JOSEPH SARWUAN TARKA UNIVERSITY, MAKURDI BENUE STATE

SUNNEX SOLUTION CENTER TUTORIAL INSTRUCTIONAL MATERIAL

COURSE CODE : CHM 122. COURSE TITTLE : PHYSICAL CHEMISTRY

SOURCE AND COMPILE BY : EMMANUEL SUNDAY (sunnex)

COURSE SYNOPSES/ CONTENT

1. UNITS AND MEASUREMENTS IN PHYSICAL CHEMISTRY

2. STATE OF MATTER AND CHANGE OF STATE

3. GASES AND THEIR PROPERTIES

4. THERMOCHEMISTRY

5. INTRODUCTORY CHEMICAL KINETICS AND CHEMICAL EQUILIBRIA

6. ACIDS AND BASES AND SALTS

7. REDOX REACTION AND REDOX POTENTIAL.

OUR OTHER MATERIALS INCLUDE

1. CHM 152 MANUAL SOLUTION

2. BIO101 MANUAL SOLUTION

3. MTH122 CALCULUS MATHEMATICS

4. MTH132 APPLIED MATHEMATICS

5. GST 114 USE OF LIBRARY

6. CHM 132 ORGANIC CHEMISTRY

For more infor about our Tutorial program , instructional material and notes contact sunnex solution
center contact

Sunnex : 08120753140,. Isaac : 08107055259

Quote of the day:

It is only in dictionary that success come before work, but in reality Work come before success.

UNITS AND MEASUREMENTS IN PHYSICAL CHEMISTRY

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 Chemistry is a quantitative science that requires measurements, those measured quantities such as
mass,volume, density,and temperature. Usually they have units associated with them. The unit used in
chemistry are based on international systems of unit popularly know as S.I unit.

The study of chemistry depends heavily on measurements. A number of devices makes us to make
simple measurements such as metre stick,used in measuring length, burret, volumetric
flask,pippete,cylinder,are used to measure volume, the balance measure mass. These instrument
mention are know as macro properties because they measure in large quantity.

S.I UNIT

For many years scientist have been making use of metric unit measurements but after a conference on
measurements in 1960 S.I unit was derived.

Quantity Unit Symbol

Length Metre m

Mass Kilograms Kg

Time Seconds s

Electric current Ampere A

Temperature Kelvin K

Amount of substance Mole Mol.

S.I UNIT PREFIX

The prefix used are...

Prefix Symbol Meaning

Tera T 10¹²

Giga G 10⁹

Mega M 10⁶

Kilo K 10³

MASS AND WEIGHT

Mass is a quantity of matter (a substance). The S.I unit of mass I kilograms where 1kg =1000g.

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In chemistry we use the smallest unit which is grams (g) for special convenience.

Weight deal with force of attraction. Weight= mg

VOLUME

Volume S.I unit is cubic metre, cubic centimeters,and cubic decimeters. Litre sometimes can also be the
S.I unit of volume. Litre is a volume occupied by 1cubic decimeters

1litre( L)= 1000millitre (mL) = 1000cm³ =1dm³

DENSITY

Density is the mass of an object divided by the volume . The S.I unit of density is kg/m³. The smallest unit
is g/cm³ or g/mL.

Mathematically density= mass/volume

Examples:

1.A piece of gold induct with a mass of 257g has a volume of 13.3cm³. Calculate the density of gold.

2. A piece of metal with a density of 21.5g/cm³ and a volume of 4.49cm³. what is it's mass?

ATTEMPT

1. Density = mass / volume = 257g/13.3cm³ = 19.32g/cm³

2. Mass = density × volume = 21.5 × 4.49 = 96.54g.

TEMPERATURE SCALE.

Temperature commonly have three (3) scale.

1. Degree Fahrenheit 2. Degree Celsius 3. Degree kelvin.

Degree Fahrenheit : is commonly used at the united state outside the laboratory and it defines normal
freezing and boiling points of water to be 32⁰f and 212⁰f.

Degree Celsius : The freezing point of ⁰c is 0⁰c and the boiling point is 100⁰c.

Degree kelvin : ⁰K is the lowest temperature obtain which is absolutely zero. The absolute temperature
is at 273⁰c. The size of a degree on the ⁰f scale is only 100/180 or 5/9 of a degree on Celsius scale.

⁰C = 0⁰C -100⁰C

⁰F = 32⁰F - 212⁰F

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 TEMPERATURE SCALE CONVERSION

To convert from ⁰F to ⁰C and vice versa

⁰C = (⁰f -32⁰f) × ⁵/⁹(⁰f +0⁰C)

⁰f = ⁹/⁵ ×(⁰c) +32⁰f (⁰c +⁰f)

⁰k = (⁰c +273).

Example; A metal is made up of tin and lead that is used in electronic circuit. These metal has a melting
point of 224⁰c. Whag is it's melting point in ⁰f

ATTEMPT

⁹/⁵ ײ²⁴ ׳² = ⁹ײ²⁴׳²/⁵ =409.6⁰f

2. STATE OF MATTER AND CHANGE OF STATE

Matter is divided into three (3) parts namely , solid,liquid and gas. The same substance may exist as
solid,liquid and gas depending on the physical condition.

SOLID STATE

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 In a solid the particles are closely packed together and unable to move , the particles are held together
by coercive force and it maybe electrovalent,covalent, hydrogen or even vanderwall forces.

The particles of solid can only vibrate and rotate about a fixed position that is they will not move from
one place to another, a solid as a definite shape and volume and cannot be compressed.

LIQUID STATE

The particles in a liquid can move about because they have more kinetic energy than the solid and they
are no longer held in a fixed position because they have more kinetic energy. The forces of attraction are
weaker than the solid, there movement are restricted because they are still under the influence of
coercive forces,it does not have a fixed shape but Maintain the shape of the container.

GASEOUS STATE

The forces of attraction between the particles in a gas are very weak so that the particles are free to
move about with very great speed colliding with one another and with the wall of the container because
these particles are moving freely about in the container we say gas can easily be compress.

KINETIC THEORY OF GASES

1. The gas molecules randomly in straight lines coliding with one another and with the walls ofghe
container

2. The collision of gas molecules are perfectly elastic that means no loss of energy

3. The actual volume occupied by a gas molecules is negligible relative to the volume of the container.

4. The coercive force between the gas molecules are negligible (no force is holding the particles)

5. The temperature of the gas is a measure of the ½ range.

NB: the four most important quantity in all experimental work , measurements and calculation involving
gas are volume, pressure, temperature and amount of mole.

GAS LAWS AND GENERAL GAS EQUATIONS

Introduction: What are the Gas Laws?

The gas laws are a group of laws that govern the behaviour of gases by providing relationships between
the following:

1. The volume occupied by a gas.

2. The pressure exerted by a gas on the walls of its container.

3. The absolute temperature of the gas.

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4. The amount of gaseous substance (or) the number of moles of gas.

The gas laws were developed towards the end of the 18th century by numerous scientists (after whom,
the individual laws are named). The five gas laws are:

Boyle’s Law, which provides a relationship between the pressure and the volume of a gas.

Charles’s Law, which provides a relationship between the volume occupied by a gas and the absolute
temperature.

Gay-Lussac’s Law, which provides a relationship between the pressure exerted by a gas on the walls of
its container and the absolute temperature associated with the gas.

Avogadro’s Law, which provides a relationship between the volume occupied by a gas and the amount
of gaseous substance.

The Combined Gas Law (or the Ideal Gas Law), which can be obtained by combining the four laws listed
above.

Under standard conditions, all gasses exhibit similar behaviour. The variations in their behaviours arise
when the physical parameters associated with the gas (such as temperature, pressure, and volume) are
altered. The gas laws basically describe the behaviour of gases and have been named after the scientists
who discovered them.

Boyle’s Law

Boyle’s law gives the relationship between the pressure of a gas and the volume of the gas at a constant
temperature. Basically, the volume of a gas is inversely proportional to the pressure of a gas at a
constant temperature.

Boyle’s law equation is written as:

V ∝ 1/P Or P ∝ 1/V

Where V is the volume of the gas, P is the pressure of the gas and K1 is the constant. Boyle’s Law can be
used to determine the current pressure or volume of gas and can be represented also as;

P1V1 = P2V2

EXAMPLE

An 18.10mL sample of gas is at 3.500 atm. What will be the volume if the pressure becomes 2.500 atm,
with a fixed amount of gas and temperature?

Solution:

By solving with the help of Boyle’s law equation

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P1V1 = P2V2

V2 = P1V1 / P2

V2 = (18.10 * 3.500atm)/2.500atm

V2 = 25.34 mL

Charle’s Law

Charle’s law states that at constant pressure, the volume of a gas is directly proportional to the
temperature (in Kelvin) in a closed system. Basically, this law describes the relationship between the
temperature and volume of the gas.

Mathematically, Charle’s law can be expressed as;

V∝T

Where, V = volume of gas, T = temperature of the gas in Kelvin. Another form of this equation can be
written as;

V1 / T1 = V2 / T2

EXAMPLE

A sample of Carbon dioxide in a pump has a volume of 21.5 mL and it is at 50.0 oC. When the amount of
gas and pressure remain constant, find the new volume of Carbon dioxide in the pump if the
temperature is increased to 75.0 oC.

Solution:

V2 = V1T2/T1

V2 = 7,485.225/ 323.15

V2 = 23.16 mL

Gay-Lussac Law

Gay-Lussac law gives the relationship between temperature and pressure at constant volume. The law
states that at a constant volume, the pressure of the gas is directly proportional to the temperature for a
given gas.

If you heat up a gas, the molecules will be given more energy, they move faster. If you cool down the
molecules, they slow down and the pressure decreases. The change in temperature and pressure can be
calculated using Gay-Lussac law and it is mathematically represented as;

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P ∝ T Or P / T = k1

or P1 / T1 = P2 / T2

Where P is the pressure of the gas and T is the temperature of the gas in Kelvin.

EXAMPLE

Determine the pressure change when a constant volume of gas at 2.00 atm is heated from 30.0 °C to
40.0 °C.

Solution:

P1 = 2.00 atm, P2 =?, T1 = (30 + 273) = 303 K, T2 = (40 + 273) = 313 K

According to the Gay-Lussac law

P∝T

P/T = constant

P1/T1 = P2/T2

P2 =( P1 T2 ) / T1

= (2 x 313) / 303

=2.06 atm

Avogadro’s Law

Avogadro’s law states that if the gas is an ideal gas, the same number of molecules exists in the system.
The law also states that if the volume of gases is equal it means that the number of the molecule will be
the same as the ideal gas only when it has equal volume. This above statement can be mathematically
expressed as;

V / n = constant Or V1 / n1 = V2 / n2

Where V is the volume of an ideal gas and n in the above equation represent the number of gas
molecules.

EXAMPLE

At constant temperature and pressure, 6.00 L of a gas is known to contain 0.975 mol. If the amount of
gas is increased to 1.90 mol, what new volume will result?

Solution:

V1 = 6.00 L ,V2 = ? ;n1 = 0.975mol n2 = 1.90 mol

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According to Avogadro’s law

V∝n

V/n = constant

V1 / n1 = V2 / n2

V2 = V1n2/n1

V2 = (6 x 1.90)/ 0.975 = 11.69 L

Combined Gas Law

The combined gas law is also known as a general gas equation is obtained by combining three gas laws
which include Charle’s law, Boyle’s Law and Gay-Lussac law. The law shows the relationship between
temperature, volume and pressure for a fixed quantity of gas.

The general equation of combined gas law is given as;

PV / T = k

If we want to compare the same gas in different cases, the law can be represented as;

P1V1 / T1 = P2V2 / T2

Ideal Gas Law

Much like the combined gas law, the ideal gas law is also an amalgamation of four different gas laws.
Here, Avogadro’s law is added and the combined gas law is converted into the ideal gas law. This law
relates four different variables which are pressure, volume, no of moles or molecules and temperature.
Basically, the ideal gas law gives the relationship between these above four different variables.

Mathematically Ideal gas law is expressed as;

PV=nRT

Where, V = volume of gas. T = temperature of the gas. P = pressure of the gas.

R = universal gas constant. And n denotes the number of moles.

We can also use an equivalent equation given below.

PV = kNT

Where, k = Boltzman constant and N = number of gas molecules.

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 EXAMPLE

A sealed jar whose volume is exactly 1L which contains 1 mole of air at temperature 20-degree Celcius,
assuming that the air behaves as an ideal gas. So what is the pressure inside the jar in Pa?

Solution:

By solving with the help of ideal gas equation

PV=nRT

(1) By rearranging the equation we can get,

P=nRT/V

(2) Write down all the values which are known in S.I unit

n= 1, R= 8.314J/K/mol ,T= 20degree celcius=(20+273.15)K=293.15K ,V=1L=0.001m3

(3) Put all the values in the equation

P= nRT/V

P=(1*8.314*293.15)/0.001

P= 2,437,249

P=2.437*10^6 Pa

The pressure is almost 24atm

3. THERMOCHEMISTRY

Thermochemistry is a branch of chemistry that describes the energy changes that occur during
chemical reaction.

TERMS USED IN THERMOCHEMISTRY

ENERGY

Energy is the capacity or the ability to do work.

WORK

Work is the energy transferred between a system and it's surrounding that can be expressed as a force
moving through a system in a distance.

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 FORMS OF ENERGY

1. Thermal energy 2. Electrical energy 3. Nuclear energy

4.chemical energy 5. Radiant energy 6. Mechanical energy

SYSTEM, SURROUNDING &UNIVERSE

SYSTEM : A system is the set of substances and energy that is being studied. If, for example, reactions
are occurring in a jar, everything inside the jar is the system.

TYPE OF SYSTEM

1. Open system : In this system,there is exchange of mass and energy.

2. Closed system: In this system,there is no exchange of mass and energy

3. Isolated system : This system does not permit the exchange of energy and matter.

SURROUNDING

The surroundings are everything not in the system, which means the rest of the universe.

If, for example, reactions are occurring in a jar, everything inside the jar is the system, and everything
outside the jar is the surroundings.

ENDOTHERMIC AND EXOTHERMIC REACTION

Endothermic reaction : An endothermic reaction is any chemical reaction that absorbs heat from its
environment. The absorbed energy provides the activation energy for the reaction to occur. A
hallmark of this type of reaction is that it feels cold.

Endothermic Processes

These examples could be written as chemical reactions, but are more generally considered to be
endothermic or heat-absorbing processes:

1.Melting ice cubes

2.Melting solid salts

3.Evaporating liquid water

4.Converting frost to water vapor (melting, boiling, and evaporation, in general, are endothermic
processes

5.Making an anhydrous salt from a hydrate

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6.Forming a cation from an atom in the gas phase

7.Splitting a gas molecule

8.Separating ion pairs

9.Cooking an egg

10.Baking bread

Exothermic reaction : An exothermic reaction is a chemical reaction that produces heat (has a
negative ΔH). In other words, the activation energy needed to initiate the reaction is less than the
energy it releases. Examples of exothermic reactions include

1. neutralization reactions,

2.the Haber process

3.the thermite reaction, and

4.combustion reactions

STATE FUNCTION AND PATH FUNCTION

A state function is a property whose value does not depend on the path taken to reach that specific
value. In contrast, functions that depend on the path from two values are call path functions. Both
path and state functions are often encountered in thermodynamics.

In our study of thermodynamics and thermochemistry, we are primarily interested in 4 state

functions: internal energy, U, entropy, S, gibbs free energy, G, and enthalpy, H.

Path functions are properties or quantities whose values depends on the transaction of a system
from the initial state to the final state. The two most common path functions are heat and work.

INTERNAL ENERGY ,ENTHALPY, ENTROPY, AND FREE ENERGY

INTERNAL ENERGY : Internal energy U of a system or a body with well defined boundaries is the total
of the kinetic energy due to the motion of molecules and the potential energy associated with the
vibrational motion and electric energy of atoms within molecules. Internal energy also includes the
energy in all the chemical bonds.

ENTHALPY (H)

Enthalpy is a thermodynamic property of a system. It is the sum of the internal energy added to the
product of the pressure and volume of the system. It reflects the capacity to do non-mechanical work
and the capacity to release heat. Enthalpy is denoted as H; specific enthalpy denoted as h.

It is the heat absorbed or released by a system at constant pressure.

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NB : It is impossible to measure enthalpy directly,only change in enthalpy ∆H are used in this CHM122
course.

∆H = H(final) - H (initial)

NB: joules or kilojoules will be used as heat energy measurement.

∆H°(rxn) = £n∆H°(product) - £n∆H°(reactant)

Example 1.

Consider the evaporation of water

H20(l) ----------- H20(g)

Find the standard change in enthalpy for this reaction and state whether the reaction is exothermic or
endothermic. Use the table of standard enthalpies of formation.

SOLUTION

∆H°(rxn) = £n∆H°(product) - £n∆H°(reactant)

∆H°(rxn) = (-241.81) - (-285.8)

∆H°(rxn) = -241.81+285.8 = 43.99kj/mol

(b) It is an endothermic because heat is taken in and (∆H) is positive. This makes sense because energy
is received in order for liquid water to become gaseos state.

EXAMPLE 2.

Consider the condensation of water vapour. Find the standard change of enthalpy for this reaction
and state whether the reaction is exothermic or endothermic reaction,use the table of standard
enthalpies of formation.

Solution

H2O(g) -----------H2O (l)

∆H°(rxn) = £n∆H°(product) - £n∆H°(reactant)

= (-285.8) - (-241.81) = -43.99kj/mol

(b) Exothermic because heat is released and ∆H is negative. You have to remove energy from water
steam/vapour in order to make it a liquid.

EXAMPLE 3.

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Burning natural gas in the lab is described by the following chemical equation

CH4 + 2O2 ---------- CO2 + 2H2O

Find the standard change in enthalpy for this reaction and state whether the reaction is exothermic or
endothermic reaction,use the table of standard enthalpies of formation.

Solution

∆H°(rxn) = £n∆H°(product) - £n∆H°(reactant)

= [(2×H2O)+(CO2)] - [(CH4)+(2×02)]

[(2×241.81)+(-393.5)] -[(74.8)+(2×0)]

[(-483.64)+(-395.5)]-[-74.8)+(2×0)]

[(-483.64)+(-395.5)]-[(-74.8)+(0)

[-877.14] -[-74.8] = [-802.3kj/mol]

(b) Exothermic because ∆H is negative as you would expect burning gas gives off heat.

ENTROPY (S)

Entropy is the randomness or disorder of a system.

NOTE 1: Only change in entropy ∆S are used in this course CHM122.

NOTE 2 : When a reaction has a positive ∆S that is favourable condition.

NOTE 3: When a reaction has a negative ∆S that is an unfavourable condition.

GIBBS FREE EVERGY

Gibbs free energy, also known as the Gibbs function, Gibbs energy, or free enthalpy, is a quantity that
is used to measure the maximum amount of work done in a thermodynamic system when the
temperature and pressure are kept constant. Gibbs free energy is denoted by the symbol 'G'.

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 5. ACIDS AND BASES AND SALTS

ARRHENIUS DEFINITION OF ACID

An Arrhenius acid is a substance that dissociates in water to form hydrogen ions (H+). In other words, an
acid increases the concentration of H+ ions in an aqueous solution. This protonation of water yields the
hydronium ion (H3O+); in modern times, H+ is used as a shorthand for H3O+ because it is now known
that a bare proton (H+) does not exist as a free species in aqueous solution.

ARRHENIUS DEFINITION OF BASE

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An Arrhenius base is a substance that dissociates in water to form hydroxide (OH–) ions. In other words,
a base increases the concentration of OH– ions in an aqueous solution.

Limitations of the Arrhenius Definition

The Arrhenius definitions of acidity and alkalinity are restricted to aqueous solutions and refer to the
concentration of the solvated ions. Under this definition, pure H2SO4 or HCl dissolved in toluene are not
acidic, despite the fact that both of these acids will donate a proton to toluene. In addition, under the
Arrhenius definition, a solution of sodium amide (NaNH2) in liquid ammonia is not alkaline, despite the
fact that the amide ion (NH2)) will readily deprotonate ammonia. Thus, the Arrhenius definition can only
describe acids and bases in an aqueous environment.

Arrhenius Acid-Base Reaction

An Arrhenius acid-base reaction is defined as the reaction of a proton and an hydroxide ion to form
water:

Thus, an Arrhenius acid base reaction is simply a neutralization reaction.

BRONSTED-LOWRY DEFINITION OF ACID AND BASE

The Arrhenius definition of acid and base is limited to aqueous (that is, water) solutions. Although this is
useful because water is a common solvent, it is limited to the relationship between the H+ ion and the
OH− ion. What would be useful is a more general definition that would be more applicable to other
chemical reactions and, importantly, independent of H2O.

In 1923, Danish chemist Johannes Brønsted and English chemist Thomas Lowry independently
proposed new definitions for acids and bases, ones that focus on proton transfer. A Brønsted-Lowry acid
is any species that can donate a proton (H+) to another molecule. A Brønsted-Lowry base is any species
that can accept a proton from another molecule. In short, a Brønsted-Lowry acid is a proton donor (PD),
while a Brønsted-Lowry base is a proton acceptor (PA).

It is easy to see that the Brønsted-Lowry definition covers the Arrhenius definition of acids and bases.
Consider the prototypical Arrhenius acid-base reaction:

H+(aq) + OH−(aq) → H2O(ℓ)

(acid) (base)

The acid species and base species are marked. The proton, however, is (by definition) a proton donor
(labelled PD), while the OH− ion is acting as the proton acceptor (labelled PA):

H+(aq) + OH−(aq)→ H2O(ℓ)

(PD) (PA)

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 proton donor is a Brønsted-Lowry acid, and the proton acceptor is the Brønsted-Lowry base:

H+(aq) + OH−(aq) →  H2O(ℓ)

(BL acid) (BL base)

Thus H+ is an acid by both definitions, and OH− is a base by both definitions.

Ammonia (NH3) is a base even though it does not contain OH− ions in its formula. Instead, it generates
OH− ions as the product of a proton-transfer reaction with H2O molecules; NH3 acts like a Brønsted-
Lowry base, and H2O acts like a Brønsted-Lowry acid:

A reaction with water is called hydrolysis; we say that NH3 hydrolyzes to make NH4+ ions and OH−
ions.

Even the dissolving of an Arrhenius acid in water can be considered a Brønsted-Lowry acid-base
reaction. Consider the process of dissolving HCl(g) in water to make an aqueous solution of hydrochloric
acid. The process can be written as follows:

HCl(g) + H2O(ℓ) → H3O+(aq) + Cl−(aq)

HCl(g) is the proton donor and therefore a Brønsted-Lowry acid, while H2O is the proton acceptor and a
Brønsted-Lowry base. These two examples show that H2O can act as both a proton donor and a proton
acceptor, depending on what other substance is in the chemical reaction. A substance that can act as a
proton donor or a proton acceptor is called amphiprotic. Water is probably the most common
amphiprotic substance we will encounter, but other substances are also amphiprotic.

Example 1

Identify the Brønsted-Lowry acid and the Brønsted-Lowry base in this chemical equation.

C6H5OH + NH2− → C6H5O− + NH3

Solution

The C6H5OH molecule is losing an H+; it is the proton donor and the Brønsted-Lowry acid. The NH2− ion
(called the amide ion) is accepting the H+ ion to become NH3, so it is the Brønsted-Lowry base.

Example 2.

Identify the Brønsted-Lowry acid and the Brønsted-Lowry base in this chemical equation.

Al(H2O)63+ + H2O → Al(H2O)5(OH)2+ + H3O+

Answer

Brønsted-Lowry acid: Al(H2O)63+; Brønsted-Lowry base: H2O

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In the reaction between NH3 and H2O, the chemical reaction does not go to completion; rather, the
reverse process occurs as well, and eventually the two processes cancel out any additional change. At
this point, we say the chemical reaction is at equilibrium. Both processes still occur, but any net change
by one process is countered by the same net change by the other process; it is a dynamic, rather than a
static, equilibrium. Because both reactions are occurring, it makes sense to use a double arrow instead
of a single arrow:

NH3 with water dynamic

What do you notice about the reverse reaction? The NH4+ ion is donating a proton to the OH− ion,
which is accepting it. This means that the NH4+ ion is acting as the proton donor, or Brønsted-Lowry
acid, while OH− ion, the proton acceptor, is acting as a Brønsted-Lowry base. The reverse reaction is also
a Brønsted-Lowry acid base reaction:

BL Acid-Base Reaction

This means that both reactions are acid-base reactions by the Brønsted-Lowry definition. If you consider
the species in this chemical reaction, two sets of similar species exist on both sides. Within each set, the
two species differ by a proton in their formulas, and one member of the set is a Brønsted-Lowry acid,
while the other member is a Brønsted-Lowry base. These sets are marked here:

BL Acid-Base Reaction 2

The two sets—NH3/NH4+ and H2O/OH−—are called conjugate acid-base pairs. We say that NH4+ is the
conjugate acid of NH3, OH− is the conjugate base of H2O, and so forth. Every Brønsted-Lowry acid-base
reaction can be labelled with two conjugate acid-base pairs.

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 Example 3

Identify the conjugate acid-base pairs in this equilibrium.

(CH3)3N + H2O ⇄ (CH3)3NH+ + OH–

Solution

One pair is H2O and OH−, where H2O has one more H+ and is the conjugate acid, while OH− has one less
H+ and is the conjugate base. The other pair consists of (CH3)3N and (CH3)3NH+, where (CH3)3NH+ is
the conjugate acid (it has an additional proton) and (CH3)3N is the conjugate base.

Test Yourself

Identify the conjugate acid-base pairs in this equilibrium.

NH2– + H2O ⇄ NH3 + OH–

Answer

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H2O (acid) and OH− (base); NH2− (base) and NH3 (acid

LEWIS CONCEPT ABOUT ACID AND BASE

Gilbert Lewis (1875–1946) proposed a third theory of acids and bases that is even more general than
either the Arrhenius or Brønsted-Lowry theories. A Lewis acid is a substance that accepts a pair of
electrons to form a covalent bond. A Lewis base is a substance that donates a pair of electrons to form a
covalent bond. So, a Lewis acid-base reaction is represented by the transfer of a pair of electrons from a
base to an acid. A hydrogen ion, which lacks any electrons, accepts a pair of electrons. It is an acid under
both the Brønsted-Lowry and Lewis definitions. Ammonia consists of a nitrogen atom as the central
atom with a lone pair of electrons. The reaction between ammonia and the hydrogen ion can be
depicted as shown in the Figure 1. Reaction between ammonia and proton.

The lone pair on the nitrogen atom is transferred to the hydrogen ion, making the NH3 a Lewis base
while the H + is a Lewis acid.

Some reactions that do not qualify as acid-base reactions under the other definitions do so under only
the Lewis definition. An example is the reaction of ammonia with boron trifluoride.

Boron trifluoride is a Lewis acid but not a Bronsted acid

Figure 2. Ammonia and boron trifluoride.

Boron trifluoride is the Lewis acid, while ammonia is again the Lewis base. As there is no hydrogen ion
involved in this reaction, it qualifies as an acid-base reaction only under the Lewis definition. The Table
below summarizes the three acid-base theories.

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 Type Acid Base

Arrhenius H + ions in solution OH − ions in solution

Bronsted-lowry H + donor H + acceptor

Lewis electron-pair acceptor electron-pair donor

6. REDOX REACTION AND REDOX POTENTIAL.

Oxidation

Oxidation is defined as the addition of oxygen/electronegative element to a substance or rememoval of

hydrogen/ electropositive element from a susbtance

• Reduction

Reduction is defined as the memoval of oxygen/electronegative element from a substance or addition of

hydrogen or electropositive element to a substance.

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• Redox Reactexamplesion in Terms of Electron Transfer Reaction

A few of redox reaction on the basis of electronic concept are given below:

According to electronic concept every redox reaction consists of two steps known as half reactions.

(i) Oxidation reaction: Is a reactions that involve loss of electrons are called oxidation reactions.

(ii) Reduction reaction: Is a reactions that involve gain of electrons are called reduction reactions.

Oxidising agent: Acceptor of electrons.

Reducing agent: Donor of electrons.

• Oxidation Number

It is the oxidation state of an element in a compound which is the charge assigned to an atom of a
compound is equal to the number of electrons in the valence shell of an atom that are gained or lost
completely or to a large extent by that atom while forming a bond in a compound.

• Rules for Assigning Oxidation Numbers

(i) The oxidation number of an element in its elementary form is zero.

For example, H2, 02, N2 etc. have oxidation number equal to zero.

(ii) In a single monoatomic ion, the oxidation number is equal to the charge on the ion. For example, Na+
ion has oxidation number of +1 and Mg2+ ion has +2.

(iii) Oxygen has oxidation number -2 in its compounds. However, there are some exceptions.

Compounds such as peroxides. Na202, H202

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oxidation number of oxygen = – 1 In OF2

O.N. of oxygen = +2 02F2

O.N. of oxygen = +1

(iv) In non-metallic compounds of hydrogen like HCl, H2S, H2O oxidation number of hydrogen = + 1 but
in metal hydrides oxidation number of hydrogen = -1

[LiH, NaH, CaH2 etc.]

(v) In compounds of metals and non-metals metals have positive oxidation number while non-metals
have negative oxidation number. For example, In NaCl. Na has +1 oxidation number while chlorine has -
1.

(vi) If in a compound there are two non-metallic atoms the atoms with high electronegativity is assigned
negative oxidation number while other atoms have positive oxidation number.

(vii) The algebraic sum of the oxidation number of all atoms in a compound is equal to zero.

(viii) In poly atomic ion the sum of the oxidation no. of all the atoms in the ion is equal to the net charge
on the ion.

For example, in (C03)2—Sum of carbon atoms and three oxygen atoms is equal to -2.

Fluorine (F2) is so highly reactive non-metal that it displaces oxygen from water.

Disproportionation Reaction. In a disproportionation reaction an element in one oxidation state is

simultaneously oxidises and reduced.

Hence, the oxygen of peroxide, which is present in -1 oxidation state is connected to zero oxidation state
and in 02 and in H2O decreases to -2 oxidation state.

Balancing Redox Reactions

Method 1: Oxidation Number Method

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Step 1: Assign oxidation numbers to each atom.

Step 2: Determine the net change in charge to determine the ratio of atoms

Step 3: Use the ratio to eliminate the net charge change

Step 4: Use the ratio as coefficients for the elements

Step 5: Add H+ (under acidic conditions), OH- (under basic conditions), and H2O to balance charges.

Method 2: Half-Reaction Method

Step 1: Determine oxidation numbers for each atom

Step 2: Use oxidation numbers to determine what is oxidized and what is reduced.

Step 3: Write a half-reaction for reduction

Step 4: Write a half-reaction for oxidation

Step 5: Balance all elements except H and O

if have acid redox reaction: Balance the O using H2O , balance the H using protons

if have base redox reaction: Balance O using OH−

Step 6: Add up the charge on each side

Step 7: Balance the charges by adding electrons

Step 8: Multiply the half-reactions by factors that cancel out electrons

Step 9: Add the two half-reactions back together to eliminate out intermediates

REDOX POTENTIAL

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What Does Redox Potential Mean?

Redox potential is defined as the specific indicator of the extent to which the oxidizing as well as
reducing powers of a substance which has both reducing and oxidizing ingredients, have achieved
equilibrium.

Redox potential is used as:

An indicator of electrochemical reactivity of substances in environmental conditions

For predicting corrosion protection of various substances and systems

NB: Redox is a shortened form of the term oxidation-reduction.

Compiled by COMR SUNNEX 4 sunnex solution centre Tutorial

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