CHEM 1024 Chemistry for Operators JJ Nunes 2019

Reaction Rates (Kinetics)

At the end of this module, you should be able to:

 Define the term rate of a reaction

 Explain the factors affecting rates in a processing environment

A reaction is defined by its reactants and products. An equation is written and balanced for the
reactants and products and stoichiometric calculations can be carried out. An important
characteristic of a chemical reaction is spontaneity.

Spontaneity is the inherent tendency for a process to occur – however, it does not
mean that it happens fast.

There are many spontaneous reactions that are so slow that no apparent reaction can be seen
for months or even years at normal temperatures. For example, hydrogen gas and oxygen gas
have a strong inherent tendency to combine and form water but at room temperature, these
two gases will coexist indefinitely. Similarly, the reaction between chlorine gas and hydrogen gas
should proceed but it does not under normal conditions.

To be useful, a reaction must occur at a reasonable rate. Thus we must understand the factors
that govern the rate of a reaction. This is known as the study of chemical kinetics. To enhance
the rate at which a reaction occurs, we must first determine the mechanism (series of steps) by
which the reaction takes place.

1. Reaction Rate (Chemical Kinetics)

Let’s consider the decomposition reaction of nitrogen dioxide to nitric oxide and oxygen:

2 NO2 (g)  2 NO (g) + O2 (g)

The NO2 is in a flask at room temperature at the start. At this temperature it is very stable and
will not decompose. When we heat the flask to 3000C, the NO2 decomposes according to the
reaction above, producing NO and O2. We can now measure the change in concentration of
both the reactant and the products over time.
CHEM 1024 Chemistry for Operators JJ Nunes 2019

Concentration, M
Time, s NO2 NO O2
0 0.0100 0 0
50 0.0079 0.0021 0.0011
100 0.0065 0.0035 0.0018
150 0.0055 0.0045 0.0023
200 0.0048 0.0052 0.0026
250 0.0043 0.0057 0.0029
300 0.0038 0.0062 0.0031
350 0.0034 0.0066 0.0033
400 0.0031 0.0069 0.0035

Results:

 The concentration of the reactant, NO2, decreases with time

 The concentrations of the products NO and O2 increase with time

The rate of the reaction is defined as the change in the concentration of a

reactant or product over a specific period of time

Thus for a reactant or product X, Rate is defined as:

[𝑿]𝟐 – [𝑿]𝟏 𝑪𝒐𝒏𝒄𝒆𝒏𝒕𝒓𝒂𝒕𝒊𝒐𝒏 𝒐𝒇 𝑿 𝒂𝒕 𝒕𝒊𝒎𝒆 𝒕𝟐 – 𝑪𝒐𝒏𝒄𝒆𝒏𝒕𝒓𝒂𝒕𝒊𝒐𝒏 𝒐𝒇 𝑿 𝒂𝒕 𝒕𝒊𝒎𝒆 𝒕𝟏

𝑹𝒂𝒕𝒆 = =
𝒕𝟐 −𝒕𝟏 𝒕𝟐 −𝒕𝟏

∆𝑿
𝑹𝒂𝒕𝒆 =
∆𝒕

Thus for the decomposition of NO2 we can calculate the average rate of reaction for any two
time points:

Reactant Products

−∆[𝑵𝑶𝟐 ] ∆[𝑵𝑶] ∆[𝑶𝟐 ]

𝑹𝒂𝒕𝒆 = 𝑹𝒂𝒕𝒆 = 𝑹𝒂𝒕𝒆 =
∆𝒕 ∆𝒕 ∆𝒕
CHEM 1024 Chemistry for Operators JJ Nunes 2019

 Concentrations of reactants always decrease with time, so the rate expression includes
a negative sign

2. Rate Laws

Chemical Reactions are reversible. In the previous example we only considered the
forward reaction, but the reverse reaction can occur where NO and O2 react to re-form NO2
once they have accumulated.

Forward: 2 NO2 (g)  2 NO (g) + O2 (g)

Reverse: 2 NO (g) + O2 (g)  2 NO2 (g)

The reverse reaction becomes important after a period of time in which the products have
accumulated enough to produce NO2. When this happens, the change in concentration of NO2
now depends on the difference in the rates of the forward and reverse reactions. To avoid this,
we study the reaction to a time point soon after the reactants are mixed, before the products
have built up to significant levels. This allows us to ignore the reverse reactions since its
contribution would be negligible up to that point.

Once we can neglect the reverse reaction, the reaction rate depends only on the
concentrations of the reactants. Thus the rate law is written as:

𝑹𝒂𝒕𝒆 = 𝒌 [𝑵𝑶𝟐 ] 𝒏

k = rate constant
n = order of the reactant (where n is an integer)

 The concentrations of the products are not in the rate law because the reverse reaction
is not contributing to the overall rate
 The value of the exponent n has to be determined by experiment. It cannot be written
from the balanced equation
CHEM 1024 Chemistry for Operators JJ Nunes 2019

Order of the Reaction

The sum of the exponents in the rate law equation is known as the reaction order. There are
four common orders of a reaction. Consider the following reaction:

𝑎𝐴 + 𝑏𝐵  𝑐𝐶 + 𝑑𝐷

1. Zero Order: The rate is independent of the concentration of the reactants – constant
rate
Rate = k

2. First Order: The rate is proportional to the concentration of one of the reactants

Rate = k [A]

3. Second Order: The rate is proportional to the squared concentration of a single

reactant or the product of the concentrations of two reactants

Rate = k [A]2
Rate = k [B]2
Rate = k [A] [B]

4. Mixed order: In more complicated systems, the order can be a fraction

Rate = k [A] 1/3

3. COLLISION THEORY
For a reaction to proceed, molecules have to collide and will react when they have enough
energy.
CHEM 1024 Chemistry for Operators JJ Nunes 2019

Any factor that increases the number of molecules, the position, or speed of the
molecules will increase the rate of reaction.

For an effective collision to occur, the reactant molecules must be oriented in space correctly
to facilitate breaking and forming bonds. The rearrangement of the atoms results in the
formation of product molecules.

During a collision, the molecules must have the minimum amount of kinetic energy for an
effective collision to occur, which varies for each reaction. This is known as the activation
energy (Ea). Reactions with a higher activation energy means that less molecules will have
sufficient energy to undergo a collision.

https://opentextbc.ca/introductorychemistry/chapter/factors-that-affect-the-rate-of-reactions-2/
CHEM 1024 Chemistry for Operators JJ Nunes 2019

4. Factors affecting the rate of a reaction

(a) Concentration of reactants

- If the concentration of a reactant increases, the frequency of collisions between
reactants also increases because the number of molecules available to collide
increases.

(b) Temperature
- As temperature increases the molecules gain energy and move faster, which causes
more collisions in a period of time

(c) Pressure
- For gaseous reactions, an increase in pressure (maybe by decrease in volume)
causes the molecules to come closer together, so the frequency of collisions
increases

(d) Catalysts
- Catalysts lower the activation energy of a reaction by allowing the reaction to
proceed by a different pathway. It also alters the orientation of the molecules so that
collisions are more effective.
CHEM 1024 Chemistry for Operators JJ Nunes 2019

(e) Surface area

- If a reactant is solid, a larger surface area results in a faster reaction because there
are more points available for the reaction to take place

WORKSHEET (with answers)

1. Explain each of the following observations:

a. Why would a mixture of gases react faster when the volume they occupy is
decreased? (Section 4c)
b. Why would iron filings rust faster than an iron nail? (Section 4e)
c. Milk will sour in a couple of days when left at room temperature yet can remain
unspoiled for 2 weeks when refrigerated. (Section 4b)
d. Due to decomposition reactions with oxygen or carbon dioxide in the air, meat
begins to feel slimy and smell spoiled. Explain, using your knowledge of chemical
kinetics, why meat spoils less rapidly when left unsliced. (Section 4e)

2. For the following reaction: 3 𝐸 + 2 𝐹 → 2 𝐺, the rate law is:

𝑅𝑎𝑡𝑒 = 𝑘[𝐹]2

a. How does the rate change if [E] is doubled? [No change]

b. How does the rate change is [F] is doubled [Rate quadruples]
c. What is the overall reaction order? [2nd order]

3. For the reaction 2 𝐴 + 𝐵 + 2𝐶 → 𝐷 + 2 𝐸, the rate law is 𝑅𝑎𝑡𝑒 = 𝑘[𝐴]2 [𝐵]1 [𝐶]1 .
What is the overall order of the reaction? [4th order]

4. a. The reaction 𝐴 + 2𝐵 → 𝐶 is first order in A and B. Write the rate law for this
reaction. Rate = k [A][B]
b. What is the overall order of the reaction? [2nd order]
c. If [A] is 0.5 M and [B] is 0.2 M, what will be the value of the rate constant given that
the rate of the reaction was determined to be 2.5 M/s? [25 M-1s-1]

5. The first order reaction 𝐴 → 𝐵 has k = 5.67 s-1. Calculate the concentration of [A] if
the rate of the reaction is 0.7 M/s. [0.124 M]