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Specification Reference:
Present and interpret the results of kinetic measurements in graphical form, including
concentration-time and rate-concentration graphs.
k =
Page 8 of 20
Rate-Concentration Graphs
If the rate of a reaction, or some quantity
that is proportional to the rate, is plotted
against the concentration of one reactant,
the order with respect to that reactant can
be found.
1/time for the reaction to proceed to a
certain point is often used as a measure of
the rate.
If the graph of rate (or 1/time)
against [reactant] is a straight line,
the reaction is first order with
respect to that reactant.
If the graph of rate (or 1/time)
against [reactant]
2
is a straight line,
the reaction is second order with
respect to that reactant.
Page 9 of 20
Deducing the Order of Reaction from Initial Rate Data
To do this, you need data from at least three experiments. For example, data from
the reaction below could be used:
xA + yB products
Experiment [A] /mol dm
-3
[B] /mol dm
-3
Initial Rate / mol dm
-3
1 0.1 0.1 p
2 0.2 0.1 q
3 0.2 0.2 r
Comparing experiments 1 and 2 showed that [A] has doubled but [B] has
stayed the same.
If the rate is unaltered (q = p), the order with respect to A is 0.
If the rate doubles (q = 2p), the order with respect to A is 1.
If the rate quadruples (q = 4p), the order with respect to A is 2.
The order with respect to B can be determined in a similar way, by
analysing experiments 2 and 3.
Worked Example
In the table above, suppose p = 0.0024, q = 0.0096 and r = 0.0096.
(1) Determine the partial orders of A and B.
From experiments 1 and 2: when [A] doubles, the rate quadruples (0/0096 = 4 x
0.0024). Therefore the order with respect to A is 2.
From experiments 2 and 3: when [B] doubles, the rate is unaltered. Therefore,
the order with respect to B is 0.
(2) Determine the total order.
Total Order is 2 + 0 = 2.
(3) Write the rate equation.
The rate equation is: Rate = k[A]
2
(4) Calculate the value of the rate constant.
k = rate/[A]
2
= 0.0024 mol dm
-3
s
-1
/(0.1 mol dm
-3
)
2
= 0.24 mol
-1
dm
3
s
-1
.
Specification Reference:
Investigate the reaction of iodine with propanone in acid to obtain data for the order
with respect to the reactants and the hydrogen ion and make predictions about
molecules/ions involved in the rate-determining step and possible mechanism (details of
the actual mechanism can be discussed at a later stage in this topic).
Page 10 of 20
Iodine-Propanone Reaction
In acid solution iodine reacts with propanone to form iodopropanone and hydrogen
iodide.
CH
3
COCH
3(aq)
+ I
2(aq)
CH
3
COCH
2
I
(aq)
+ HI
(aq)
This reaction can be monitored by the following method:
Place 25cm
3
of iodine solution of known concentration in a flask and add
25cm
3
of sulfuric acid solution (an excess) and 50cm
3
of water. Add 5cm
3
of
pure propanone from a burette, start the clock as you do so.
At noted intervals of time remove 10cm
3
of the reaction mixture (aliquots)
and quench it by adding it to a slight excess of aqueous sodium
hydrogencarbonate. (This reacts with the acid catalyst, stopping the
reaction ensuring no further change in iodine concentration occurs during
titration.)
Quickly titrate the remaining iodine against standard sodium thiosulfate
solution, using starch as an indicator, near the end-point.
If the starch is added too soon, an insoluble starch-iodine complex is formed
and the titre will be too low.
Repeat by removing samples at regular intervals.
The rate equation is of the form:
Rate = k[propanone]
x
[H
+
]
y
[I
2
]
z
Because a large excess of propanone was taken, the concentration of propanone,
written as [propanone], remains approximately constant. Even though acid is
produced in the reaction, the original amount of acid catalyst was large and so [H
+
]
remains effectively constant. This means that the rate equation becomes:
Rate = k
[I
2
]
z
where k = k[propanone]
x
[H
+
]
y
The volume of sodium thiosulfate is proportional to the amount of iodine and
hence the iodine concentration. So a graph of volume of sodium thiosulfate against
time will have the same shape as the graph of [I
2
] against time.
The result of this experiment is shown in the graph below:
As this graph is a straight line, the slope and
hence the rate is constant and so the
reaction is zero order with respect to iodine.
A conclusion that can be drawn from this is
that iodine must enter the mechanism after
the rate-determining step.
H
+
(aq)
Page 11 of 20
Experiment [CH
3
COCH
3
]
/mol dm
-3
[I
2
]
/mol dm
-3
[H
+
]
/mol dm
-3
Relative Rate
1 0.1 0.1 0.1 2
2 0.1 0.2 0.1 2
3 0.1 0.2 0.2 4
4 0.2 0.1 0.1 4
5 0.1 0.1 0.2 4
The table above is an example of some results obtained from this experiment. We
can conclude that:
Doubling the concentration of iodine has no effect on the relative rate of
reaction (experiments 1 and 2)
Doubling the concentration of propanone doubles the relative rate of
reaction (experiments 1 and 4)
Doubling the concentration of hydrogen ions doubles the relative rate of the
reaction (experiments 1, 3 and 5)
Mechanism for the Reaction of Iodine and Propanone in Acid Solution
The reaction involves various steps and the slowest step, the rate-determining
step, does not involve iodine. This is why iodine does not appear in the rate
equation. Hydrogen ions act as a catalyst they are regenerated during the
reaction.
A possible mechanism for the reaction of iodine and propanone in acid solution is
given below.
Step 1
An H
+
ion protonates the oxygen atom in propanone:
(CH
3
)
2
C=O + H
3
O
+
(CH
3
)
2
C=O
+
H + H
2
O
This is a reversible reaction involving proton transfer (acid-base reaction).
Remember that a protonated water molecule, H
3
O
+
, behaves as an H
+
ion.
Step 2
The electrons in the C=O bond partly shift to form a carbocation i.e. the positive
charge is transferred from the oxygen to the carbon:
(CH
3
)
2
C=O
+
H
(CH
3
)
2
C
+
-OH
Step 3
This carbocation loses a proton and slowly changes into the enol form. The enol
has both alkene and alcohol functional groups and is isomeric with the original
ketone:
(CH
3
)
2
C
+
-OH + H
2
O CH
3
C(OH)=CH
2
+ H
3
O
+
Page 12 of 20
This involves breaking a strong C-H bond, hence this step has a high activation
energy and slow speed. The positive charge on the adjacent carbon of the
carbocation facilitates in pulling the C-H bond pair to form the C=C bond and
releases the proton to form an H
3
O
+
ion.
The rate of formation of the enol thus depends on the concentrations of the
ketone and the acid.
Step 4
The iodine molecule acts as an electrophile and undergoes a quick electrophilic
addition reaction (like other alkenes). This produces a protonated iodoketone:
CH
3
C(OH)=CH
2
+ I
2
CH
3
C(=O
+
H)-CH
2
I + I
-
Step 5
A water molecule then rapidly removes the proton in another acid-base reaction to
form the iodoketone:
CH
3
C(=O
+
H)-CH
2
I + H
2
O CH
3
COCH
2
I + H
3
O
+
In this example the low, rate-determining steps 1, 2 and 3 are the first stage in the
reaction and need only CH
3
COCH
3
and H
+
. The remaining steps happen very
quickly. This is also the case when oxygen and hydrogen bromide react together at
700K. However, the slowest reaction is not always the first.
In the reaction between bromide ions and bromate (V) ions in acid solution the
most likely mechanism is that HBr and HBrO
3
are made very rapidly before the
third, relatively slow, reaction between the two of them takes place. This is the
rate-determining step, and is followed by two more rapid steps to complete the
reaction.
Page 13 of 20
Using a Colorimeter
A colorimeter measures the absorption of light during the progress of the
experiment. First, the colorimeter has to be calibrated using standard iodine
solutions. The reaction mixture containing iodine will be light brown in colour and
as the reaction proceeds the solution becomes paler and more light is transferred
(when using a colorimeter there is no need for starch indicator).
Rate-Determining Steps
Reaction do not just happen whenever all the relevant molecules collide at once
they happen in steps. The slowest step controls how fast the overall reaction
occurs it is called the rate-determining step.
Kinetic measurements establish the order of the reaction for each species. For a
reaction between A, B and C the rate equation could be:
Rate = k[A][C]
2
Since substance B does not occur in the rate equation, any step involving molecule
B must be fast. This rate equation demonstrates that:
The reaction is first order with respect to A so A is involved in the rate
determining step.
The reaction is second order with respect to substance C so two moles of C
are involved in the rate-determining step.
Specification Reference:
Deduce from experimental data for reactions with zero, first and second order kinetics:
(i) Half-life (the relationship between half-life and rate constant will be given if
required)
(ii) Order of Reaction
(iii) Rate Equation
(iv) Rate-determining step related to reaction mechanisms
(v) Activation energy (by graphical methods only; the Arrhenius equation will be given if
needed).
The chosen filter should let through
only the wavelength to be absorbed
by the coloured iodine solution.
Since iodine is brown-red, a blue-
green filter is used.
Page 14 of 20
Activation Energy and Catalysts
When reactant molecules collide, it may result in a chemical reaction. There is an
energy requirement before this can happen. The activation energy is the minimum
energy needed by reactant particles (molecules or ions) before products can form.
The diagram shows that the reaction is:
Exothermic the products are at a lower energy level than the reactants
Subject to an energy barrier, the activation energy, in route 1
Able to follow an alternative pathway in route 2, with a lower barrier
A catalyst increases the reaction rate by providing an alternative reaction pathway
with a lower activation energy. Such catalysed reactions are faster.
Catalysts and reactants can be in the same physical state/phase, called
homogeneous - for example, all liquids. Or they can be in different states/phases,
when they are called heterogeneous.
Process Reactants Catalyst Type of Catalysis
Haber Synthesis Nitrogen,
Hydrogen
Iron Heterogeneous
Catalytic
Converter on car
Exhaust Gases Platinum Heterogeneous
Contact Process,
Sulfuric Acid
manufacture
Sulfur Dioxide,
Oxygen Gases
Vanadium (V)
Oxide
Heterogeneous
Esterification Solutions of Acid,
Alcohol
Hydrogen Ions Homogeneous
Page 15 of 20
Most catalysts are transition metals (or their compounds) because they have
variable oxidation states and can alter the number of bonds available to reactants.
Inorganic catalysts are used to catalyse a wide range of different reactions.
Although catalysts are not permanently altered during the reactions that they
catalyse, they can be poisoned by some impurities and will not work again.
Catalytic Converters
A catalytic converter removes pollutant gases from the exhaust by oxidising or
reducing them. The exhaust gases pass through a converter containing a precious
metal catalyst, usually an alloy of platinum or rhodium. Several reaction may take
place. NO
x
and CO may take part in a redox reaction which removes both of them
at the same time. NO
x
oxidises CO to CO
2
, and is itself reduced to harmless N
2
gas.
2NO
(g)
+ 2CO
(g)
N
2(g)
+ 2CO
2(g)
CO and C
x
H
y
are oxidised by air:
2CO
(g)
+ O
2(g)
2CO
2(g)
C
7
H
16(g)
+ 11O
2(g)
7CO
2(g)
+ 8H
2
O
(g)
Page 16 of 20
For all three of these reaction to happen, you need a three-way converter. An
oxygen monitor is fitted to the engine. This checks the quantity of oxygen going
into the engine to make sure there is enough to carry out the oxidation reactions.
The overall result of passing exhaust
gases through this kind of catalyst
system is to convert NO
x
, CO and C
x
H
y
to relatively harmless N
2
, CO
2
and H
2
O.
The catalytic reactions do not start
working until the catalyst has reached
a temperature of about 200C, so they
are not effective until the engine has
warmed up.
Catalyst systems of this type cost several hundred dollars, mainly because of the
high cost of the precious metals they contain. The catalyst is poisoned by lead,
so unleaded fuel must always be used.
Unfortunately, the major environmental impact of motor vehicles cannot be solved
by catalytic converters Climate Change.
Worked Example
1) Natural gas (methane) and air react exothermically in a Bunsen flame.
Explain why mixtures of these gases do not ignite spontaneously at room
temperature.
The activation energy barrier for this combustion reaction is too high at room
temperature. Colliding molecules have insufficient energy to react. Once ignited,
the Bunsen flame heats arriving gases before they react so that enough molecules
have energy equal to or greater than the minimum required for reaction.
Effect of Temperature on Rates
When the temperature increases, the rate of a reaction increases too because the
rate constant increases.
The rate constant k is only a constant for a particular temperature. Changing the
temperature changes the value of k because the proportion of molecules that have
the required energy (greater than the activation energy) is increased and the
colliding particles have a greater average energy.
The Arrhenius equation shows the relationship between the rate constant k and
the temperature T (in kelvin). The logarithmic (ln) form of this equation is:
lnk =
+ a constant
Page 17 of 20
Remember units for
activation energy are kJ mol
-1
E
A
is the activation energy for the reaction
R is the gas constant and has the value 8.31 J K
-1
mol
-1
T is the kelvin temperature (absolute temperature)
Gradient =
Investigating the Activation Energy of a Reaction
If we know the rate equation for a reaction, it is easy to calculate the rate
constant k using the rate of reaction for a known concentration of reactants.
Calculating the activation energy requires the results from experiments at a range
of different temperatures, to give values of the rate constant k at each
temperature. A suitable reaction to study is the oxidation of iodide ions by iodate
(V) ions in acidic solution. The equation is:
IO
3
-
(aq)
+ 5I
-
(aq)
+ 6H
+
(aq)
3I
2(aq)
+ 3H
2
O
(l)
A small known amount of sodium thiosulfate is added at the start of the reaction
together with starch as the indicator. The iodine released by the oxidation of the
iodide ions first reacts with the thiosulfate, so the mixture remains colourless
initially but then suddenly turns starch blue-black when all the thiosulfate has
reacted. This is an example of a clock reaction with a built-in time delay that
depends only on the concentration of the iodide and iodate ions. The relative
initial rate of production of iodine can be found from 1/t, where t is the time
delay.
The value for the activation energy can be found graphically as described above.
Examiners Tip
Working out the value of an
activation energy. This shows
that a plot of lnk against 1/T
gave a straight line whose
gradient is
Specification Reference:
Investigate the activation energy of a reaction, e.g. oxidation of iodide ions by iodate (V)
Page 18 of 20
Hydrolysis of Halogenoalkanes
There are three different types of halogenoalkane. They can all be hydrolysed
(split) by heating them with sodium hydroxide but they react using different
mechanisms.
Primary Halogenoalkanes
halogen is joined to a carbon
with one alkyl group
attached.
Secondary Halogenoalkanes
halogen is joined to a carbon
with two alkyl groups
attached.
Tertiary Halogenoalkanes
halogen is joined to a carbon
with three alkyl groups
attached.
Two substitution mechanisms are possible when an iodoalkane reacts with aqueous
alkali:
R-I + OH
-
R-OH + I
-
Only the experimental rate data can show which mechanism actually takes place.
Specification Reference:
Apply knowledge of the rate equations for the hydrolysis of halogenoalkanes to deduce
the mechanisms for primary and tertiary halogenoalkane hydrolysis and to deduce the
mechanism for the reaction between propanone and iodine.
Demonstrate that the mechanisms proposed for the hydrolysis of halogenoalkanes are
consistent with the experimentally determined orders of reactions, and that a proposed
mechanism for the reaction between propanone and iodine is consistent with the data
from the experiment in 4.3e.
Use kinetic data as evidence for S
N
1
or S
N
2 mechanisms in the nucleophilic substitution
reactions of the halogenoalkanes.
Page 19 of 20
The single step illustrated for the substitution of 1-iodopropane, a primary
halogenoalkane, involves two different species both the hydroxide ion and
the primary halogenoalkane.
The reaction will be second order it depends on the concentration of both
the hydroxide ion and the primary halogenoalkane.
The hydroxide ion joins onto the central carbon atom at the same time as
the halogen atom was leaving.
Part of the energy required to break the C-Halogen bond was supplied by
the energy released on producing the C-OH bond.
Calculations show that the approach of the hydroxide ion along the line of
centres of the carbon an bromine atoms is that of lowest energy
requirement.
So, rate = k[RI][OH
-
]
We call this an S
N
2 mechanism, meaning substitution/nucleophilic/second order.
Tertiary halogenoalkanes hydrolyse by the alternative S
N
1 mechanism, meaning
substitution/nucleophilic/first order.
The C-halogen bond heterolytically breaks first (slow step) forming a
tertiary carbocation which are relatively stable.
Followed by attack by the hydroxide ion (fast step).
The slow step involves only one species and does not depend on the
concentration of hydroxide ions. Hence the reaction is first order overall.
The mechanism must be consistent with the evidence:
If the reaction is second order overall it must involve two different species
If the reaction is first order overall (only one species in the rate equation)
then this is the rate-determining step and it must be a two-step reaction.
Nucleophile a species that is attracted to an electron-deficient centre, of
an atom, molecule or ion that donates a pair of electrons to
form a new covalent bond.
Electrophile an atom, molecule or ion that accepts a pair of electrons to
form a new covalent bond. An electrophile is therefore a
species that bonds to an electron-rich site in a molecule.
Substitution - one atom or group of atoms is replaced by another atom or
group of atoms.
Hydrolysis - when a molecule is broken down by the addition of water. This
may involve water, acid or alkali as the inorganic reagent.
Summary
Page 20 of 20
Primary Halogenoalkanes only react by S
N
2 mechanism.
Secondary Halogenoalkanes can react by both the S
N
1 and S
N
2 mechanisms
it depends what mood theyre in.
Tertiary Halogenoalkanes only react by the S
N
1 mechanism.
It is an S
N
2 mechanism if the rate is dependent on the concentration of both
the reactants and the order with respect to each is 1.
It is an S
N
1 mechanism if the rate is only dependent on the concentration of
the halogenoalkane.
Other Experimental Methods to Determine Rate of Reaction
Titration
If the concentration of a reactant or product can be estimated by a titration, the
reaction can be followed using this technique:
Measure out samples of the reactants with known concentration.
Mix them together, start a clock and stir the mixture thoroughly.
At regular time intervals, withdraw samples using a pipette and quench
(stop) the reaction. Quenching can usually be achieved either by adding the
solution from the pipette to ice-cold water or to a solution that reacts with
one of the reactants, to prevent further reaction from taking place. The
time at which half the contents of the pipette have been added to the
quenching solution is noted.
The quenched solution is then titrated against a suitable standard solution.
The titre is proportional to the concentration of the reactant or product being
titrated.
This method can be used when an acid, alkali or iodine is a reactant or product.
Acids can be titrated with a standard alkali, alkalis with a standard acid and iodine
with a standard solution of sodium thiosulfate.
Infrared Spectroscopy
Infrared spectroscopy can be used in a similar way to colorimetry. The
spectrometer is set at a particular frequency and the amount of infrared radiation
absorbed at that frequency is measured at regular time intervals. The oxidation of
propan-2-ol to propanone by acidified potassium dichromate (VI) can be followed
by setting the spectrometer at 1700cm
-1
(the absorption frequency due to the
stretching of the C=O bond) and measuring the increase in absorption as the CHOH
group is oxidised to the C=O group.
Conductimetric Analysis
If the number of ions changes, so will the electrical conductivity.