Lecture

Chemical Equilibrium

176
 Chemical Equilibrium

N2O4(g) 2NO2 (g)

177
 Equilibrium Basic Concepts
v Equilibrium - a state of balance between opposing forces or actions

In chemistry, Equilibrium relates to Reversible reactions - do not go to completion. They can occur in either
direction

A + B C + D
v Chemical equilibrium exists when the rate of forward reaction rate is equal to the rate of reverse reaction in a
reversible reaction

v Chemical equilibria are dynamic equilibria (continuously changing)

§ Molecules are continually reacting, even though the overall composition of the reaction mixture does not change.

§ Double arrow (⇋) indicates that both the forward and reverse reactions are occurring simultaneously and is read “is in
equilibrium with”

§ At equilibrium, reactants & products do not change over time (macroscopic) but a lot of action on the
molecular level; dynamic balance

§ Composition of an equilibrium mixture is independent of the direction from which equilibrium is approached
 Equilibrium Constant

v The relationship between the amounts of products and reactants present at equilibrium in a reversible
chemical reaction at a given temperature is given by the equilibrium constant

v For a general reaction: aA + bB cC + dD

The Law of mass action

[C ] c [ D ] d
Equilibrium constant,
K =
[ A] a [ B ] b
Where:

§ Superscript letters are the stoichiometry coefficients

§ [A] concentration chemical species A relative to standard state

Equilibrium constant (K): A reaction is favored when K > 1

K has no units, dimensionless

v Concentration of solutes are expressed as moles per liter (M).

v Concentrations of gases are expressed as pressure in bars. 1 bar = 105 Pa; 1 atm = 1.01325
bar

v Concentrations of pure solids, pure liquids and solvents are omitted = unity, standard state is the
pure liquid or solid

Manipulating Equilibrium Constants

Consider the following reaction:
[ H + ][ A - ]
K1 =
[ HA]
Reversing the reaction results in a reciprocal equilibrium reaction:

[ HA]
K '1 = = 1 / K1
+ -
[ H ][ A ]
 The magnitude of Equilibrium Constant

v The magnitude of the equilibrium constant, K, indicates the extent to which a reaction will proceed

v We can use K values to predict the position of he equilibrium

o K >>1 - indicate a strong tendency for reactants to form products, so equilibrium lies to the right,
favoring the formation of products (kforward >>kreverse)

o K << 1 - indicate that the ratio of products to reactants at equilibrium is very small; reactants do not
tend to form products readily, and equilibrium lies to the left, favoring the formation of reactants
(kforward<<kreverse)

o Kforward = kreverse - there is no strong tendency to form either products or reactants, at equilibrium,
there are significant amounts of both products and reactants in the system.
 The Equilibrium Constant

v Equilibrium can be approached from either direction in a chemical reaction, so the equilibrium constant
expression and the magnitude of the equilibrium constant depend on the form in which the chemical
reaction is written.

v When a reaction is written in the reverse direction,

cC + dD ⇋ aA + bB

K and the equilibrium constant expression are inverted:

K´= [A]a [B]b
[C]c [D]d
so K´ = 1/K
 Equilibrium Constant in terms of Concentration KC

For a reversible reaction at equilibrium, forward rxn For the reverse reaction,
aP + bQ Û cR + dS cR + dS Û aP + bQ
reactants products reactants products

Kc = [products]m Kc’ = [P]a [Q]b

[R]c [S]d
[reactants]n
= [R]c [S]d = 1/Kc
[P]a [Q]b

v Kc is constant as long as temperature is constant

v Magnitude of Kc indicates extent of a chemical reaction or the position of the equilibrium

Eg large Kc [products] > [reactants] - almost complete reaction

v Kc gives no information about rate of reaction

 Examples
For the reaction
v CH3COOH (aq) + C2H5OH (aq) Û CH3COOC2H5 (aq) + H2O (l)

Kc = [CH3COOC2H5][H2O]
[CH3COOH][C2H5OH

Notes
v N2O4(g) Û 2NO2(g)
v Concentration of a pure solid is constant , not included
in Kc expressions.
Kc = [NO2]2
[N2O4]
vConcentration expressed as amount per unit volume.

v CaCO3(s) Û CaO(s) + CO2(g) vFor solid – mass per unit volume→ density.

Kc = [CaO(s)] [CO2]
[CaCO3 (s)]
vDensity is constant , concentration of solid is constant.
Kc = [CO2]
 Kc Exercise
v Write the expression for the equilibrium constant for the following reactions:
 Equilibrium Constant in terms of Partial Pressures Kp
v When the reactants and products are gases, we can determine the equilibrium constant in terms of partial
pressures.

v Dalton’s Law of Partial Pressures – the total pressure in a system is equal to the sum of the individual
pressures.

v Total = Pressure of + Pressure of ….

Pressure Gas #1 Gas #2

Pressure is measured in atmospheres.

If the values at equilibrium are given in atmospheres, then solving for the constant is the same, but use Kp
instead of Kc.

What makes them different:

Kc = equilibrium constant based on molarity and concentration.
Kp = equilibrium constant based on partial pressures.

Note/ These two values are usually different even for the same reaction!
 Examples

2NO2 (g) 2NO (g) + O2 (g)

v At equilibrium, the pressure of nitrogen dioxide is 0.425 atm, nitrogen monoxide is 0.270 atm,
and oxygen is 0.100 atm. Determine the Kp for the above reaction.

v Use the law of mass action to solve for Kp and similar steps because problem gives the
pressures at equilibrium

Kp = [NO]2 [O2]
[NO2]2

Kp = [0.270]2 [0.100]
[0.425]2
Kp = 0.0404
 Relation between Kc and Kp

vFor gas phase reactions the equilibrium constants can be expressed in partial pressures rather than
concentrations.

Remember
from ideal gas
Law

Rearranging

Rearranging
And again:

mol/L
 Relationship between Kc and Kp
Carbon monoxide gas and chlorine gas react to from form phosgene (COCl2),
CO(g) + Cl2(g) COCl2(g)

Equilibrium the concentrations at 740 C for the reaction above are [CO] = 0.012 M, [Cl2] = 0.054 M, and [COCl2] =
0.14 M. Calculate the equilibrium constants Kc and Kp.

Kp = Kc (RT)Dn Start with the equilibrium expression for Kc:

Kc = [COCl2]
[CO][Cl2]
Kp = Equilibrium constant in partial pressure Kc = [0.14 ] = 216
Kc = Equilibrium constant in molar concentrations [0.012][0.054]
R = Ideal Gas constant (always 0.082)
T = Temperature (in Kelvin)
To solve for Kp we use the Ideal gas law eq.
Dn = Change in moles of GASES ONLY
Kp = Kc (RT)Dn
(moles of gas products) – (moles of gas reactants)
Kp = 216 x (.082 x 347)(1-2)
Kp = 7.6
 Relationship Between Kp and Kc

v Kc is 49 for the following reaction at 450oC. If 1.0 mole of H2 and 1.0 mole of I2 are allowed to
reach equilibrium in a 3.0-liter vessel, What is the equilibrium constant Kp?

® 2 HI
H 2 (g ) + I 2 (g ) ¬ (g )
 Homogeneous and Heterogeneous Equilibria

v Homogeneous equilibrium
o When the products and reactants of an equilibrium reaction form a single phase, whether gas or liquid.

o Concentrations of the reactants and products can vary over a wide range, Examples:

® 2 HI
H 2 (g ) + I 2 (g ) ¬ (g )

v Heterogeneous equilibrium
o A system whose reactants, products, or both are in more than one phase

o An example is the reaction of a gas with a solid or liquid

v Molar concentrations of pure liquids and solids do not vary with temperature, so they are treated as
constants, this simplifies their equilibrium constant expressions
 Heterogeneous Equilibria
v Heterogeneous equilibria have more than one phase present.
For example, a gas and a solid or a liquid and a gas.

v How does the equilibrium constant differ for heterogeneous equilibria?

o Pure solids and liquids have activities of unity.

o Solvents in very dilute solutions have activities that are essentially unity.
o The Kc and Kp for the reaction shown above are:
 The Reaction Quotient

v The mass action expression or reaction quotient has the symbol Q.

Q has the same form as Kc

v The major difference between Q and Kc is that the concentrations used in Q are not necessarily
equilibrium values.

v Why do we need another “equilibrium constant” that does not use equilibrium concentrations?

v Q will help us predict how the equilibrium will respond to an applied stress.

v Q may be derived from a set of values measured at any time during the reaction of any mixture of the
reactants and products, regardless of whether the system is at equilibrium.

v To make this prediction we compare Q with Kc.

 The Reaction Quotient (Q)

• Comparing the magnitudes of Q and K allows the

determination of whether a reaction mixture is already at
equilibrium and, if it is not, how to predict whether its
composition will change with time (whether the reaction will
proceed to the right or to the left)

1. If Q = K, the system is at equilibrium, no further change in

the composition of the system will occur unless the
conditions are changed

2. If Q < K, then the ratio of the concentrations of products to

the concentration of reactants is less than the ratio at
equilibrium; reaction will proceed to the right, forming
products at the expense of reactants

3. If Q > K, then the ratio of the concentrations of products to

the concentrations of reactants is greater than at
equilibrium; reaction will proceed to the left, forming
reactants at the expense of products
 Reaction Quotient (Q)

v Defined the same as K, (products ÷ reactants, raised to stoichiometric coefficients)

o K is at equilibrium

o Q can be determined at any point in the reaction.

v Compare Q and K to see if the reaction will go “forward” “reverse” or if it is already at

equilibrium

o Q<K Reaction moves forward, aka from left to right

o Q>K Reaction moves in reverse, aka right to left

o Q=K the reaction is already at equilibrium and stays the same

Q compared to K

v Q<K
o Products are smaller/reactants are bigger than K, so
must shift to adjust.
o Reaction moves forward, to create more products, and
less reactants
v Q>K
o Reactants are smaller/products are bigger than K, so
must shift to adjust
o Reaction moves to left to create more reactants and
less products.

v Q=K the reaction is already at equilibrium and stays

the same
 Example: Using Q to predict reaction direction

For the synthesis of ammonia the Kc at 375oC is 1.2. The initial concentrations are H2=0.76 M N2=0.60 M
and NH3 = 0.48 M. Which way will the reaction shift? What will happen to the concentration of each gas?

Find Q and compare it to K

Shifts forward,
or to the right.
 Examples: Using Q to predict reaction direction

The Kp for the reaction below is 5.60x104 at 350 oC the initial pressures are SO2= 0.350 and O2=0.762. Is the
total pressure at the end, less, greater or the same as intial?

No product. So the reaction MUST shift forward.

Reactants = 3 moles. Products = 2 moles.

Total moles are lower on side of reaction it is shifting toward, So the ideal gas law says that pressure goes
down.
Review

1. The reaction quotient (Q) is products over reactants, raised to their stoichiometric coefficents.

2. It differs from K, because K is the value at equilibrium while Q is the value at any given point.

3. We can determine which way the reaction will shift by comparing Q and K
If Q is less than K the reaction shifts right

If Q is greater than K the reaction shifts left

 Le Châtelier’s Principle

When a system at equilibrium is perturbed in some way, the effects of the perturbation can be predicte
qualitatively using Le Châtelier’s principle.

• This principle states that “if a stress is applied to a system at equilibrium, the composition of the system will
change to relieve the applied stress.”.

Stress occurs when any change in the system affects the magnitude of Q or K.

• Three types of stresses can change the composition of an equilibrium mixture:

1. A change in the concentrations (or partial pressures) of the components by the addition or removal
of reactants or products
2. A change in the total pressure or volume
3. A change in the temperature of the system
200
 Disturbing a System at Equilibrium: Predictions

1 Changes in Concentration of Reactants and/or Products

• Also true for changes in pressure for reactions involving gases.

An equilibrium is disturbed by adding or removing a reactant or product

v Stress of an added reactant or product is relieved by reaction in the direction that consumes the added
substance
a. Add reactant—reaction shifts right toward product
b. Add product—reaction shifts left toward reactant

v Stress of removing reactant or product is relieved by reaction in the direction that replenishes the removed
substance
a. Remove reactant—reaction shifts left
b. Remove product—reaction shifts right
 Disturbing a System at Equilibrium: Predictions

2 Changes in Volume (and pressure for reactions involving gases)

• Increase in pressure (due to decrease in volume) results in a reaction in the direction of a fewer number of
moles of gas

• Decrease in pressure (due to increase in volume) results in a reaction in the direction of a greater number of
moles of gas

1. Decrease volume on reactant side ( increase Pressure) — More NH3 gas is formed ( equilibrium shifts forward)

2. Increase in volume on reactant side (decrease Pressure) – NH3 dissociates to from N2 and H2 gases ( equilibrium
shifts backwards
 Disturbing a System at Equlibrium: Predictions
3 Changing the Reaction Temperature

v Predictions on the response of a system to a change in Temperature

1. Exothermic (DH < 0): reactants ⇋ products + heat
2. Endothermic (DH > 0): reactants + heat ⇋ products

v Le Châtelier’s principle predicts

o Exothermic reaction will shift backward (toward reactants) if the temperature of the system is
increased

o Endothermic reaction will shift forward (toward the products) if the temperature of the system is
increased

o If DHrxn = 0, then a change in temperature has no affect on composition.

v Increasing the temperature increases the magnitude of the equilibrium constant for an endothermic reaction

v Increasing the temperature decreases the equilibrium constant for an exothermic reaction
 Disturbing a System at Equilibrium: Predictions
v Introduction of a Catalyst
o Catalysts decrease the activation energy of both the forward and reverse reaction equally.

v Catalysts do not affect the position of equilibrium.

o The concentrations of the products and reactants will be the same whether a catalyst is introduced or not.

o Equilibrium will be established faster with a catalyst.

 Disturbing a System at Equilibrium: Predictions

Home work
a) A 2.00 liter vessel in which the following system is in equilibrium contains 1.20 moles of COCl2, 0.60 moles of
CO and 0.20 mole of Cl2. Calculate the equilibrium constant.

b) An additional 0.80 mole of Cl2 is added to the vessel at the same temperature. Calculate the molar
concentrations of CO, Cl2, and COCl2 when the new equilibrium is established.
 Controlling the Products of Reactions

One of the primary goals of modern chemistry is to control the identity and quantity of the products of chemical
reactions.

Two approaches

v Kinetic control - altering reaction conditions to control reaction rates, thereby obtaining a single product or
set of product

v Thermodynamic control—adjusting conditions so that at equilibrium only the desired products are present in
significant quantities.
 An Application of Equilibrium: The Haber Process
The Haber process is used for the commercial production of ammonia.

o This is an enormous industrial process in the US and many other countries.

o Ammonia is the starting material for fertilizer production.

Fritz Haber
1868-1934
Nobel Prize, 1918

Carl Bosch
1874-1940
Nobel Prize, 1931
 An Application of Equilibrium: The Contact process

The Contact Process of sulphur trioxide production must be economically efficient for the manufacture of the important
industrial chemical sulphuric acid.

In the reactor the sulphur dioxide is

oxidised in the reversible exothermic reaction

2SO2(g) + O2(g) 2SO3(g) (ΔH = –196 kJ mol

pSO32
Kp = –––––––––––
pSO22 pO2
Lecture
Acid Base Equilibria

209
 Acid-base equilibria

Arrhenius (or Classical) Acid-Base Definition

v An acid is a substance that contains hydrogen and dissociates in water to yield a hydronium ion : H3O+

v A base is a substance that contains the hydroxyl group and dissociates in water to yield : OH –

v Neutralization is the reaction of an H+ (H3O+) ion from the acid and the OH - ion from the base to form water,
H2O.
H+(aq) + OH-(aq) H2O(l) H0rxn = -55.9 kJ

Brønsted-Lowry Acid-Base

v An acid is a proton donor, species that donates an H+ ion eg. HNO3 and H3PO4. all Arrhenius acids are
Brønsted-Lowry acids

v A base is a proton acceptor, species that accepts an H+ ion. must contain a lone pair of electrons to bind
the H+ ion; NH3, CO32-, F -, as well as OH –
Brønsted-Lowry bases are not Arrhenius bases, but all Arrhenius bases contain the Brønsted-Lowry base
OH-
an acid-base reaction is a proton transfer process.
Lewis acid-base definition :

v A base is any species that donates an electron pair.

v An acid is any species that accepts an electron pair

v Protons act as Lewis acids in that they accept an electron pair in all reactions:
B + H+ B H+

v The product of any Lewis acid-base reaction is called an adduct, a single species that contains a new
covalent bond:

A Lewis base is a lone pair of electrons to donator.

A Lewis acid is a vacant orbital

 Acid Strength: The Acid-Dissociation Constant (Ka)
v Strong acids dissociate completely into ions in water:

HA(g or l) + H2O(l) H3O+(aq) + A-(aq)

v In a dilute solution of a strong acid, almost no HA molecules exist: [H3O+] = [HA]init or [HA]eq = 0

[H3O+][A-] at equilibrium, Qc = Kc >> 1

Qc =
[HA][H2O]
Nitric acid is an example: HNO3 (l) + H2O(l) H3O+(aq) + NO3-(aq)

v Weak acids dissociate very slightly into ions in water:

HA(aq) + H2O(aq) H3O+(aq) + A-(aq)

In a dilute solution of a weak acid, the great majority of HA molecules are undissociated: [H3O+] << [HA]init or
[HA]eq = [HA]init
[H3O+][A-]
Qc = at equilibrium, Qc = Kc << 1
[HA][H2O]
 The Meaning of Ka, the Acid Dissociation Constant

For the ionization of an acid, HA:

HA(aq) + H2O(l) H3O+(aq) + A-(aq)

[H3O+] [A-] [H3O+] [A-]

Ka = Therefore: Ka =
[HA] [H2O] [HA]

v The stronger the acid, the higher the [H3O+] at equilibrium, and the larger the Ka:

Stronger acid higher [H3O+] larger Ka

v For many practical purposes it is more convenient to discuss the logarithmic constant, pKa

v Relationship between Ka, pKa and acid strength: The smaller the value of Ka, the larger the
value of pKa, the weaker the acid.
The Extent of Dissociation for Strong and Weak Acids
The Relationship Between Ka and pKa

Acid Name (Formula) Ka at 25oC pKa

Hydrogen sulfate ion (HSO4-) 1.02 x 10-2 1.991

Nitrous acid (HNO2) 7.1 x 10-4 3.15

Acetic acid (CH3COOH) 1.8 x 10-5 4.74

Hypobromous acid (HBrO) 2.3 x 10-9 8.64

Phenol (C6H5OH) 1.0 x 10-10 10.00

The Conjugate Pairs in Some Acid-Base Reactions
Conjugate Pair
Acid + Base Base + Acid
Conjugate Pair

Reaction 1 HF + H2O F– + H3O+

Reaction 2 HCOOH + CN– HCOO– + HCN

Reaction 3 NH4+ + CO32– NH3 + HCO3–

Reaction 4 H2PO4– + OH– HPO42– + H2O

Reaction 5 H2SO4 + N2H5+ HSO4– + N2H62+

Reaction 6 HPO42– + SO32– PO43– + HSO3–

 Autoionization of Water

H2O(l) + H2O(l) H3O+ + OH-

[H3O+][OH-]
Kc =
[H2O]2

v The ion-product for water, Kw:

Kc[H2O]2 = Kw = [H3O+][OH-] = 1.0 x 10-14 (at 25°C)

v For pure water the concentration of hydroxyl and hydronium ions must be equal:

[H3O+] = [OH-] = (1.0 x 10-14 )1/2 = 1.0 x 10 -7 M (at 25°C)

 Acid and Base Character and the pH Scale
In acidic solutions, the protons that are released into solution will not remain alone due to their large
positive charge density and small size.

They are attracted to the negatively charged electrons on the oxygen atoms in water, and form hydronium
ions.
H+(aq) + H2O(l) = H3O+(l) [H+] = [H3O+]

To handle the very large variations in the concentrations of the hydrogen ion in aqueous solutions, a scale
called the pH scale is used which is:
pH = - log[H3O+] = pH = - log[H+]

Examples: 1) What is the pH of a solution that is 10-12 M in hydronium ion ?

pH of a neutral solution = 7.00

pH = -log[H3O+] = (-1)log 10-12 = (-1)(-12) = 12 pH of an acidic solution < 7.00

pH of a basic solution > 7.00

2) What is the pH of a solution that is 7.3 x 10-9 M in H3O+ ?

pH = -log(7.3 x 10-9) = -1(log 7.3 + log 10-9) = -1[(0.863)+(-9)] = 8.14

(a) Measuring the pH of vinegar. (b) Measuring the pH
of aqueous ammonia.
 Methods for Measuring the pH of an
Aqueous Solution

(a) pH paper (b) Electrodes of a pH meter

The pH scale and pH values of some common
substances