Chemical Equilibrium

Equilibrium
• Equilibrium is a state in which there are
no observable changes as time goes by.
• Chemical equilibrium is achieved when:
1) the rates of the forward and reverse
reactions are equal and
2) the concentrations of the reactants and
products remain constant
 Equilibrium
There are two types of equilibrium: Physical
and Chemical.
Physical Equilibrium (no change in molecules)
• H20 (l) ↔ H20 (g)
Chemical Equilibrium (there is change in
molecules)
• N2O4 (g) ↔ 2NO2
 Law of Mass Action

• Law of Mass Action- For any reversible reaction at

equilibrium and constant temperature, a certain ratio of
reactant and product concentrations has a constant
value (K).

• The Equilibrium Constant (K)- A number equal to the

ratio of the equilibrium concentrations of products to
the equilibrium concentrations of reactants each raised
to the power of its stoichiometric coefficient.
 Law of Mass Action
• For the general reaction:

aA (g) + bB (g) cC (g) + dD (g)

K=[C]c[D]d
[A]a[B]b
 Chemical Equilibrium
• Chemical equilibrium is defined by K.
• The magnitude of K will tell us if the equilibrium
reaction favors the reactants or the products.
• If K ≫ 1……..favors products
• If K ≪ 1……..favors reactants
 Equilibrium Constant Expressions
• Equilibrium constants can be expressed using Kc or Kp.
• Kc uses the concentration of reactants and products to
calculate the eq. constant.

• Kp uses the pressure of the gaseous reactants and

products to calculate the eq. constant.
 Equilibrium Constant Expressions
• Equilibrium Constant
aA (g) + bB (g) cC (g) + dD (g) Equations

Kc=[NO2]2 KP=PNO 2

PN2O24
[N2O4]
Homogeneous Equilibrium
• Homogeneous Equilibrium- applies to reactions in
which all reacting species are in the same phase.
N2O4 (g) ↔ 2NO2 (g)
Kc = [NO2] Kp = P2N O2 4

[N2O4] PN2O4
In most cases
Kc ¹ Kp
 Equilibrium Constant Expressions
• Relationship between Kc and Kp
Kp = Kc(RT)Dn
• Dn = moles of gaseous products – moles of gaseous
reactants
= (c + d) – (a + b)
Heterogeneous Equilibrium
• Heterogeneous Equilibrium- results from a reversible
reaction involving reactants and products that are in
different phases.
• Can include liquids, gases and solids as
either reactants or products.
• Equilibrium expression is the same as that for a
homogeneous equilibrium.
• Omit pure liquids and solids from the equilibrium
constant expressions.
Heterogeneous Equilibrium Constant
• CaCO3 (s) CaO (s) + CO2 (g)
[CaCO3] = constant
[CaO] = constant
Kp = PCO2

The concentration of solids and pure liquids are not

included in the expression for the equilibrium constant.
Heterogeneous Equilibrium Constant
Writing Equilibrium Constant
Expressions
• The concentrations of the reacting species in the condensed
phase are expressed in M. In the gaseous phase, the
concentrations can be expressed in M or in atm.
• The concentrations of pure solids, pure liquids and solvents do
not appear in the equilibrium constant expressions.
• The equilibrium constant is a dimensionless quantity.
• In quoting a value for the equilibrium constant, you must specify
the balanced equation and the temperature.
• If a reaction can be expressed as a sum of two or more reactions,
the equilibrium constant for the overall reaction is given by the
product of the equilibrium constants of the individual reactions.
What does the Equilibrium Constant
tell
us?
• We can:
– Predict the direction in which a reaction
mixture will proceed to reach equilibrium
– Calculate the concentration of reactants
and products once equilibrium has been
reached
Predicting the Direction of a
Reaction
• The Kc for hydrogen iodide in the following equation is
53.4 at 430oC. Suppose we add 0.243 mol H2, 0.146 mol
I2 and 1.98 mol HI to a 1.00L container at 430oC. Will
there be a net reaction to form more H2 and I2 or HI?
H2 (g) + I2 (g) → 2HI (g)

Kc = K= Kc = 111
 Reaction Quotient
• The reaction quotient (Qc) is calculated by substituting the
initial concentrations of the reactants and products into
the equilibrium constant (Kc) expression.
IF
• Qc > Kc system proceeds from right to left to reach
equilibrium
• Qc = Kc the system is at equilibrium
• Qc < Kc system proceeds from left to right to reach
equilibrium
 Factors that Affect Chemical
Equilibrium
• Chemical Equilibrium represents a balance
between forward and reverse reactions.
• Changes in the following will alter the
direction of a reaction:
– Concentration
– Pressure
– Volume
– Temperature
 Le Chatlier’s Principle
• Le Châtlier’s Principle- if an external
stress is applied to a system at
equilibrium, the system adjusts in such
a way that the stress is partially offset
as the system reaches a new
equilibrium position.
• Stress???
 Changes in Concentration
Change Shift in Equilibrium
• Increase in [Products] left
• Decrease in [Products] right
• Increase in [Reactants] right
• Decrease in [Reactants] left
 Changes in Volume and Pressure
• Changes in pressure primarily only concern gases.
• Concentration of gases are greatly affected by pressure
changes and volume changes according to the ideal gas
law.
PV = nRT
P = (n/V)RT
 Changes in Pressure and Volume
Change Shift in Equilibrium
• Increase in Pressure Side with fewest
moles
• Decrease in Pressure Side with most
moles
• Increase in Volume Side with most moles
• Decrease in Volume Side with fewest moles
 Changes in Temperature
• Equilibrium position vs. Equilibrium constant
• A temperature increase favors an endothermic reaction
and a temperature decrease favors and exothermic
reaction.
• Change Endo. Rx Exo. Rx
• Increase T K decreases K increases
• Decrease T K increases K decreases
 Changes in Temperature
• Consider: N2O4(g) ↔ 2NO2(g)
• The forward reaction absorbs heat; endothermic
heat + N2O4(g) ↔ 2NO2(g)
• So the reverse reaction releases heat; exothermic
2NO2(g) ↔ N2O4(g) + heat
• Changes in temperature??
 Effect of a catalyst

• How would the presence of a

catalyst affect the equilibrium
position of a reaction?
Effect of a catalyst
• In the presence of a catalyst, both the forward and
reverse reaction rates will speed up equally, thereby
allowing the system to reach equilibrium faster.

• However, it is very important to keep in mind that the

addition of a catalyst has no effect whatsoever on the
final equilibrium position of the reaction.
ELECTROCHEMISTRY
 Introduction

• What is electrochemistry?

• Definitions: Electrochemistry is the study of the relationship

between chemical reactions and electricity

• Electricity is the movement of electrons through an object

eg wire, these electrons move between atoms

• Hence chemical reactions like oxidation and reduction

involves movement of electrons

• Therefore, certain chemical reactions can create electricity

on the other hand; electricity can make certain chemical
reactions that would not ordinarily happen to occur
 ELECTROCHEMISTR
• Y
All electrochemical reactions involve oxidation and reduction.

• Oxidation means the loss of electrons (it does not always involve
oxygen) while Reduction means the gain of electrons (gaining
of negatives, that is electrons, reduces the oxidation number of an
atom.

• Whenever electrons are lost by one substance they must be gained

by
another.

• The substance that loses electrons is referred to as a reducing

agent
(it lets another substance be reduced, that is, gain the electrons)
and the substance that gains electrons is referred to as an 2
9
oxidizing agent
 OXIDATION &
• OXIDATION
REDUCTION
:  Zn+2(aq) + 2 e-
Zn(s)
•Metallic zinc is oxidized to zinc ion. Metallic zinc is serving as a
reducing agent.(electron loser)
• REDUCTION:
+ 2 e- Cu(s)
Cu+2(aq)
Copper ion is reduced to copper metal. Copper ion is
serving as an oxidizing agent (electron gainer)
• In the overall reaction two electrons are transferred
from the zinc metal to the copper ion.

Zn(s) + Cu+2(aq) Zn+2(aq) + Cu(s)

3
0
 OXIDATION
• NUMBERS
In the previous reactions the loss and gain of
electrons was obvious. Zn(s) must lose two
negative electrons in order to form a Zn+2(aq)
ion. And Cu+2(aq) must
gain two negative electrons to form a Cu(s)
atom.
• What about more complicated reactions? How
do we tell which substance loses and which
gains+ electrons
MnO +and Clhow
 Mnmany?+For
Cl example:
+ HO
4 2 2
H+ - - +2

Here we need oxidation 3

numbers! 1
 OXIDATION
NUMBERS
• Before discussing the mechanics of oxidation numbers it
is important to realize that:
• oxidation numbers have no physical significance.
They are merely a way to tell which substances gain or
lose electrons and how many.
• Oxidation numbers are assigned to atoms never
molecules. Molecules contain atoms with oxidation
numbers but they themselves cannot be assigned
oxidation numbers.
• There a several rules used to assign oxidation
numbers. They must be observed carefully.
3
2
 OXIDATION NUMBERS
RULES
• (1) Elements have oxidation numbers of zero. For
example Cu has an oxidation number of zero. In
Cl2 each atom of chlorine has an oxidation number
of zero.
• (2) The oxidation number of a monatomic ion
(consisting of one atom) is the charge on the ion.
In Cu+2 the oxidation number is +2. In Cl- the
oxidation number is –1.
• (3) The oxidation number of combined oxygen is
always –2 except in peroxides such as hydrogen
peroxide, H2O2. In CO2 each oxygen atom has an
oxidation number of –2. In SO3 each oxygen is –2.

3
3
 OXIDATION NUMBERS
• RULES
(4) Combined hydrogen is always +1 except in hydrides (metal
atoms and hydrogen like NaH). In water H2O each hydrogen
has an oxidation number of +1. In methane, CH4, each
hydrogen is
+1.

• (5) The sum of all of the oxidation numbers of the atoms in a

molecule equal its charge. If no charge is shown the sum must
equal zero. This allows us to determine the oxidation numbers
of elements not discussed in the first four oxidation number
rules!

• Oxidation numbers of other elemental

groups: Elements of Column I in a compound
7
= +1 Elements of Column II in a compound =
 FINDING UNKNOWN OXIDATION NUMBERS
• Problem: What is the oxidation number of Mn in MnO4-, the
permanganate ion?
• Solution: Mn is
unknown Each O is –2
(rule 3)
All of the oxidation
numbers must add up to –
1 (rule 5)
Mn + 4(-2) = -1, Mn
= +7 in permanganate
• Problem: What is the
oxidation number
of Cr in K2Cr2O7,
2(+1) + 2 Cr + 7(-2) = 0,
potassium 2 Cr = 12, Cr = 12 / 2 =
+6
dichromate?
8
 USING OXIDATION NUMBERS TO DETERMINE ELECTRON
TRANSFERS
• Using oxidation numbers we will find the oxidizing agent, the
reducing agent, the number of electrons lost and gained, the
oxidation half-reaction, the reduction half-reaction and the
final balanced equation for:
+ MnO - + Cl-  Mn+2 + Cl2 + H2O
H + 4
• Step I – Find the oxidation number of each atom.
+ MnO - + Cl-  Mn+2 + Cl2 + H2O
H + 4

• +1 (+7, -2) -1 +2 0 (+1, -

Step II – Determine which oxidation numbers change
2)
MnO4-  Mn+2 2 Cl-  Cl2
If oxidization # s decrease,
+7  2(-1)  0 Reduction occurs
+2 2 If oxidization # s
5 electrons gained electrons increase, Oxidation
lost It gained electrons from
(MnO4- is the oxidizing agent. Cl- )
occurs
9
(Cl- is the reducing agent. It lost electrons to MnO4- )
 USING OXIDATION NUMBERS TO DETERMINE ELECTRON
TRANSFERS
• Step III - Electrons lost by a reducing agent must always
equal electrons gained by the oxidizing agent!
• Therefore: 2 (MnO4- + 5e-  Mn+2 )
2MnO4- + 10e-  2Mn+2
• And 5(2Cl- half-reaction*)
(reduction + 2e-)
Cl2 10 Cl-  5Cl2 + 10e- (oxidation half-
reaction)
• Step IV -Completing the first half-reaction with H+ ions and H2O
molecules: 16 H+ + 2MnO4- + 10e-  2Mn+2 + 8 H2O
• Step V - Adding the oxidation half-reaction and reduction half-
reaction the 10 electrons gained and lost cancel to give the
overall reaction:
16 H+ + 2MnO4- + 10 Cl-  2 Mn+2 + 5 Cl2 + 8 H2O
• * Half-reaction refers to the reaction showing either the electron
gain (reduction) or the electron loss (oxidation) step of the reaction.
ELECTRICAL POTENTIAL, CHARGE,
ELECTRON FLOW
• For electrons to transfer from one substance to another the
oxidizing agent (electron gainer) must have a greater
attraction for those electrons than the reducing agent
(electron loser). This where electrical potentials come into
play.
• Electrical potential is measured in volts. Electrical charge
is measured in coulombs. The flow of electrons from
one substance to another is measured in amperes.
• 1 coulomb is the charge on 6.25 x 1018 electrons.(The
charge on 1 electron is –1.6 x 10-19 coulombs).
1 ampere (amp) is the flow rate of 1 coulomb per second
1 volt is 1 joule of energy moving 1 coulomb of charge
between two substances. 11
ELECTRICAL POTENTIAL
• Electrical potential is measured in volts and indicates the
tendency of electrons to move from one substance to
another. Potential depends on a variety of factors such as
the concentration of reactant materials, temperature, gas
pressures and the nature of the materials involved.
• Standard Reduction Potentials (measuring the tendency
of a substance to gain electrons) are determined at 25 0C,
1 molar concentrations, 1 atm pressures and are
compared to hydrogen ion’s tendency to be reduced
(gain electrons) to hydrogen gas (2H+(aq) + 2e-
 H2(g))
which is assigned a potential of 0.00 volts.
• Substances which gain electrons better than H+ ion are
assigned positive potentials. Those which gain electrons
more poorly than H+ ion are assigned negative potentials.
39
ELECTRICAL POTENTIALS
• The very best oxidizing agent (electron gainer) available is
flourine gas, F2. Its reduction potential is +2.87 volts.
• The very best reducing agent (electron loser) is lithium
metal, Li. Its oxidization potential is +3.05 volts.
• When Li is combined with F2, the reaction is highly
spontaneous. Electrons move readily from the Li to the F2.
The standard potential of this cell (redox reaction) is
+5.92 volts.
• By contrast, combining Li+ ion with F- ion results in a
nonspontaneous process.(Li+ has already lost its electrons
and F- has already gained its electrons). The standard
potential for this cell is –5.92 volts 40
 ELECTRICAL
• POTENTIALS
From the Standard Reduction Potential Table:
(1) F2(g) + 2e-  2 F- 2.87 volts
(aq)
(2) Li + + 1 e  Li
-
-3.05 volts
(aq)
• Since(s) Li metal serves as a reducing agent, it must be shown to
lose electrons, and the half-reaction must be reversed. This
requires that the E0 sign be changed.
(3) Li(s)  Li + 1e- +3.05
+
volts
• and since 2(aq)electrons must be transferred to F2
(4) 2 Li(s)  2 Li + 2e- +3.05
+
volts
(note that the E0 is (aq)
not multiplied by two.)
• Combining half-reaction (1) and (4) we get
Li(s) + F2(g)  Li+ + 2 F- +
5.92 volts
(aq) (aq)
For the reverse reaction which is nonspontaneous, the
potential is
–5.92 volts. 41
 APPLICATION OF ELECTROCHEMISTRY IN
PHARMACEUTICS

• Electrochemistry is a highly interdisciplinary branch,

finding applications in many fields of chemical like
pharmacy, medicine, biochemistry, synthesis of new
materials, and nano-chemistry technology.

• The major aspect of electrochemistry that

distinguishes it from other branches of physical
chemistry is the uniqueness of its applications.
 APPLICATION OF ELECTROCHEMISTRY IN
PHARMACEUTICS
• Electrochemistry studies not only the processes of
charge (electron and ion) transfer but also important
phenomena such as adsorption, phase
transformation, chemical reactivity, catalysis, energy
conversion, and many more which apply in
pharmaceutics.

• The molecular systems that are analysed with

electrochemical techniques are very versatile,
ranging from small ions, molecules, compounds to
large biomolecules like enzymes which equally apply
in pharmaceutics.