Ib PPT 6 HL PDF

16.
1 Rate expression and reaction mechanism
Higher level
OBJECTIVES
• Reactions may occur by more than one step and the slowest step determines
the rate of reaction (rate determining step/RDS).
• The molecularity of an elementary step is the number of reactant particles
taking part in that step.
• The order of a reaction can be either integer or fractional in nature. The order
of a reaction can describe, with respect to a reactant, the number of particles
taking part in the rate-determining step.
• Rate equations can only be determined experimentally.
www.mrwengibchemistry.com
• The value of the rate constant (k) is affected by temperature and its units are
determined from the overall order of the reaction.
• Catalysts alter a reaction mechanism, introducing a step with lower activation
energy.
• Deduction of the rate expression for an equation from experimental data and
solving problems involving the rate expression.
• Sketching, identifying, and analysing graphical representations for zero, first
and second order reactions.
• Evaluation of proposed reaction mechanisms to be consistent with kinetic and
stoichiometric data.
Math revision - powers
x-1 = 1/x
The Rate Equation
Higher level
• links the rate of reaction to the concentration of reactants
• it can only be found by doing actual experiments
• it cannot be found by just looking at the equation
Chemical equation: A+BC+D

Possible rate equation: r = k[A][B]2
If [A] is doubled, then the rate doubles, if [B] doubles then the
rate quadruples (22).
r = rate of reaction (mol.dm-3s-1)

k = rate constant (units depend on the rate equation)
Catalysts speed up reactions so also need to be included in

the rate equations.
Order of reaction
Higher level
Individual order The power to which a concentration is
raised in the rate equation
Overall order The sum of all the individual orders in

the rate equation.
e.g. in the rate equation r = k[A][B]2

the order with respect to A is 1 1st Order
the order with respect to B is 2 2nd Order
the overall order is 3 3rd Order
The value is zero if the rate is unaffected by how much of a

substance is present.
Units for the Rate Constant (k)
Higher level
The units of k depend on the overall order of reaction.
Divide the rate by as many concentrations (mol dm-3) as

appear in the rate equation.
Overall 0 1 2 3
Order
Units
of k
mol dm-3 sec-1 sec-1 mol-1 dm3 sec-1 mol-2 dm6 sec-1
r = k[A] k will have units of sec-1
r = k[A]2 k will have units of dm3 mol-1 sec-1
r = k[A][B]2 k will have units of dm6 mol-2 sec-1

Graphical determination of rate
Higher level
The variation in rate can be investigated by measuring the change in concentration of one of
the reactants or products, plotting a graph and then finding the gradients of the curve at
different concentrations.
In the reaction… RATE CALCULATION

The rate of reaction at any
A(aq) + B(aq)  C(aq) + D(aq) moment can be found from
the gradient of the tangent
the concentration of B was measured at that point. The steeper
every 200 minutes. The reaction is the gradient, the faster the
rate of reaction
obviously very slow!
www.mrwengibchemistry.com Place a rule on the outside
of the curve and draw a
line as shown on the
graph.
gradient = y / x
Higher level
concentration = 1.20 mol dm-3
gradient = - 1.60 mol dm-3
1520 min
rate = - 1.05 x 10-3 mol dm-3
The rate is negative because

the reaction is slowing down
1. Order – concentration vs time
Higher level
The order of reaction can be found by measuring the rate at different
times during the reaction and plotting the rate against either
concentration or time. The shape of the curve provides an indication of
the order.
ZERO ORDER
A straight line showing a constant decline in
concentration.
CONCENTRATION (mol dm-3)
FIRST ORDER
www.mrwengibchemistry.com A slightly sloping curve which drops with a constant half-
life. (molecules harder to find)
SECOND ORDER
The curve declines steeply at first then levels out.
TIME (s)
2. Order – rate vs concentration
Higher level
SECOND ORDER – the
RATE OF REACTION / mol dm-3 s-1
rate is proportional to the

square of the concentration.
You get an upwardly sloping
curve.
ZERO ORDER – the rate

does not depend on the
www.mrwengibchemistry.com concentration. The line is
parallel to the x axis.
FIRST ORDER – the rate is

proportional to the
concentration so you get a
straight line of fixed gradient.
The gradient of the line
CONCENTRATION / mol dm-3 equals the rate constant for
the reaction.
ORDER OF REACTION
Higher level
GRAPHICAL
DETERMINATION
Calculate the rate of reaction at

1.0, 0.75, 0.5 and 0.25 mol dm-3
Plot a graph of rate v [A]
Calculate the time it takes

for [A] to go from...
1.00 to 0.50 mol dm-3
0.50 to 0.25 mol dm-3
Deduce from the graph

that the order wrt A is 1
Calculate the value and

units of the rate constant, k
Experimental determination of order
Higher level
Method 1 – Plotting a graph
Plot a concentration / time graph and calculate the rate (gradient) at points on the
curve
Plot another graph of the rate (y axis) versus the concentration at that point (x axis)
If it gives a straight line, the rate is directly proportional to concentration - 1st
ORDER.
If the plot is a curve then it must have another order. Try plotting rate v. (conc.) x 2.
A straight line would mean 2nd ORDER. This method is based on trial and error.
Method 2 - The initial rates method.
Do a series of experiments (at the same temperature) at different concentrations of
a reactant but keeping all others constant. Plot a series of concentration/time
graphs and calculate the initial rate (slope of curve at start) for each reaction. From
the results calculate the relationship between concentration and rate and hence
deduce the rate equation. To find order directly, logarithmic plots are required.
Problem 1: In an experiment between A and B the initial
Higher level
rate of reaction was found for various starting
concentrations of A and B. Calculate...
a. the individual orders for A and B

b. the overall order of reaction
c. the rate equation
d. the value of the rate constant (k)
e. the units of the rate constant
Experiment [A] [B] Initial rate (r)

1 0.5 1 2
2 1.5 1 6
3 0.5 2 8
a. the individual orders for A and B
Higher level
Experiment [A] [B] Initial rate (r)
1 0.5 1 2
2 1.5 1 6
3 0.5 2 8
When [B] is kept constant [A] is tripled. The rate also triples (2
to 6). Therefore rate  [A], so the order of reaction with
respect to A is 1.
When [A] is kept constant [B] is doubled. The rate quadruples

(2 to 8). Therefore rate  [B]2, the order of reaction with
respect to B is 2.
b. the overall order of reaction

The overall order is the sum of the individual orders
=1+2=3
c. the rate equation
Higher level
By combining the two proportionality relationships you can
construct the overall rate equation
 rate = k[A][B]2
d. the value of the rate constant (k)

rate 8
k= = =4
[A][B]2 (0.5)(0.2)2
e. the units of the rate constant
Divide rate (mol.dm-3s-1) by 3x concentration (mol.dm-3)
mol dm−3 s−1 mol dm−3 s−1 s−1

= = = dm6 mol−2 s−1
mol dm
3 −9 mol dm
3 −9 mol dm
2 −6
 k = 4 dm6 mol−2 s−1

Reaction Mechanisms
Higher level
• Reactions may occur all at once or through several
discrete steps.
• In a multistep process, one of the steps will be slower
than all others.
• The overall reaction cannot occur faster than this
slowest, rate-determining step.
• The order of reaction for this step will be the same as the
order of reaction for the entire reaction
38.
Slow Initial Step
Higher level
NO2(g) + CO(g)  NO(g) + CO2(g)
• The rate law for this reaction is found experimentally to

be
Rate = k [NO ]2 2
• CO is necessary for this reaction to occur, but the rate of
the reaction does not depend on its concentration.
• This suggests the reaction occurs in two steps.
39.
Slow Initial Step
Higher level
• A proposed mechanism for this reaction is
Step 1: NO2 + NO2  NO3 + NO (slow)
Step 2: NO3 + CO  NO2 + CO2 (fast)
• The NO3 intermediate is consumed in the second step.
• As CO is not involved in the slow, rate-determining step,
it does not appear in the rate law.
40.
Molecularity of the reaction
Higher level
mechanism
Unimolecular steps involve a single species as a
reactant.
A/ Products
Bimolecular steps involve collisions of two
species (that form a transition state or an
activated complex that cannot be isolated).
A+B/ Products
Differences between intermediates
Higher level
and transition states
Differences between intermediates
Higher level
and transition states
43.
Determining order of reaction from
Higher level
reaction mechanism
For the following assume a bimolecular reaction:
A+BC+D
Use the rate limiting step and in the reaction
mechanism to determine the reaction order of the
reaction in the preceding slides...
Higher level
reaction mechanism
Mechanism Rate expression (overall order)
r = k[A][B]
Order = 2
Higher level
reaction mechanism
r = k[A][X]
= k[A][A][B]
= k[A]2[B]
X does not exist Order = 3

in the initial
reaction.
Higher level
reaction mechanism
r = k[A]2
Order = 2
Higher level
reaction mechanism
r = k[B]
Order = 1
Higher level
reaction mechanism
r = k[A2][B]
= k[A][A][B]
= k[A]2[B]
Order = 3
B must exist
in the initial
reaction.
Guessing the rate determining steps
Higher level
(RDS)
1. Determine possible mechanism
2. See which fits the rate equation
Example: A + B + C  ABC rate = k[A][B]

What is the mechanism and RDS?
Hint: The chances of 3 substance all hitting at the right place
at the same time is unlikely….so…
1. A + B  AB, then AB + C  ABC or
2. A + C  AC, then AC + B  ABC or
3. B + C  BC, then BC + A  ABC
As C is zero order and the rate is first order A and B, situation
1 seems most likely, with the first reaction the RDS.
Problem 1: 2N2O  2N2 + O2 rate = k[N2O]2,
Higher level
what is the RDS?
1. 2N2O  N2 + O2 rate agrees or
2. N2O  N2 + O (if RDS then rate disagrees here)
then N2O + O  N2 + O2 Must be RDS
rate = [N2O][O]
= [N2O][N2O]
= [N2O]2 rate agrees too!
16.2 Activation energy
Higher level
OBJECTIVES
• The Arrhenius equation uses the temperature dependence of
the rate constant to determine the activation energy.
• A graph of 1/T against ln k is a linear plot with gradient – Ea/R
and intercept, lnA.
• The frequency factor (or pre-exponential factor) (A) takes into
account the frequency of collisions with proper orientations.
• Analysing graphical representation of the Arrhenius equation
in its linear form .
•Using the Arrhenius equation .
• Describing the relationships between temperature and rate
constant; frequency factor and complexity of molecules
colliding.
• Determining and evaluating values of activation energy and
frequency factors from data.
Math revision logs
b = ac can be described as c = logab “b to base a is c”
Eg. 8 = 23
The two most common are logs:

• base 10 = log(x), or log10(x), or lg(x)
• base e (2.718...) = loge(x), or ln(x) ‘’natural log”
Higher level
Arrhenius Equation
Svante Arrhenius developed a mathematical
relationship between k and Ea:
where A is the frequency factor (or Arrhenius

constant), a number that represents the likelihood that
collisions would occur with the proper orientation for
reaction. Ea is the activation energy. T is the Kelvin
temperature and R is the universal thermodynamics
(gas) constant.
R = 8.314 J mol-1 K-1 or 8.314 x 10-3 kJ mol-1 K-1
54.
Higher level
Arrhenius plot: ln(k) vs 1/T
Taking the natural
logarithm of both
sides, the equation
becomes
1
RT
y = mx + b
When k is determined experimentally at
several temperatures, Ea can be calculated
from the slope of a plot of ln k vs. 1/T.
55.
Determining Ea
Higher level
1. Convert the rate
constants (k) to
natural logs: ln(k)
2. Convert temperatures
to Kelvin by adding
273 and then convert
them to 1/T
3. Draw an Arrhenius
plot of ln(k) vs 1/T
4. Measure the gradient
of the line (y = mx + c)
5. Gradient = -Ea/R
6. Solve for Ea
Rule of thumb
Higher level
For most equations, an increase of 10°C will
double the rate of the reaction.
57.
Higher level
Problem 1: Use a graphical method to determine Ea
Answer:
Higher level
Higher level
Higher level

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16.

1 Rate expression and reaction mechanism

Chemical equation: A+BC+D

r = rate of reaction (mol.dm-3s-1)

Catalysts speed up reactions so also need to be included in

Overall order The sum of all the individual orders in

e.g. in the rate equation r = k[A][B]2

The value is zero if the rate is unaffected by how much of a

Divide the rate by as many concentrations (mol dm-3) as

r = k[A] k will have units of sec-1

r = k[A]2 k will have units of dm3 mol-1 sec-1

r = k[A][B]2 k will have units of dm6 mol-2 sec-1

In the reaction… RATE CALCULATION

The rate is negative because

rate is proportional to the

ZERO ORDER – the rate

FIRST ORDER – the rate is

Calculate the rate of reaction at

Calculate the time it takes

Deduce from the graph

Calculate the value and

a. the individual orders for A and B

Experiment [A] [B] Initial rate (r)

When [A] is kept constant [B] is doubled. The rate quadruples

b. the overall order of reaction

d. the value of the rate constant (k)

mol dm−3 s−1 mol dm−3 s−1 s−1

 k = 4 dm6 mol−2 s−1

• The rate law for this reaction is found experimentally to

X does not exist Order = 3

Example: A + B + C  ABC rate = k[A][B]

The two most common are logs:

where A is the frequency factor (or Arrhenius

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