KIN2PP

TH E R AT E
EQU AT IO N
A guide for A level students
KNOCKHARDY PUBLISHING
KNOCKHARDY PUBLISHING
THE RATE EQUATION

INTRODUCTION
This Powerpoint show is one of several produced to help students understand
selected topics at AS and A2 level Chemistry. It is based on the requirements of
the AQA and OCR specifications but is suitable for other examination boards.
Individual students may use the material at home for revision purposes or it
may be used for classroom teaching if an interactive white board is available.
Accompanying notes on this, and the full range of AS and A2 topics, are
available from the KNOCKHARDY SCIENCE WEBSITE at...
www.argonet.co.uk/users/hoptonj/sci.htm
Navigation is achieved by...

either clicking on the grey arrows at the foot of each page
or using the left and right arrow keys on the keyboard
THE RATE EQUATION
CONTENTS
• Collision theory
• Methods for increasing rate
• Rate changes during a reaction
• The rate equation
• Worked examples
• Graphical methods for determining rate
• Half-life
• Rate determining step
• Check list
THE RATE EQUATION
Before you start it would be helpful to…
• know how the energy changes during a chemical reaction

• know the basic ideas of Kinetic Theory
• know the importance of catalysts in industrial chemistry
REVISION
COLLISION THEORY
Collision theory states that...
• particles must COLLIDE before a reaction can take place

• not all collisions lead to a reaction
• reactants must possess at least a minimum amount of energy - ACTIVATION ENERGY
plus
• particles must approach each other in a certain relative way - the STERIC EFFECT
REVISION
COLLISION THEORY
Collision theory states that...
• particles must COLLIDE before a reaction can take place

• not all collisions lead to a reaction
• reactants must possess at least a minimum amount of energy - ACTIVATION ENERGY
plus
• particles must approach each other in a certain relative way - the STERIC EFFECT
According to collision theory, to increase the rate of reaction you therefore need...
more frequent collisions increase particle speed or

have more particles present
more successful collisions give particles more energy or

lower the activation energy
REVISION
INCREASING THE RATE
The following methods may be used to

increase the rate of a chemical reaction
• INCREASE THE SURFACE AREA OF SOLIDS
• INCREASE TEMPERATURE
• SHINE LIGHT
• ADD A CATALYST
• INCREASE THE PRESSURE OF ANY GASES
• INCREASE THE CONCENTRATION OF REACTANTS

REVISION
RATE CHANGE DURING A REACTION
Reactions are fastest at the start and get slower as the reactants concentration drops.
In a reaction such as A + 2B ——> C the concentrations might change as shown
Reactants (A and B)
Concentration decreases with time
Product (C)
CONCENTRATION
C
Concentration increases with time
• the steeper the curve the faster the

rate of the reaction
• reactions start off quickly because of B A

the greater likelihood of collisions
TIME
• reactions slow down with time as
there are fewer reactants to collide
MEASURING THE RATE
Experimental Investigation
• the variation in concentration of a reactant or product is followed with time

• the method depends on the reaction type and the properties of reactants/products
e.g. Extracting a sample from the reaction mixture and analysing it by titration.
- this is often used if an acid is one of the reactants or products
Using a colorimeter or UV / visible spectrophotometer.
Measuring the volume of gas evolved.
Measuring the change in conductivity.
More details of these and other methods can be found in suitable text-books.
MEASURING THE RATE
RATE How much concentration changes with time. It is the equivalent of velocity.
THE SLOPE OF THE GRADIENT OF THE

CURVE GETS LESS AS THE
REACTION SLOWS DOWN
CONCENTRATION WITH TIME
gradient = y
x
TIME
• the rate of change of concentration is found from the slope (gradient) of the curve
• the slope at the start of the reaction will give the INITIAL RATE
• the slope gets less (showing the rate is slowing down) as the reaction proceeds
THE RATE EQUATION
Format 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
the equation... A + B ——> C + D
might have a rate equation like this r = k [A] [B]2
r rate of reaction units of conc. / time usually mol dm-3 s-1

k rate constant units depend on the rate equation
[] concentration units of mol dm-3
Interpretation
The above rate equation tells you that the rate of reaction is...
proportional to the concentration of reactant A doubling [A] doubles rate
proportional to the square of the concentration of B doubling [B] quadruples (22) rate
ORDER OF REACTION
Order tells you how much the concentration of a reactant affects the rate
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.
ORDER OF REACTION
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
and the overall order is 3 3rd Order
Value(s) need not be whole numbers

can be zero if the rate is unaffected by how much of a substance is present
ORDER OF REACTION
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
and the overall order is 3 3rd Order
Value(s) need not be whole numbers

can be zero if the rate is unaffected by how much of a substance is present
NOTES
The rate equation is derived from experimental evidence not by looking at an equation.
Species appearing in the stoichiometric equation sometimes aren’t in the rate equation.
Substances not in the stoichiometric equation can appear in the rate equation - CATALYSTS
THE RATE EQUATION
Experimental determination of order
Method 1
Plot a concentration / time graph qnd 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.)2.
A straight line would mean 2nd ORDER. This method is based on trial and error.
THE RATE EQUATION
Experimental determination of order
Method 1
Plot a concentration / time graph qnd 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.)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.
THE RATE CONSTANT (k)
Units The units of k depend on the overall order of reaction.
e.g. if the rate equation is... rate = k [A]2 the units of k will be dm3 mol-1 sec-1
Divide the rate by as many concentrations as appear in the rate equation.
Overall Order 0 1 2 3
units of k mol dm-3 sec-1 sec-1 dm3 mol-1 sec-1 dm6 mol-2 sec-1
example in the rate equation r = k [A] k will have units of sec-1
in the rate equation r = k [A] [B]2 k will have units of dm6 mol-2 sec-1
RATE EQUATION - SAMPLE CALCULATION
[A] [B]
Initial In an experiment between A and B the
rate (r)
initial rate of reaction was found for
1 0.5 1 2 various starting concentrations of A and B.
2 1.5 1 6 Calculate...
3 0.5 2 8
• the individual orders for A and B
• the overall order of reaction
r initial rate of reaction mol dm-3 s-1 • the rate equation
[] concentration mol dm-3 • the value of the rate constant (k)
• the units of the rate constant
[A] [B]
Initial CALCULATING ORDER wrt A
rate (r)
1 0.5 1 2 Choose any two experiments where...
2 1.5 1 6 [A] is changed and, importantly,

[B] is KEPT THE SAME
3 0.5 2 8
Compare Experiments 1 & 2 See how the change in [A] affects the rate
[B] same
[A] 3 x bigger As you can see, tripling [A] has exactly
rate 3 x bigger ∴ rate ∝ [A] the same effect on the rate so...
FIRST ORDER with respect to (wrt) A THE ORDER WITH RESPECT TO A = 1

(it is FIRST ORDER)
CALCULATING ORDER wrt B [A] [B]

Initial
rate (r)
Choose any two experiments where... 1 0.5 1 2
[B] is changed and, importantly,
2 1.5 1 6
[A] is KEPT THE SAME
3 0.5 2 8
See how a change in [B] affects the rate Compare Experiments 1 & 3
[A] same
As you can see, doubling [B] quadruples [B] 2 x bigger
the rate so... rate 4 x bigger ∴ rate ∝ [B]2
THE ORDER WITH RESPECT TO B = 2 SECOND ORDER wrt B
It is SECOND ORDER
Initial Initial
[A] [B] rate (r) [A] [B] rate (r)
1 0.5 1 2 1 0.5 1 2
2 1.5 1 6 2 1.5 1 6
3 0.5 2 8 3 0.5 2 8
Compare Experiments 1 & 2 Compare Experiments 1 & 3

[B] same [A] same
[A] 3 x bigger [B] 2 x bigger
rate 3 x bigger ∴ rate ∝ [A] rate 4 x bigger ∴ rate ∝ [B]2
FIRST ORDER with respect to (wrt) A SECOND ORDER wrt B
OVERALL ORDER = THE SUM OF THE INDIVIDUAL ORDERS

= 1 + 2
= 3
Initial Initial
1 0.5 1 2 1 0.5 1 2
2 1.5 1 6 2 1.5 1 6
3 0.5 2 8 3 0.5 2 8

[B] same [A] same
By combining the two proportionality relationships

∴ rate = k [A] [B]2 you can construct the overall rate equation
Initial Initial
1 0.5 1 2 1 0.5 1 2
2 1.5 1 6 2 1.5 1 6
3 0.5 2 8 3 0.5 2 8

[B] same [A] same
∴ rate = k [A] [B]2 Chose one experiment (e.g. Expt. 3) and

substitute its values into the rate equation
re-arranging k = rate
[A] [B]2 k = 8 = 4 dm6 mol-2 sec-1
(0.5) (2)2
RATE EQUATION - SAMPLE CALCULATION SUMMARY
Initial Initial
1 0.5 1 2 1 0.5 1 2
2 1.5 1 6 2 1.5 1 6
3 0.5 2 8 3 0.5 2 8

[B] same [A] same
∴ rate = k [A] [B]2 Chose one experiment (e.g. Expt. 3) and

substitute its values into the rate equation
re-arranging k = rate
[A] [B]2 k = 8 = 4 dm6 mol-2 sec-1
(0.5) (2)2
RATE EQUATION QUESTIONS
No 1 [A] / mol dm-3 [B] / mol dm-3 Rate / mol dm-3 s-1
Expt 1 0.25 0.25 4
Expt 2 0.25 0.50 8
Expt 3 0.50 0.25 8
CALCULATE THE ORDER WITH RESPECT TO A

THE ORDER WITH RESPECT TO B
THE OVERALL ORDER OF REACTION
THE FORMAT OF THE RATE EQUATION
THE VALUE AND UNITS OF THE RATE CONSTANT
ANSWER ON NEXT PAGE

ANSWER
Expt 1 0.25 0.25 4
Expt 2 0.25 0.50 8
Expt 3 0.50 0.25 8
Expts 1&2 [A] is constant [B] is doubled Rate is doubled

Therefore rate ∝ [B] 1st order wrt B
Explanation: What was done to [B] had exactly the same effect on the rate
ANSWER
Expt 1 0.25 0.25 4
Expt 2 0.25 0.50 8
Expt 3 0.50 0.25 8

Expts 1&3 [B] is constant [A] is doubled Rate is doubled

Therefore rate ∝ [A] 1st order wrt A
Explanation: What was done to [A] had exactly the same effect on the rate
ANSWER
Expt 1 0.25 0.25 4
Expt 2 0.25 0.50 8
Expt 3 0.50 0.25 8


Rate equation is r = k[A][B]

ANSWER
Expt 1 0.25 0.25 4
Expt 2 0.25 0.50 8
Expt 3 0.50 0.25 8


Value of k Substitute numbers from Exp 1 to get value of k

k = rate / [A][B] = 4 / 0.25 x 0.25 = 64
ANSWER
Expt 1 0.25 0.25 4
Expt 2 0.25 0.50 8
Expt 3 0.50 0.25 8



k = rate / [A][B] = 4 / 0.25 x 0.25 = 64
Units of k rate / conc x conc = dm3 mol-1 s-1

No 2 [C] / mol dm-3 [D] / mol dm-3 Rate / mol dm-3 s-1
Expt 1 0.40 0.40 0.16
Expt 2 0.20 0.40 0.04
Expt 3 0.40 1.20 1.44
CALCULATE THE ORDER WITH RESPECT TO C

THE ORDER WITH RESPECT TO D
ANSWER ON NEXT PAGE

RATE EQUATION QUESTIONS ANSWER
Expt 1 0.40 0.40 0.16
Expt 2 0.20 0.40 0.04
Expt 3 0.40 1.20 1.44
Expts 1&3 [C] is constant [D] is tripled Rate is 9 x bigger

Therefore rate ∝ [D] 2
2nd order wrt D
Explanation: Squaring what was done to D affected the rate (32 = 9)
Expt 1 0.40 0.40 0.16
Expt 2 0.20 0.40 0.04
Expt 3 0.40 1.20 1.44

2nd order wrt D
Expts 1&2 [D] is constant [A] is halved Rate is quartered

Therefore rate ∝ [C] 2 2nd order wrt C
Explanation: One half squared = one quarter
Expt 1 0.40 0.40 0.16
Expt 2 0.20 0.40 0.04
Expt 3 0.40 1.20 1.44

2nd order wrt D

Rate equation is r = k[C]2[D]2

Expt 1 0.40 0.40 0.16
Expt 2 0.20 0.40 0.04
Expt 3 0.40 1.20 1.44

2nd order wrt D

Rate equation is r = k[C]2[D]2

k = rate / [C]2[D]2 = 0.04 / 0.22 x 0.42 = 6.25
Units of k rate / conc2 x conc2 = dm9 mol-3 s-1

No 3 [E] / mol dm-3 [F] / mol dm-3 Rate / mol dm-3 s-1
Expt 1 0.40 0.40 0.16
Expt 2 0.80 0.80 0.32
Expt 3 0.80 1.20 0.32
CALCULATE THE ORDER WITH RESPECT TO E

THE ORDER WITH RESPECT TO F
ANSWER ON NEXT PAGE

Expt 1 0.40 0.40 0.16
Expt 2 0.80 0.80 0.32
Expt 3 0.80 1.20 0.32
Expts 2&3 [E] is constant [F] is x 1.5 Rate unchanged

Rate is UNAFFECTED ZERO order wrt F
Explanation: Concentration of [F] has no effect on the rate
Expt 1 0.40 0.40 0.16
Expt 2 0.80 0.80 0.32
Expt 3 0.80 1.20 0.32

Expts 1&2 [E] is doubled [F] is doubled Rate is doubled

Therefore rate ∝ [E] 2 2nd order wrt E
Explanation: Although both concentrations have been doubled, we know [F]
has no effect. The change must be all due to [E]
Expt 1 0.40 0.40 0.16
Expt 2 0.80 0.80 0.32
Expt 3 0.80 1.20 0.32


Rate equation is r = k[E]

Expt 1 0.40 0.40 0.16
Expt 2 0.80 0.80 0.32
Expt 3 0.80 1.20 0.32


Rate equation is r = k[E]

k = rate / [E] = 0.16 / 0.4 = 0.40
Units of k rate / conc = s-1

GRAPHICAL DETERMINATION OF RATE
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.
RATE CALCULATION
In the reaction…
The rate of reaction at
A(aq) + B(aq) ——> C(aq) + D(aq) any moment can be
found from the gradient
the concentration of B was measured of the tangent at that
point. The steeper the
every 200 minutes. The reaction is
gradient, the faster the
obviously very slow! rate of reaction
Place a rule on the
outside of the curve and
draw a line as shown on
the graph.
gradient = y / x
one reactants or product, plotting a graph and then finding the gradients of tangents to
the curve at different concentrations.
concentration = 1.20 mol dm-3 RATE CALCULATION

The rate of reaction at
gradient = - 1.60 mol dm-3 any moment can be
found from the gradient
1520 min
of the tangent at that
rate = - 1.05 x 10-3 mol dm- point. The steeper the
3 gradient, the faster the
rate of reaction
The rate is negative because Place a rule on the

the reaction is slowing down draw a line as shown on
the graph.
gradient = y / x
one of the reactants or products, plotting a graph and then finding the gradients of the
curve at different concentrations.
The gradients of tangents at several other RATE CALCULATION

concentrations are calculated. The rate of reaction at
any moment can be
Notice how the gradient gets less as the found from the gradient
reaction proceeds, showing that the reaction of the tangent at that
point. The steeper the
is slowing down. gradient, the faster the
The tangent at the start of the reaction is used rate of reaction
to calculate the initial rate of the reaction. Place a rule on the
draw a line as shown on
the graph.
gradient = y / x
FIRST ORDER REACTIONS AND HALF LIFE
One characteristic of a FIRST ORDER REACTION

is that it is similar to radioactive decay. It has a
half-life that is independent of the concentration.
It should take the same time to drop to one half of
the original concentration as it does to drop from
one half to one quarter of the original.
The concentration of a reactant

falls as the reaction proceeds
The concentration of reactant A

The concentration drops from

4 to 2 in 17 minutes


2 to 1 in a further 17 minutes


1 to 0.5 in a further 17 minutes


1 to 0.5 in a further 17 minutes
A useful relationship
k t½ = loge 2
= 0.693
where t½ = the half life
Half life = 17 minutes
k t½ = 0.693
k = 0.693
t½
k = 0.693 = 0.041 min-1

17
ORDER OF REACTION – GRAPHICAL DETERMINATION
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.
PLOTTING RATE AGAINST CONCENTRATION

RATE OF REACTION / mol dm-3 s-1
CONCENTRATION / mol dm-3


ZERO ORDER – the rate does not

depend on the 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
equals the rate constant for the
reaction.

SECOND ORDER – the rate is

proportional to the square of the
concentration. You get an

upwardly sloping curve.


reaction.

SECOND ORDER – the rate is

proportional to the square of the
concentration. You get an

upwardly sloping curve.


reaction.

PLOTTING RATE AGAINST TIME
ZERO ORDER
A straight line showing a constant decline in concentration.
FIRST ORDER
A slightly sloping curve which drops with a constant half-life.
SECOND ORDER
The curve declines steeply at first then levels out.
TIME / s
ORDER OF REACTION
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
RATE DETERMINING STEP
Many reactions consist of a series of separate stages.
Each step has its own rate and rate constant.
The overall rate of a multi-step process is governed by the slowest

step (like a production line where overall output can be held up by
a slow worker).
This step is known as the RATE DETERMINING STEP.
If there is more than one step, the rate equation may not contain
all the reactants in its format.
THE REACTION BETWEEN PROPANONE AND IODINE
Iodine and propanone CH3COCH3 + I2 CH3COCH2I + HI

react in the presence of acid
The rate equation is... r = k [CH3COCH3] [H+]
Why do H+ ions appear in

the rate equation?
Why does I2 not appear

in the rate equation?

Why do H+ ions appear in The reaction is catalysed by acid

the rate equation? [H+] affects the rate but is unchanged overall
Why does I2 not appear The rate determining step doesn’t involve I2

Why do H+ ions appear in The reaction is catalysed by acid

the rate equation? [H+] affects the rate but is unchanged overall
Why does I2 not appear The rate determining step doesn’t involve I2
The slowest step of any multi-step reaction is known as the rate determining step and it
is the species involved in this step that are found in the overall rate equation.
Catalysts appear in the rate equation because they affect the rate but they do not appear
in the stoichiometric equation because they remain chemically unchanged
HYDROLYSIS OF HALOALKANES
Haloalkanes (general formula RX) are RX + OH- ROH + X-

hydrolysed by hydroxide ion to give alcohols.
With many haloalkanes the rate equation is... r = k [RX][OH-] SECOND ORDER
This is because both the RX and OH- must
collide for a reaction to take place in ONE STEP
HYDROLYSIS OF HALOALKANES
Haloalkanes (general formula RX) are RX + OH- ROH + X-

hydrolysed by hydroxide ion to give alcohols.
With many haloalkanes the rate equation is... r = k [RX][OH-] SECOND ORDER
This is because both the RX and OH- must
collide for a reaction to take place in ONE STEP
but with others it only depends on [RX]... r = k [RX] FIRST ORDER
The reaction has taken place in TWO STEPS...

- the first involves breaking an R-X bond i) RX R+ + X- Slow
- the second step involves the two ions joining ii) R+ + OH- ROH Fast
The first step is slower as it involves bond breaking and energy has to be put in.
The first order mechanism is favoured by tertiary haloalkanes because the hydroxide ion is hindered in
its approach by alkyl groups if the mechanism involves the hydroxide ion and haloalkane colliding.
The reaction H2O2 + 2H3O+ + 2I¯ I2 + 4H2O takes place in 3 steps
Step 1 H2O2 + I¯ IO¯ + H2O SLOW
Step 2 IO¯ + H3O+ HIO + H2O FAST
Step 3 HIO + H3O+ + I¯ I2 + 2H2O FAST
The rate determining step is STEP 1 as it is the slowest

The reaction H2O2 + 2H3O+ + 2I¯ I2 + 4H2O takes place in 3 steps
Step 1 H2O2 + I¯ IO¯ + H2O SLOW
Step 2 IO¯ + H3O+ HIO + H2O FAST
Step 3 HIO + H3O+ + I¯ I2 + 2H2O FAST
The rate determining step is STEP 1 as it is the slowest
The reaction 2N2O5 4NO2 + O2 takes place in 3 steps
Step 1 N2O5 NO2 + NO3 SLOW
Step 2 NO2 + NO3 NO + NO2 + O2 FAST
Step 3 NO + NO3 2NO2 from another Step 1 FAST
The rate determining step is STEP 1 rate = k [N2O5]

OTHER TOPICS
Autocatalysis
A small number of reactions appear to speed up, rather than slow down, for a time.
This is because one of the products is acting as a catalyst and as more product is
formed the reaction gets faster. One of the best known examples is the catalytic
properties of Mn2+(aq) on the decomposition of MnO4¯(aq). You will notice it in a
titration of KMnO4 with either hydrogen peroxide or ethanedioic (oxalic) acid.
Molecularity The number of individual particles of the reacting species taking

part in the rate determining step of a reaction
e.g. A + 2B C+D molecularity is 3 - one A and two B’s need to collide
A 2B however has a molecularity of 1 - only one A is involved

REVISION CHECK
What should you be able to do?
Explain how the rate changes during a chemical reaction
Recall and understand the terms... rate equation, individual order and overall order
Interpret and calculate data to derive a rate equation
Construct graphs to find the order of reaction
Understand the importance of the rate determining step
CAN YOU DO ALL OF THESE? YES NO

You need to go over the
relevant topic(s) again
Click on the button to
return to the menu
WELL DONE!
Try some past paper questions
TH E R AT E
EQU AT IO N
The End
© 2003 JONATHAN HOPTON & KNOCKHARDY PUBLISHING

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TH E R AT E

THE RATE EQUATION

Navigation is achieved by...

• know how the energy changes during a chemical reaction

• particles must COLLIDE before a reaction can take place

• particles must COLLIDE before a reaction can take place

more frequent collisions increase particle speed or

more successful collisions give particles more energy or

The following methods may be used to

• INCREASE THE SURFACE AREA OF SOLIDS

• INCREASE THE PRESSURE OF ANY GASES

• INCREASE THE CONCENTRATION OF REACTANTS

In a reaction such as A + 2B ——> C the concentrations might change as shown

• the steeper the curve the faster the

• reactions start off quickly because of B A

• the variation in concentration of a reactant or product is followed with time

Using a colorimeter or UV / visible spectrophotometer.

Measuring the volume of gas evolved.

Measuring the change in conductivity.

THE SLOPE OF THE GRADIENT OF THE

the equation... A + B ——> C + D

might have a rate equation like this r = k [A] [B]2

r rate of reaction units of conc. / time usually mol dm-3 s-1

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

the order with respect to A is 1 1st Order

Value(s) need not be whole numbers

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

the order with respect to A is 1 1st Order

Value(s) need not be whole numbers

Method 2 - The initial rates method.

Divide the rate by as many concentrations as appear in the rate equation.

example in the rate equation r = k [A] k will have units of sec-1

1 0.5 1 2 Choose any two experiments where...

2 1.5 1 6 [A] is changed and, importantly,

FIRST ORDER with respect to (wrt) A THE ORDER WITH RESPECT TO A = 1

CALCULATING ORDER wrt B [A] [B]

THE ORDER WITH RESPECT TO B = 2 SECOND ORDER wrt B

Compare Experiments 1 & 2 Compare Experiments 1 & 3

FIRST ORDER with respect to (wrt) A SECOND ORDER wrt B

OVERALL ORDER = THE SUM OF THE INDIVIDUAL ORDERS

Compare Experiments 1 & 2 Compare Experiments 1 & 3

FIRST ORDER with respect to (wrt) A SECOND ORDER wrt B

By combining the two proportionality relationships

Compare Experiments 1 & 2 Compare Experiments 1 & 3

FIRST ORDER with respect to (wrt) A SECOND ORDER wrt B

∴ rate = k [A] [B]2 Chose one experiment (e.g. Expt. 3) and

Compare Experiments 1 & 2 Compare Experiments 1 & 3

FIRST ORDER with respect to (wrt) A SECOND ORDER wrt B

∴ rate = k [A] [B]2 Chose one experiment (e.g. Expt. 3) and

CALCULATE THE ORDER WITH RESPECT TO A

ANSWER ON NEXT PAGE

Expts 1&2 [A] is constant [B] is doubled Rate is doubled

Expts 1&2 [A] is constant [B] is doubled Rate is doubled

Expts 1&3 [B] is constant [A] is doubled Rate is doubled

Expts 1&2 [A] is constant [B] is doubled Rate is doubled

Expts 1&3 [B] is constant [A] is doubled Rate is doubled

Rate equation is r = k[A][B]

Expts 1&2 [A] is constant [B] is doubled Rate is doubled

Expts 1&3 [B] is constant [A] is doubled Rate is doubled

Rate equation is r = k[A][B]

Value of k Substitute numbers from Exp 1 to get value of k

Expts 1&2 [A] is constant [B] is doubled Rate is doubled

Expts 1&3 [B] is constant [A] is doubled Rate is doubled