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Unit 4: Chapter 1 How Fast? - Rates





Rates Definitions

Rate of reaction is the change in the amount or
concentration of reactants or products per unit
time (normally per second).
Rate equation (rate = k[A]
m
[B]
n
). This is known
as a rate equation. [A] and [B] represent the
concentrations of A and B in mol dm
-3
, and k is
called the rate constant. The indices m and n are
usually whole numbers (1, 2 ) but they can be
fractional or zero.
Order of reaction the order of reaction is the
sum of the powers to which the concentrations of
the reactants are raised in the experimentally determined rate equation (m +
n).
Partial order of one reactant is the power to which the concentration of that
reactant is raised in the rate equation.
Rate constant the rate constant, k, is the constant of proportionality that
connects the rate of the reaction with the concentration of the reactants. Its
value alters with temperature. A reaction with a large activation energy has a
low value of k.
Half-life is the time taken for any reactant concentration to fall to half of its
initial value.
Rate-determining step is the slowest step that controls how fast the overall
reaction occurs.
Activation energy is the minimum energy needed by reactant particles
(molecules or ions) before products can form.
Heterogeneous catalyst these are catalysts that are in a different phase from
the reactants.
Homogeneous catalyst the catalyst and the reactants are in the same phase,
usually the gas phase or in solution.



Specification Reference:
Demonstrate an understanding of the terms rate of reaction, rate equation, order of
reaction, rate constant, half-life, rate-determining step, activation energy,
heterogeneous and homogeneous catalyst.
Page 2 of 20






Experimental Methods




1) Colorimetry

If a reactant or product is coloured, the concentration of the coloured species can
be measured using a spectrophotometer. The amount of light of a particular
frequency that is absorbed depends on the concentration of the coloured
substance.

Colorimetry measures the intensity of a colour in the
reaction mixture with time, such as the in the oxidation
of iodide ions to give brown iodine. In clock reactions
the reaction is timed until a sudden colour change
happens when a certain amount of product is formed.

For example, in the reaction between propanone and
iodine, the brown colour fades.

CH
3
COCH
3(aq)
+ I
2(aq)
CH
3
COCH
2
I
(aq)
+ H
+
(aq)
+ I
+
(aq)
Colourless Brown
Colourless

2) Mass Change

Mass change is used when a gas is produced. For example, when calcium carbonate
reacts with acids to release carbon dioxide the mass of the flask decreases.
















Specification Reference:
Select and describe a suitable experimental technique to obtain rate data for a given
reaction, e.g. colorimetry, mass change and volume of gas evolved.
Rate of Reaction (mol dm
-3
s
-1
) =



Page 3 of 20

CaCO
3(s)
+ 2HCl
(aq)
CaCl
2(aq)
+ H
2
O
(l)
+ CO
2(g)

Recording the loss in mass over a certain period of time at regular intervals using
the apparatus shown gives an indication of the rate of reaction.


3) Volume of Gas Evolved

If the reaction produces a gas, the volume of gas produced can be measured at
regular time intervals. The volume of gas is proportional to the moles of gas and
can, therefore, be used to measure the concentration of the product.

The rate of the reaction of an acid with a solid carbonate can be studied in this
way. The acid is added to the carbonate and the volume of carbon dioxide noted
every 30 seconds.

CaCO
3(s)
+ 2H
+
(aq)
Ca
2+
(aq)
+ H
2
O
(l)
+ CO
2(g)
























Clock Reactions

In a clock reaction, the reactants are mixed and the time taken to produce a
fixed amount of product is measured. The experiment is then repeated several
different times using different starting concentrations.




Specification Reference:
Investigate reactions which produce data that can be used to calculate the rate of the
reaction, its half-life from concentration or volume against time graphs, e.g. a clock
reaction.
Page 4 of 20

1) The Iodine Clock

The oxidation of iodide ions by hydrogen peroxide in acid solution can be
considered a clock reaction:

H
2
O
2(aq)
+ 2I
-
(aq)
+ 2H
+
(aq)
I
2(s)
+ 2H
2
O
(l)

25cm
3
of hydrogen peroxide solution is mixed in a beaker with 25cm
3
of
water and a few drops of starch solution are added.
25cm
3
of potassium iodide solution and 5cm
3
of a dilute solution of sodium
thiosulfate are placed in a second beaker.
The contents of the two beakers are mixed and the time taken for the
solution to go blue is measured.
The experiment is repeated with the same volumes of potassium iodide and
sodium thiosulfate but with 20cm
3
of hydrogen peroxide and 30cm
3
of
water, and then with other relative amounts of hydrogen peroxide and
water, totalling 50cm
3
.
















The reaction produces iodine, which reacts with the sodium thiosulfate. When all
the sodium thiosulfate has been used up, the next iodine that is produced reacts
with the starch to give an intense blue-black colour.

The amount of iodine produced in the measured time is proportional to the volume
of sodium thiosulfate solution taken. Therefore, the average rate of reaction for
each experiment is proportional to 1/time.









Page 5 of 20

2. The Sulfur Clock

Sodium thiosulfate is decomposed by acid, producing a precipitate of sulfur.

S
2
O
3
2-
(aq)
+ 2H
+
(aq)
S
(s)
+ SO
2(aq)
+ H
2
O
(l)

A large X is drawn on a white tile with a marker pen.
2cm
3
of sodium thiosulfate solution is mixed with 25cm
3
of water in a
beaker.
25cm
3
of dilute nitric acid is placed in a second beaker.
The first beaker is placed on top of the X and the contents of the second
one are added.
The mixture is stirred and the time (t) taken for sufficient sulfur to be
produced to hide the X when looking down through the beaker is measured.
The experiment is repeated with different relative amounts of sodium
thiosulfate and water, totalling 50cm
3
.

The number of moles of sulfur produced is the same in all experiments. Therefore,
the average rate of reaction for each experiment is proportional to 1/t.












Half-life

Half-life is the time taken for any reactant concentration to fall to half of its
initial value.

Half-life of First Order Reaction

The following equation and graph shows the decomposition of sulfur dichloride
oxide:




SO
2
Cl
2(g)
SO
2(g)
+ Cl
2(g)




Page 6 of 20

The time it takes SO
2
Cl
2
to halve is 2300 seconds.
Notice that this time is constant it takes the same time for the concentration
to fall from 0.50 mol dm
-3
to 0.25 mol dm
-3
as it takes to fall from 0.25 mol dm
-3
to 0.125 mol dm
-3
.
If the half-life is short, the reaction is rapid; if the half-life is long, the reaction
is slow.
The half-life is independent of concentration.
All first order reactions have constant half-lives at a given temperature.


Half-life and Radioactive Decay

Radioactive decay is an example of a first order reaction because its rate is
independent of the concentration of the radioactive material.

Many radioactive elements have very long half-lives and scientists use these to
help to work out the age of rocks in the Earths crust.

Carbon-14 is radioactive.
Radioactivity of carbon-14 halves every 5730 years.
The difference between the historical ratio and that measured in the mass
spectrometer is the basis of carbon-14 i.e. the percentage abundance of
radioactive isotopes is measured.


Half-life in Second Order Reactions

The half-life of a first order reaction is independent of the initial concentration of
the reactants. However, the half-life of a second order reaction does depend on
the initial concentrations of the reactants.
















The graph above shows the change in concentration of HI with time for the
reaction:
2HI
(g)
H
2(g)
+ I
2(g)
(@508C)
Page 7 of 20

The initial HI concentration is 0.10 mol dm
-3
and it takes 125 seconds for the
concentration to drop to 0.05 mol dm
-3
the half-life for the first part is 125
seconds.
Think of 0.05 mol dm
-3
as the new initial concentration, which takes 250
seconds to fall to 0.0250 mol dm
-3
. So in second order reactions, halving the
initial concentration doubles the half-life.

Half-life is inversely proportional to the initial concentration of the reactants.











Concentration-Time Graphs

The simplest type of relationship between variables is the linear one of general
form y = mx + c, where m is the slope or gradient and c the intercept on the y-axis.

The gradient of a curve is found by drawing a tangent. The gradient of the
tangent to the concentrationtime graph at a particular time gives the rate
at that moment (concentration).
The initial rate of reaction is found from the gradient of the tangent to the
concentrationtime graph at t = 0.
It is often difficult to monitor reaction rates or concentration continuously.
In practice you carry out a series of reactions where you vary the initial
concentration of each reactant in turn. You then plot a graph of initial rate
against initial concentration for each reactant.
You can find the orders from the shape of each graph, and the value of k
and units by substituting your measurements into the rate equation:




If it is a horizontal line, it means that the reaction is not taking place (rate
of reaction = 0).
If a straight line sloping downwards is obtained, the slope is constant. This
means that the rate is constant. This only occurs when the reaction is zero
order.
If a downward curve is obtained, with decreasing slope, the rate is
decreasing as [A] falls. Therefore, the reaction is first order or greater.

T
1/2
=
1


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.