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Chemical Kinetics (Pt.

1)

Introduction and Factors


Affecting Reaction Rates

By Shawn P. Shields, Ph.D.

This work is licensed by Shawn P. Shields-Maxwell under a Creative Commons Attribution-NonCommercial-ShareAlike 4.0
International License.
What is Chemical Kinetics?

Chemical kinetics is the study of chemical


reaction rates.

Kinetics can be more simply described as how


the concentration of a given reactant or
product changes in time during a chemical
reaction.
What is Chemical Kinetics?

In kinetics experiments, reaction conditions


are changed in a systematic way.

The effect on the rate of the reaction


(i.e., speed of reaction) is measured.

Reaction rates can be measured using a


variety of spectroscopic methods.
Kinetics and Mechanism

Kinetics provides a way to study complicated


reactions and determine how they proceed.

Once we know how a reaction proceeds, we


may be able to learn to control it.

Kinetic studies can also provide evidence and


support for a theory about how a reaction
works (its mechanism), but can never “prove”
the mechanism.
Macroscopic vs Microscopic Aspects of Kinetics

The macroscopic aspect involves how fast


the reaction runs (overall).

Rate laws are determined by experiment.

Rate laws show the dependence on


concentrations and/or partial pressures of
reactants.
Macroscopic vs Microscopic Aspects of Kinetics

The microscopic aspect of reactions


involves how the reaction proceeds at
the molecular level.
A reaction mechanism is determined,
which includes a series of elementary
steps in converting reactants to
products.
Kinetics and Mechanism

Example: SN1 Reaction

t-butyl bromide methanol methyl-t-butyl ether

When t-butyl bromide is boiled in methanol, the reaction


produces methyl-t-butyl ether.

This looks like a very specific reaction, but it can actually be


placed in a large category of reactions called “First-Order
Nucleophilic Substitution” (or SN 1).
Mechanism for SN1 Reaction

Step 1 (slow):

Step 2 (fast):

Step 3 (fast):
Collision Theory and Reaction Rate

Collision theory offers the basic framework


for understanding chemical kinetics.

The basic assumption is that molecules must


come into contact (collide) to react.

Therefore, (forward) reaction rates are


affected by several factors.
Factors Affecting Reaction Rates

1) Concentration of the reactants (higher


concentration leads to a faster rate because
there are more collisions)

2) Temperature (higher T leads to more collisions


and with greater energy, which leads to a faster
rate)
Factors Affecting Reaction Rates

3) The physical state of the reactants:


Molecules must mix to react (solutions provide
more opportunities for mixing)
The amount of surface area on a solid available
for reaction
Nanoparticles have more surface area than
larger particles.
More surface area; faster rate
Factors Affecting Reaction Rates

4) The addition of a catalyst (usually involves a


different mechanism of reaction)

Enzymes, such as
Trypsin, act as catalysts
in chemical reactions.

Trypsin Active Site by Fdardel (Own work) [CC BY-SA 3.0 (http://creativecommons.org/licenses/by-sa/3.0)], via
Wikimedia Commons
Next up…

Reaction rates and how


they change with
concentration (Pt. 2)

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