CHM 101

INTRODUCTORY CHEMISTRY I

COURSE LECTURER: Azeez Luqmon A., PhD.,

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 COURSE SYNOPSIS
chemical equilibria: reversible reactions and dynamic
equilibrium. Factors affecting chemical equilibria. Le Chatelier’s
principles. Equilibrium constraints; their definition and
calculation in terms of concentrations. Effects of temperature
on equilibrium constants. Ionic equilibria: Bronsted-Lowry
theory of acids and bases. Strong and weak acids in terms of
conductivity. Strong and weak electrolytes. Degree of
dissociation. The ionic product of water (Kw). pH and
calculation, pH indicators; choice of indicators, buffer solutions.

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 Course Objectives
With this course, students will

 Understand comprehensively chemical and ionic equilibria

 Understand different concepts of acids and bases

 Understand buffer, its properties and preparation

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 Course Schedule

Week 1 : Chemical equilibria

Week 2: Application of equilibrium constants

Weeks 3 and 4: Acid-Base equilibrium

Week 5: Buffer

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 CHEMICAL EQUILIBRIA
Chemical equilibrium can be defined two different ways: (i) It is the condition in which the concentrations of all
reaction species do not change with time, or (ii) It is the condition of opposing reactions proceeding at the same
rate. Equilibrium is a state in which there is no observable change as time goes by. A chemical equilibrium is
reached when the concentrations of reactants and products remain constant over time.

Characteristics of chemical equilibrium

1. A chemical equilibrium can only be achieved in a closed system
2. A chemical equilibrium can be approached from the point of view of either forward or backward reaction
3. A chemical equilibrium is dynamic in nature
4. The concentration of all chemical species present in a system at dynamic equilibrium remain constant as long as
the reaction conditions are not changed
5. A catalyst can be used to alter the time required to reach the equilibrium

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 THE EQUILIBRIUM SYSTEM
For a reversible reaction at equilibrium
aA + bB cC + dD

A and B are reactants, C and D are products; a,b,c and d are the stoichiometric coefficients. Then, the equilibrium constant is
written as

e.g
2SO2 + O2 2SO3

2
¿ [ SO 3 ]
=
¿ 𝐾c ¿¿

Examples
For the reaction, CO + 3H2 CH4 + H2O, calculate Kc from the following equilibrium

K c =¿ ¿
K c =¿ ¿ = 0.00149769
0.0003812463217 = 3.93 6
Calculate the equilibrium constant, K, for the following reaction at 25 oC
H2 + I2 2HI if the equilibrium concentrations are [H2] = 0.106M, [I2] = 0.0222M and [HI] = 1.29M
Kc = [HI]2
[H2][I2]
= [1.29]2
[0.106][0.0222] = 1.6641
0.0023532 = 707.165

For the hydrogen-iodine equilibrium: H 2 + I2 2HI

Determine the value of Kc if the initial amount of H2 is a moles, I2 is b moles and the amount of H2 or I2 reacted is x moles

H2 + I2 2HI
Initial a b 0
Reaction of x moles gives
a-x b-x 2x
Kc = [HI]2

[H2][I2]

Kc = [2x]2
[a-x][b-x]
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= 4x2
Equilibrium constant in terms of partial pressure
For a gaseous reaction at equilibrium aAgas + bBgas cCgas + dDgas
The equilibrium constant can be expressed in terms of partial pressure.
Kp = PCc PDd

PAaPBb In which PA, PB, PC, PD are the equilibrium partial pressures of gases A, B, C, D respectively
Example
Calculate Kp for the reaction CH3OH CO + 2H2 Given the equilibrium pressures as follows

PCH3OH = 6.10 x 10-4atm, PCO = 0.387atm PH2 = 1.34atm

Kp = PCO PH22

PCH3OH
= 0.387x(1.34)2
6.10 x 10-4
= 0.6948972
6.10 x 10-4
= 1139.18atm
Recall PV = nRT
P = n/V RT 8
Example
A mixture of 5.000 x 10-3 mol H2 and 1.000 x 10-2 mol I2 is placed in a 5.000 L container @ 448 ºC. Calculate Kp at 448 ºC if the
pressure of HI is 0.1106 atm.
H2 + I2 2HI
Converting mole to concentration
For H2 = 5 x 10-3 mol = 0.001mol/L
5 L
For I2 = 1 x 10-2 mol = 0.002mol/L
5 L
Calculating pressure for concentration
P = CRT
PH2 = 0.001 x 0.08206 x 721 = 0.0592

PI2 = 0.002 x 0.08206 x 721 = 0.1183

Kp = PHI2
PI2 PH2
= (0.1106)2
0.1183x 0.0592
= 0.01223236
0.00700336
= 1.747 9
 Applications of Equilibrium Constants
Prediction of the Direction of Reaction
Changes in Reactant or Product Concentrations

Adding a reactant or product, the equilibrium shifts away from the increase in order to consume part of the added substance.
Removing a reactant or product, the equilibrium shifts toward the decrease to replace part of the removed species.

Effects of Volume and Pressure Changes

i. If P increases (V decreases), the system shifts to the side with a smaller number of gas molecules (this effectively reestablishes
equilibrium by decreasing the pressure).
ii. If P decreases (V increases), the system shifts to the side with a greater number of gas molecules.

Effect of Temperature Changes

The reaction shifts right when T is increased for an Endothermic Reaction or T is decreased for an Exothermic reaction.
The reaction shifts left when T is decreased for an Endothermic Reaction or T is increased for an Exothermic reaction

The Effect of Catalysts

The position of the equilibrium does not change when a catalyst is added but the speed at which equilibrium is reached
increases.

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Examples
Nitrogen gas and oxygen gas combine @ 25oC in a closed container to from nitrogen (II) oxide as follows
N 2 + O2 2NO Kp = 3.3x1030 @ 25 oC ∆H = +1.81KJ Endo

What would be the effect on the direction of equilibrium if the following changes are made to the system?

a N2 is added

b He is added
c The container is made larger
d The system is cooled
a. The reaction will shift right

b. Since He is not one of the components, it does not affect the position of equilibrium

c. The system will remain at equilibrium since both sides have equal number of molecules

d. The reaction will shift towards reactants because it is endothermic to make products and exothermic to make reactants.

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ACID-BASE EQUILIBRIUM

Arrhenius concept
Acid is a substance which dissociates in water to give H+ while a base is a substance which gives OH- in water.
Arrhenius definition of acid and base cannot be applied to reactions that do not occur in water. The definition is also invalid as
there can never be free protons.
NaOH(s) H2O
Na+(aq) + OH-(aq) HCl(g) H2O
H+(aq) + Cl-(aq)

Bronsted-Lowry concept
Acid is a proton donor and base is a proton acceptor. When a substance is dissolved in water, it is said to react with water e.g
NH3 + H2O NH4+ + OH-; NH3 takes H+ from water, hence base
HCl + H2O H3O+ + Cl- ; HCl donates H+ to water, hence acid.

H2SO4 + 2H2O 2H3O+ + SO42-

Acid base conjugate acid conjugate base
H2O + NH3 H3O+ + OH-
Acid base conjugate acid conjugate base
NH3 + H2O NH4+ + OH-
Acid base conjugate acid conjugate base 12
Lewis Concept: Acids are substances which accept a pair of electrons to form a coordinate bond and bases are the substances
which donate a pair of electrons to form a coordinate bond.
NH:3 + BF3 NH3+-BF3-

Base acid product form coordinate bonding

Lewis Acids : As for Lewis concept, following species can acts as Lewis Acids :
(i) Molecules in which central atom has incomplete octet. (e.g. BF3, AlCl3 etc.)

(ii) Molecules which have a central atom with empty d-orbitals (e.g. SiX4, GeX4,

PX3, TiCl4 etc.)

(iii) Simple Cations: Though all cations can be expected to be Lewis acids, Na+,
Ca2+, K+ etc.
(iv) Molecules having multiple bonds between atoms of dissimilar electronegativity.
e.g. CO2, SO2, SO3

Lewis bases are typically:

(i) Neutral species having at least one lone pair of electrons. e.g. NH 2: NH3:, R-OH
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(ii) Negatively charged species (anions). e.g. CN , OH , Cl etc.
- - -
DISSOCIATION OF WATER
Auto-ionization of water is a very important chemical equilibrium and it should be noted that when water dissociates, it gives

2H2O H3O+ + OH-

Kb = [H3O+][OH-]
[H2O]2
Keeping the concentration of water constant because the amount of water that dissociates is negligible, therefore, the equation
becomes
Kw = [H3O+][OH-]
Kw is known as ionic product of water.
At 25 oC, water dissociates into equal amount of H3O+ and OH-
H3O+ + OH-
2H2O
1x10-7 1x10-7 in M
[H3O+] = [OH-]
Kw = [1x10-7]2 = 1x10-14 M

pH SCALE
pH = -log [H+] or [H3O+]

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Examples pH = -log[H3O+]
•Calculate the pH of the following
•0.1M HCl 2.5 = -log[H3O+]
•0.005M NaOH [H3O+] = 10-2.5
•Calculate the concentration of H3O+ ions in Coca cola if its pH is 2.50 [H3O+] = 3.16x10-3M

1a. 0.1M HCl HCl H + + Cl-

At equilibrium 0.1M 0.1M 0.1M
pH = -log [H+]
= -log(0.1)
=1
•0.005M NaOH

NaOH Na+ + OH-

0.005 0.005 0.005
[OH-] = 0.005M
[OH-][H+] = 1x10-14

[H+] = 1x10-14
= 1x10-14
[OH-]
0.005
= 2x10-12
pH = -log[H+]
= -log (2x10-12)
= 11.7 15
STRENGTH OF ACIDS AND BASES
STRONG AND WEAK ACIDS
Strong acids completely dissociate in water whereas weak acids slightly dissociate in water. This statement is too general for
treating the strength of acids, therefore the quantity called “dissociation constant”
HCl + H2O H3O+ + Cl-
Kc = [H3O+][Cl-]
[HCl][H2O]
As the amount of water remains constant, the concentration of liquid water can be considered as a constant, the equation then
becomes
Ka = [H3O+][Cl-]
[HCl]
Ka is the equilibrium constant for the dissociation of an acid. Dissociation constant is also equilibrium constant. Equilibrium of
weak acids and bases shift to the left because they do not dissociate completely.
Sometimes it is convenient to use pKa to compare the strength of acids where pKa = -log Ka
The smaller the pKa value, the stronger is the acid.

STRONG AND WEAK BASES

When a base is dissolved in water, it will accept a proton from water. The resultant ions and the neutral molecules are in
dynamic equilibrium.
B + H2O HB+ + OH-
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 Kb = [H3O+][Cl-]
[HCl]
Kb is the dissociation constant of base. Bases having larger Kb values are strong bases. In terms of pKb, the smaller the pKb value,
the stronger the base
Kc = [HB+][OH-]
[B][H2O]
Keeping concentration of water constant, the equation becomes
Examples
Calculate the pH and percentage dissociation of periodic acid in a 0.5M aqueous solution. Given that K a of acid is 2.3x10-2
HIO4 + H2O H3O+ + IO4-
Initial 0.5 0 0
At equi 0.5-x x x
Ka = [H3O+][IO4-]
[HIO4]
Ka = x.x
0.5-x
2.3x10-2 = x2
0.5-x
Expanding the equation
x2 = 0.023 (0.5-x)
x2 + 0.023x-0.0115 = 0
using quadratic equation 17
Alternatively, for weak acid, dissociation value is very small and the concentration of HIO 4 can be approximated to be the original

concentration. Also, on dissociation, equimolar concentrations of H3O+ and IO4- are formed. Therefore,

[H3O+] = [IO4-]
Ka = [H3O+]2

[HIO4]

[H3O+] = 0.5(-Ka+Ka2+4KaC

Where C is concentration
[H3O+] = 0.5(-0.023+0.0232+4x0.023x0.5)

= 0.0964
pH = -log[H3O+]
= -log (0.0964)
= 1.02
% dissociation = 0.0964
0.5
= 19.28%

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BUFFER
They are the solutions whose pH does not change significantly on adding a small quantity of strong base or acid or on little
dilution. The pH of the buffer does not change on addition of a small amount of acid or alkali because the components in the
buffer can convert the acid or alkali into weak acid or weak base, which is only slightly dissociated.
The weak acid component neutralizes added base and the weak base component neutralizes added acid so that the pH of the
buffer solution remains relatively constant. The components of a buffer do not neutralize one another when they are a conjugate
acid/base pair.
These are typically made by mixing a weak acid (or base) with its conjugate base (or acid). e.g. CH 3COOH with CH3COONa, NH3(aq)
with NH4Cl etc
Acidic buffer
Acidic buffers contain high concentrations of an undissociated weak acid and its conjugate base. It is made by dissolving a weak
acid and its sodium or potassium salt in water. The weak acid absorbs any additional OH -(aq) and the conjugate base absorbs
additional H+(aq).
A solution of equal concentrations of ethanoic acid and sodium ethanoate constitutes an acidic buffer solution: its pH is below 7.
In this buffer solution the equilibrium is:
CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq)
CH3COONa(aq) CH3COO-(aq) + Na+(aq)
We can consider the action of a buffer quantitatively by using the equilibrium law. For a weak acid, such as ethanoic acid
CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq)

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Ka = [H3O+][ CH3COO-]
[CH3COOH]
Making [H3O+] the subject of the formula, we have
[H3O+] = Ka x [CH3COOH]
[CH3COO-]
Taking the negative logarithm, we have
-log [H3O+] = -logKa -log [CH3COOH]
[CH3COO-]
Then the equation becomes
pH = pKa + log [CH3COO-]
[CH3COOH]
Substituting [salt] for [CH3COO-] and acid for [CH3COOH], the equation becomes
pH = pKa + log [Salt]
[Acid] Henderson-Hasselbalch Equation

Basic buffer
Basic buffers contain high concentrations of an undissociated weak base and its conjugate acid. It is made by dissolving a weak
base and one of its soluble salts in water. The weak base absorbs any additional H +(aq) and the conjugate acid absorbs additional
OH-(aq).
A solution of equal concentrations of ammonia and ammonium chloride constitutes a basic buffer solution: its pH is above 7. In
this buffer solution the equilibrium is: 20
 NH3(aq) + H2O(l) NH4+(aq) + OH-(aq) Since pOH = 14 – pH
NH4Cl(aq) NH4+(aq) + Cl-(aq) Then we have
The pH of a basic buffer can be found in the same as for the acid pH = 14 - pKb - log [Salt]
[Base]
NH3(aq) + H2O(l) NH +
4 (aq)
+ OH (aq)
-

Kb = [NH4+][OH-]
[NH3]
Making [OH-] the subject of the formula, we have
[OH-] = Kb x [NH3]
[NH4+]
Taking the negative logarithm, we have
-log [OH-] = -logKb -log [NH3]
[NH4+]
Then the equation becomes
pOH = pKb + log [NH4+]
[NH3]
Substituting [salt] for [NH4+] and base for [NH3], the equation becomes
pOH = pKb + log [Salt]
[Base]

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Significance of buffers in industry and biological systems
Buffer solutions are used to calibrate indicators and pH meters, control pH of solutions in which chemical reactions are
performed. In electroplating, an optimum pH is maintained by buffer in order to control the preferential discharge of ions and the
plating quality. Buffer is also used in the preservation of food and medicines. Buffer is also important in biological systems, which
are efficient within a narrow pH range. For example, the pH of blood is controlled within strict limits (7.4) for it contains various
salts (e.g. hydrogencarbonate) which behave as buffers.
Example
A buffer is made by adding 4.1g of sodium ethanoate to 1 dm 3 of 0.01M ethanoic acid. What is the pH of the buffer?
(Ka = 1.74x10-5 M, molar mass of sodium ethanoate = 82gmol-1)

pH = pKa + log [Salt]

[Acid]

No of moles of CH3COONa = 4.1

82 = 0.05 mol
[CH3COONa] = 0.05
1 = 0.05M
[CH3COOH] = 0.01M

pH = -log(1.74x10-5) + log 0.05

0.01
pH = 4.76 + 0.70 = 5.46
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•If 2.50 g of ammonium chloride is added to 250 cm 3 of 0.100 mol dm-3 ammonia solution at 298 K, what will the pH of the
solution become? (Molar mass of ammonium chloride = 53.5 g mol-1; Kb for ammonia at 298K = 1.74 x 10-5 mol dm-3)
pH = 14 - pKb - log [Salt]
[Base]

No of moles of NH4Cl = 2.5

53.5 = 0.047 mol
[NH4Cl] = 0.047
250x10-3 = 0.188M
[NH3] = 0.1M

pH = 14 – [(-log 1.74 x 10-5) - log 0.188 ]

0.1
pH = 14 – [4.7595) - 0.2742
pH = 14 – 4.485
= 9.51

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 Reading List:

 Satya Prakash, G. D. Tuli, S.K. Basu and .D. Madan. Advanced Inorganic Chemistry Vol 1. S. Chand and Company
Ltd. 2009

 Paul Kelter, Micheal Mosher and Andrew Scott. Chemistry: The practical Science. Houghton Mifflin Company,
New York. 2008

 Wong Y.C., Wong C.T., Onyinruka S.O., Akpanisi L.E. University General Chemistry Inorganic and Physical. Africana-
FEP Publishers LTD

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