of produce if you start with 4 moles of propane in 2dm3 of ethanol (acting as a
solvent).
3

Initial moles
Equilibrium
Moles
Concentration
s at
Equilibrium
moldm-3
Kc Expression

Units of Kc

-1

CH3COCH3
4
3
3
2

-1

HCN
X
X-1

CH3C(CN)(OH)CH3
0
+1
1

X-1
2

1
2

[CH3C(CN)(OH)CH3]
[CH3COCH3] [HCN]
[moldm-3]
[moldm-3][ moldm-3]

Calculation
[ ] = 30 dm3mol-1
[3/2] [ (X-1)]

14

 = 45( (X-1) )
= 22.5(X-1)
1 = 45 (X-1)
1 = 45X - 45
45X = 46
X = 46/45
X=1.022 (rounded)
X = 1.022 mol of HCN

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