Factors That Affect Reaction Rates

1. Last updated
Jul 2, 2014
2.
o Stopped Flow

o First-Order Reactions
3. Donate
Table of contents

Factors that influence the reaction rates of chemical reactions include the concentration of
reactants, temperature, the physical state of reactants and their dispersion, the solvent, and the
presence of a catalyst.

Introduction
Although a balanced chemical equation for a reaction describes the quantitative relationships
between the amounts of reactants present and the amounts of products that can be formed, it
gives us no information about whether or how fast a given reaction will occur. This information
is obtained by studying the chemical kinetics of a reaction, which depend on various factors:
reactant concentrations, temperature, physical states and surface areas of reactants, and solvent
and catalyst properties if either are present. By studying the kinetics of a reaction, chemists gain
insights into how to control reaction conditions to achieve a desired outcome.

Concentration Effects
Two substances cannot possibly react with each other unless their constituent particles
(molecules, atoms, or ions) come into contact. If there is no contact, the reaction rate will be
zero. Conversely, the more reactant particles that collide per unit time, the more often a reaction
between them can occur. Consequently, the reaction rate usually increases as the concentration
of the reactants increases.

Temperature Effects
Increasing the temperature of a system increases the average kinetic energy of its constituent
particles. As the average kinetic energy increases, the particles move faster and collide more
frequently per unit time and possess greater energy when they collide. Both of these factors
increase the reaction rate. Hence the reaction rate of virtually all reactions increases with
increasing temperature. Conversely, the reaction rate of virtually all reactions decreases with
decreasing temperature. For example, refrigeration retards the rate of growth of bacteria in foods
by decreasing the reaction rates of biochemical reactions that enable bacteria to reproduce.
In systems where more than one reaction is possible, the same reactants can produce different
products under different reaction conditions. For example, in the presence of dilute sulfuric acid
and at temperatures around 100°C, ethanol is converted to diethyl ether:

2CH3CH2OH−→−−−H2SO4CH3CH2OCH2CH3+H2O(14.1)(14.1)2CH3CH2OH→H2SO4CH3
CH2OCH2CH3+H2O

At 180°C, however, a completely different reaction occurs, which produces ethylene as the major
product:

CH3CH2OH−→−−−H2SO4C2H4+H2O(14.2)(14.2)CH3CH2OH→H2SO4C2H4+H2O

Phase and Surface Area Effects

When two reactants are in the same fluid phase, their particles collide more frequently than when
one or both reactants are solids (or when they are in different fluids that do not mix). If the
reactants are uniformly dispersed in a single homogeneous solution, then the number of
collisions per unit time depends on concentration and temperature, as we have just seen. If the
reaction is heterogeneous, however, the reactants are in two different phases, and collisions
between the reactants can occur only at interfaces between phases. The number of collisions
between reactants per unit time is substantially reduced relative to the homogeneous case, and,
hence, so is the reaction rate. The reaction rate of a heterogeneous reaction depends on the
surface area of the more condensed phase.

Automobile engines use surface area effects to increase reaction rates. Gasoline is injected into
each cylinder, where it combusts on ignition by a spark from the spark plug. The gasoline is
injected in the form of microscopic droplets because in that form it has a much larger surface
area and can burn much more rapidly than if it were fed into the cylinder as a stream. Similarly, a
pile of finely divided flour burns slowly (or not at all), but spraying finely divided flour into a
flame produces a vigorous reaction.

Solvent Effects
The nature of the solvent can also affect the reaction rates of solute particles. For example, a
sodium acetate solution reacts with methyl iodide in an exchange reaction to give methyl acetate
and sodium iodide.

CH3CO2Na(soln)+CH3I(l)→CH3CO2CH3(soln)+NaI(soln)(14.3)(14.3)CH3CO2Na(soln)+CH3I(l)
→CH3CO2CH3(soln)+NaI(soln)

This reaction occurs 10 million times more rapidly in the organic solvent dimethylformamide
[DMF; (CH3)2NCHO] than it does in methanol (CH3OH). Although both are organic solvents
with similar dielectric constants (36.7 for DMF versus 32.6 for methanol), methanol is able to
hydrogen bond with acetate ions, whereas DMF cannot. Hydrogen bonding reduces the reactivity
of the oxygen atoms in the acetate ion.

Solvent viscosity is also important in determining reaction rates. In highly viscous solvents,
dissolved particles diffuse much more slowly than in less viscous solvents and can collide less
frequently per unit time. Thus the reaction rates of most reactions decrease rapidly with
increasing solvent viscosity.

Catalyst Effects
A catalyst is a substance that participates in a chemical reaction and increases the reaction rate
without undergoing a net chemical change itself. Consider, for example, the decomposition of
hydrogen peroxide in the presence and absence of different catalysts. Because most catalysts are
highly selective, they often determine the product of a reaction by accelerating only one of
several possible reactions that could occur.

Most of the bulk chemicals produced in industry are formed with catalyzed reactions. Recent
estimates indicate that about 30% of the gross national product of the United States and other
industrialized nations relies either directly or indirectly on the use of catalysts.

Conceptual Problems

1. What information can you obtain by studying the chemical kinetics of a reaction?
Does a balanced chemical equation provide the same information? Why or why
not?
2. If you were tasked with determining whether to proceed with a particular reaction
in an industrial facility, why would studying the chemical kinetics of the reaction
be important to you?
3. What is the relationship between each of the following factors and the reaction
rate: reactant concentration, temperature of the reaction, physical properties of
the reactants, physical and chemical properties of the solvent, and the presence
of a catalyst?
4. A slurry is a mixture of a finely divided solid with a liquid in which it is only
sparingly soluble. As you prepare a reaction, you notice that one of your
reactants forms a slurry with the solvent, rather than a solution. What effect will
this have on the reaction rate? What steps can you take to try to solve the
problem?
5. Why does the reaction rate of virtually all reactions increase with an increase in
temperature? If you were to make a glass of sweetened iced tea the old-
fashioned way, by adding sugar and ice cubes to a glass of hot tea, which would
 you add first?
6. In a typical laboratory setting, a reaction is carried out in a ventilated hood with
air circulation provided by outside air. A student noticed that a reaction that gave
a high yield of a product in the winter gave a low yield of that same product in the
summer, even though his technique did not change and the reagents and
concentrations used were identical. What is a plausible explanation for the
different yields?
7. A very active area of chemical research involves the development of solubilized
catalysts that are not made inactive during the reaction process. Such catalysts
are expected to increase reaction rates significantly relative to the same reaction
run in the presence of a heterogeneous catalyst. What is the reason for
anticipating that the relative rate will increase?
8. Water has a dielectric constant more than two times greater than that of
methanol (80.1 for H2O and 33.0 for CH3OH). Which would be your solvent of
choice for a substitution reaction between an ionic compound and a polar
reagent, both of which are soluble in either methanol or water? Why?

Answers

1. Kinetics gives information on the reaction rate and reaction mechanism; the
balanced chemical equation gives only the stoichiometry of the reaction.
3. Reaction rates generally increase with increasing reactant concentration,
increasing temperature, and the addition of a catalyst. Physical properties such
as high solubility also increase reaction rates. Solvent polarity can either increase
or decrease the reaction rate of a reaction, but increasing solvent viscosity
generally decreases reaction rates.
5. Increasing the temperature increases the average kinetic energy of molecules
and ions, causing them to collide more frequently and with greater energy, which
increases the reaction rate. First dissolve sugar in the hot tea, and then add the
ice.

 CDLI
 Chemistry 3202
 Intro

 Units
 Unit 01: Kinetics and Equilibrium
  Collision Theory, Reaction Mechanisms and Catalysts: Factors Affecting
Reaction Rates

 Get Ready
 Go to Work

Lesson

Chemical reactions proceed at different rates. The factors that affect reaction rates are:

 surface area of a solid reactant

 concentration or pressure of a reactant
 temperature
 nature of the reactants
 presence/absence of a catalyst.

A change in one or more of these factors may alter the rate of a reaction. In this
lesson, you will define these factors, and describe and predict their effects on reaction
rates.

Surface Area

Surface area is the exposed matter of a solid substance.

Imagine that you are holding a perfect cube of magnesium. The surface area is the
sum of the area of all six sides of the cube. The surface area of the cube can be
increased by dividing the cube into smaller cubes. Surface area is maximized when a
single large cube is crushed to fine powder.

The rate of reaction of a solid substance is related to its surface area. In a reaction
between a solid and an aqueous/liquid/gas species, increasing the surface area of the
solid-phase reactant increases the number of collisions per second and therefore
increases the reaction rate.

In a reaction between magnesium metal and hydrochloric acid, magnesium atoms

must collide with the hydrogen ions. When the magnesium atoms form one big
lump...

however, ...
the number of collisions per second between magnesium and hydrogen is higher, and
the rate of reaction is faster.

Increasing the surface area of a solid reactant increases the reaction rate.

By increasing surface area, there are more collisions per unit of time. That's why
many solids are powdered using a mortar and pestle before being used in a reaction.

Examples of other reactions where surface area is important are:

 active metals with acids, e.g. HCl with zinc

 coal dust with oxygen gas
 grain dust with oxygen gas

Concentration

The concentration of a substance can be expressed in a variety of ways depending on

the nature of a substance. Aqueous solutions typically have their concentrations
expressed in mol/L. For example, a solution made by dissolving sodium hydroxide in
water has its concentration expressed as moles of NaOH per litre of solution. Gases
can also have their concentrations expressed in mol/L.

In terms of the collision theory, increasing the concentration of a reactant increases in

the number of collisions between the reacting species per second and therefore
increases the reaction rate.

Consider the reaction between hydrochloric acid and zinc

metal.

In one beaker, 6.00 mol/L HCl is reacted with 2.00 g of Zn.

In another, 1.00 mol/L HCl is reacted with 2.00 g of Zn.

Which reaction should occur at the faster rate?

In terms of the collision theory, collisions between zinc atoms and hydrochloric acid
are more frequent in the beaker containing 6.0 M HCl - there is more acid per unit of
volume.
You can change the concentration of an aqueous species by simply adding more
solute (to make it more concentrated) or adding more solvent (to make it more dilute).

You can change the concentration of a gas by adding more gas to a fixed volume or
by decreasing the volume of the container. Conversely, the concentration of a gas can
be decreased by removing (evacuating) a gas from a fixed volume or by increasing the
volume of the container.

Pressure

The concentration of a gas is a function of the pressure on the gas. Increasing the
pressure of a gas is exactly the same as increasing its concentration. If you have a
certain number of gas molecules, you can increase the pressure by forcing them into a
smaller volume.

Under higher pressure or at a higher concentration, gas molecules collide more

frequently and react at a faster rate. Conversely, increasing the volume of a gas
decreases pressure which in turn decreases the collision frequency and thus reduces
the reaction rate.
It is important to note however that there are reactions involving gases in which a
pressure change does not affect the reaction rate. For this reason, the rates of reactions
involving gases have to be determined by experiment.

Also note that solids and liquids are not affected by pressure changes.

Need a good analogy for the effect of concentration on the rate of a chemical
reaction?

Temperature

With the exception of some precipitation reactions involving ionic compounds in

solution, just about all chemical reactions take place at a faster rate at higher
temperatures. The question is why?

Temperature (in Kelvin degrees) is proportional to the

kinetic energy of the particles in a substance. For
example, if the Kelvin temperature of a substance is
doubled, then the average kinetic energy of the
particles in that substance is doubled.

At higher temperatures, particles collide more

frequently and with greater intensity.

Here's an analogy.

Imagine that you are baby-sitting a bunch of 6 year olds. You put them in a yard and
you let them run around. Every now and then a couple of kids will run into each other.
Now imagine that you decide to feed them some sugar. What happens? They run
around faster and of course there are many more collisions. Not only that, the
collisions are likely to be a lot harder/more intense.

Now, let's look at the effect graphically. Recall that in any sample of matter (the
example we used previously was a gas), individual particles have different kinetic
energies. Some are moving fast some are moving slowly, and most are moving at
some intermediate speed.
Increasing the temperature by say 10°C causes some of the intermediate speed
molecules to move faster. The result is more molecules with sufficient kinetic energy
to form an activated complex upon collision!

Now consider the relationship between threshold kinetic energy and activation energy.
Threshold kinetic energy is the minimum amount of energy required for colliding
particles to react - it is the equivalent of activation energy or the minimum potential
energy gain required to form an activated complex.

As you can see on the graph, a small increase in temperature can double the number
of molecules with the threshold kinetic energy.
Thus there are two effects of increasing temperature: greater collision intensity and
more frequent collisions.

A general rule is that a 10°C temperature increase can double a reaction rate. It turns
out that the increase in the reaction rate is mainly a function of the more intense
collisions. Increased collision frequency is not as significant a factor.

Nature of Reactants

Individual properties of substances also affect reaction rates. The scope of these
properties is broad and there are few generalizations that you can apply consistently.
Some of the properties in this category are state of matter, molecular size, bond type
and bond strength.

State of Matter

Gases tend to react faster than solids or liquids: It takes energy to separate particles
from each other. In order to burn candle wax, the solid wax has to be melted and then
vaporized before it reacts with oxygen. Methane gas is already in the gas state so it
burns faster than wax.

fast

slow

Aqueous ions tend to react faster than species in other states of matter: Solid lead(II)
nitrate will react with solid potassium iodide, but the reaction is really, really slow.
That's because the ionic bonding in each reactant is strong and the ions in each
compound are hard to separate from each other. When aqueous solutions of these
compounds are mixed, the formation of lead(II) iodide is rapid. In aqueous solutions,
the ions of each compound are dissociated. When the two the solutions are mixed
together, all that is required for a reaction to occur is contact between the lead(II) ions
and the iodide ions.
Bond Type

Reactions involving ionic species tend to proceed faster than reactions involving
molecular compounds.

Bond Strength

Reactions involving the breaking of weaker bonds proceed faster than reactions
involving the breaking of stronger bonds. For example, double carbon to carbon bonds
are stronger than single C-C bonds.

Number of Bonds/Molecular Size

Reactions involving the breaking of fewer bonds per reactant proceed faster than those
involving the breaking of a larger number of bonds per reactant.

The simple ion Fe2+ reacts faster than oxalate (OOCCOO2-).

Kerosene burns more slowly than methane because there are more bonds to be broken
per molecule of kerosene than there are per molecule of methane. Kerosene is a larger
molecule

fast

slow

Catalyst
A catalyst is a species that speeds up a chemical reaction without being chemically
changed upon completion of the reaction. In other words, the mass of a catalyst is the
same before and after a reaction occurs.

Common examples of catalysts include:

 MnO2 in the decomposition of H2O2

 Fe in the manufacture of NH3
 Pt in the conversion of NO and CO to N2 and CO2

Recall that collisions only result in reactions if the particles collide with enough
energy to get the reactions started (i.e. to overcome the activation energy barrier).

Also recall that activation energy corresponds to threshold energy.

Only collisions involving particles with sufficient kinetic energy result in the
formation of an activated complex. Particles possessing less than the threshold energy
simply bounce apart upon collision.

The number of successful collisions per unit of time be increased by lowering the
threshold energy (or in terms of potential energy, lowering the activation energy).
Adding the appropriate catalyst to a chemical system has exactly this effect on
threshold/activation energy.

A catalyst provides an alternative pathway for the reaction - a pathway that has a
lower activation energy. Be careful how you say it.

The catalyzed pathway (shown as a dotted green line above) has lower activation
energy.

Relating this back to the kinetic energy diagram, you see that more particles will have
sufficient kinetic energy to react. In other words, the addition of the catalyst increases
the reaction rate.
You'll explore the effect of a catalyst further on reaction rate in the next lesson.

Activity
Textbook Readings

 page 466: Method for Measuring Reaction Rates

 page 467: Factors That Affect Reaction Rate
 pages 470-471: Collision Theory and ... Concentration, Surface Area, Nature of
Reactants, and Temperature.

Textbook Practice Items

 pages 467-468: items 1, 2, 4, 5, and 6

 page 484: items 1 and 2
 pages 486-487: items 1, 2, 3, 4, 5, 6, 9, 12, and 13
 pages 538-541: items 12, 13, 28, 32, 34 and 35

More Practice Items

1. Why is kindling used to start a fire in a wood stove?

2. Consider this chemical equation:

What effect would increasing the temperature from 25°C to 100°C have on the
rate of this reaction? Explain.
3. 10.0 g pieces of zinc are added to 1.00 M and 6.00 M hydrochloric acid
solutions at the same time. Assuming there is excess acid in each container,
which reaction will proceed faster? Explain.
4. In terms of the effect of the nature of reactants on reaction rates, explain the
following observations.
a. the reaction between perchloric acid and iron is faster than the reaction
between nitrous acid and iron.
b. sulfur powder reacts slowly with silver, but sulfide ions are rapidly
precipitated out of solution in a reaction with silver ions.
c. barium reacts with water more readily than calcium
d. methane burns more rapidly in air than kerosene (C14H30).
5. Cane sugar (sucrose) can be hydrolysed to produce two glucose
molecules. This reaction is very slow.
 If an acid is added to the reactants, the reaction rate is much faster. What is
the role of the acid? Explain.

Test Yourself

© 2007 CDLI. All Rights Reserved.