Chapter 18 - Chemical Equilibrium

Chapter 18 – Chemical
Equilibrium
Reversible Reactions
• Most chemical equations are reversible, at
least to some degree
– The products will reform the reactants
2HgO (s)  2Hg (l) + O2 (g)
But when heated:

2Hg (l) + O2 (g)  2HgO (s)
Chemical Equilibrium
• Equilibrium is reached when the rate of the
forward reaction is equal to the rate of the
reverse reaction.
• At equilibrium, the concentrations of the

products and reactants do not change
– Both the forward and reverse reactions are still
occurring
Graph of Reaction Rate
• Pg 591
aA + bB ↔ cC + dD
• Double arrow shows reversible reaction
• The numerical value of that ratio is the equilibrium

constant (K)
K is specific for a given reaction and temperature

It does not depend on initial concentrations
aA + bB ↔ cC + dD
The units on K depend on the reaction.

Concentrations are in molarity (M).
The unit on K is
M(c+d-a-b)
Homogeneous equilibrium (all same phase)
CO(g) + 3H2(g) ↔ CH4(g) + H2O(g)
2H2S (g) ↔ 2H2 (g) + S2 (g)
N2O4 (g) ↔ 2NO2 (g)
Heterogeneous equilibrium (different phases)
C2H5OH(l) ↔ C2H5OH(g)
NaHCO3(s) ↔ Na2CO3(s) + CO2(g) + H2O(g)
CaCO3(s) ↔ CaO(s) + CO2(g)

What is the expression for the equilibrium
constant?
2H2S (g) ↔ 2H2 (g) + S2 (g)

What is the expression for the equilibrium
constant?
CO (g) + 3H2 (g) ↔ CH4 (g) + H2O (g)

H2 (g) + I2 (g) ↔ 2HI (g)
Calculate the K for the following equilibrium when [H2] =
0.0659 mol/L, [I2] = 1.0659 mol/L,
[HI] = 1.8682 mol/L .
CO (g) + 3H2 (g) ↔ CH4 (g) + H2O (g)
Calculate the K for the following equilibrium when [CO] =
0.0613 M, [CH4] = 0.0387 M,
[H2] = 0.1839 M , and [H2O] = 0.0387 M.
N2 (g) + 3H2 (g) ↔ 2NH3 (g)
The equilibrium constant for the above reaction is known to
be 0.399 M-2. If 0.533 M N2 and 1.6 M H2 are at equilibrium,
what is the concentration of NH3?
Homework
• Pg 622
– #4-7
Le Chatelier’s Principle
If a stress is applied to a system at equilibrium,
the system shifts in the direction that relieves
the stress.
Pressure Changes
Pressure depends on the moles of gas
2 N2 (g) + 3 H2 (g) ↔ 2 NH3 (g)
What would happen if pressure is decreased?

To counteract the change, more moles of gas
need to be produced to try to increase
pressure. The reaction shifts left.
Which direction would equilibrium shift if
pressure is increased on the following
equation:
GeS (g) + 3H2 (g) ↔ GeH4 (g) + H2S (g)
Concentration Changes
2 N2 (g) + 3 H2 (g) ↔ 2 NH3 (g)
What would happen if the concentration of H2

is increased?
To counteract the change, more moles of H2
gas need to be used. This causes more NH3 to
be produced and shifts the reaction right.
Temperature Changes
2 N2 (g) + 3 H2 (g) ↔ 2 NH3 (g) + 92 kJ
What would happen if the temperature is

increased?
Increasing temperature is in essence, adding heat.
To counteract this, the system needs to use as
much of that heat as possible. Since the reaction
is exothermic (produces heat), the equilibrium
shifts left so that heat is not produced.
2SO2 (g) + O2 (g) ↔ 2SO3 (g)
Which direction does the equilibrium shift when the
following changes are applied?
– Increase the amount of oxygen
– Decrease the amount of oxygen
– Assume it’s exothermic. Increase the temp.
– Decrease the volume

Common Ion Effect
• The shift in equilibrium that occurs because of the
addition of an ion already involved in the
equilibrium reaction.
AgCl(s)  Ag+(aq) + Cl(aq)
• If NaCl (aq) is added, it dissolves and adds Cl- and

Na+ ions.
– Increasing the amount of Cl- shifts equilibrium to the
left.
Le Chatelier’s Principle wks
Ionization Constant of Water
• The self-ionization of water is an equilibrium reaction.
H2O ↔ H+ + OH-
• Equilibrium is established with a very low concentration

of H3O+ and OH− ions.
Kw=[H3O+][OH–] = 1.0  10-14

Ionization Constant of a Weak Acid
• The term Ka is called the acid ionization constant.
• The acid ionization constant, Ka , is dependent on

temperature
• For weak acids, Ka is small

• Most of the acid does not break apart, [H+] is small
HA + H2O ↔ H+ + A-
The equilibrium equation for the ionization of acetic acid
is
CH3COOH + H2O ↔ H+ + CH3COO-
• The equation for Ka is
𝑲 𝒂 =¿ ¿
• Water is a liquid and therefore pure. Do not include it
in the expression.
• Since Ka is small, the reactants are favored

• At constant temperature, an increase in the
concentration of CH3COO− ions through the addition of
sodium acetate, NaCH3COO, disturbs the equilibrium.

• This disturbance causes a shift left.
• Ka is the same, but decrease in [H+]. Causes an

increase in pH.
Buffers
Buffered solutions resist changes in pH.
• Buffered solutions contains both a weak acid and a
salt of the weak acid
• example: CH3COOH and NaCH3COO–
• Buffered solution can react with either an acid or a

base. When small amounts of acids or bases are
added, the pH of the solution remains nearly
constant.
• If a small amount of acid is added to the acetic acid–
sodium acetate solution, acetate ions react with most of
the added hydronium ions to form nonionized acetic
acid molecules.
• The hydronium ion concentration and the pH of

the solution remain practically unchanged.
• If a small amount of a base is added, the OH− ions of the
base react with and remove hydronium ions to form
nonionized water molecules. Acetic acid molecules then
ionize and mostly replace the hydronium ions
neutralized by the added OH− ions.
• The hydronium ion concentration and the pH of the

solution remain practically unchanged.
Hydrolysis of Salt
• When a salt dissolves in water, it produces
• positive ions (cations) of the base from which it was
formed
• negative ions (anions) of the acid from which it was
formed
• If the ions formed are from weak acids or bases,

they react chemically with the water molecules,
and the pH of the solution will have a value other
than 7.
Basic Salts
• If the anion (-) of a salt is the conjugate base of
a weak acid and the cation (+) is the conjugate
acid of a strong base
• Example, NaF
– The conjugate of F- is HF, which is a weak acid
– The conjugate of Na+ is NaOH, which is a strong base
• Dissolving NaF in water creates a basic solution

Acidic salts
• A salt with the cation (+) of a weak base and the
anion (-) of a strong acid will be acidic.
• Example, NH4Cl
– The conjugate of Cl- is HCl, which is a strong acid
– The conjugate of NH4+ is NH3, which is a weak base
• Dissolving NH4Cl in water creates an acidic

solution
• The equilibrium equation for a typical weak acid in water,
HA, is
HA + H2O ↔ H+ + A-
• The general equilibrium equation is
𝑲 𝒂 =¿ ¿
• Dissolving salts adds the anion, A−. This anion can react
with water to reform HA.
A- + H2O ↔ HA + OH-
• The weaker the acid, the more HA is formed.
• Also creates OH- which increases pH.
Neutralization Curve for a Weak Acid and a
Strong Base
Homework
• Pg 612
– #1-6 and 9
Solubility Review
• Defined as the amount of a substance that is
required to form a saturated solution at a
specific temperature and pressure
• Saturated Solution
A solution that contains the maximum of
dissolved solute it can hold for that T & P.
Solubility and Equilibrium
What about salts that are only slightly soluble?
• When silver ions and chloride ions are mixed,
only a small amount of silver chloride is
formed
• We think about solubility in terms of the

compound breaking apart
AgCl (s) ↔ Ag+ (aq) + Cl- (aq)
Using our equation:
We can develop an expression for K

Ksp = [Ag+][Cl-]
(remember AgCl is a solid and left out of the equation)
Since we are talking about solubility, we call

this version of the equation Ksp
A table of Ksp values can be found on pg 615

Ksp = [Ag+][Cl-]
Using solubility data:

If AgCl has a solubility of 1.9 x 10-4 g/100g H2O,
what is the Ksp?
If CaF2 has a solubility of 8.6 x 10-3 g/100g H2O,
what is the Ksp?
If BaCO3 has a Ksp = 5.1 x 10-9, what is the
solubility?
The Ksp of Mg(OH)2 is 1.8 x 10-11, what is the
solubility?
Precipitation
• When ions are dissolved in water, some will
combine and form a solid (precipitate)
• To determine if a solid will form, plug ion

concentrations into the equation for Ksp.
– If ion product is greater than Ksp, a precipitate
forms
Will a precipitate form if 20.0 mL of 0.010 M
BaCl2 is mixed with 20.0 mL of 0.0050 M N2SO4?
Homework
• Pg 623
– #28-31 and 35

Chapter 18 - Chemical Equilibrium

Uploaded by

Copyright:

Available Formats

Chapter 18 - Chemical Equilibrium

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Chapter 18 - Chemical Equilibrium

Uploaded by

Copyright:

Available Formats

Chapter 18 – Chemical

2HgO (s)  2Hg (l) + O2 (g)

But when heated:

• At equilibrium, the concentrations of the

• The numerical value of that ratio is the equilibrium

K is specific for a given reaction and temperature

The units on K depend on the reaction.

2H2S (g) ↔ 2H2 (g) + S2 (g)

N2O4 (g) ↔ 2NO2 (g)

Heterogeneous equilibrium (different phases)

NaHCO3(s) ↔ Na2CO3(s) + CO2(g) + H2O(g)

CaCO3(s) ↔ CaO(s) + CO2(g)

2H2S (g) ↔ 2H2 (g) + S2 (g)

CO (g) + 3H2 (g) ↔ CH4 (g) + H2O (g)

2 N2 (g) + 3 H2 (g) ↔ 2 NH3 (g)

What would happen if pressure is decreased?

What would happen if the concentration of H2

What would happen if the temperature is

– Decrease the amount of oxygen

– Assume it’s exothermic. Increase the temp.

– Decrease the volume

AgCl(s)  Ag+(aq) + Cl(aq)

• If NaCl (aq) is added, it dissolves and adds Cl- and

• Equilibrium is established with a very low concentration

Kw=[H3O+][OH–] = 1.0  10-14

• The acid ionization constant, Ka , is dependent on

• For weak acids, Ka is small

• Since Ka is small, the reactants are favored

CH3COOH + H2O ↔ H+ + CH3COO-

• Ka is the same, but decrease in [H+]. Causes an

• Buffered solution can react with either an acid or a

• The hydronium ion concentration and the pH of

CH3COOH + H2O ↔ H+ + CH3COO-

• The hydronium ion concentration and the pH of the

• If the ions formed are from weak acids or bases,

• Dissolving NaF in water creates a basic solution

• Dissolving NH4Cl in water creates an acidic

• We think about solubility in terms of the

We can develop an expression for K

(remember AgCl is a solid and left out of the equation)

Since we are talking about solubility, we call

A table of Ksp values can be found on pg 615

Using solubility data:

• To determine if a solid will form, plug ion

You might also like