Chem 534 – Rates of Rxn & Equi

Intro to Reaction Rates

Chapter 17 pg. 395

Rate of Reaction -
 the change in “something” of the reactants or products over time or per unit time
 Ex. mass or moles over time
concentration over time
color over time
electrical conductivity etc.

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

Chemical reactions –
 are the result of collisions between atoms, ions or molecules
 involve bond breaking (releases energy) & bond making (requires energy)

Collision Theory -
 explains why reactions have different reaction rates
1. the reacting particles must collide
2. the particles must have sufficient energy for the breaking &
making of chemical bonds
3. the colliding particles must collide at the right orientation or
geometry

 explains why some exothermic reactions don’t occur at room

temp. ex. burning of coal
(not enough energy to break & form bonds!)

Activation Energy –
 the minimum amount of energy colliding particles must have in order to react
o “barrier” or “hurdle” reactants must overcome
Energy

Reaction Progress
Examples:

1. The diagram shows the following reaction: A + B → AB.

Enthalpy
(kJ/mol)
35 A + B
0

AB
-135

Progress of reaction

According to this diagram, what is the activation energy of the reaction?

2. The graph below shows the potential energy changes.

A +B→C + D
Enthalpy (kJ)
+800

+600
+400

+200
0
A+B
-200
-400
-600

-800
-1000
C+D
-1200
Progress of the reaction

What is the activation energy of the reaction? What is the change in enthalpy?

Homework:
1- Draw the energy diagram of a reaction that has an initial energy of 110kJ, an
activation energy of 70kJ and a ∆H of –45kJ.
Chemistry 534 – Rate of Rxn & Equi
Factors Affecting Reaction Rates
1. Temperature

 Increasing the temperature, increases the rate of reaction

 Decreasing temp, decreases the rate
 Why?
o Increasing temp, increases the number of collisions, allowing the reactants
to step over the activation energy barrier
pg 397 #1

2. Concentration

 Recall concentration is the # of moles/volume

 Increasing concentration, increases the rate of reaction
 Decreasing concentration, decreases the rate of reaction
 Why?
o Increasing concentration, increases the number of particles, therefore more
frequent collisions

3. Particle Size

 Smaller particles/larger surface area have increased rates of reaction

 Larger particles/smaller surface area have decreased rates of reaction
 Why?
o Small particles have a large surface area, therefore a larger area for
collisions
o Ex. kindling burns faster than an log
o Ex. a spoonful of sugar dissolves faster than a cube of sugar

4. Catalysts
 Catalysts increase the rate of reaction
 Added to the reaction, but not used up in the reaction
 Why?
o Catalysts provides reactants with a reaction path of
lower activation energy then it would normally take
Energy

Reaction Progress
Examples:

1. 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 most probably responsible for the pathway in curve 2?

A) Increase in temperature
B) Increase in contacting surface area
C) Decrease is concentration of reactants
D) Presence of a catalyst

2. 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. Increased surface area = more area
for collisions, increasing rate.

3. 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 Number of
molecules molecules

Kinetic energy (kJ) Kinetic energy (kJ)

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

Kinetic energy (kJ) Kinetic energy (kJ)

4. The graph shows the kinetic energy distribution of the reactant molecules of a
chemical reaction at a certain temperature.
Number of E
average
molecules
Threshold energy

Kinetic Energy ( E )
K

Based on the graph below, explain what has brought about an increase in the rate of the chemical
reaction.
Number of E
average
molecules
Threshold energy

Kinetic Energy ( E K )

A catalyst has been added. The catalyst lowers the threshold energy so that there are
more effective collisions between molecules.

5.
Given the system A + B → C + D

The energy distribution graph for a given reaction is

shown on the right.

Which energy distribution graph below shows the

effect of an increase in temperature on the rate of
this reaction?
Homework
Pg 424 #18, 20, 23
Old Exam Question

Homework Question:

1. The spontaneous reaction of a solid piece of phosphorous (P 4) with oxygen (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)

Below is a list of five changes in reaction conditions, along with five kinetic energy
distribution curves. Which distribution curve best corresponds to each change in
conditions listed below?

Changes in conditions:

1. The concentration of oxygen gas is increased.

2. An inhibitor (negative catalyst) is added.
3. The temperature is lowered.
4. A positive catalyst is added.
5. The temperature is raised.

n A n B n C

Ek Ek Ek

D n E
n

Ek Ek
 Answer: 1 = E 2=B 3=A 4=C 5=D

Chem 534 – Rate of Rxn & Equi

Rate Laws
Rate Law –
 An expression relating the rate of a reaction to the concentration of reactants
 For the reaction:
aA + bB → cC + dD
 Rate eqauation:
Rate = k[A]a[B]b

 k = rate constant which is determined experimentally for each

reaction
• k = s-1 or L/mol*s
• large k = fast reaction
• small k = slow reaction

 a & b = coefficients in the reaction become exponents

 the order of the reaction is the sum of the exponents for each
reactant

Examples:
1) NO2(g) + O3(g) → NO3(g) + O2(g)

a) What is the rate equation for the formation of NO3(g) and O2(g)?

b) If the initial concentration of NO2(g) and O3(g) is 1.0M, what happens to the rate if the
concentration of NO2(g) is increased to 2.0M?
2) 2NO + O2 → 2NO2

If the initial concentration is 1.0M for both reactants, by what factor will the rate
increase if:
a) [O2] is 2.0M

b) [NO] is 2.0M

Chem 534 – Rates of Reaction

Calculating Rate of Reaction
Recall rate is change in “something” over time.

You can calculate rate if:

1. Given info.
2. Given a set of data
3. Given a graph

Examples:

1. Given Info:

a. A bottle of wine contains approximately 72 g of ethyl alcohol, C 2H5OH. When left open, the
ethyl alcohol changes into acetic acid according to the following equation:

C2H5OH(l) + O2(g) → CH3CO2H(l) + H2O(l)

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?
b. Below is a balanced equation:
A(s) + B(aq) → C(aq) + 2D(g)

A student dissolved 0.15 mol of substance A(s) in solution B(aq). After a ten-minute period of
reaction, 0.05 mol of A(s) is recovered.

What is the average rate of formation for gas D in mol/sec?

2. Given Data:

a. The combustion of a candle is recorded in the table below.

Before combustion After combustion
Mass of candle (g) 165.5 162.0
Time (h:min:s) 13:42:00 13:47:00

The equation is: C25H52(s) + 38 O2(g) → 25 CO2(g) + 26 H2O(g)

Calculate the rate of this combustion reaction in moles/hour.

3. Given a Graph:

a. Given A(g) + B(g) → C(g)

The graph below shows the number of moles of substance 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 substance C during the first three seconds?
Chem 534 – Rates of Reaction Name:
Practice Problem
Zinc, Zn, reacted with hydrochloric acid, HCl, to produce hydrogen gas & magnesium
chloride. The following table shows the volume of hydrogen gas 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 hydrogen gas between the 25th and 75th second?

Note : To find this value, draw the graph showing the volume of hydrogen gas formed during the
reaction as a function of time.

Volume
of H 2
(mL) 60

50

40

30

10
20

10

0 20 40 60 80 100 120 140 160

140 Time (s)

The average rate of formation of hydrogen gas is _____________________.