Kinetics 3

-] rate = k
= k [IO 3 [N O2 ] 2
r a t e

rate = k [A] m [B] n

-]
][O H
B r
k [ CH 3
e =
rat

16.1: Rate Expression

Reference: Higher Level Chemistry, pp.
 Rates and Concentrations of Reactants
Consider this raw experimental data showing how the concentration of
a reactant changes over time for a particular reaction:
450"

reactant'concentra)on'(mol'dm^/3)'
400"
350"
300"
250"
200"
150"
100"
50"
0"
0" 1" 2" 3" 4" 5" 6"
)me'(s)'

What does this graph show about the effect of concentration on reaction rate?
Remember rate = slope of a conc. vs time graph
Consider the instantaneous rate at various concentrations (or times)
using the slope of the tangent line at those points.

As reactant concentration decreases, rate decreases.

 Rate Expressions (aka Rate Laws)

Now consider this same data

rate (mol dm-3 s-1)

transformed to show how the
rate of reaction changes with
reactant concentration.

0 50 100 150 200 250 300

reactant concentration (mmol dm-3)

As concentration increases, the rate increases.

or

As concentration decreases, the rate decreases.

Why do we need to predict how concentration affects rate?

 Rate Expressions (aka Rate Laws)
The rate of reaction can be expressed a function of the
concentration of the reactants.

Consider the simpli ed reaction: A→ B

rate = k [A] m

rate rate constant order of

(in mol dm-3 s-1) (variable units) reaction
fi
 Order of Reaction
The “order of reaction” indicates the effect on the rate of
an increase in a given reactant concentration.

Consider these three reactions shown as

rate vs concentration graphs:

y = mx + b = b
rate = k[reactant]0 = k
The reaction is ZERO order.
The concentration has no
effect on rate.
y = mx + b
rate = k[reactant]1
The reaction is FIRST order.
There is a linear relationship
between concentration and
rate.
y = mx2
rate = k[reactant]2
The reaction is SECOND
order. The rate is
proportional to the
concentration squared (of
the reactant).
 Order of Reaction
Another way to look at the meaning of “order of reaction”:

1. A → B rate = k[A]0 [A] rate

zero order 1 k
2 k
3 k
1/2 k

2. X → Y rate = k[X]1 [X] rate

rst order k
1
2 2k

3 3k
1/2 1/2 k
fi
 Order of Reaction
Another way to look at the meaning of “order of reaction”:

3. W → Q rate = k[W]2 [W] rate

second order 1 k
2 4k
3 9k
1/2 1/4 k

Practice:
1. When the concentration of a reactant changes from 0.45 mol dm-3 to 1.35 mol dm-3, the
rate increases from 0.32 mol dm-3 s-1 to 2.88 mol dm-3 s-1.
What is the order of the reaction with respect to the reactant? m=2
2. When the concentration of a reactant is halved, the rate is reduced by 1/2.
What is the order of the reaction with respect to the reactant? m=1

3. When the concentration of a reactant doubles, the time of reaction changes from 8 s to 2 s.
What is the order of the reaction with respect to the reactant? m=2
 Rate Expressions (aka Rate Laws)
Now consider the general equation for a reaction with two reactants:

aA + bB → cC + dD
rate constant (variable units)

rate = k [A] [B]

m n
rate
in mol dm-3 s-1 orders of reaction
with respect to A or B

m + n = overall order of reaction

The values of m and n depend on the reaction mechanism (Keynote 4).

 Rate Expressions (aka Rate Laws)
Consider rate laws with two reactants:

1. A + B → C [A] [B] rate

rate = k[A][B] 1 1 k

rst order w.r.t A and B 2 1 2k

(m = 1 and n = 1)
1 2 2k
second order overall 2 2 4k
(m + n = 2)
3 1 3k
1 3 3k
3 3 9k
fi
 Rate Expressions (aka Rate Laws)
Consider rate laws with two reactants:

2. A + B → C [A] [B] rate

rate = k[A]2 1 1 k
second order w.r.t A and 2 1 4k
zero order w.r.t. B
1 2 k
(m = 2 and n = 0)
2 2 4k
second order overall
(m + n = 2) 3 1 9k
1 3 k
3 3 9k
 Rate Expressions (aka Rate Laws)
Consider rate laws with two reactants:

3. A + B → C [A] [B] rate

rate = k[A]2[B] 1 1 k
second order w.r.t A and 2 1 4k
rst order w.r.t. B
1 2 2k
(m = 2 and n = 1)
2 2 8k
third order overall
(m + n = 3) 3 1 9k
1 3 3k
3 3 27k
fi
 Rate Expressions (aka Rate Laws)
Consider rate laws with two reactants:

Practice Given a reaction: A + B → C rate = k[A]m[B]n

1. When the concentration of both A and B double, the rate of the reaction
doubles. When the concentration of B only doubles, the rate of the
reaction doubles. State the order of reaction with respect to A and B.
m=0 n=1

2. When the concentration of both A and B doubles, the rate of the

reaction increases by a factor of eight. When the concentration of B only
doubles, the rate of the reaction doubles. State the order of reaction with
respect to A and B. m=2 n=1

3. When the concentration of A triples and B is halved, the rate of the

reaction changes from 5 mol dm-3 s-1 to 22.5 mol dm-3 s-1. State the general
rate law for this reaction. rate = k [A]2 [B]1
 Rate Constants
rate = k [A]m[B]n
1. For any given reaction, the value of k depends on the temperature.

Example: cyclopropane (C3H6) → propene (C3H6)

rate = k[C3H6]1

T = 477 K: rate = 0.00018 s-1[C3H6]1

T = 577 K: rate = 0.030 s-1[C3H6]1

2. The units for the rate constant k depend on the OVERALL order of the reaction.

rate rate units in mol dm-3 s-1

k= m n
[A] [B] conc’n units in mol dm-3
 Rate Constants and Units
rate units
ZERO ORDER overall k=
(concentration units)0
mol dm−3 s−1
= −3 0
(mol dm )
−3 −1
mol dm s
=
1
= mol dm−3 s−1

rate units
FIRST ORDER overall k=
(concentration units)1
mol dm−3 s−1
=
mol dm−3
= s−1
 Rate Constants and Units
rate units
SECOND ORDER overall k=
(concentration units)2
mol dm−3 s−1
=
(mol dm−3 )2
mol dm−3 s−1
=
mol2 dm−6
= mol−1 dm3 s−1

rate units
THIRD ORDER overall k=
(concentration units)3
mol dm−3 s−1
=
(mol dm−3 )3
mol dm−3 s−1
=
mol3 dm−9
= mol−2 dm6 s−1
 Rate Expressions from Experimental Data
Method of Initial Rates
The initial rate is calculated using different initial reactant concentrations (at a set T).
The order of the reaction, and the rate constant, can be determined.

Example 1: 2 N2O5 → 4 NO2 + O2

When the concentration of N2O5 changes from 0.40 mol dm-3 to 0.80 mol dm-3 at
25˚C, the initial rate of reaction doubles.
At [N2O5] =0.40 mol dm-3, the rate is 2.1 x 10-4 mol dm-3 s-1.

1. general rate expression: 3. rate constant value

rate = k [N2O5 ]1
rate = k [N2O5]m
rate
k=
[N2O5 ]1
2. order w.r.t. N2O5: 2.1 x 10-4 mol dm-3 s-1
=
m=1 0.40 mol dm-3
= 5.3 x 10-4 s-1
When [N2O5] doubles, the
4. rate expression at 25ºC
rate doubles.
rate = 5.3 x 10-4 s-1 [N2O5]1
 Rate Expressions from Experimental Data
Example 2: A + B → 2C
The initial rate of reaction for a series of experiments was performed with varying
initial concentrations of A and B. The data is shown below.

rate = k[A]m[B]n
[A] [B] rate
trial
mol dm-3 mol dm-3 mol dm-3 s-1
[B] is xed; 1 0,2 0,1 2
[A] is xed;
only [A]
2 0,4 0,1 8 only [B]
changes
3 0,4 0,3 24 changes

1. use trials 1+2 to nd m 2. use trials 2 + 3 to nd n 3. nd k

Using trial 1 data:
m=2 n=1
rate = k [A]2 [B]
The rate quadruples The rate triples when
when [A] doubles. [B] triples. 2 = k(0.2)2 (0.1)
k = 500 mol-2 dm6 s-1
fi
fi
fi
fi
fi
 Rate Expressions from Experimental Data
Example 3: 2 BrO3– + 5 HSO3– → Br2 + 5 SO42- + H2O + 3 H+

rate = k[BrO3–]m[HSO3–]n
[BrO3–] [HSO3–] rate (at 30º C)
trial
(mol dm-3) (mol dm-3) (mol dm-3 s-1)
1 0. 0154 0,0543 1.58 x 10-4
2 0,00750 0,0178 9.14 x 10-6
3 0,00760 0,0550 8.12 x 10-5

An alternate approach to nding order:

m
1. Like before, choose two trials where
the concentration of one reactant is ⎛ [A] ⎞ ⎛ rate ⎞
xed and the other changes. ⎜⎜ trial 1
⎟⎟ = ⎜⎜ 1
⎟⎟
2. Set up a ratio as shown at the right
⎝ [A]trial 3 ⎠ ⎝ rate3 ⎠
and solve for the order.
Use the trial with the higher
concentration in the numerator.
fi
fi
 Rate Expressions from Experimental Data
Example 3 continued 2 BrO3– + 5 HSO3– → Br2 + 5 SO42- + H2O + 3 H+

1. use trials 1 + 3 to nd m 2. use trials 2 + 3 to nd n

(order w.r.t. BrO3–) (order w.r.t. HSO3–)
m n
⎛ [BrO ]– ⎞ ⎛ rate ⎞ ⎛ [HSO ] – ⎞ ⎛ rate ⎞
⎜⎜ 3 trial 1 ⎟
= ⎜
⎜ rate ⎟⎟
1 ⎜⎜ 3 trial 3 ⎟
⎟ = ⎜
⎜ rate ⎟⎟
3
– ⎟ –
⎝ [BrO3 ]trial 3 ⎠ ⎝ 3⎠ ⎝ [HSO3 ]trial 2 ⎠ ⎝ 2⎠

⎛ 0.0154 ⎞
m
⎛1.58 x 10-4 ⎞ ⎛ 0.0550 ⎞
n
⎛ 8.12 x 10-5 ⎞
⎜ ⎟ = ⎜⎜ ⎟
-5 ⎟
⎜ ⎟ = ⎜⎜ ⎟
-6 ⎟
⎝ 0.00760 ⎠ ⎝ 8.12 x 10 ⎠ ⎝ 0.0178 ⎠ ⎝ 9.14 x 10 ⎠
2.03m = 1.95 3.09n = 8.88
∴ m=1 ∴ n=2

3. nd the rate constant and state the rate expression at 30ºC

using trial 1 data to nd k: rate = k[BrO3–]1[HSO3–]2
1.58 x 10-4 = k (0.0154)(0.0543)2
k = 3.48 mol-2 dm6 s-1

rate expression at 30ºC: rate = 3.48 mol-2 dm6 s-1[BrO3–]1[HSO3–]2

fi
fi
fi
fi
 Graphs Graphs Graphs
Know the difference and relationships between
concentration vs time and rate vs concentration graphs.

zero order reaction

reactant concentration

rate = k[A]0 = k

rate
time reactant concentration

The slope is constant, so The concentration of the

the rate is constant at any reactant has no effect on
reactant concentration. the rate.
 Graphs Graphs Graphs
Know the difference and relationships between
concentration vs time and rate vs concentration graphs.

rst order reaction

rate = k[A]1
reactant concentration

rate
time reactant concentration

The instantaneous rate There is a linear

(slope of the tangent line) relationship between the
decreases as the reactant reactant concentration
concentration decreases. and the rate .
fi
 Graphs Graphs Graphs
Know the difference and relationships between
concentration vs time and rate vs concentration graphs.

second order reaction

rate = k[A]2
reactant concentration

rate
time reactant concentration

The instantaneous rate

The rate is proportional to
(slope of the tangent line)
the concentration squared
decreases as the reactant
(of the reactant).
concentration decreases.
 Graphs Graphs Graphs
HALF LIFE:
another way to distinguish between zero, rst and second order reactions

rate = k[A]0 rate = k[A]1 rate = k[A]2

half life decreases half life is constant half life increases

fi
 Graphs Graphs Graphs
You try it!
rate = k[A]0 rate = k[A]1 rate = k[A]2
reactant concentration

reactant concentration

reactant concentration
time time time
rate

rate

rate
reactant concentration reactant concentration reactant concentration