7 ENERGY,

RATE, &
EQUILIBRIUM
GROUP 7
SUB-TOPICS 2
7.1 Thermodynamics
Green Chemistry: Twenty-First
Century Energy
A Medical Perspective: Hot and
Cold packs
7.2 Experimental Determination
of Energy Change in Reactions
7.3 Kinetics
A Human Perspective: Too Fast
or Too Slow?
7.4 Equilibrium
A Human Perspective: An
 IN THIS CHAPTER, WE INVESTIGATE THE
FUNDAMENTALS OF THERMODYNAMICS AND
KINETICS. WITH EMPHASIS ON THE CRITICAL
ROLE THAT ENERGY CHANGES PLAY IN
CHEMICAL REACTIONS.
7.1 THERMODYNAMICS
Thermodynamics is the study of energy, work, and heat. It
may be applied to chemical change, such as the calculation
of the quantity of heat obtainable from the combustion of 1
gallon (gal) of fuel oil. Similarly, energy released of
consumed in physical change, such as the boiling or
freezing of water may be determined.
3 basic laws of thermodynamics:
1. Energy cannot be created or destroyed, only
converted from one form to another
2. The universe spontaneously tends toward increasing
disorder or randomness.
3. The disorder of a pure, perfect crystal to absolute Zero
(0 Kelvin) is zero.
THE CHEMICAL REACTION AND ENERGY
John Dalton believed that chemical change involved
joining, separating, or rearranging atoms. Two centuries
later, this statement stands as an accurate description of
chemical reactions. However, we now know much more
about the energy changes that are an essential part of
every reaction.
Keep in mind that molecules and atoms are in
constant, random motion and frequently collide with each
other. Remember that the average kinetic energy of the
atoms or molecules increases with increasing temperature.
In addition to these statements of the kinetic molecular
theory, we will add the following concepts as they pertain
to chemical reactions:
• some collisions, those with sufficient energy, will
break bonds in molecules, and
• when reactant bonds are broken, new bonds may
be formed and products result.
It is worth noting that we cannot measure an
absolute value for energy stored in a chemical
system. We can only measure the change in energy
(energy absorbed or released) as a chemical
reaction occurs. Also, it is often both convenient
and necessary to establish a boundary between the
system and its surroundings.
The system contains the process under study. The
surroundings encompass the rest of the universe. Our
universe is composed of the system and its surroundings.
Energy is lost from the system to the surroundings, or
energy is gained by the system at the expense of the
surroundings. This energy change, most often in the
form of heat, may be experimentally determined
because the temperature of the system or surroundings
will change. and this change can be measured. This
process is illustrated in Figure 7.1. Heat flow is a term
that describes the transfer of heat when the direction of
transfer is specified. For example, we often use the term
heat flow to describe the transfer of thermal energy
from a hot object to a cold one.
Figure 7.1 Illustration of heat flow in
(a) exothermic and (b) endothermic
reactions.
Consider the combustion of methane, that is, the
reaction of methane and oxygen to form carbon
dioxide and water. If we define the reaction as
the system, the temperature of the air
surrounding the reaction increases, indicating
that some of the potential energy (energy stored
in the bonds) is converted to kinetic energy,
causing the molecules surrounding the reaction
to speed up. This type of kinetic energy is called
thermal energy. The transfer of thermal energy
to the surroundings is known as heat and is
sometimes called heat flow.
THE FIRST LAW OF THERMODYNAMICS
Exothermic and Endothermic Reactions
The first law of thermodynamics states that the
energy of the universe is constant. It is the law ol
conservation of energy. The study of energy changes
that occur in chemical reactions is a very practical
application of the first law. Consider, for example, the
generalized reaction:
A-B+ C-D→A-D+C-B
An exothermic reaction releases energy to the
surroundings. The surroundings become warmer.
• Each chemical bond is stored chemical energy (potential
energy). For the reaction to take place, bond A-B and bond C-D
must break; this process always requires energy. At the same
time, bonds A-D and C-B must form; this process always
releases energy.
• If the energy required to break the A-B and C-D bonds is less
than the energy given off when the A-D and C-B bonds form, the
reaction will release the excess energy. The energy is a product,
and the reaction is called an exothermic (Greek exo, “out," and
Greek therm, "heat") reaction.
An example of an exothermic reaction is the combustion of
methane, represented by a thermochemical equation, a chemical
equation that also shows energy as a product or reactant.
CH4(g)+2O2(g)→CO2(g)+2H2O(g)+211
Kilocalories(kcal)
• This thermochemical equation reads: the combustion of l
mole (mol) of methane releases 211 kcal of heat.
An endothermic reaction absorbs energy from the
surroundings. The surroundings become colder.
If the energy required to break the A-B and C-D bonds is
greater than the energy released when the A-D and C-B bonds
form, the reaction will need an external supply of energy.
Insufficient energy is available in the system to initiate the
bond-breaking process. Such as reaction is called an
endothermic (Greek endo, “within”, and Greek therm, “Heat”)
reaction, and energy is a reactant.
The decomposition of ammonia into nitrogen and
hydrogen is one example of an endothermic reaction:
22 kcal + 2NH3(g)→N2(g)+3H2(g)
Endothermic Reaction
ENTHALPY OF REACTIONS
• A chemical reaction may involve the
breaking and forming of many bonds. Our
interest is often focused on the total
amount of heat released or absorbed by the
overall reaction.
• Enthalpy is the term used to represent heal
and is symbolized as H. The change in
enthalpy is the energy difference between
the products and reactants of a chemical
reaction and is symbolized as AH.
By convention, energy released is
represented with a negative sign
(indicating an exothermic reaction),
and energy absorbed is shown with a
positive sign (indicating an exothermic
reaction). The change in enthalpy is
represented by the relationship:
∆H reaction=H products-H reactants
GREEN CHEMISTRY
Twenty-First Century Energy
• When we purchase gasoline for our automobiles
or oil for the furnace, we are certainly buying
matter. But that matter is only a storage device:
we are really purchasing the energy stored in
the chemical bonds. Combustion, burning in
oxygen, releases the stored energy (potential
energy) in a form suited to its function:
mechanical energy to power a vehicle or heat
energy to warm a home.
• If Hreactants> Hproducts, ∆H must be negative and
reaction is exothermic.
• If Hreactants< Hproducts, ∆ H must be positive and
reaction is endothermic.
For the combustion of methane, an
exothermic process, energy is a product in the
thermochemical equation:
CH4(g)+2O2(g)→ CO2(g)+2H2(g)+211 Kcal
• If Hreactants> Hproducts, ∆H must be negative and
reaction is exothermic.
• If Hreactants< Hproducts, ∆ H must be positive and
reaction is endothermic.
For the combustion of methane, an
exothermic process, energy is a product in the
thermochemical equation:
CH4(g)+2O2(g)→ CO2(g)+2H2(g)+211 Kcal
And
∆H=-211 Kcal
 For the decomposition of ammonia, and
endothermic process, energy is a reactant in the
thermochemical equation:
22 Kcal+2NH3(g)→N2(g)+3H2(g)
And
∆H=+22 Kcal
Diagrams representing changes in enthalpy for
exothermic (a) and (b) endothermic reactions
are shown in Figure 7.2.
SPONTANEOUS AND NONSPONTANEOUS REACTIONS
• It seems that all exothermic reactions
should be spontaneous. After all, an
external supply of energy does not appear
to be necessary; in fact, energy is a
product of the reaction. It also seems that
all endothermic reactions should be
nonspontaneous; energy is a reactant that
we must provide. However, these
hypotheses are not supported by
experimentation.
SPONTANEOUS AND NONSPONTANEOUS REACTIONS
• Experimental measurement has shown that
most but not all exothermic reactions are
spontaneous. Likewise, most but not all,
endothermic reactions are not
spontaneous. There must be some factor in
addition to enthalpy that will help us to
explain the less obvious cases of
nonspontaneous exothermic reactions and
spontaneous endothermic reactions. This
other factor is entropy.
 THE SECOND LAW OF
THERMODYNAMICS

• The first law of thermodynamics

considers the enthalpy of chemical
reactions. The second law states that the
universe spontaneously tends toward
increasing disorder or randomness.
ENTROPY
• A measure of the randomness of a
chemical system is its entropy. The
entropy of a substance is represented by
the symbol S. A random, or disordered,
system is characterized by high entropy;
a well-organized system has low entropy.
• The drive toward increased entropy, along
with a tendency to achieve a lower potential
energy, is responsible for spontaneous
chemical reactions. Reactions that are
exothermic and whose products are more
disordered (higher in entropy) will occur
spontaneously, whereas endothermic
reactions producing products of lower
entropy will not be spontaneous. If they are
to take place at all, they will need some
energy input.
FREE ENERGY
• The two situations just described are clear-cut
and unambiguous. In any other situation, the
reaction may or may not be spontaneous. It
depends on the relative size of the enthalpy and
entropy values.
• Free energy, symbolized by ∆G, represents the
combined contribution of the enthalpy und
entropy values for a chemical reaction. Thus, free
energy is the ultimate predictor of reaction
spontaneity and is expressed as
FREE ENERGY
∆G= ∆H-T ∆ S
∆H represents the change in enthalpy between
products and reactants, ∆S represents the
change in entropy between products and
reactants, and T is the Kelvin temperature of the
reaction.
• A reaction with a negative value of ∆G will always
be spontaneous.
• A reaction with a positive ∆ G will always be
nonspontaneous.
We need to know both ∆H and ∆S in order to predict the sign
of AG and make a definitive statement regarding the
spontaneity of the reaction. Additionally, the temperature may
determine the direction of spontaneity. Consider the four
possible situations:
• ∆H positive and ∆S negative: ∆G is always positive,
regardless of the temperature. The reaction is always
nonspontaneous.
• ∆H negative and ∆S positive: ∆G is always negative,
regardless of the temperature. The reaction is always
spontaneous.
• Both ∆H and ∆S positive: The sign of ∆G depends on the
temperature.
• Both ∆H and ∆S negative: The sign of ∆G depends on the
temperature.
7.2 EXPERIMENTAL DETERMINATION
OF ENERGY CHANGE IN REACTIONS
• The measurement of heat energy changes in a chemical
reaction is calorimetry. This technique involves the
measurement of the change in the temperature of a
quantity of water or solution that is in contact with the
reaction of interest and isolated from the surroundings. A
device used for these measurements is a calorimeter,
which measures heat changes in calories (cal) or joules
(J).
• The specific heat of a substance is defined as the
number of calories of heat needed to raise the
temperature of 1 gram of the substance 1 degree Celsius
(°C). Knowing the specific heat of the water or the
aqueous solution along with the total number of g of
solution and the temperature increase (measured as the
difference between the final and initial temperatures of
the solution) enables the experimenter to calculate the
heat released during the reaction.
• The solution behaves as a "trap" or "sink" for energy
released in an exothermic process. The temperature
increase indicates a gain heat energy. Endothermic
reactions, on the other hand, take heat energy away
from the solution, lowering its temperature. The
quantity of heat absorbed or released by the reaction
(Q) is the product of the mass of solution in the
calorimeter (mS), the specific heat of the solution
(SHS), and the change in temperature (∆TS) of the
solution as the reaction proceeds from the initial to
final state.
The heat is calculated by using the following
equation:
Q=ms × ∆TS × SHS
with units
cal= g × ×
(carbohydrates, proteins, and fats;
chapters 21-23) are oxidized to release
energy. Fuel value is the amount of
energy per g of food. Example 7.5
demonstrates the calculation of fuel
value.
The fuel value of food is an
important concept in nutrition science.
The fuel value is
generally reported in units of
nutritional Calories. One nutritional
Calorie (Cal) is equivalent to one
kilocalorie (1000 cal). It is also known
as the large Calorie(uppercase C).
• Energy necessary for our daily activity
and bodily function comes largely from
the reaction of oxygen with
carbohydrates. Chemical energy from
foods that is not used to maintain
normal body temperature or in
muscular activity is stored in the bonds
of chemical compounds known
collectively as fat. Thus, consumption
of "high calorie“ foods is implicated in
the problem of obesity.
A special type of
calorimeter, a bomb
calorimeter, is useful for
the measurement of the
fuel value (cal) of foods.
7.3 KINETICS
CHEMICAL KINETICS
Chemical kinetics is the study of the rate (or
speed) of chemical reactions. Kinetics also gives
an indication of the mechanism of a reaction, a step-
by-step description of how reactants become
products. Kinetic information may be represented as
the disappearance of reactants or appearance of
product over time. A typical graph of number of
molecules versus time is shown in Figure 7.7.
FIGURE 7.7
 ACTIVATION ENERGY AND
ACTIVATED COMPLEX
Consider the exothermic reaction we discussed in 7.1:
CH4(g)+2O2(g)→ CO2(g)+2H2(g)+211 Kcal
For the reaction to proceed, four C-H and two O=O bonds
must be broken, and two C=O and four H-O bonds must be
formed. Sufficient energy must be available to cause the
bonds to break if the reaction is to take place. This energy is
provided by the collision of molecules. If sufficient energy is
available at the temperature of the reaction, one or more
bonds will break, and the atoms will recombine in a lower
energy arrangement. in this case as carbon dioxide and
water. A collision producing product molecules is termed an
effective collision. An effective collision requires sufficient
energy and, in the case of complex molecules, the proper
orientation of reacting molecules. Only effective collisions
lead to chemical reactions.
ACTIVATION ENERGY AND
ACTIVATED COMPLEX
 The minimum amount of energy required to
initiate a chemical reaction is called the activation
energy, Ea, for the reaction.
We can picture the chemical reaction in terms of
the changes in potential energy that occur during the
reaction. Figure 7.10a graphically shows these
changes for an exothermic reaction, and Figure 7.10b
shows these changes for an endothermic reaction.
Important characteristics of these graphs include the
following:
• The reaction proceeds from reactants to products
through an extremely unstable state that we call
the activated complex. The activated complex
cannot be isolated from the reaction mixture but
may be thought of as a short-lived group of atoms
structured in such a way that it quickly and easily
breaks apart into the products of the reaction.
• Formation of the activated complex requires energy.
The difference between the energy of reactants and
that of the activated complex is the activation energy.
This energy must be provided by the collision of the
reacting molecules or atoms at the temperature of the
reaction.
Note the difference in activation energy between
an exothermic reaction (Figure 7.10a) and an
endothermic reaction (Figure 7.10b).
• The endothermic reaction takes place slowly because
of the large activation energy required for the
conversion of reactants into products.
Another difference between an exothermic reaction
and endothermic reaction is the net energy.
• In an exothermic reaction, the overall energy change
must be a net release of energy. The net release of
energy is he difference in energy between products
 FACTORS THAT AFFECT
REACTION RATE
• STRUCTURE OF THE REACTING SPECIES
Reactions among ions in solution are usually very
rapid. Ionic compounds in solution are dissociated;
consequently, their bonds are already broken, and
the activation energy for their reaction should be
very low. On the other hand, reactions involving
covalently bonded compounds may proceed more
slowly. Covalent bonds must be broken and new
bonds formed. The activation energy for this process
would be significantly higher than that for the
reaction of free ions. Bond strengths certainly play a
role in determining reaction rates because the
magnitude of the activation energy, or energy
barrier, is related to bond strength.
• MOLECULAR SHAPE AND
ORIENTATION
The size and shape of reactant
molecules influence the rate of the
reaction. Large molecules, containing
bulky groups of atoms, may block the
reactive part of the molecule from
interacting with another reactive
substance, causing the reaction to
proceed slowly. Only molecular collisions
that have the correct collision orientation,
as well as sufficient energy, lead lo
product formation. These collisions are
• THE CONCENTRATION OF REACTANTS
The rate of a chemical reaction is often a complex
function of the concentration of one or more of the
reacting substances. The rate will generally increase
as concentration increases simply because a higher
concentration means more reactant molecules in a
given volume and therefore a greater number of
collisions per unit time. If we assume that other
variables are held constant, a larger number of
collisions leads to a larger number of effective
collisions. For example, the rate at which a fire burns
depends on the concentration of oxygen in the
atmosphere surrounding the fire, as well as the
concentration of the fuel (perhaps methane or
propane). A common fire- fighting strategy is the use
of fire extinguishers (filled with carbon dioxide. The
carbon dioxide dilutes the oxygen to a level where the
combustion process can no longer be sustained.
• THE TEMPERATURE OF REACTANTS
The rate of a reaction increases as the
temperature increases, because the
average kinetic energy of the reacting
particles is directly proportional to the
Kelvin temperature. Increasing the speed
of particles increases the likelihood of
collision, and the higher kinetic energy
means that a higher percentage if these
collisions will result in product formation
(effective collisions). A 10°C rise in
temperature has often been found to
double the reaction rate.
• THE PHYSICAL STATE OF
REACTANTS
The rate of a reaction depends on the
physical state of the reactants: solid,
liquid, or gas. For a reaction to occur, the
reactants must collide frequently and
have sufficient energy to react. In the
solid state, the atoms, ions, or molecules
are restricted in their motion. In the
gaseous and liquid states, the particles
have both free motion and proximity to
each other. Hence, reactions tend to be
fastest in the gaseous and liquid states
• THE PRESENCE OF A CATALYST
A catalyst is a substance that increases
the reaction rate. If added to a reaction
mixture, the catalytic substance
undergoes no net change, nor docs it
alter the outcome of the reaction.
However, the catalyst interacts with the
reactants to create an alternative
pathway for production of products. This
alternative path has a lower activation
energy. This makes it easier for the
reaction to take place and thus increases
the rate. This effect is illustrated in Figure
• THE PRESENCE OF A CATALYST
A catalyst is a substance that increases
the reaction rate. If added to a reaction
mixture, the catalytic substance
undergoes no net change, nor docs it
alter the outcome of the reaction.
However, the catalyst interacts with the
reactants to create an alternative
pathway for production of products. This
alternative path has a lower activation
energy. This makes it easier for the
reaction to take place and thus increases
the rate. This effect is illustrated in Figure
MATHEMATICAL REPRESENTATION OF
REACTION RATE
Consider the decomposition reaction of N2O5
(dinitrogen pentoxide) in the gas phase. When
heated, N2O5 decomposes and forms two products:
NO2 (nitrogen dioxide) and O2 (diatomic oxygen).

2N2O5(g)
The balanced chemical equation for the reaction is

When all of the factors that affect the rale of the

reaction (except concentration) are held constant
(that is, the nature of the reactant, temperature
and physical state of the reactant, and the
presence or absence of a catalyst), the rate of the
reaction is proportional
to the concentration of N2O5, the reactant.
 A HUMAN PERSPECTIVE
TOO FAST OR TOO SLOW?
Kinetics plays a vital
role in the development
of a wide range of
commercial products.
We will consider a few
of these applications
that contribute to our
health, our enjoyment,
and the preservation of
our environment.
 Rate Concentration N2O5
We will represent the concentration of N2O5 in
units of molarity and represent molar
concentration using brackets.
Concentration N2O5= [N2O5]
Then,
Rate [N2O5]
Laboratory measurement shows that the
rate of the reaction depends on the molar
concentration raised to an experimentally
determined exponent, which we will symbolize
as n, the reaction order. The reaction order
represents the number of molecules that are
involved in the formation of product.
 Rate [N2O5]ⁿ
In expressions such as the one shown,
the proportionality symbol, a, may be
replaced by an equality sign and a
proportionality constant that we
represent as k, the rate constant.
Ratek[N2O5]ⁿ
Equations that follow this format,
the rate being equal to the rate constant
multiplied by the reactant concentration
raised to an exponent that is the
reaction order, are termed rate laws.
For the reaction described here, n has
been experimentally determined and
is equal to 1; hence, the reaction is
first order in N2O5 and the rate law for
the reaction is:
Ratek[N2O5]
In general, the rate of reaction for an
equation of the general form:
A→product
Is represented by the rate law
Ratek[A]ⁿ
In which
n= reaction order
k= rate constant of the reaction
[A]= molar concentration of the reactant
An equation involving two reactants
A + B → products
has a rate law of the form
Rate=k[A]ⁿ [B]ⁿ
7.4 EQUILIBRIUM
PHYSICAL EQUILIBRIUM
Physical equilibrium is one that occurs between
two phases of the same substance. Examples of
physical equilibria include:
• Liquid water in equilibrium with either ice or
water vapor
• A saturated solution (Section 6.1) consisting of
an ionic solid, such as silver chloride, in
equilibrium with a solution of silver ions and
chloride ions
• A saturated solution consisting of a covalent
solid, such as glucose, in equilibrium with a
 Dissolution of sugar in water,
producing a saturated solution, is
a convenient illustration of a state
of dynamic equilibrium.
A dynamic equilibrium is a
situation in which the rate of the
forward process in a reversible
reaction is exactly balanced by
the rate of the reverse process.
A physical equilibrium, such as sugar dissolving in water, is a reversible
reaction. A reversible reaction is a process that can 0ccur in both
directions. It is indicated by using the equilibrium arrows (↔)symbol.
Sugar in Water
Imagine that you mix a small amount of sugar (2 or 3 g) in 100 milliliters
(mL) of water. After you stir it for a short time, all of the sugar dissolves;
there is o residual solid sugar because the sugar has dissolved
completely. The reaction clearly has converted all solid sugar to its
dissolved state, an aqueous solution of sugar, or
sugar(s) → sugar(aq)
Now, suppose that you add a very large amount of sugar (100 g), more
than can possibly dissolve, to he same volume of water. As you stir the
mixture, you observe more and more sugar dissolving. After some time,
the amount of solid sugar remaining in contact with the solution appears
constant. Over time, you observe no further decrease in the amount of
undissolved sugar. Although nothing further appears to be happening, in
The rates of the forward and reverse
reactions are identical, and the amount of
sugar present as solid and in solution is
constant. The system is al equilibrium. The
equilibrium arrows serve as
• an indicator of a reversible process,
• an indicator of an equilibrium process,
and
• a reminder of the dynamic nature of the
process.
CHEMICAL EQUILIBRIUM
We have assumed that most chemical
reactions considered thus far proceed to
completion, A complete reaction is one in
which all reactants have been converted to
products. However, many important chemical
reactions do not go to completion. As a result,
after no further obvious change is taking
place, measurable quantities of reactants and
products remain. Reactions of this type
(incomplete reactions) are called equilibrium
reactions. Chemical equilibrium is the state
of a reaction in which the rates of the forward
and reverse reactions are equal.
THE REACTION ON N2 AND H2
When we mix nitrogen gas (N2) and
hydrogen gas (H2) at an elevated temperature
(perhaps 500°C), some of the molecules will
collide with sufficient energy and proper
orientation to break N≡N and H-H bonds.
Rearrangement of the atoms will produce the
product (NH3):
N2(g)+3H2(g) 2NH3(g)
Beginning with a mixture of hydrogen and
nitrogen, the rate of the reaction is initially
rapid, because the reactant concentration is
high; as the reaction proceeds, the
concentration of reactants decreases.
At the same time, the
concentration of the
product, ammonia, is
increasing. At
equilibrium, the rate of
depletion of hydrogen
and nitrogen is equal
to the rate of depletion
of ammonia. In other
words, the rates of the
forward and reverse
reactions are equal.
THE GENERALIZED EQUILIBRIUM CONSTANT
EXPRESSION FOR A CHEMICAL REACTION
We write the general form of an
equilibrium chemical reaction as,
aA + bB cC+ Dd
in which A and B represent reactants, C
and D represent products, and a, b, c, and
d are the coefficients of the balanced
equation. The equilibrium constant
expression for this general case is
For the ammonia system, it follows that
the appropriate equilibrium expression is:

It does not matter what initial amounts

(concentrations) of reactants or products
we choose. When the system reaches
equilibrium, the calculated value of will
not change. The magnitude of Can be
altered only by changing the temperature.
Thus, is temperature dependent. The
chemical industry uses this fact to its
advantage by choosing a reaction
temperature that will maximize the yield
 WRITING EQUILIBRIUM
CONSTANT EXPRESSION
An equilibrium constant expression can be
written only after a correct, balanced chemical
equation that describes the equilibrium system
has been developed. A balanced equation is
essential because the coefficients in the equation
become the exponents in the equilibrium constant
expression.
Each chemical reaction has a unique
equilibrium constant value al a specified
temperature. Equilibrium constants listed in the
chemical literature are often reported at 25°C, to
allow comparison of one system with any other.
For any equilibrium reaction, the value of the
The brackets represent molar
concentration or molarity:
recall that molarity has units of
moles per liter (mol/). In our
discussion of equilibrium, all
equilibrium constants are
shown as unitless.
 INTERPRETING
EQUILBRIUM CONSTANTS
What utility does the equilibrium
constant have? The reversible arrow in
the chemical equation alerts us to the
fact that an equilibrium exist. Some
measure quality quantity of the product
and reactant remains. However, there is
no indication whether products
predominate, reactants predominate, or
significant concentrations of both
products and reactants are present at
 The numerical value of the equilibrium
constant provides this additional
information. It tells us the extent to which
reactants have converted to products. This
is important information for anyone who
wants to manufacture and sell the product.
It also is important to anyone who studies
the effect of equilibrium reactions on
environmental systems and living
organisms.
Although an absolute interpretation of
the numerical value of the equilibrium
constant depends on the form of the
equilibrium constant expression, the
• Keq greater than 1 x 10³. A large numerical
value of K indicates that the numerator
(product term) is much larger than the
denominator (reactant terin) and that at
equilibrium mostly product is present.
• Keq less than 1 × 10̄ ³ , A small numerical
value of Keq indicates that the numerator
(product term) is much smaller than the
denominator (reactant term) and that at
equilibrium mostly reactant is present.
• Keq between 1 × 10̄ ³ and 1x 10³. In this
case, the equilibrium mixture contains
significant concentrations of both
reactants and products.
 CALCULATING EQUILBRIUM
CONSTANTS
The magnitude of the equilibrium constant
for a chemical reaction is determined
experimentally. The reaction under study is
allowed to proceed until the concentration of
products and reactants no longer changes (Figure
7.14). This may be a matter of seconds, minutes,
hours, or even months or years, depending on the
rate of the reaction. The reaction mixture is then
analyzed to determine the molar concentration of
each of the products and reactants. These
concentrations are substituted in the equilibrium
constant expression, and the equilibrium constant
is calculated. Example 7.9 illustrates this process.
 USING EQUILBRIUM
CONSTANTS
We have seen that the equilibrium
constant fora reaction can be calculated if we
know the Equilibrium concentrations of all of
the reactants and products. Once known, the
equilibrium constant can be used to obtain
equilibrium concentrations of one or more
reactants or products for a variety of different
situations. These calculations can be quite
complex. Let's look at one straightforward
but useful case, one where the equilibrium
concentration of reactants is known and we
wish to calculate the product concentration.
 LECHATELIER'S PRINCIPLE
In the nineteenth century, the French chemist H. L.
LeChatelier discovered that changes in equilibrium depend
on the amount of "stress" applied to the system. The
stress may take the form of an increase or decrease of the
temperature of the system at equilibrium, or perhaps a
change in the amount of reactant or product present in a
fixed volume (the concentration of reactant or product).
LeChatelier's principle states that if a stress is placed
on a system at equilibrium, the system will respond by
altering the equilibrium composition in such a way as to
minimize the stress.
Consider the equilibrium situation discussed earlier:
 N2(g) + 3H2(g) 2NH3(g)
If the reactants and products are present in a fixed
volume, such as 1 liter (L), and more NH3 (the product) is
introduced into the container, the system will be stressed
the equilibrium will be disturbed. The system will try to
alleviate the stress (as we all do) by removing as much of
the added material as possible. How can it accomplish
this? By converting some NH, to H, and N,. The position of
the equilibrium shifts to the left, and a new dynamic
equilibrium is soon established.
Adding extra H2 or N2 would apply the stress to the
reactant side of the equilibrium. To minimize the stress,
the system would “use up“ some of the excess H2 or N2 to
make product, NH3. The position of the equilibrium would
What would happen if some of the ammonia molecules were
removed from the system? The loss of ammonia represents a
stress on the system; to relieve that stress, the ammonia would
be replenished by the reaction of hydrogen and nitrogen. The
position of the equilibrium would shift to the right.
 EFFECT OF CONCENTRATION
Addition of extra product or reactant to a
fixed reaction volume is just another way of
saying that we have increased the concentration
of product or reactant. Removal of material from
a fixed volume decreases the concentration.
Therefore, changing the concentration of one or
more components of a reaction mixture is a way
to alter the equilibrium composition of an
equilibrium mixture (Figure 7.15). Let's look at
some additional experimental variables that may
 EFFECT OF HEAT
The change in equilibrium composition
caused by the addition or removal of heat
from an equilibrium mixture can be
explained by treating heat as a product or
reactant. The reaction of nitrogen and
hydrogen is an exothermic reaction:
N2(g) + 3H2 (g) 2NH3(g) + 22 Kcal
Adding heat by raising the temperature is similar to
increasing the amount of product. The position of the
equilibrium will shift to the left, increasing the
amounts of N2 and H2 and decreasing the amount of
NH3. If the reaction takes place in a fixed volume,
the concentrations of N2 and H2 increase and the
NH3 concentration decreases.
Removal of heat by lowering the temperature
produces the reverse effect. More ammonia is
produced from N2 and H2 and the concentrations of
these reactants must decrease.
In the case of an endothermic reaction, such as
39 kcal + 2N2 (g) + O,(g) 2N2O(g)
 EFFECT OF PRESSURE
Only gases are affected significantly by
changes in pressure because gases are free to
expand and compress in accordance with Boyle's
law. However, liquids and solids are not
compressible, so their volumes are unaffected by
pressure.
Therefore, pressure changes will alter
equilibrium composition only in reactions that
involve a gas or variety of gases as products
and/or reactants. Again, consider the ammonia
 N2(g) + 3H2 (g) 2NH3(g)
One mole of N2 and three moles of H3 (total of 4 mol
of reactants) react to form two moles of NH3 (2 mol
of product). The equilibrium mixture (perhaps at
25°C) contains N2 and H2 and NH3 An increase in
pressure will cause a stress to the system because
the pressure is greater than the equilibrium pressure.
To relieve the stress, the system will shift toward the
side of the reaction that has fewer mol of gas. As the
number of mol decreases, the pressure will decrease.
In the example of ammonia, an increase in pressure
will shift the position of the equilibrium to he right,
producing more NH3 at the expense of N2 and H2 .
A decrease in pressure will be countered by the
reaction shifting toward the side that contains
more mol of gas because the pressure is less than
the equilibrium pressure. As the number of mol of
gas increases, the pressure will increase.
Therefore, in the equilibrium reaction of ammonia,
a decrease in pressure will cause the position of
the equilibrium to shift to the left, and ammonia
decomposes to form more nitrogen
and hydrogen.
In contrast, the decomposition of hydrogen
iodide,
2HI(g) H2(g) + I2(g)
is unaffected by pressure. The number of mol of
gaseous product and reactant is
identical. No volume advantage is gained by a shift in
equilibrium composition. In summary:
• Pressure affects the equilibrium composition only of
reactions that involve at least one gaseous
substance.
• Additionally, the relative number of mol of gaseous
products and reactants must differ.
• The equilibrium composition will shift to increase the
number of mol of gas when
• the pressure decreases; it will shift to decrease the
number of mol of gas when the pressure increases.
 EFFECT OF CATALYST
A catalyst has no effect on the equilibrium
composition. A catalyst increases the rates
of both forward and reverse reactions to the
same extent. The equilibrium composition
and equilibrium concentration do not
change when a catalyst is used, but the
equilibrium composition is achieved in a
shorter time. The role of a solid-phase
catalyst in the synthesis of ammonia is
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