Rates of Reaction

Introduction to Rate
Rate of Reaction:
 the change in “something” of the reactants or
products over time or per unit time
 mass or moles over time**
 concentration over time

 color over time

 the rate of a reaction can be fast, slow or zero

Chemical Reactions

are the result of collisions between atoms, ions or molecules

Cl Na

 involve bond breaking (releases energy)

 involve bond making (requires energy)
 Collision Theory
c c u r
 explains why reactions have different rates
n ’ t o
s d o
c t io n
r ea o n d s
1. the reacting o m e
particles m p
must collide
r m b
h y s m t e & fo
in s w t r o o e ak
p la a b r
Ex g y to
e n
2. thegparticles e r must have enough energy
o u h
t n
e for the breaking & making of bonds
N o

3. the colliding particles must collide at the

right orientation or geometry
 io n
ta t o n
i
r ien N!! t at !!
d O IO ien ON
o T r I
Go EAC g O C T
R n A
ro O RE
W N

W
ro
ng
NO O
Wrong Orientation RE rien
AC ta
NO REACTION!! TI tion
ON
!!
 Activation Energy
 the min amount of energy that colliding particles
must have in order to react

 “barrier”
or “hurdle” reactants must
overcome
 Activation Energy
Energy of
Activation
Complex

Energy/Enthalpy
Products
Energy

Activation
Energy (EA)

Progress of Reaction
Energy
Reactants
 The diagram shows the following reaction
A + B → AB
Enthalpy
(kJ/mol)
35 A + B EA 35 kJ/mol – 0 kJ/mol
0
EA = 35 kJ/mol

AB
-135

Progress of reaction
According to this diagram, what is the
activation energy of the reaction?
 The graph below shows the potential
energy changes for: A + B → C + D
Enthalpy (kJ)
+800

+600
550 – 100 kJ/mol
+400 EA
+200 EA = 450 kJ/mol
0
A+B
-200

-1000 – 100 kJ/mol

-400
-600
∆H
∆H = -1100kJ/mol
-800
-1000
C+D
-1200
Progress of the reaction

What is the activation energy of the

reaction? The enthalpy?
Draw the energy diagram of a reaction that
has an initial energy of 110kJ, an activation
energy of 70kJ and a ∆H of –45kJ.

180

110

65
 Another Way to Graph EA
Area under
Number of Particles

the curve
represents
EA the # of
molecules
that have
reached EA

Energy
Factors Affecting Rates of
Reactions
 Factors Affecting Rates:
 Various factors will either increase or
decrease a reaction’s rate

 We will study:
 Temperature
 Concentration

 Particle Size / Surface Area

 Catalyst
 Temperature:
 Increasing the temp, increases the rate
 Decreasing temp, decreases the rate
 Why?
 Molecules absorb energy, so…
 the reactants reach activation energy &
 the number of collisions increase, so reactants step

over the activation energy barrier

 More molecules with enough energy to reach E
A
 At 50oC
Room Temp
Particles
absorb
Number of Particles

energy, so
EA more
particles
(area under
curve) are
able to reach
EA

Energy
 Concentration:
 Increasing concentration, increases the rate
 Decreasing concentration, decreases the rate
 Why?
 Increasing conc increases the number of particles:
 therefore more frequent collisions
 allowing reactants to reach activation energy

Increase Conc
 Particle Size & Surface Area:
 Larger surface area (smaller particles)
have increased rates
 Smaller surface area (larger particles)
have decreased rates
 Why?
 Large SA gives a larger area for collisions,
allowing reactants to reach EA

Increase SA
 Catalysts:
Tunnel = Catalyst
 Catalysts increase the rate
 Why?
 Catalysts provide reactants with another reaction
path that has a lower activation energy
 EA is LOWER
with CATALYST
Activation
Energy (EA)
Energy

Activation Energy (EA)

with CATALYST

Progress of Reaction
Number of Particles CATALYST

EA is LOWER
EA
with CATALYST
EA

Energy
Inhibitors
 Inhibitors decrease the rate
 Why?
 Inhibitorsprovide reactants with
another reaction path that has a
higher activation energy
 EA is HIGHER
with INHIBITORS
EA with
INHIBITOR
Energy

Activation
Energy (EA)

Progress of Reaction
Number of Particles INHIBITOR

EA

EA

EA is HIGHER
Energy with INHIBITOR
 Curves 1 and 2 on the graph below represent energy
pathways for the same chemical reaction. The reaction
rate is faster for pathway number 2.
ENERGY
1--

2--

Reactants

Products

REACTION PROCEEDS

Which factor is responsible for curve 2?

A) Increase in Temp C) Decrease in Conc

B) Increase in SA D) Presence of Catalyst

When you light a fire you use paper and kindling wood
rather than trying to light a log with a match.

Use the collision theory to explain why.

Kindling has a greater surface area than a log

Increase SA = more area for collisions

More collisions = faster rate

b/c reach EA sooner
The four graphs below represent the number of molecules
of reactants as a function of their kinetic energy.

Which graph represents the fastest reaction?

A) E C) E
Number of
molecules EA isNumber
molecules lowest, so
the of

probably reached
Kinetic energy (kJ)
fastest! Kinetic energy (kJ)

B) E D) E
Number of
Number of
molecules
molecules

Kinetic energy (kJ) Kinetic energy (kJ)

 The graph shows the energy distribution of the
reactants of a reaction at a certain temp
Number of E average
molecules Number of E
average
Threshold energy molecules
Threshold energy

Kinetic Energy ( E )
K Kinetic Energy ( E K )

Based on the next graph, explain what has brought

about an increase in the rate of the chemical reaction.
A catalyst has been added.
The catalyst lowers the threshold energy so that there
are more effective collisions between molecules
 The energy distribution graph for a given
reaction is shown below
Which graph below
shows the affect of
increased
temperature?

EA is same, but less

molec needed to
reach EA
 Pg 424 #18, 20 & 23
 Old Exam Question
The spon reaction of a solid piece of P4 with O2 in air has
an activation energy of 30 kJ/mol and is represented by
the following equation.

P4(s) + 5 O2(g) → P4O10 (s) ∆ H = −700 kJ/mol

Here is a sketch of the kinetic energy distribution curve

that corresponds to this reaction at 20°C and 101 kPa.
Number of
moles of Ea
reactant molecules
(n)

Kinetic energy (Ek)

 Number of
moles of Ea
reactant molecules
Below is a list of 5 changes
(n)in reaction conditions, along
with 5 graphs. Which graph best corresponds to each
change in conditions listed
Kinetic below?
energy (E k)

Changes in conditions:
1. The conc of oxygen gas is increased
2. An inhibitor is added 3. The temp is lowered
4. A catalyst is added 5. The temp is raised

n A n B n C

2 4
3

Ek Ek Ek

D n E
n

1
5
Ek Ek
Rate Laws & Estimating Rate
 Rate Law:

 An expression relating the rate of reaction to the

concentration of the reactants
 For: aA + bB → cC +
dD

 Rate equation: Rate = k [A]a

[B]b
Rate constant:
•determined experimentally
for each reaction at given Coefficients:
temp •Coefficients
•L/mol•s or s-1 become the
exponents
•Large k = fast reaction
 REMEMBER:
Rate in this equation
is dependant on the
concentration of
reactants only.
NO2(g) + O3(g) → NO3(g) + O2(g)

What is the rate equation for the formation of

NO3(g) and ORate
2(g)?= k [NO2]

[O3]
If the initial conc of NO2(g) and O 3 (g) is
1.0M, what would happen to the rate if we
increased the conc of NO3 to 2.0M? Rate
Rate = k [1] Rate = k [2] doubles!
[1] [1]
Rate = Rate =
 2NO + O2 → 2NO2

What is the rate equation for the formation of

NO2? Rate = k
If the initial conc [O
[NO] of2]both reactant is 1.0M,
2

what would happen to the rate if we

increased the conc of O2 to 2.0M?
Rate = k Rate = k Rate
[1]2[1] [1]2[2] doubles!
Rate = Rate =
1k 2k
NO to Rate
2.0M?
Rate =k Rate = quadruples
2
Predicting Rates of Reactions:
 Reactions that have reactants:

 With oppositely charged ions are very fast

Ag+ + Cl-  AgCl

 With few or weak bonds are faster than those

with many or strong bonds

Mg + HCl  MgCl + H2
C2H5OH + 3O2  2CO2 + 3H2O
Predicting Rates of Reactions:
 Inthe same phases are faster that those in
different phases

H2 (g) + F2 (g)  2HF (g)

Mg (s) + 2H2O (l)  2Mg2+ (aq) + 2OH-

(aq) + H2 (g)
 Undergoing a two particle collision are faster
than those requiring many particle collisions

2H2 (g) + O2 (g)  2H2O (g)

4NH3 (g) + 7O2 (g)  4NO2 (g) +
Rank the following from fastest to slowest.
1H2 (g) + F2 (g)  2HF (g)
.
2 Ag+ + Cl-  AgCl
.
3 C2H5OH + 3O2  2CO2 + 3H2O
.

2 1 3
Which would have the greatest rate?
A Hg (l) + Br2 (g)  HgBr2 (s)
.
B 2H2 (g) + O2 (g)  2H2O
. (g)+
C. Ag (aq) + Cl- (aq)  AgCl (s)

D. 4NH3 (g) + 7O2 (g)  4NO2 (g) +

6H2O (g)
C
Calculating Rate of Reaction
Calculating Rate:
 Recall, rate is the change in
something over time

 You can calculate rate if:

1. Given info
2. Given a set of Data
3. Given a Graph
A bottle of wine contains approximately 72 g of
ethyl alcohol, C2H5OH. When left open, the ethyl
alcohol changes into acetic acid according to the
following equation:

C2H5OH + O2 → CH3COOH + H2O

The ethyl alcohol changed completely into acetic

acid after 60 days (d).

What is the average reaction rate, in moles

per day (mol/d), of the transformation of the
alcohol?
Calculate the number of moles of
alcohol:
moles = 72/ 46
moles = 1.57 mol of alc.

Calculate the average rate:

number of moles (mol)
Rate =
number of days (d)

Rate = 1.57 / 60

Rate = 0.026 mol/day

Below is a balanced equation:
A + B → C + 2D

A student dissolved 0.15 mol of substance

A in solution B. After a ten-minute period
of reaction, 0.05 mol of A is recovered.

What is the average rate of formation of D

in mol/sec?
 Calculate the number of moles of
A used in rxn:

Moles used of A = 0.15 – 0.05 mol

moles of A used = 0.1 mol

Calculate the number of moles of

D produced:

moles of D produced = 0.2 mol

Calculate the length of rxn:
10 min = ? sec
time = 600 sec

Calculate the average rate:

number of moles of D (mol)
Rate =
number of sec ( s )

Rate = 0.2 / 600

Rate =3.3 x 10-4 mol/sec

 The combustion of a candle is recorded in
the table below.
Before After
combustion combustion
Mass of candle 165.5 162.0
(g)
Time (h:min) 1:00 6:00

The equation is:

C25 H52 + 38 O2 → 25 CO2 + 26 H2O

Calculate the rate of this combustion

reaction in moles/hour
 Calculate the # moles burned:

moles = 3.5/ 352

moles = 0.01 mol of candle burned

Calculate the average rate:

number of moles (mol)
Rate =
number of hours (hr )

Rate = 0.01 / 5
Rate = 0.002 mol/hr are burned
 Given: A(g) + B(g) → C(g)
The graph below shows the # of moles of C
formed by the reaction, as a function of
time.
Number of
moles of 0.40
substance C

0.30

0.20

0.10

1 2 3 4 5
Time (s)
What is the average rate for the formation of
C during the first three seconds?
 Calculate the # C moles formed
in first 3 seconds:
moles = 0.25 mol of C formed

Calculate the average rate of C:

number of moles (mol)
Rate =
number of sec (s)

Rate = 0.25 / 3
Rate = 0.083 mol/s of C are
formed
 Zinc reacted with HCl, to produce H2 &
MgCl2. The following table shows the
volume of H2 formed during the reaction as
a function of time.
Time (s) Volume of H2 (mL)
0 0
10 8
50 32
100 45
150 50

What is the average rate of formation of H2

between the 25th and 75th second?
 Vol of H2 = 39mL – 19mL
Vol of H2 = 20 mL
vol of H2 (mL)
Rate =
number of sec (s)

Volume Rate = 20 / 50
ofVolume
H2
of H 2
(mL)
(mL) 60 39mL
19mL
60
50
50 of H2
of H2
40
40

30
30
10
20
10
20 Rate = 0.40mL/s
10
10

0 20 40 60 80 100 120 140 140

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