1

3. Chemical Equilibrium

3.1. The Concept of Equilibrium

In the last chapter, we discussed the principles of chemical kinetics, which deal with
the rate of change, or how quickly a given chemical reaction occurs. We now turn our
attention to the extent to which a reaction occurs and how reaction conditions affect the
final concentrations of reactants and products. For most of the reactions that we have
discussed so far, you may have assumed that once reactants are converted to products,
they are likely to remain that way. In fact, however, virtually all chemical reactions
are reversible to some extent. That is, an opposing reaction occurs in which the products
react, to a greater or lesser degree, to re-form the reactants. Eventually, the forward and
reverse reaction rates become the same, and the system reaches chemical
equilibrium, the point at which the composition of the system no longer changes with
time.

Figure 3.1.1: Dinitrogen tetroxide is a powerful oxidizer that reacts spontaneously upon contact with
various forms of hydrazine, which makes the pair a popular propellant combination for rockets. Nitrogen
dioxide (NO2) at −196 °C, 0 °C, 23 °C, 35 °C, and 50 °C converts to the colourless dinitrogen tetroxide
(N2O4) at low temperatures, and reverts to NO2 at higher temperatures. (CC BY-SA 3.0; Eframgoldberg)

Chemical equilibrium is a dynamic process that consists of a forward reaction, in which

reactants are converted to products, and a reverse reaction, in which products are
converted to reactants. At equilibrium, the forward and reverse reactions proceed at
equal rates. Consider, for example, a simple system that contains only one reactant and
one product, the reversible dissociation of dinitrogen tetroxide (N2O4) to nitrogen dioxide
(NO2). You may recall that NO2 is responsible for the brown colour we associate with
smog. When a sealed tube containing solid N2O4 (mp = −9.3 °C; bp = 21.2 °C) is heated

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from −78.4 °C to 25 °C, the red-brown colour of NO2 appears (Figure 3.1.1). The reaction
can be followed visually because the product (NO2) is coloured, whereas the reactant
(N2O4) is colourless:
N2 O4 (𝑔) ⇌ 2NO2 (𝑔) (3.1.1)

The double arrow indicates that both the forward reaction

N2 O4 (𝑔) → 2NO2 (𝑔) (3.1.2)

and reverse reaction

2NO2 (𝑔) → N2 O4 (𝑔) (3.1.3)

occurring simultaneously (i.e, the reaction is reversible). Figure 3.1.2 shows how the
composition of this system would vary as a function of time at a constant temperature. If
the initial concentration of NO2 were zero, then it increases as the concentration of N2O4
decreases. Eventually the composition of the system stops changing with time, and
chemical equilibrium is achieved. Conversely, if we start with a sample that contains no
N2O4 but an initial NO2 concentration twice the initial concentration of N2O4 (Figure
3.1.2a), in accordance with the stoichiometry of the reaction, we reach exactly the same
equilibrium composition (Figure 3.1.2b). Thus, equilibrium can be approached from either
direction in a chemical reaction.

Figure 3.1.2 The Composition of N2O4/NO2 mixtures as a function of time at room temperature.

Figure3.1.3 shows the forward and reverse reaction rates for a sample that initially
contains pure NO2. Because the initial concentration of N2O4 is zero, the forward reaction
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rate (dissociation of N2O4) is initially zero as well. In contrast, the reverse reaction rate
(dimerization of NO2) is initially very high, but it decreases rapidly as the concentration
of NO2 decreases. As the concentration of N2O4 increases, the rate of dissociation of N2O4
increases—but more slowly than the dimerization of NO2. Eventually, the forward and
reverse reaction rates become identical and the system has reached chemical equilibrium.
If the forward and reverse reactions occur at different rates, then the system is not at
equilibrium.

Figure 3.1.3 The forward and reverse reaction rates as a function of time for the system N2 O4 (𝑔) ⇌
2NO2 (𝑔) shown in Part (b) in Figure 3.1.2.

The rate of dimerization of NO2 (reverse reaction) decreases rapidly with time. Because
the initial concentration of N2O4 is zero, the rate of the dissociation reaction (forward
reaction) at t=0 is also zero. As the dimerization reaction proceeds, the N2O4
concentration increases, and its rate of dissociation also increases. Eventually the rates
of the two reactions are equal: chemical equilibrium has been reached, and the
concentrations of N2O4 and NO2 no longer change.

3.2. Developing an Equilibrium Constant

In 1864, the Norwegian chemists Cato Guldberg (1836–1902) and Peter Waage (1833–
1900) carefully measured the compositions of many reaction systems at equilibrium. They
observed that at constant temperature in an equilibrium mixture of reactants and
products regardless of the initial concentrations, the reaction quotient has a constant
value. The reaction quotient (QC) is a fraction with product concentrations in the
numerator and reactant concentrations in the denominator – with each concentration
raised to a power equal to their corresponding stoichiometric coefficient in the balanced
chemical equation.
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That is, for the general reaction

𝑎A + 𝑏B ⇌ 𝑐C + 𝑑D (3.2.1)

the reaction quotient, 𝑄𝑐 is

[C]𝑐 [D]𝑑
𝑄𝑐 = = 𝐾𝑐 (at equilibrium) (3.2.2)
[A]𝑎 [B]𝑏

This expression is known as the law of mass action. Kc is the equilibrium constant for the
reaction. The subscript “c” stands for concentration, referring to the molar concentrations
in the expression.) Equation 3.2.1 is called the equilibrium equation, and the right side
of Equation 3.2.2 is called the equilibrium constant expression. The relationship shown
in Equation 3.2.2 is true for any reversible reaction regardless of the mechanism of the
reaction or the number of steps in the mechanism.

Table 3.2.1 lists the initial and equilibrium concentrations from five different experiments
using the reaction system described by Equation 2.1.1. At equilibrium, the magnitude of
the quantity [NO2]2/[N2O4] is essentially the same for all five experiments. In fact, no matter
what the initial concentrations of NO2 and N2O4 are, at equilibrium the quantity
[NO2]2/[N2O4] will always be constant (the average is 4.63 ×10−3) within the limits of
experimental error. That is, at a given temperature, the equilibrium constant for a reaction
always has the same value, even though the specific concentrations of the reactants and
products vary depending on their initial concentrations.

Table 3.2.1 Initial and equilibrium concentrations of N2O4 and NO2 at 25 °C.
Initial Concentrations (M) Equilibrium Concentrations (M)
Exp [𝐍𝟐 𝐎𝟒 ] [𝐍𝐎𝟐 ] [𝐍𝟐 𝐎𝟒 ] [𝐍𝐎𝟐 ] [𝐍𝐎𝟐 ]𝟐
[𝐍𝟐 𝐎𝟒 ]
1 0.670 0.0000 0.6430 0.0547 4.65  10−3
2 0.446 0.0500 0.4480 0.0457 4.66  10−3
3 0.500 0.0300 0.4910 0.0475 4.60  10−3
4 0.600 0.0400 0.5950 0.0523 4.60  10−3
5 0.000 0.2000 0.0898 0.0204 4.63  10−3

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Example 3.2.1: Expressions for Reaction Quotient

Write the reaction quotient for the following reactions:
a) N2 (g) + 3H2 (g) ⇌ 2NH3 (g)
b) H2 (g) + I2 (g) ⇌ 2HI(g)
c) Cd2+ (aq) + 4Br − (aq) ⇌ CdBr42− (aq)

Solution
a) For the reaction N2 (𝑔) + 3H2 (𝑔) ⇌ 2NH3 (𝑔)

[NH3 ]2
𝑄𝑐 =
[H2 ]3 [N2 ]

b) For the reaction H2 (g) + I2 (g) ⇌ 2HI(g)

[HI]2
𝑄𝑐 =
[H2 ][I2 ]

c) For the reaction Cd2+ (aq) + 4Br − (aq) ⇌ CdBr42− (aq)

[CdBr42− ]
𝑄𝑐 =
[Cd2+ ][Br − ]4

3.2.1. The Value of the Reaction Quotient, Q

The numeric value of Qc for a given reaction can vary prior to equilibrium. The value of
Qc depends on the concentration of products and reactants present at that particular
moment. To illustrate this point, consider the oxidation of sulphur dioxide:

2SO2 (𝑔) + O2 (𝑔) ⇌ 2SO3 (𝑔) (3.2.3)

Two different experimental scenarios are depicted in Figure 3.2.1, one in which this
reaction is initiated with a mixture of reactants only, SO2 and O2, and another that begins
with only product, SO3. For the reaction that begins with a mixture of reactants only, Q is
initially equal to zero:

[SO3 ]2 0
𝑄𝑐 = 2
= 2
(3.2.4)
[SO2 ] [O2 ] [SO2 ] [O2 ]

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Figure 3.2.1 Changes in concentrations and Qc for a chemical equilibrium achieved beginning with (a) a
mixture of reactants only and (b) products only. Access for free at https://openstax.org/books/chemistry-
2e/pages/1-introduction

As the reaction proceeds toward equilibrium in the forward direction, reactant

concentrations decrease (as does the denominator of Qc), product concentration
increases (as does the numerator of Qc), and the reaction quotient consequently
increases. When equilibrium is achieved, the concentrations of reactants and product
remain constant, as does the value of Qc.
If the reaction begins with only product present, the value of Qc is initially undefined
(immeasurably large, or infinite):

[SO3 ]2 [SO3 ]2
𝑄𝑐 = = →∞ (3.2.5)
[SO2 ]2 [O2 ] 0

In this case, the reaction proceeds toward equilibrium in the reverse direction. The
product concentration and the numerator of Qc decrease with time, the reactant
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concentrations and the denominator of Qc increase, and the reaction quotient

consequently decreases until it becomes constant at equilibrium.

Example 3.2.2: Reaction Quotient and Equilibrium Constant

Gaseous nitrogen dioxide forms dinitrogen tetroxide according to this equation:

2NO2 (g) ⇌ N2 O4 (g)

When 0.10 mol NO2 is added to a 1.0 L flask at 25 °C, the concentration changes so that
at equilibrium, [NO2] = 0.016 M and [N2O4] = 0.042 M.

a) What is the value of the reaction quotient before any reaction occurs?
b) What is the value of the equilibrium constant for the reaction?

Solution
a) Before any reaction occurs

[N2 O4 ] 0
𝑄𝑐 = = =0
[NO2 ] 2
0.01 2
( 1.0 )

b) At equilibrium [NO2] = 0.016 M and [N2O4] = 0.042 M

[N2 O4 ] 0.042
𝐾𝑐 = = = 164
[NO2 ]2 (0.016)2

3.2.2. Predicting the Direction of a Reaction

The equilibrium constant for a reaction can be used to predict the behaviour of mixtures
containing its reactants and/or products. As demonstrated by the sulphur dioxide
oxidation process described above, a chemical reaction will proceed in whatever direction
is necessary to achieve equilibrium. Comparing Q to K for an equilibrium system of
interest allows prediction of what reaction (forward or reverse), if any, will occur.

To further illustrate this important point, consider the reversible reaction shown below:
CO(g) + H2O(g) ⇌ CO2 (g) + H2 (g) Kc = 0.640 at T = 800 °C
The bar charts in Figure 3.2.2 represent changes in reactant and product concentrations
for three different reaction mixtures. The reaction quotients for mixtures 1 and 3 are
initially lesser than the reaction’s equilibrium constant, so each of these mixtures will
experience a net forward reaction to achieve equilibrium. The reaction quotient for
mixture 2 is initially greater than the equilibrium constant, so this mixture will proceed in
the reverse direction until equilibrium is established.
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Figure 3.2.2 Compositions of three mixtures before ( Qc ≠ Kc) and after (Qc = Kc) equilibrium is established
for the reaction CO(g) + H2O(g) ⇌ CO2 (g) + H2 (g). Access for free at https://openstax.org/books/chemistry-
2e/pages/1-introduction

In general:

Q<K The ratio of the initial concentrations of products to reactants

is too small. To reach equilibrium, reactants must be converted
to products. The system proceeds in the forward direction (left
to right).

Q>K The ratio of the initial concentrations of products to reactants

is too large. To reach equilibrium, products must be converted
to reactants. The system proceeds in the reverse direction
(right to left).

Example 3.2.3: Reaction Quotient and Equilibrium Constant

For the reaction: H2(g) + I2(g) ⇌ 2HI(g), Kc = 160 at 500K. A particular reaction mixture
had the composition 4.8 mmol/L H2, 2.4 mmol/L I2 and 2.4 mmol/L HI.
a) Calculate the reaction quotient.
b) Is the reaction mixture at equilibrium?
c) If not, is there a tendency to form more reactants or products?

Solution
a) The reaction quotient

[HI]2 (2.4)2
𝑄𝑐 = = = 0.5
[H2 ][I2 ] 4.8 × 2.4

b) Qc < Kc and so the reaction is not at equilibrium

c) Since Qc < Kc there will be a tendency to form more products.
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3.2.3. Magnitude of the Equilibrium Constant

By its definition, the magnitude of an equilibrium constant explicitly reflects the
composition of a reaction mixture at equilibrium, and it may be interpreted with regard
to the extent of the forward reaction. A reaction exhibiting a large K will reach equilibrium
when most of the reactant has been converted to product, whereas a small K indicates
the reaction achieves equilibrium after very little reactant has been converted. It’s
important to keep in mind that the magnitude of K does not indicate how rapidly or
slowly equilibrium will be reached. Some equilibria are established so quickly as to be
nearly instantaneous, and others so slowly that no perceptible change is observed over
the course of days, years, or longer.

When the magnitude of Kc is very large,

the reaction is said to favour products.

When the magnitude of Kc is very small,

the reaction is said to favour reactants.

3.3. Heterogenous Reactions

A homogenous equilibrium is one in which all of the reactants and products are present
in the same phase.
Some reaction mixtures contain reactants and products that are in two or more different
phases. These systems are called heterogeneous equilibria.
CaCO3 (s) ⇌ CaO(s) + CO2 (g) (3.3.1)
Pure solids and pure liquids do not appear in the K expression. Thus, the equilibrium
expression for the equilibrium above is
𝐾𝑐 = [CO2 ] (3.3.2)

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Example 3.2.4 Heterogenous equilibria

A 25.0 g sample of ammonium carbamate, NH4(NH2CO2)(s), was placed in an evacuated
250 mL flask and kept at 25 C. At equilibrium, 17.4 mg of CO2 was present. What is
the value of Kc for the decomposition of ammonium carbamate. The reaction is:

NH4(NH2CO2)(s) ⇌ 2NH3(g) + CO2(g)

Solution
This is a heterogenous equilibrium with an equilibrium constant given by

𝐾𝑐 = [CO2 ][NH3 ]

At equilibrium
g
17.4 mg × 1000 mg
moles CO2 44.00 g/mol
[CO2 ] = = = 1.58 × 10−3 M = [NH3 ]
V 0.250 L

Therefore

𝐾𝑐 = [CO2 ][NH3 ] = (1.58 × 10−3 )2 = 2.50 × 10−6

3.4. Manipulating equilibrium expressions

The table below summarises the various ways that chemical equations can be
manipulated and the corresponding ways that must be made to the equilibrium
expression and equilibrium constant.
Equation Equilibrium Relationship to Equilibrium
Expression original Kc constant
A(g) + B(g) ⇌ 2C(g) [C]2 4.39 × 10−3
𝐾𝑐1 =
[A][B]
2C(g) ⇌ D(g) + E(g) [D][E] 1.15 × 104
𝐾𝑐2 =
[C]2
2C(g) ⇌ A(g) + B(g) [A][B] 1 2.28 × 102
𝐾𝑐′ =
[C]2 𝐾𝑐1

2A(g) + 2B(g) ⇌ 4C(g) [C]4 (𝐾𝑐1 )

2
1.93 × 10−5
𝐾𝑐" =
[A]2 [B]2
1 1
A(g) + 2B(g) ⇌ C(g) [C] 6.63 × 10−2
2 𝐾𝑐′′′ = √𝐾𝑐1
[A] [B]1/2
1/2

A(g) + B(g) ⇌ D(g) + E(g) [D][E] 𝐾𝑐1 × 𝐾𝑐2 50.5

𝐾𝑐3 =
[A][B]

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3.5. Gaseous equilibria

For gas-phase solutions, the equilibrium constant may be expressed in terms of either
the molar concentrations (Kc) or partial pressures (Kp) of the reactants and products.

For the equilibrium

N2 O4 (g) ⇌ 2NO2 (g) (3.5.1)

[NO2 ]2
𝐾𝑐 = (3.5.2)
[N2 O4 ]

or as
2
(𝑃NO2 )
𝐾𝑃 = (3.5.3)
𝑃N2O4

The relationship between Kc and Kp:

𝐾𝑃 = 𝐾𝑐 (𝑅𝑇)∆𝑛 (3.5.4)

Δn is the change in the number of moles of gas = ∑ 𝑛𝑔 (𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠) − ∑ 𝑛𝑔 (𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠)

R = 0.08206 L ∙ atm/mol ∙ K
T is temperature in Kelvin.

Example 3.2.5 Gaseous equilibria

Calculate the Kc at 303 K for the reaction given below if the Kp is 34.5 at the same
temperature.

SO2(g) + Cl2(g) ⇌ SO2Cl2(g)

Solution
𝐾𝑃 = 𝐾𝑐 (𝑅𝑇)∆𝑛

∆𝑛 = ∑ 𝑛𝑔 (𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠) − ∑ 𝑛𝑔 (𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠) = 1 − 2 = −1
Then

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𝐾𝑐
𝐾𝑃 = 𝐾𝑐 (𝑅𝑇)−1 =
𝑅𝑇

𝐾𝑐 = 𝐾𝑃 (𝑅𝑇) = 34.5 × 0.080206 × 303 = 858

3.6. Equilibrium calculations

Having covered the essential concepts of chemical equilibria in the preceding sections of
this chapter, this section will demonstrate the more practical aspect of using these
concepts and appropriate mathematical strategies to perform various equilibrium
calculations. These types of computations are essential to many areas of science and
technology—for example, in the formulation and dosing of pharmaceutical products.
After a drug is ingested or injected, it is typically involved in several chemical equilibria
that affect its ultimate concentration in the body system of interest. Knowledge of the
quantitative aspects of these equilibria is required to compute a dosage amount that will
solicit the desired therapeutic effect.
Many of the useful equilibrium calculations that will be demonstrated here require terms
representing changes in reactant and product concentrations. These terms are derived
from the stoichiometry of the reaction, as illustrated by decomposition of ammonia:

2NH3 (𝑔) ⇌ N2 (𝑔) + 3H2 (𝑔) (3.6.1)

As shown earlier in this chapter, this equilibrium may be established within a sealed
container that initially contains either NH3 only, or a mixture of any two of the three
chemical species involved in the equilibrium. Regardless of its initial composition, a
reaction mixture will show the same relationships between changes in the concentrations
of the three species involved, as dictated by the reaction stoichiometry (see also the
related content on expressing reaction rates in the chapter on kinetics). For example, if
the nitrogen concentration increases by an amount x:
∆[N2 ] = +𝑥 (3.6.2)
the corresponding changes in the other species concentrations are
3 mol H2
∆[H2 ] = ∆[N2 ] ( ) = +3𝑥 (3.6.3)
1 mol N2

2 mol NH3
∆[NH3 ] = −∆[N2 ] ( ) = −2𝑥 (3.6.4)
1 mol N2

where the negative sign indicates a decrease in concentration.

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Example 3.2.6 Equilibrium concentrations

Iodine molecules react reversibly with iodide ions to produce triiodide ions.

I2 (𝑎𝑞) + I − (𝑎𝑞) ⇌ I3− (𝑎𝑞)

If a solution with the concentrations of I2 and I− both equal to 1.000×10−3 M before

reaction gives an equilibrium concentration of I2 of 6.61×10−4 M, what is the equilibrium
constant for the reaction?

Strategy
A. Write the equilibrium constant expression for the reaction. Construct a table showing
the initial concentrations, the changes in concentrations, and the final concentrations
(as initial concentrations plus changes in concentrations).
B. Calculate all possible initial concentrations from the data given and insert them in
the table.
C. Use the coefficients in the balanced chemical equation to obtain the changes in
concentration of all other substances in the reaction. Insert those concentration
changes in the table.
D. Obtain the final concentrations by summing the columns. Calculate the equilibrium
constant for the reaction.

Solution
For this reaction
[I3− ]
𝐾𝑐 =
[I2 ][I− ]

and

At equilibrium
[I2 ] = 6.61 × 10−4 M = [I− ]

So
1.000 × 10−3 − 𝑥 = 6.61 × 10−4

Therefore
𝑥 = 3.39 × 10−4

The ICE table may now be updated with numerical values for all its concentrations:

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Then

[I3− ] 3.39 × 10−4

𝐾𝑐 = = = 776
[I2 ][I− ] (6.61 × 10−4 )(6.61 × 10−4 )

Example
Kc for the reaction of hydrogen and iodine to produce hydrogen iodide,

H2 (𝑔) + I2 (𝑔) ⇌ 2HI(𝑔)

is 54.3 at 430 C. What will the concentrations be at equilibrium if we start with 0.240 M
concentrations of both H2 and I2?

Solution
The equilibrium constant is given by
[HI]2
𝐾𝑐 =
[I2 ][H2 ]

The ICE table is

Thus
[HI]2 (2𝑥)2
𝐾𝑐 = 54.3 = =
[I2 ][H2 ] (0.240 − 𝑥)2

(2𝑥)2
√54.3 = √
(0.240 − 𝑥)2

2𝑥
7.37 =
0.240 − 𝑥

7.37(0.240 − 𝑥) = 2𝑥

𝑥 = 0.188
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Therefore, at equilibrium

[I2 ] = [H2 ] = (0.240 − 0.188)M = 0.051 M

[HI] = 2𝑥 = 2(0.188)M = 0.378 M

3.7. Le Chatelier's Principle

As we saw in the previous section, reactions proceed in both directions (reactants go to
products and products go to reactants). We can tell a reaction is at equilibrium if the
reaction quotient (Q) is equal to the equilibrium constant (K). We next address what
happens when a system at equilibrium is disturbed so that Q is no longer equal to K. If
a system at equilibrium is subjected to a perturbance or stress (such as a change in
concentration) the position of equilibrium changes. Since this stress affects the
concentrations of the reactants and the products, the value of Q will no longer equal the
value of K. To re-establish equilibrium, the system will either shift toward the products
(if (Q ≤ K) or the reactants (if (Q ≥ K) until Q returns to the same value as K. This process
is described by Le Chatelier's principle.

When a chemical system at equilibrium is disturbed, it returns to equilibrium by

counteracting the disturbance. As described in the previous paragraph, the disturbance
causes a change in Q; the reaction will shift to re-establish Q = K.

3.7.1. Adding or Removing a Reactant or Product

Le Chatelier's principle can be used to predict changes in equilibrium concentrations
when a system that is at equilibrium is subjected to a stress. However, if we have a
mixture of reactants and products that have not yet reached equilibrium, the changes
necessary to reach equilibrium may not be so obvious. In such a case, we can compare
the values of Q and K for the system to predict the changes.
A chemical system at equilibrium can be temporarily shifted out of equilibrium by adding
or removing one or more of the reactants or products. The concentrations of both
reactants and products then undergo additional changes to return the system to
equilibrium.
The stress on the system in Figure 3.7.1 is the reduction of the equilibrium concentration
of SCN− (lowering the concentration of one of the reactants would cause Q to be larger
than K). As a consequence, Le Chatelier's principle leads us to predict that the
concentration of Fe(SCN)2+ should decrease, increasing the concentration of SCN− part
way back to its original concentration, and increasing the concentration of Fe3+ above its
initial equilibrium concentration.

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 16

Figure 3.7.1 (a) The test tube contains 0.1 M Fe3+. (b) Thiocyanate ion has been added to solution in (a),
forming the red Fe(SCN)2+ ion, Fe3+ (𝑎𝑞) + SCN − (𝑎𝑞) ⇌ Fe(SCN)2+ (𝑎𝑞). (c) Silver nitrate has been added
to the solution in (b), precipitating some of the SCN− as the white solid AgSCN, Ag + (𝑎𝑞) + SCN − (𝑎𝑞) ⇌
Ag(𝑠). The decrease in the SCN− concentration shifts the first equilibrium in the solution to the left,
decreasing the concentration (and lightening colour) of the Fe(SCN)2+. (credit: modification of work by Mark
Ott).

Thus
• If a chemical equilibrium is disturbed by adding a reactant or product, the system
will proceed in the direction that consumes part of the added species.
• If a chemical equilibrium is disturbed by removing a reactant or product, the
system will proceed in the direction that restores part of the removed species.
• The system responds in the way that restores equilibrium and therefore allows Q
= K again.
• Adding or removing a pure liquid or
solid has no effect on the system unless all of
the liquid or solid is removed.
• This is because pure liquids and solids
do not appear in the equilibrium expression.

Figure 3.7.2 Effect of the Amount of Solid Present on

Equilibrium in a Heterogeneous Solid–Gas System. In the
system, the equilibrium composition of the gas phase at
a given temperature, 1000 K in this case, is the same
whether a small amount of solid carbon (left) or a large
amount (right) is present.

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3.7.2. Effect of Change in Temperature on Equilibrium

Changing concentration or pressure perturbs an equilibrium because the reaction
quotient is shifted away from the equilibrium value. Changing the temperature of a system
at equilibrium has a different effect: A change in temperature actually changes the value
of the equilibrium constant. However, we can qualitatively predict the effect of the
temperature change by treating it as a stress on the system and applying Le Chatelier's
principle.

When hydrogen reacts with gaseous iodine, heat is evolved.

H2 (𝑔) + I2 (𝑔) ⇌ 2HI(𝑔) ∆𝐻 = −9.4 𝑘𝐽 (3.7.1)

Because this reaction is exothermic, we can write it with heat as a product.

H2 (𝑔) + I2 (𝑔) ⇌ 2HI(𝑔) + ℎ𝑒𝑎𝑡 (3.7.2)

Increasing the temperature of the reaction increases the internal energy of the system.
Thus, increasing the temperature has the effect of increasing the amount of one of the
products of this reaction. The reaction shifts to the left to relieve the stress, and there is
an increase in the concentration of H2 and I2 and a reduction in the concentration of HI.
Lowering the temperature of this system reduces the amount of energy present, favours
the production of heat, and favours the formation of hydrogen iodide.
When we change the temperature of a system at equilibrium, the equilibrium constant for
the reaction changes. Lowering the temperature in the HI system increases the
equilibrium constant: At the new equilibrium, the concentration of HI has increased and
the concentrations of H2 and I2 decreased. Raising the temperature decreases the value
of the equilibrium constant, from 67.5 at 357 °C to 50.0 at 400 °C.

Temperature affects the equilibrium between NO2NO2 and N2O4N2O4 in this reaction

N2 O4 (𝑔) ⇌ 2NO2 ∆𝐻 = 57.2 𝑘𝐽 (3.7.3)

The positive ΔH value tells us that the reaction is endothermic and could be written

ℎ𝑒𝑎𝑡 + N2 O4 (𝑔) ⇌ 2NO2 (3.7.4)

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At higher temperatures, the gas mixture has a deep brown colour, indicative of a
significant amount of brown NO2 molecules. If, however, we put a stress on the system
by cooling the mixture (withdrawing energy), the equilibrium shifts to the left to supply
some of the energy lost by cooling. The concentration of colourless N2O4 increases, and
the concentration of brown NO2 decreases, causing the brown colour to fade.

3.7.3. Catalysts Do Not Affect Equilibrium

As we learned during our study of kinetics, a catalyst can speed up the rate of a reaction.
Though this increase in reaction rate may cause a system to reach equilibrium more
quickly (by speeding up the forward and reverse reactions), a catalyst has no effect on
the value of an equilibrium constant nor on equilibrium concentrations.

Some content reproduced from:

1. OpenStax Chemistry 2e: Access for free at https://openstax.org/books/chemistry-2e/pages/1-introduction
2. A general chemistry Libretexts Textmap organized around the textbook Chemistry: The Central Science by Brown, LeMay, Busten,
Murphy, and Woodward