UNIT 4.

3-
How Fast – Rates
 Define “rate of a reaction”

• How fast products are formed

• How fast reactants are used up

Change in concentr ation / time

3 1
mol dm s
 A + 2B → C

C
CONCENTRATION

A
B

TIME
• Concentration
Increases number of
• Pressure
effective collision
• Surface area

• Temperature More particle with activation

• Catalyst energy
 Measuring rate

• Rate of a reaction can only be measured by

experiments

CaCO3(s) + 2HCl(aq)  CaCl2(s) + CO2(g) + H2O(l)

X
 Methods to measure rate

1. measuring volume of a gas produced

2. measuring change in mass

3. monitoring colour change

4. titration

5. Conductimetric analysis

6. Polarimetry
 If the reaction produces a gas
1. Measuring volume of a gas
2. Measuring change in mass

HCOOH(aq) + Br2(aq) → 2H+(aq) + 2Br- (aq) + CO2(g)

 3. Colorimetry
H2O2(aq) + 2I- (aq) + 2H+(aq) → 2H2O(l) + I2(aq)
 4. Titration
• Mix known amount of reactants and start the
clock
• At regular intervals, withdraw sample using
pipette
• Quench the reaction
By adding it to ice cold water
By using quenching agent
• Quenched solution is then titrated against
suitable standard solution
HCOOCH3(aq) + NaOH(aq) → HCOONa(aq) + CH3OH(aq)
NaOH could be titrated with an acid

BrO3–(aq) + 5Br–(aq) + 6H+(aq) → 3Br2(aq) + 3H2O(l)

H+ could be titrated with an alkali

CH3COCH3(aq) + I2(aq) → CH3COCH2I(aq) + H+(aq) + I–(aq)

I2 could be titrated with sodium thiosuplate
 5. Measuring change in electrical
conductivity
• Can be used if there is a change in the number
of ions in the reaction mixture

HCOOH(aq) + Br2(aq) → 2H+(aq) + 2Br- (aq) + CO2(g)

 6. pH
• If one of the reactants or products is an acid
or an alkali
Colorimetry If one of the products or reactants is coloured, the concentration
of it can be monitored with a spectrophotometer. (change in absorbance of a
particular wavelength of light over time)

Mass change If one of the products or reactants is gas, the progress of the
reaction can be monitored using a sensitive balance.

Volume of If one of the products is gas, the progress of the reaction can be
Gas Evolved monitored using a gas syringe or any other gas collection
measuring device.

Polarimetry If one of the products or reactants is optically active, the progress

of the reaction can be monitored using polarimeter. (change in rotation of
plane polarised light over time)

Titration Removing a sample of a reaction, quenching with ice and

conducting a titration to find the concentration of one of the
reactants/products.

Conductivity If there are ions present as reactants or products. (change in conductivity is

proportional to [ions])
CH3COCH3 (aq) + I2 (aq) → CH3COCH2I(aq) + H+(aq) + I–(aq)

HCOOH(aq) + Br2(aq) → 2H+(aq) + 2Br – (aq) + CO2(g)

H2O2(aq) + 2H+(aq) + 2I–(aq) → 2H2O(l) + I2(aq)

I2(aq) + HSO3– (aq) + H2O(l) → 2I–(aq) + HSO4–(aq) + 2H+(aq)

Rate Equations
and Order of
Reactions
 The Rate Equation
aA + bB  cC + dD

[ ] indicates
Rate = k[A]x [B]y concentration in
mol dm-3
k is the rate constant

Rate equations are determined

by experiment only
For the reaction aA + bB  cC + dD

Rate  k[A]x[B]y
where x and y are the orders of reaction

order of the reaction with respect

to A is x

order of the reaction with respect

to B is y
overall order of reaction is x  y
 2A + 5B + 3C g 2D + E
Rate = k [A] [B]2 [C]0

order w.r.t. A is 1 [A] x 2 rate (21 = 2)

order w.r.t. B is 2 [B] x 2 rate (22 = 4)

order w.r.t. C is 0 [C] x 2 rate (20 = 1)

 Rate = k [A] [B]2

doubling both [A] and [B]

Rate increases by 2 x 4 = 8 times

 H2O2 + 2I- + 2H+ g 2H2O + I2

Rate = k[H2O2]2[I-]

What is the order of reacting with respect to

H2O2
I-
H+
What is the overall order of the reaction?
 H2O2 + 2I- + 2H+ g 2H2O + I2
Rate = k[H2O2]2[I-]

What will happen to the rate of the reaction if the concentration

of following are doubled

• I-
• H2O2
• H+
• All the reactants
 BrO3– + 5Br– + 6H+ → 3Br2 + 3H2O

The rate equation for this reaction is

rate = k[BrO3–][Br–][H+]2

When the concentrations of all of the reactants

are doubled, the rate increases by a factor of

A2
B4
C8
D 16
For the reaction aA + bB  cC + dD

Rate  k[A]x[B]y

k is the rate constant

• Temperature-dependent
• Can only be determined from experiments
Unit of rate constant
 First order reaction
For the reaction aA + bB  cC + dD

Rate  k[A]
rate 3 1
k  mol dm s
[A] mol dm 3

units of k : - S-1
 Second order reaction

For the reaction aA + bB  cC + dD

Rate  k[A][B]

3 1
rate mol dm s
k 
[A] [B] (mol dm 3 )(mol dm 3 )

units of k : - mol 1 dm3 s1

 Zero order reaction

For the reaction aA + bB  cC + dD

Rate  k

units of k : - mol dm3 s1

 Third order reaction

For the reaction aA + bB  cC + dD

Rate  k[A]2 [B]

units of k : - mol 2 dm6 s1

 Measuring rate

1. Concentration time graph

2. Initial rate method

 Hydrogen peroxide, H2O2, decomposes spontaneously:

2H2O2(aq) 2H2O(l) + O2(g)

In an experiment, the concentration of the H2O2 was

measured over a period of time. The results are shown
in the table.

Time (s) 0 15 30 60 100 180

Conc H2O2 0.40 0.28 0.19 0.07 0.03 0.01
(mol dm-3)
 Time (s) 0 15 30 60 100 180
Conc H2O2 0.40 0.28 0.19 0.07 0.03 0.01
(mol dm-3)
0.45

0.4

0.35

0.3

0.25
Conc H2O2
(mol dm-3)
0.2

0.15

0.1

0.05

0
0 20 40 60 80 100 120 140 160 180 200
Time (s)

c) t=0s, rate approx. 0.4/40 = 0.01 mol dm-3 s-1

t=20s, rate approx. 0.355/60 = 0.006 mol dm-3 s-1
t=90s, rate approx. 0.095/140 = 0.00065 mol dm-3 s-1
 INITIAL RATE METHOD
In an experiment between A and B the initial rate of reaction was found
for various starting concentrations of A and B. Determine the format of
the rate equation.

Experiment [A] [B] Initial Rate

moldm-3 moldm-3 moldm-3s-1
1 0.5 1 2
2 1.5 1 6
3 0.5 2 8
 Experiment [A] [B] Initial Rate
moldm-3 moldm-3 moldm-3s-1
1 0.5 1 2
2 1.5 1 6
3 0.5 2 8

To find order w.r.t. A:

Choose any 2 experiments where [A] is changed, and [B] is the same

From Experiments 1 & 2

[A] x 3 rate x 3

Therefore the reaction must be 1st order w.r.t A.

 A Worked Example
Experiment [A] [B] Initial Rate Order w.r.t. A = 1
moldm-3 moldm-3 moldm-3s-1
1 0.5 1 2
2 1.5 1 6
3 0.5 2 8

order w.r.t. B:

From Experiments 1 & 3

[B] x 2 rate x 4

therefore the reaction must be 2nd order w.r.t B.

Rate = k [A] [B]2

Overall Experiment [A] [B] Initial Rate
moldm-3 moldm-3 moldm-3s-1
1 0.5 1 2
2 1.5 1 6
3 0.5 2 8
Compare Experiments 1 & 2 Compare Experiments 1 & 3
[B] same [A] same
[A] x3 [B] x2
rate x3  rate  [A] rate x4  rate  [B]2

FIRST ORDER w.r.t. A SECOND ORDER wrt B

OVERALL ORDER = THE SUM OF THE INDIVIDUAL ORDERS

= 1 + 2
= 3
Rate = k [A] [B]2
 Calculating the Rate Constant with its units
Experiment [A] [B] Initial Rate Order w.r.t. A = 1
moldm-3 moldm-3 moldm-3s-1
Order w.r.t. B = 2
1 0.5 1 2
2 1.5 1 6 Rate = k[A][B]2
3 0.5 2 8
So what is the value for k?
Easy! Use the rate equation and one set of experimental results.
Units:
Using Experiment 1:
mol dm-3s-1 = k[mol dm-3][mol dm-3]2
Rate = k[A][B] 2
mol dm-3s-1 = k[mol3 dm-9]
2 = k[0.5][1]2 mol dm-3s-1 = k s-1 =k
mol3 dm-9 mol2 dm-6
2 = k[0.5] k= 2 k=4
0.5 k = mol-2 dm6 s-1
 Speeeeed

Rate
Zero constant
order
Hi mol 1 dm3 s1

Catalyst Rate
 5Cl(aq) + ClO3(aq) + 6H+(aq)  3Cl2(aq) + 3H2O(l)

[Cl(aq)] [ClO3(aq)] [H+(aq)] Initial rate

Expt
/ mol dm3 / mol dm3 / mol dm3 / mol dm3 s1
1 0.15 0.08 0.20 1.0105
2 0.15 0.08 0.40 4.0105
3 0.15 0.16 0.40 8.0105
4 0.30 0.08 0.20 2.0105

rate  k[Cl(aq)]x[ClO3(aq)]y[H+(aq)]z
 Q.15 2C + 3D + E  P + 2Q

[C] [D] [E] Initial rate

Expt
/ mol dm3 / mol dm3 / mol dm3 / mol dm3 s1
1 0.10 0.10 0.10 3.0103
2 0.20 0.10 0.10 2.4102
3 0.10 0.20 0.10 3.0103
4 0.10 0.10 0.30 2.7102

(a) rate  k[C]x[D]y[E]z

work out the rate equation for the reaction, between X
and Y, using the initial rate data in the table
The kinetics of the reaction below was investigated in a series of experiments.
x
A + B → C + D

the order of reaction with respect to A is 1

By analyzing the following data, State the order with respect to B

and hence deduce the order with respect to X

Form the rate equation and calculate the value of rate constant
 ORDER FROM GRAPH

The shape of the graph of concentration of reactant against time are

dependent on the order with respect to the reactant.

ZERO ORDER
A straight line showing a constant decline
CONCENTRATION mol dm-3

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. (Not a constant half life)
TIME / s

A different shape will identify the order w.r.t. the reactant.

 FIRST ORDER
First Order reactions &Half Life A slightly sloping curve which drops with a
constant half-life.

The concentration
drops from:
4 to 2 in 17 mins
2 to 1 in 17 mins
1 to 0.5 in 17 mins
There is a
constant half life!
 Half-Life
ALL reactions have a half-life (t1/2).
It is the time taken for half of the reactant to
be used up.
t=0, [N2O] is 1 mol dm-3

t=54s, [N2O] is 0.5 mol dm-3

t=108s, [N2O] is 0.25 mol dm-3

t=162s, [N2O] is 0.125 mol dm-3

 Run your experiment.
Plot concentration against time

Zero Order First Order Second Order

Half-life decreases Half-life constant Half-life increases
4.3c) 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

Half life Plot a graph of [A] against time:

[A] [A]

Time (s) Time (s)

A zero order reaction wrt A The time taken for [A] to half is constant.
So the order of the reaction wrt A is 1st order
As [A] changes, the rate doesnt!
 Plotting rate against concentration
What format will these graphs have?
Zero Order First order Second order
rate

rate

rate
concentration concentration concentration

Rate = k [A]n

rate
The rate equation
describes the shape
of these graphs (concentration)2
The table shows the results of an experiment on the
decomposition of nitrogen(V)oxide at constant
temperature.
2N2O5 4NO2 + O2

Time (s) 0 50 100 150 200 250 300

[N2O5] 2.50 1.66 1.14 0.76 0.50 0.32 0.22
(mol dm-3)

a) Plot a graph of these results.

b) From the graph, find the times for the concentration of N2O5
to decrease:
i) to half it original concentration.
ii) from 2.0mol dm-3 to 1.0mol dm-3.
c) Giving a reason, deduce the order of this reaction.
Iodine reacts with propanone, CH3COCH3, in the presence of a catalyst of dilute
hydrochloric acid.
CH3COCH3(aq) + I2(aq) → CH3COCH2I(aq) + HI(aq)

a) Use the graphs to deduce the orders of reaction with respect to propanone,
iodine and H+ ions. Explain your reasoning. (4)

b) Write the rate equation for the reaction. (1)

 Iodine and propanone
• Propanone reacts with iodine in acidic
solution

CH3COCH3 + I2 → CH3COCH2I + + + I–

• Rate equation ?
• Removing small samples from the reaction
mixture with a volumetric pipette.
• Quench by adding excess sodium hydrogen
carbonate
• Neutralize acid catalyst
• Then the sample can be titrated with sodium
thiosulphate using a starch indicator.
This reaction is
• zero order with respect to I2
• 1st order w r to the propanone and acid
catalyst

Rate = k[CH3COCH3][H+]
 Activation energy and catalysis
• The activation energy is the minimum energy
needed by reactant
A catalyst
• increases the reaction rate by
• providing an alternative reaction pathway
• with a lower activation energy.
 Homogenous catalysts
Reactants and catalyst are in same phase

Acid-catalysed reaction of propanone and iodine

Heterogenous catalysts
Reactants and catalyst are in same phase
 How it works
 Reactants are adsorbed on to the catalyst surface

 Attraction to the catalyst weakens bond in reactant

molecules making them break

 New bonds form between the reactants held close

together on catalyst surface to form products

 This weakens the bond between products and

catalyst, products leave the surface
 Effect of temperature on rates

When the temperature increases

• Rate of a reaction increases

• Rate constant increases.

• Changing the temperature changes the value

of k
 The effect of temperature on k
When temperature increases, rate of reaction increases.
This is because the rate constant, k, increases with temperature.

rate constant, k (mol dm3

temperature (K) s–1)

556 4.45 × 10–5

575 1.37 × 10–4

k (mol dm3 s–1)

629 2.52 × 10–3

666 1.41 × 10–2

700 6.43 × 10–2

temp. (K)
781 1.34
The Arrhenius equation shows the
relationship between
• the rate constant k and
• the temperature T (in kelvin).
 The Arrhenius Equation
You do not have to remember it, just use it.

lnk = lnA – EA 1
R T
k = the rate constant
A = Arrhenius constant
EA = Activation energy
R = Universal gas constant (8.31 J K-1 mol-1)
T = Temperature (in K)
lnk = lnA – EA 1
R T
 The Arrhenius Equation

Equation of a straight line graph: y = mx + c

y = the y axis value y = mx + c
x = the x axis value
m = gradient

lnk = lnA – EA 1
R T
So in order to calculate the activation enthalpy for a reaction we can use
this equation:
If we plot a straight line graph of lnK against 1/T
If you plot a graph of lnk against 1/T, the gradient of the slope is –EA/R

Gradient = –EA/R

y2–y1
= –EA/R
X2-X1
ln k

As we know R = 8.31 J K-1 mol-1

EA = - Gradient x 8.31

Units will be J mol-1

1/T (K-1)
 Mechanisms and Rate Determining Steps
reactions may take place in steps/stages

The overall rate of a reaction is determined by the slowest step

This step is the Rate Determining Step

H2O2 + 2H+ + 2I- g I2 + 2H2O Mechanism has 3 stages:

1 H2O2 + I- g IO- + H2O Slow

2 IO- + H+ g HIO Fast
3 IHO + H+ g I2 + H2O Fast

Rate = k[H2O2][I-]
 Mechanisms and Rate Determining Steps

2A + 2B g A2B2
Mechanism has 3 stages:

1 A + A g A2 Fast
2 A2 + B g A2B Slow
3 A2B + B g A2B2 Fast

Rate = k[A2][B]
1. The reaction 2N2O5 4NO2 + O2 takes place in 3 steps

Step 1 N2O5 NO2 + NO3 SLOW

Step 2 NO3 NO + O2 FAST

Step 3 NO + NO3 2NO2 FAST

From another Step 1

a) Which is the rate determining step?

b) What will the rate equation look like?
Nitrogen dioxide reacts with carbon monoxide.
NO2 (g) + CO(g) → NO(g) + CO2(g)

The reaction is second order with respect to nitrogen

dioxide, and zero order with respect to carbon monoxide.

(i) Suggest a possible two-step mechanism for this

reaction.
Write the rate determining step first.
 H+
Iodine + Propanone g 1-iodopropanone + HI

H O H O
H+
I2 + H C C CH3 H C C CH3 + HI
H I

Reactions which vary the concentrations of Iodine, Propanone, and Acid in

order produce the following results:

Exp [I2] [(CH3)2CO] [H+] Rate Order

Rate = k [(CH3)2CO] [H+]
1 0.1 0.1 0.1 2 N/A
2 0.2 0.1 0.1 2 0 2 = k [0.1][0.1]
3 0.1 0.2 0.1 4 1st 2/[0.1][0.1] = k
4 0.1 0.1 0.2 4 1st k = 200mol-1dm3s-1
Mechanism of the reaction
+
H O H O H
H
H + H
H O H O

H C C CH3 H C C CH3

H H

H
I
H O
H I H
H
+
+ H C C CH33
H
H O
O
H O
H
H C
C C
C CH
CH33 +
H
H C C CH3 I
II
I I

I
 Substitution reaction

CH3CH2 - Br + OH- → CH3CH2 - OH + Br-

(CH3)3C - Br + OH- → (CH3)3C - OH + Br-

CH3
l
CH3 - C - Br
l CH3CH2 - Br
CH3
Tertiary halogenoalkane Primary halogenoalkane
(CH3)3C - Br + OH- → (CH3)3C - OH + Br-

Rate = k [(CH3)3CBr]

Substitution
Nucleophile
1
SN1
 CH3CH2 - Br + OH- → CH3CH2 - OH + Br-

Rate = k [CH3CH2 - Br ][OH-]

Slow
CH3 - CH2 - Br → CH3CH2 - OH + :Br-

:OH-
 Slow

Substitution
Nucleophile
2
SN2
 Primary halogenoalkanes always react with an SN2 mechanism

rate = k [Nu-][Halogenoalkane]

Tertiary halogenoalkanes always react with an SN1 mechanism

rate = k [Halogenoalkane]

Secondary halogenoalkanes react with EITHER an SN1 or SN2 mechanism, this is

found from experimentation:
 Substitution reaction
RX + OH- → ROH + X-

step 1 RX → R+ + X- slow SN1 reaction

step 2 R+ + OH- → ROH fast RX can be tertiary

rate = k[RX] first order

RX + OH- → HO--R—X → HO—R + X SN2 reaction

rate = k[RX][OH-] second order RX can be priamry

4.8.1d
Reaction Profiles
SN 2
SN 1
5 bonded
transition ion

Carbocation
intermediate

Halogenoalkane Halogenoalkane

Alcohol Alcohol

The RDS involves 1 molecule. The RDS involves 2 molecules.

The reaction is 1st order. The reaction is 2nd order.
SN1 has 1st order kinetics SN2 has 2nd order kinetics
Rate = k [RX] Rate = k [RX][OH-]
Which classes of halogenoalkane can react with
alkali by an SN2 mechanism?

A Primary and secondary.

B Secondary and tertiary.
C Primary and tertiary.
D Primary, secondary and tertiary.
A bromoalkane was hydrolysed by an aqueous alkaline solution.
The reaction was found to be

first order with respect to the bromoalkane and

zero order with respect to hydroxide ions.

bromoalkane consistent with this information is

A CH3Br

B CH3CH2Br

C CH3CH2CH2Br

D (CH3)3CBr
The decomposition of hydrogen peroxide is catalysed by
iodide ions.
2H2O2 → 2H2O + O2
The rate equation for this reaction is
rate = k[H2O2][I–]

This is consistent with a reaction mechanism in which

A there is only one step.

B the catalyst is used up.
C the slowest step is the reaction of two molecules of
hydrogen peroxide with an iodide ion.
D the slowest step is the reaction of one molecule of
hydrogen peroxide with an iodide ion.
4.3a) 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”

“rate of reaction”
The rate of change of concentration of a reactant or product with time.
Measured in units mol dm-3 s-1 Moles per cubic
“rate equation” decimetre per second
aA + bB g cC + dD
Rate = k[A]x[B]y
x and y are the partial orders for that reactant determined from an experiment-
it has NOTHING to do with the stoicheometry of the reaction equation
“order of reaction”
The sum of the powers to which the concentrations of the reactants are
raised in the experimentally determined rate equation
“rate constant”
(k) Is the constant of proportionality in the rate equation
It is dependant on the reaction and the temperature
4.3a)

“half-life”
The time taken for the concentration of a reactant to halve

“rate-determining-step”
The slowest step is the slowest step in a multi-step mechanism

“activation energy”
The minimum energy for a chemical reaction to take place

“heterogeneous catalyst”
Catalyst is in a different state to the reactants

“homogeneous catalyst”
Catalyst is in the same state as the reactants
4.3b) 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

Colorimetry If one of the products or reactants is coloured, the concentration

of it can be monitored with a spectrophotometer. (change in absorbance of a
particular wavelength of light over time)

Mass change If one of the products or reactants is gas, the progress of the
reaction can be monitored using a sensitive balance.

Volume of If one of the products is gas, the progress of the reaction can be
Gas Evolved monitored using a gas syringe or any other gas collection
measuring device.

Polarimetry If one of the products or reactants is optically active, the progress

of the reaction can be monitored using polarimeter. (change in rotation of
plane polarised light over time)

Titration Removing a sample of a reaction, quenching with ice and

conducting a titration to find the concentration of one of the
reactants/products.

Conductivity If there are ions present as reactants or products. (change in conductivity is

proportional to [ions])