CH-202

Chemical Equilibrium
-In doing stoichiometric calculations, we assume that reactions proceed to completion
(when one of the reactants is totally consumed)
-Many reactions do proceed to completion. On the other hand, there are many chemical
reactions that stop far short of completion and tend to have to go back and forth from
consuming reactants to form products and from consuming products to form back the
reactants
-Such reactions are said to move to the right to form products (forward reaction) or to
move to the left to form the reactants (reverse reaction)
-The forward and reverse reactions will both have specific rates at which they occur
-When the rates of the forward and reverse reactions become equal, chemical
equilibrium is then reached
-Chemical Equilibrium is the state reached by a reaction mixture when the rates of
forward and reverse reactions have become equal.
The Equilibrium Condition
-Equilibrium is not static, but is a highly dynamic state.
-At the macro level everything appears to have stopped but at the molecular level, there
is activity.
-The concentration of products builds as the reaction proceeds. There will come a time,
in some reactions, where the products will collide and thus react and reform the
reactants.
-When both the forward and reverse reaction occur at the same rate there is no change in
concentration reactants and products and the reaction is said to be at equilibrium.
-A double arrow (
) is used to show that a reaction can occur in either direction.
Example: consider the following reaction
CO (g) + 3H2 (g)

CH4 (g) + H2O (g)

-This is a gaseous reaction in which carbon monoxide and hydrogen react to form
methane and steam. It consists of forward and reverse reactions as presented above.
-Suppose we place 1mol of CO and 3 moles of H2 into a 10-L closed vessel at 1200K
(927oC)
rate of reaction of CO and H2 depends on the concentrations of CO and H2.
before the reaction occurs, the reactants are present at their maximum
concentrations

 as they react, their concentrations begin to fall

the rate of the forward reaction is large at first but steadily decreases as
reactants are consumed.
the concentrations of CH4 and H2O, which was zero at first, will increase
steadily. The rate steadily increases
the forward rate decreases and the reverse rate increases until they both become
equal
when that happens, CO and H2 molecules are formed as fast as they react
concentrations of reactants and products no longer change
observing the mixture, we see no net change, however the forward and reverse
reactions are still occurring.
We then say that, the reaction mixture has reached equilibrium
-To really understand equilibrium, we need to be sure we understand its condition: The
concentrations of reactants and products remain constant at equilibrium because the
forward and reverse reaction rates are equal
-What will happen if we add more CO(g) to the vessel?
-at this instant, what happens to the forward and the reverse rates?
The Equilibrium Constant
-Let us use the following equation:
jA + kB

mC + nD

-where A, B, C, and D represent chemical species and j, k, m, and n are their coefficients
in the balanced equation.
-Since the concentration of the products and reactants remains constant at equilibrium,
we can set up a mass action expression: Which is the concentration of the products
(raised to the power of their coefficients) divided by the concentration of the reactants
(raised to the power of their coefficients)
[C]m [D]n
K=

[A]j [B]k

This mass action expression can then be used to find a constant for the reaction at a
given temperature. This constant is known as the equilibrium expression (Kc or Keq) .
To change this into an equilibrium expression, set it equal to Kc.
[C]m [D]n
Kc = j
[A] [B]k

Three conclusions about the equilibrium expression:

1. The equilibrium expression for a reverse reaction is the reciprocal of the above
expression
2. When the balanced equation for a reaction is multiplied by a factor n, the
equilibrium expression for the new reaction is the original expression raised to
the nth power. Thus Knew = (Koriginal)n.
3. The units for K are determined by the powers of the various concentration
terms. The units for K therefore depend on the reaction being considered
-The law of mass action correctly describes the equilibrium behavior of all chemical
reaction systems
-This is associated with the law of mass action stating that the value of the equilibriumconstant Kc is constant for a given reaction, at a given temperature, no matter what the
equilibrium concentrations are!
-Equilibrium position - set of equilibrium concentrations. There is only one
equilibrium constant for a particular system at a particular temperature, but there are an
infinite number of equilibrium positions. This can tell us in what direction the reaction
will proceed (very important later on in this chapter).
Example:
CO (g) + 3H2 (g)
a)
b)

CH4 (g) + H2O (g)

Write the equilibrium constant expression Kc for the above reaction.

Write the equilibrium constant expression Kc for the reverse of the reaction
above.

Solution
a)

Kc =
b)
Kc =

Practice Example:
N2 (g) + 3H2 (g)
Forward reaction

Kc =

Reverse reaction

Kc =

2NO2 (g) + 7H2 (g)

Forward reaction

Kc =

Reverse reaction

Kc =

2NH3 (g)

2NH3 (g) + 4H2O (g)

Practice example:

The following equilibrium concentratins were observed for the

Haber process at 127oC:
[NH3] = 3.1 x 10-2 mol/L (product)
[N2] = 8.5 x 10-1 mol/L (reactant)
[H2] = 3.1 x 10-3 mol/L (reactant)
a) calculate the value of K at 127oC for this reaction
b) calculate the value of the equilibrium constant at 127oC for
the following reaction:
2 NH3 (g)
N2 (g) + 3H2 (g)
c) calculate the value of the equilibrium constant at 127oC for
the following reaction reaction :
1/2 N2 (g) + 3/2 H2 (g)
NH3 (g)

Solution:
a)
write the balanced equation for the Haber process at 127oC:

Therefore, using the law of mass action we can write the expression for K:
Kc =

=
=

b)

This reaction is written in the reverse order as compared to question a.

Therefore, this leads to the inverse of the above expression:
K'c =

=
K'c =

c)
K"c =

then,

K" = K1/2 = (

) =

Equilibrium Expressions Involving Pressures

-How is pressure related to concentration?
-A couple of chapters ago we rearranged the ideal gas law to include molarity (except
this time we are going to use C for concentration)
n
PV = nRT
or
P=
RT
=
CRT
V
where C equals n/V, or the number of moles n of gas per unit volume V. Thus C
represents the molar concentration of the gas.
-If we examine this in terms of the Haber process:
N2 + 3H2

2NH3

we see that the equilibrium expression would look like [NH3]2

CNH 2
3

Kc =

=
3

[N2] [H2]

( CN ) ( C H 3 )
2

Or in terms of the equilibrium partial pressures of the gases

PNH

Kp =
( PN ) ( PH 3 )
2

-Since we learned there is a relationship which exists between concentration and

pressure, so there must be a relationship between Kc and Kp
Kp = Kc(RT)n
where "n" is the sum of the coefficients of the gaseous products minus the sum of the
coefficients of the gaseous reactants. (you can see a derivation of this equation on p. 198
in Zumdahl, 7th edition)

- Fot the units of Kc, when the powers of the numerator are cancelled by that of the
denominator, Kc will have no units. However, when the powers are different and do not
cancel out, Kc will have units and Kc will not equal Kp.
Heterogeneous Equilibria
-Homogeneous equilibria - where all reactants and products are all in the same phase
(ex. all gaseous).
-Heterogeneous equilibria - where all reactants and products are not in the same phase.
-These equilibria do not depend on the amounts of pure solids or liquids present (ie.
pure solids and liquids are not included in the equilibrium expression).
-Therefore, the concentrations of liquid or solids are considered to be constant
Example:

CaCO3 (s)

CaO (s) + CO2 (g)

Then Kc = [ CO2] and

Kp = PCO

Therefore, if pure solids or liquids are involved in a chemical reaction, their

concentrations are not included in the equilibrium expression for the reaction
Applications of the Equilibrium Constant
-Knowing the equilibrium constant for a reaction will allow us to predict several
important features of the reaction:
-the tendency of the reaction to occur
-whether a given set of concentrations represents an equilibrium condition
-the equilibrium position that will be achieved from a set of given concentrations
The Extent of a Reaction
-The tendency for a reaction to occur is indicated by the magnitude of the equilibrium
constant (K)
-When the Value of
K >> 1 this means that at equilibrium the reaction consists
mostly of products (equilibrium lies to the right and
the reaction essentially goes to completion)
K << 1 this means that at equilibrium the reaction consists
mostly of reactants (equilibrium lies to the left and
the reaction hardly occurs)
Reaction Quotient

-When reactants and products are mixed in a given reaction, it becomes very useful to
know whether the mixture is at equilibrium, or it will shift right or left.
-One key point for predicting the direction of the reaction is to see which of the products
or reactants has a concentration of zero. The system will shift in the direction that
produces the missing component
-If all the initial concentrations (reactants and products) are not zero, it becomes more
difficult to determine the direction of the reaction for reaching equilibrium
-In such cases, for predicting the direction of a particular reaction, we use the reaction
quotient, Qc, which is an expression that has the same form as the equilibrium
constant expression (Kc) but whose concentration values are not necessarily those
at equilibrium.
Example:
CO (g) + 3H2 (g)

CH4 (g) + H2O (g)

A gaseous mixture has the following composition at 1200K: 0.0200M CO,

0.0200M H2, 0.00100M CH4, and 0.00100M H2O.
With the given conditions, would the reaction go toward the right or the left?
Solution:
We are given the concentrations at a particular instant (not necessarily at equilibrium)
We know the Kc of the reaction which has the value of ~3.92 at 1200K
We must find Qc and compare with Kc.
[CH4]i [H2O]i
i

Q2]ci3=[CO]
[H

where I indicates concentrations at a particular instant i.

Substitute the given concentrations into the Qc expression, we get:

(0.00100) (0.00100)

Qc =

(0.0200) (0.0200)3

= 6.25

Kc = 3.92

(at 1200K)

Therefore, the Qc must decrease from 6.25 to 3.92 in order to reach equilibrium.
One way to decrease it, is to decrease the numerator (concentrations of products)
and to increase the denominator (concentrations of the reactants)
The numerator is the right side of the reaction, and to decrease it, the reaction should
proceed to the left.

Similarly, the denominator is the left side of the reaction, and to increase it or make
more of, the reaction should also proceed to the left.
Therefore, this reaction, under the given conditions will proceed to the left
In General:
If Qc Kc, the reaction will go to the left
If Qc Kc, the reaction will go to the right
If Qc = Kc, the reaction mixture is at equilibrium
Practice example:
A 50.0-L reaction vessel contains 1.00 mol N2, 3.00 mol H2, and 0.500 mol NH3. Will
more ammonia, NH3, be formed or will it dissociate when the mixture goes to
equilibrium at 400oC? ( Kc= 0.500 at 400oC )
N2 (g) + 3H2 (g)

2NH3 (g)

Solution:
With the given conditions we must figure out the direction of the reaction in order for
the mixture to reach equilibrium.
Therefore, we must first figure out _____ so we can compare it to Kc
In order to figure out ______ we must find the concentrations of each component
We are given the _____ of each component and the ______ in which the reaction occurs
Hence, we have:

[N2] = (
[H2] = (
[NH3] = (

)/(
)/(
)/(

)=
)=

M
M
)=

Having the concentrations, substitute them into the expression for Qc

[

]i
i

[ Qc ]=i[

Qc =

Kc = 0.500

Therefore, the reaction will proceed to the _________, and

ammonia will __________
Calculating Equilibrium Pressures and Concentrations
-A typical equilibrium problem involves finding the equilibrium concentrations (or
pressures) of reactants and products, given the value of the equilibrium constant and the
initial concentrations (or pressures)
Example 1: Assume that the reaction for the formation of gaseous hydrogen fluoride
from hydrogen and fluorine has an equilibrium constant of 1.15 x 102 at a
certain temperature. In a particular experiment at this temperature,
3.000 mol of each component was added to a 1.500 L flask.
a) In which direction does the reaction shift?
b) Calculate the equilibrium concentrations of all species.
Solution:

Given:

Kc = 1.15 x 102
[HF]i = [H2]i = [F2]i = (3.000 mol) / (1.500 L) = 2.000 M

Find:

Qc and concentrations of all species at equilibrium

1) Write a balanced equation from the given description in the question:

H2 (g) + F2 (g)

2 HF (g)

2) Write the equilibrium expression for the reaction:

[HF]2
= 1.15 x 102

Kc =
[H2] [F2]

a) Having the value of Kc (1.15 x 102), we need to compare it to Qc:

[HF]i2

(2.000)2
10

[H2]i Q
[F2c]=
i

=
(2.000) (2.0000)

= 1.000

Therefore, Qc << Kc thus, the reaction will shift to the right to reach equilibrium

b)
(Concentrations)

H2 (g)

F2 (g)

2 HF (g)

Starting

2.000 M

2.000 M

2.000 M

Change

-x

-x

+ 2x

Equilibrium

2.000 x

2.000 x

2.000 + 2x

To solve for x, we then substitute the values at equilibrium in the equilibrium expression
Perfect square
of Kc:
[HF]2
= 1.15 x 102 =

Kc =
[H2] [F2]

(2.000 + 2x)2

(2.000 + 2x)2

=
(2.000 x) (2.000 x)

(2.000 x)2

The right side of this equation is a perfect square, so taking the square root of both sides
will give:
(2.000 + 2x)
2
1.15 x 10 =
which gives x = 1.528
(2.000 - x)
Subsitituting x = 1.528 into the equilibrium equations of each component, we get:
[H2] = [F2] = 2.000 x = 2.000 1.528 = 0.472 M
[HF] = 2.000 + 2x = 2.000 + (2)(1.528) = 5.056 M
Therefore, the equilibrium concentrations of all species are:
0.472 M H2
0.472 M F2
5.056 M HF
11

Solving Equilibrium Problems

Here are a series of steps to help aid you in the solving of equilibrium problems:
1) Write the balanced equation for the reaction.
2) Write the equilibrium expression using the law of mass action.
3) List the initial concentrations.
4) Calculate Q, and determine the direction of the shift to equilibrium.
5) Define the change needed to reach equilibrium, and difine the equilibrium
concentrations by applying the change to the initial concentrations.
6) Substitute the equilibrium concentrations into the equilibrium expression, and
solve for the unknown.
7) Check your calculated equilibrium concentrations by making sure they give the
correct value of K.
Small values of K and the resulting small shift to the right to reach equilibrium allow for
simplification. This is okay as long as the resulting change in value is less then 5% of
the original value. If not, then you must use the quadratic formula.
Example 2: Assume that the reaction for the formation of gaseous hydrogen fluoride
from hydrogen and fluorine has an equilibrium constant of 1.15 x 102 at a
certain temperature. In a particular experiment at this temperature,
3.000 mol of H2 and 6.000 mol of F2 are mixed in a 3.000 L flask.
a) In which direction does the reaction shift?
b) Calculate the equilibrium concentrations of all species.
Solution:

Given:

Kc = 1.15 x 102
[HF]i = 0
[H2]i = (3.000 mol) / (3.000 L) = 1.000 M
[F2]i = (6.000 mol) / (3.000 L) = 2.000 M

Find:

Concentrations of all species at equilibrium

12

1) Write a balanced equation from the given description in the question:

2) Write the equilibrium expression for the reaction:

Kc =

a) Here there is no need to compare Qc to Kc because the initial concentration of HF is

zero and obviously, the reaction will proceed in the direction that produces HF (thus to
the right)
b)
(Concentrations)

H2 (g)

F2 (g)

2 HF (g)

Starting
Change
Equilibrium
To solve for x, we then substitute the values at equilibrium in the equilibrium expression
of Kc:
Kc =
this will give us:

(1.5 x 102)(x2) (3.000)(1.5 x 102)(x) + (2.000)(1.5 x 102) = 4x2

(1.11 x 102)x2 (3.45 x 102)x + 2.30 x 102 = 0

the above expression is similar to the known quadratic equation:

-b
ax2 + bx + c = 0

where

b2 - 4ac

x=

13

2a
if we plug in the above values into the equation, we will get two possible values for x;
x = 2.14 mol/L and x = 0.968 mol/L
using either of these values for [H2] = 1.000 x, we find that x=2.14 gives us a negative
value for the concentration which is physically impossible to have! Therefore, the
correct value of x to be used is 0.968 mol/L.
Therefore,
Subsitituting x = 0.968 into the equilibrium equations of each component, we get:
[H2] =
[F2] =
[HF] =
Therefore, the equilibrium concentrations of all species are:
M H2
M F2
M HF
Treating Systems that Have Small Equilibrium Constants
-Under certain conditions, we are able to make simplifications (assumptions) that
greatly reduces the mathematical difficulties
-Equilibrium constants that have small values will often tell us that there will be
relatively small changes in order to reach equilibrium. In other words, there is a
relatively small change in the concentrations of the reaction components
-Lets consider an example in order to clarify this point:
Example:
Gaseous NOCl decomposes to form the gases NO and Cl2 at 35oC. at this temperature
the equilibrium constant is 1.6 x 10-5 mol/l. in an experiment in which 1.0 mol of NOCl
is placed in a 2.0 L flask, what are the equilibrium concentrations of all the species?
1) The balanced reaction is:

2NOCl(g)

2NO(g) + Cl2(g)
[NO]2 [Cl2]

2) The equilibrium expression is:

= 1.6 x 10-5 mol/L

Kc =
[NOCl]2

14

3) The initial concentration are:

[NO]i = 0
[Cl2]i = 0
[NOCl]i = (1.0 mol) / (2.0 L) = 0.50 M
4) Since there are initially no products, the reaction will shift to the right in order to
produce the missing components
5)
(Concentrations)

2 NOCl (g)

2NO(g) + Cl2(g)

Starting

0.5 M

0M

0M

Change

-2x

+2x

+x

0.5 2x

2x

Equilibrium

6) substitute the above equilibrium values into the equilibrium expression in step 2)
[NO]2 [Cl2]

(2x)2 (x)
= 1.6 x 10-5 mol/L =

Kc =
[NOCl]2

(0.5 2x)2

To solve this, it will obviously need multiplying, and collecting terms that result in an
equation that requires complicated calculations and is time consuming
This can be avoided by assuming that since Kc is so small (1.6 x 10-5 mol/L), the system
will shift to the right but not that far. This means that the change in concentration (which
is the 'x' terms) will be relatively small. And consequently, the x term could be omitted
when subtracting or adding the x term.
Therefore, [NOCl] at equilibrium = 0.5 2x 0.5
Making this assumption allows us to simplify the equilibrium expression to be:
(2x)2 (x)

(2x)2 (x)

1.6 x 10-5 =

=
(0.5 2x)

Solving for x3 gives :

4x3
=

(0.5)

(0.5)2

x3 = [ (1.6 x 10-5) (0.50)2 ] / 4 = 1.0 x 10-6

Therefore, x = 1.0 x 10-2 mol/L

7) Now we must check the validity of this assumption by comparing the value of x with
15

0.5 2x 0.5
0.5 2(1.0 x 10-2) = 0.48
Here we can see that the difference between 0.5 0.48 = 0.02 (4%) is relatively small
difference and will have relatively little effect on the outcome.
8) Now we can use the value for x = 1.0 x 10-2 mol/L to find the equilibrium
concentrations from step 5) :
[NO] = 2x = 2 (1.0 x 10-2 ) = 2.0 x 10-2 mol/L
[Cl2] = x = 1.0 x 10-2 mol/L
[NOCl] = (0.5 2x) = 0.48 mol/L 0.50 mol/L
9) Finally, it is always good to check if these concentrations, when used in the
equilibrium constant expression of K, will give the same value of K given in the
question ( K= 1.6 x 10-5 mol/L)
Check:
[NO]2 [Cl2]
Kc =

( 2.0 x 10-2)2 ( 1.0 x 10-2)

= 1.6 x 10-5 mol/L

=
[NOCl]2

(0.5)2

Such problems, where K is relatively small, suggest that the equilibrium shifts to a
very small extent, allowing us to assume that 'x' is negligible compared to the
initial starting concentration.
(divide any given concentration by the value of K. If > 100, assumption of
removing 'x' will be valid)
Le Chteliers Principle: Changing the Reaction Conditions
-Obtaining the maximum amount of product from a reaction depends on the proper
selection of reaction conditions.
-By changing these conditions, we can increase or decrease the yield of the products.
-For gaseous reactions, there are three ways to alter their equilibrium composition and
possibly increase the yield.
1. Changing the concentrations by removing products or adding reactants to the
reaction vessel.
2. Changing the partial pressure of gaseous reactants and products by changing
the volume.
16

3. Changing the temperature.

-Le Chateliers Principle states that when a system in chemical equilibrium is disturbed
by a change of temperature, pressure, or concentration, the system shifts in a way that
tends to counteract this change to reach equilibrium once again.
Changing the Concentration by Removing Products or Adding Reactants:
-One way to increase the yield is to change the concentration of a reactant or product in
the reaction mixture
-Consider the following reaction:
CO (g) + 3H2 (g)
CH4 (g) + H2O (g)
-If we increase the concentration of the reactants, we expect the reaction to
proceed to the right side so as to make more of the products and reach the
equilibrium state once again
- Similarly, if we decrease the concentration of the products, we expect the reaction to
proceed to the right side so as more of the products can be made.
Concept Check !
-If we decrease the concentration of the reactants, what do we expect to happen?

-If we increase the concentration of the products, what do we expect to happen?

Example:
Predict the direction of reaction when H2 is removed from a mixture (lowering its
concentration).
H2(g) + I2(g)
2HI(g)
When H2 is removed from the reaction mixture, lowering its concentration, the reaction
will proceed in the reverse direction (more HI dissociates to form H2 and I2) to partially
restore the H2 that has been removed.
Practice Example:
Consider the following equilibrium reaction:
CO(g) + 3H2(g)

CH4(g) + H2O(g)
17

Predict the direction of the reaction according to each change:

1increasing [CO]
goes to
2increasing [CH4]
goes to
3decreasing both reactants goes to
4decreasing both products goes to
Qualitatively, we can rephrase Le Chtelier's Principle to say:
If a gaseous reactant or product is added to a system at equilibrium, the system
will shift away from the added component.
If a gaseous reactant or product is removed, the system will shift toward the
removed component
Question: will a change in the concentration of a pure solid or liquid cause a shift
in equilibrium?

Changing the Pressure and Temperature

In general, the optimum conditions for any specific reaction will involve a set of
conditions involving variable factors such as temperature and pressure.
Changing either factors from their optimum values, will cause the reaction to behave
differently, and thus away from giving optimum results
Effect of Pressure change
-There are three ways to change the pressure of a reaction involving gaseous
components at a given temperature:
1) Add or remove a gaseous reactant or product at constant volume
2) Add an inert gas (one not involved in the reaction) at constant volume
Addition of an inert gas increases the total pressure but has no effect on the
concentrations or partial pressures of the reactants or products.
3) Change the volume of the container
When the volume of the container holding a gaseous system is reduced, the
system responds by reducing its own volume. This is done by decreasing the
total number of gaseous molecules in the system, so the reaction will shift in
the direction which has the least number of molecules.

18

-A pressure change obtained by changing the volume can affect the yield of product in a
gaseous reaction if the reaction originally involves a change in total moles of gas
CO(g) + 3H2(g)
CH4(g) + H2O(g)
-The above reaction is an example of a change in moles of gas. When the reaction
proceeds in the forward direction, a total of 4 moles of reactant gases (1CO + 3H2)
become a total of 2 moles of product gases (1CH4 + H2O).
If we decrease the volume of the reaction by half its original volume, we expect that
the pressure will increase, since we are compressing the gases! The two terms are
inversely proportional to each other. (PV = constant, at a fixed temperature)
Example:

If the volume is doubled the pressure is halfed

If the volume is tripled the presuure is divided by 3
If the pressure is increased 4 times the volume decreases by 4 times

So for the above example, if the pressure is doubled, we expect the volume to be
decreased by half, and that the concentration is increased. The mixture is no longer at
equilibrium!
The direction of the reaction then, can be predicted by using Le Chateliers Principle.
Let us restate the principle: Le Chateliers Principle states that when a system
in chemical equilibrium is disturbed by a change of temperature, pressure, or
concentration, the system shifts in a way that tends to counteract this change to
reach equilibrium once again.
In general, if the pressure is increased (compressing the mixture = decreasing the
volume), the reaction will favor the direction that contains the fewer moles of gas.
Example:

CO(g) + Cl2(g)

COCl2(g)

If the pressure is increased for the above reaction by changing the volume, in which
direction does the reaction shift in order to reach equilibrium once again?
Solution:

on the left side we have a total of 2 moles of gas (1mol CO + 1mol Cl2)
on the right side we have a total of 1 mol of gas (1mol COCl2)
Therefore, if we increase the pressure, the direction of the reaction will
favor the side that has the fewer moles.
In this case, it shifts to the _________
19

Effect of Temperature Change

-In general, temperature has a profound effect on most reactions. Reaction rates usually
increase when temperature is increased (equilibrium is reached sooner)
-Also, equilibrium constant for a particular reaction will vary with a change of
temperature
-We must also consider two new terms that describe the reaction in terms of its
temperature requirements. Endothermic and Exothermic reactions.
-An endothermic reaction is a reaction that requires heat in order to occur (+Ho)
-An exothermic reaction is a reaction that gives off heat when it occurs (-Ho)
Consider the following:
CO(g) + 3H2(g)

CH4(g) + H2O(g) + heat

Ho= -206.2 kJ

The value of Ho shows that this reaction is exothermic. As products are formed,
considerable heat is released.
In this case, if we increase the temperature, we expect that the reaction shifts to the left
to counteract this increase.
In general, energy must be treated as a reactant or product!
For an endothermic reaction (Ho positive), if the temperature is increased, the
forward reaction is favored to produce more products. If the temperature is
decreased, the reverse reaction is favored to produce more reactants.
For an exothermic reaction (Ho negative), if the temperature is decreased, the
forward reaction is favored to produce more products. If the temperature is
increased, the reverse reaction is favored to produce more reactants.

20

Example:

CO2 (g) + H2 (g) + heat

CO(g) + H2O(g)

a) Is a high or low temperature more favorable for the production of CO?

First we determine if the reaction is Endo- or Exothermic

b) Is a high or low temperature more favorable for the production of CO2?

Example:

Shifts in the Equilibrium Position for the Endothermic Reaction of:

N2O4 (g)
2NO2 (g)
Change

Shift (right, left or none)

Addition of N2O4 (g)

Addition of NO2 (g)
Removal of N2O4 (g)
Removal of NO2 (g)
Addition of He (g)
Decrease in container volume
Increase in container volume
Increase in temperature
Decrease in temperature

21

22