B.

Chemistry

B.1 General Inorganic Chemistry

B.1.1 Introduction

Inorganic Chemistry is the branch of chemistry that deals with the study of non-carbon
containing compounds or compounds classified other than organic. In this section, it
covers the Development of the Atomic Theory and Periodic Table of Elements,
Chemical Bonding and Reactions, Gases and Solutions, and Nuclear Chemistry.

B.1.2 Theory of Atoms

As early as the time of the Greek thinkers like Democritus, matter was believed to
compose of tiny indestructible particles called atoms. The word atom was derived from
the Greek word, atomos, meaning uncut or indivisible. The invention of the balance
enabled chemists to study the composition of substances and found out that matter is
formed from combination of elements in a definite mass. This observation, made by
Joseph Loius Proust, is known as the law of definite composition.
In 1803, John Dalton proposed that the atom of an element is composed of tiny
indivisible particles and all atoms of a given element are of the same shape, size and
properties. However, atoms of different elements differ chemically. Secondly, if elements
combine to form two or more compounds, the ratio of the mass of the other elements
necessary to combine stoichiometrically with a fixed amount of the other is in whole
number or simple fractions. Lastly, chemical reactions only involve rearrangement,
combination and separation of atoms. His concept of the indestructibility of atoms was
believed for a century however upturned completely by the discovery of subatomic
particles and radioactive elements, and the phenomena of radioactivity. On the other
hand, Daltons theory was found to support other universal laws that helped to stimulate
the works of modern chemists. The second statement is known as the Law of Multiple
Proportions. The third hypothesis is the Law of Conservation of Mass, which states that,
matter is neither created nor destroyed in a given chemical reaction.

B.1.3 Discovery of the Subatomic Particles and Radioactivity

At the end of the 19th century, scientists devoted so much on the study of the phenomenon
of radioactivity in which substances were found to transmit and emit energy in the form
of waves through space. A device used to study radioactivity was a cathode ray tube. This
evacuated glass tube contained two metal plates connected across a high-voltage source.

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When current passed through the metal plates, a ray was emitted from the negatively
charged plate (cathode) and drawn towards the positive plate (anode). This ray, called the
cathode ray tube, was invisible but produces a bright light upon striking a fluorescent
screen. Some experiments further characterize the nature of the ray by adding two
charged plates and a magnet. In the experiment, the ray deflected towards the positive
plate and repelled by the negative plate. Moreover, in the presence of a magnetic field the
ray deflected and appeared to interact with the magnetic field. With such attraction with
electric and magnetic fields, the particle must be negatively charged and known as
electrons. Furthermore, the nature of the cathode ray was found unaffected with the
material of which the cathode was constructed, the type of metal wires used to conduct
the current, the type of gas present in the tube and irrespective of the materials used to
generate the current.

In 1897, Joseph John Thomson determined the ratio of the charge of an electron to its
mass to be 1.76 x 108 coulomb per gram electron through the cathode ray tube. He was
then recognized as the discoverer of this negatively charged subatomic particle called
electrons. In line with this experiment, Robert Andrews Millikan determined the charge of
an electron to be 1.6 x 1019 coulomb through his oil-drop experiment.

In the same year, Wilhelm Rontgen discovered cathode rays caused metals to emit
unusual rays that penetrated matter, and are highly fluorescent. He called these rays, X-
rays. After the discovery of these rays, Antoine Becquerel happened to wrap an
unexposed photographic plate with a uranium compound that eventually darkened the
plate spontaneously. This phenomenon was called radioactivity to explain the
spontaneous emission of highly energetic radiation.

Before the discovery of the electron, Eugene Goldstein identified the presence of a bright
light within the cathode in the cathode ray tube. This signifies that positive rays were also
present in the tube. Studies show that there are different positive particles present
depending on the gas used in the tube. The lightest of these positive particles was
obtained when hydrogen gas was used. The particles had an electric charge to mass ratio
of 9.5791 x 104 coulomb per gram and its absolute charge is the same to that of an
electron. This positively charged particle is known as the proton.

In 1910, Ernest Rutherford with his associates, Johannes Geiger and Ernest Marsden,
performed an experiment that involves bombardment of a thin sheet of gold foil with
alpha particles in an evacuated tube. In the said experiment, most of the alpha particles
were observed to pass through the thin gold foil, some particles deflected and very few
particles bounced back as shown in a zinc sulfide coated glass tube. These observations
led to the explanation of the nature of the nucleus. The nucleus, based on this experiment,

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is almost an empty space where the mass of an atom is deeply concentrated and acquires
a positive charge.

After the discovery of the nature of a nucleus, it was known that a hydrogen atom
contains one proton and a helium atom with two protons. Therefore the latter is twice as
much heavy as the former. On the contrary, the helium atom was found to be four times
heavier than the hydrogen atom and therefore another particle must be responsible for
such difference. In 1932, James Chadwick was able to identify a neutral particle known
as the neutron by bombarding a beryllium atom with an alpha particle.

B.1.4 Atomic Number, Atomic Weight, Mass Number and Isotopes

With these discoveries, the atom of an element can be identified with the number of
protons and neutrons in its nucleus. The atomic number is the number of protons and the
mass number of an atom is the number of protons and neutrons in the nucleus. For a
neutral atom, the number of electron is equal to the number of protons. However, in
nature, elements were found to exist with different mass numbers. These elements with
different mass numbers are called isotopes. Hydrogen atom has three isotopes as follows:

Table B.1 Isotopes of Hydrogen

proton neutron electron
Protium 1 0 1
Deuterium 1 1 1
Tritium 1 2 1

B.1.5 Quantum Theory and Photoelectric Effect

In 1900, Max Planck discovered that when solids are heated, it emits a discrete quantity
of energy in the form of electromagnetic radiation called quanta. The energy of a single
quantum of energy is given by:
E hf (1)
34
where h Plancks constant, 6.626176 x 10 J-s
f frequency of radiation, s

In 1905, Albert Einstein proposed the photoelectric effect, a phenomenon that explains
the release of electrons when a minimum frequency of light strikes the surface of metal
plate. He was also able to establish a direct relationship between the number of electrons
ejected from metals exposed to light and the intensity of the light. He called these
particles of light photons. Einstein further suggested that these photons carry energy

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equal to hf and the higher the intensity of the light, the greater number of electrons was
emitted of high kinetic energy.
B.1.6 Quantum Numbers
The distribution of electrons in an atom is described by quantum numbers derived from
the Schrodinger equation for the hydrogen atom. The following quantum numbers are
used to describe the electron distribution on hydrogen atom and other atoms:
1. Principal Quantum Number (n) gives the distance of an electron from the nucleus
residing in an orbital. It has integral values 1,2,3 that corresponds to the energy
level the electron is located. The maximum number of electrons for every value of
n is 2n2.
2. Secondary or Angular Momentum Number (l) describes the shape of the atomic
orbital. It has integral values of 0 to n1. When l = 0, the shape of the orbital is
spherical or the s orbital. All s orbitals have the same shape but differ in size as
the value of the principal quantum number increases. When l = 1, the orbital is a p
orbital and so on.
3. Magnetic Quantum Number (m) has integral values from l to +l and describes
the orientation of the orbital in space. When l = 1, the values of m are 1,0,+1.
This means that there are three p orbitals with the same energy but differ in
orientation in space
4. Spin Quantum Number (s) denotes the spin of electron in an orbital that are
proposed to act like magnets. It has values of + (clockwise) or (counter
clockwise)

B.1.7 Electronic Configuration

In distributing the electron in the atomic orbitals, the following rules are followed:
1. Aufbau Priinciple. Electrons are distributed to subshells of lower energy to higher
energy.
2. Paulis Exclusion Principle. No two electrons will have the same set of quantum
numbers or if an electron occupies the same orbital, these electron must have
opposite spins
3. Hunds Rule of Multiplicity. The most stable arrangement of atoms in degenerate
orbitals is the one with the most parallel spins. In filling electrons in subshells, the
electrons are placed singly before any pair is made.

The following methods are used for writing the electronic configuration:
1. Orbital Method
8O 1s2 2s2 2p4

1s 2s 3s 4s 5s 6s 7s
2p 3p 4p 5p 6p 7p

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 3d 4d 5d 6d
4f 5f
2. Shell Method. In this method, the valence shell electron or the electron in the
outermost shell is shown. The first shell corresponds to the first energy level,
second shell to second energy level and so on.

8O 2e 6e

3. Rectangular Arrow Method. This method shows the degenerate orbitals of p, d

and f in a rectangle and the opposite spins of electrons in each orbiral.
8O

1s
2s 2p

4. Core Method. The noble gas of lower atomic number is used and the remaining
electrons are listed using the orbital method.

8O [He] 2s2 2p4

B.1.8 Development of the Modern Periodic Table

The development of the modern periodic table started when chemists observed similar
properties of elements. In 1829, Johann Dobereiner arranged the elements into triads.
These elements of similar properties are LiNaK, ClBrI and CaSrBa. The first
attempt to arrange the elements in increasing atomic weight was done by John Newlands.
He found out that every eighth element has similar properties. The modern periodic table
is based on the independent works of Dmitri Mendeleev and Julius Lothar Meyer. The
list of elements published by Mendeleev is arranged in columns and elements with
similar properties are in the same row. He concluded that when elements are arranged in
increasing atomic weight, their properties follow a certain periodic pattern. On the other
hand, Henry Gwyn-Jeffreys Moseley did the arrangement of the elements with respect to
its atomic number in the early 20th century. This conclusion was made when he
performed experiment involving X-ray emissions of elements bombarded by highly
energetic electrons that showed how protons in the nucleus varied for every element.
Today, the chemical and physical properties of elements are found to be periodic
functions of their atomic numbers, the modern periodic law.

B.1.9 Classification of Elements in the Periodic Table

In Figure B.1, elements are arranged in the periodic table according to their similarities in
properties. The vertical column of elements is known as the family and horizontal row of
blocks are called periods or series. The elements in the left most portions are metals and

B-5
 on the right portion are nonmetals. The elements in the ladder-like line are called
metalloids whose properties are intermediate between metals and nonmetals. Group 1A is
called alkali metals because these metals form hydroxides that are alkaline in aqueous
solutions. Group 2A is called alkaline earth metals since they can be found in the earths
crust and also forms alkaline solutions in water. Group 3A, 4A, and 5A are known as the
boron, carbon and nitrogen family, respectively. The group led by oxygen is called
chalcogens and fluorine group are collectively known as halogens.

Figure B.1 The Modern Periodic table of Elements

1A 2A 3B 4B 5B 6B 7B 8B 8B 8B 1B 2B 3A 4A 5A 6A 7A 8A
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

s block
p block
1 2
H He
3 4 5 6 7 8 9 10
Li Be B C N O F Ne
11 12 d block 13 14 15 16 17 18
Na Mg Al Si P S Br Ar
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Cl Kr
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
55 56 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
87 88 104 105 106 107 108 109
Fr Ra Rf Ha Sg Ns Hs Mt

f block
57 58 59 60 61 62 63 64 65 66 67 68 69 70 71
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
89 90 91 92 93 94 95 96 97 98 99 100 101 102 103
Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr

Aside from periods and families, elements can be classified according to how subshells
are filled. They are classified as representative elements or main group elements (s and p
block elements), transition elements (d block elements), noble gases (group 8A or 18) and
the lanthanide and actinide series (f block elements).

B.1.10 Periodic Trends in Physical and Chemical Properties

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The electronic configurations of elements show a periodic trend as the atomic number
increases in the periodic table. Physical and chemical behaviors of these elements also
vary the same way. The following atomic properties are observed in this section:

1. Atomic Size. One half the distance between two adjacent nuclei measured from
crystalline forms of the elements and molecules of gaseous elements. Generally,
the atomic radius increases down a group and decreases across a period. The
increase in atomic size down a group is due to the increase in energy level or shell
compared to the element above it. On the other hand, the increased nuclear charge
decreases the radii of the atom by drawing the electron shells together. For
elements across a given period, the element with the higher atomic number has a
greater nuclear charge than the element prior to it. The greater the nuclear charge
implies greater attraction between the electrons and the nucleus that result in the
shrinking of the atoms across a given period.
2. Ionic Size. The radius of a cation or anion measured using X-ray diffraction. If an
atom forms a cation, the nuclear charge is unaffected but the electron-electron
repulsion is reduced. This results in the shrinkage of the electron cloud. Thus, the
cation formed is smaller than the atom. On the other hand, when an atom forms an
anion by accepting an additional electron, the electron cloud increases making the
anion larger than the parent atom.
3. Ionization Energy. The energy required knocking off an electron from a gaseous
atom in its ground state. Metals have low ionization energy and nonmetals have
relatively high ionization energy. Such high ionization energy of nonmetals
particularly of noble gases explains its relative inertness or unusual stability.
Down a group, ionization energy decreases due to the increase in energy level that
results in the decrease in attraction between the nucleus and the outer-most
electrons. Within a given series, an increase in the ionization energy is observed
but not in a regular manner. Fluctuations are due to the stability attained when
subshells are being filled.
4. Electron Affinity. The energy change that accompanies the acceptance of an
electron by a gaseous atom to form an anion. It indicates how bound an additional
electron is to an atom. If the electron affinity is negative or energy is released
when an atom accepts an electron, the ion formed is less stable than the neutral
atom. Generally, electron affinity decreases from top to bottom and from right to
left.

The following general observations are summarized below for the representative
elements. Note that fluctuations may occur due to the filling of subshells.

Figure B.2 Periodic Trends in the Atomic Properties

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 1 5 6 7 8 9 10
H B C N O F Ne
3
Li
11 From right to left
Na
19
K Increasing
37 From top to bottom Atomic Size
Rb Ionic Size (anions) / (cations)
55 Metallic Property
Cs Decreasing
87 Ionization Energy
Fr Electron Affinity

B.1.11 Chemical Bonding

The concept of electronic distribution in an atom and the development of the modern
periodic table aided chemists to fully explain the formation of compounds and
molecules. Gilbert Newton Lewis proposed that atoms combine to form a more
stable electronic configuration resembling that of the noble gases. This rule is known
as the octet rule. Lewis proposed a symbol of an element with their valence electrons
as dots called the Lewis dot notation. Elements in the same family have the same
valence electrons. Figure B.3 shows the dot symbol for representative elements and
the noble gases.

Figure B.3 Lewis Dot Symbols of Representative Elements and Noble Gases

H He
Li Be B C N O F Ne
Na Mg
Ca

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B.1.12 Ionic Bond
Bond formed that involves loss and gain of electron of an atom. An ionic bond results in
the electrostatic attraction between ions. It usually involves metals and nonmetals. A
concrete example is the reaction between sodium and chlorine to form sodium
chloride. When the two atoms come in contact, the outer electron of sodium is
transferred to the chlorine atom. The reaction is shown below:
+
Na + Cl Na Cl

1s1 2s2 2p6 3s1 1s2 2s2 2p6 3s2 3p5

2e 8e 1e 2e 8e 7e

B.1.13 Covalent Bond

If the formation of compounds from a metal and a nonmetal is due to the electrostatic
attraction between two ions, the formation of a molecule is due to sharing of electrons
forming a covalent bond. He proposed the formation of a hydrogen molecule resulted
from equal sharing of electrons of two hydrogen atoms. The reaction is as follows:
H + H H H or H H

With such sharing of electrons, the hydrogen atom in the molecule is said to be more
stable than its atom by depicting the electronic configuration of the noble gas helium.

In some cases, atoms in a covalent bond do not equally share electrons. The ability of an
atom to attract towards itself the electron in a covalent bond is known as
electronegativity. Elements with high electronegativity tend to attract towards itself an
electron in the covalent bond more than elements with low electronegativity thus forming
polar covalent bonds. Polar covalent bond is the bond formed due to unequal sharing of
electrons between atoms that results in a shift of electron density towards the atom of
greater electronegativity. In the periodic table of elements, the same trend as ionization
energy and electron affinity is observed for electronegativity. Electronegativity is low for
metals and high for nonmetals. It decreases from top to bottom and from left to right.
Figure B.3 shows the electronegativity of the representative elements as devised by
Pauling:

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Figure B.3 Electronegativity of Representative Elements
2.1
H
1.0 1.5
Li Be
0.9 1.2 2.0 2.5 3.0 3.5 4.0
Na Mg B C N O F
0.8 1.0 1.5 1.8 2.1 2.5 3.0
K Ca Al Si P S Br
0.8 1.0 1.6 1.8 2.0 2.4 35
Rb Sr Ga Ge As Se Cl
0.7 0.9 1.7 1.8 1.9 2.1 2.5
Cs Ba In Sn Sb Te I
0.7 0.9 1.8 1.9 1.9 2.0 2.2
Fr Ra Tl Pb Bi Po At

Relatively, covalent bonds are weaker than ionic bonds. Covalent compounds are usually
low-melting solids, liquids or gases and ionic compounds are high-melting solids. Most
ionic compounds are soluble in water, and their aqueous solutions conduct electricity. On
the other hand, covalent compounds are insoluble or may be slightly soluble in water.
Their solutions in water do not conduct electricity or are non-electrolytes.

B.1.14 Formal Charge and Resonance

An atoms formal charge is given by the equation:
number of number of number of
Formal
= valence electrons nonbonding bonding (2)
Charge
or group number electrons electrons
In writing formal charges of an atom in a molecule, the sum of the charges in a neutral
molecule must be equal to zero. For ions like CO 32 and NH4+, the sum of the formal
charges of the atom must be equal to the charge of the anion or cation.
In some cases, molecules can be represented by more than one Lewis structures. These
structures and called resonating structures or resonance structures. Any one of these
structures, however, does not particularly represent the structure of the molecule. A
concrete example is the resonating structures of the carbonate ion.

B - 10
 O O O

O C O
O C O O C O

I II III

B.1.15 Types of Chemical Reactions

A chemical reaction is the combination of atoms or molecules to form an entirely new
substance. A chemical equation is used to denote the chemical change taking place
between atoms and molecules. The following are general types of chemical reactions:
1. Combination Reaction or Synthesis (A + B AB)
a. metal + O2 metallic oxide (basic anhydride)
Na + O2 Na2O
b. nonmetal + O2 nonmetallic oxide (acid anhydride)
S + O2 SO2
c. metallic oxide + H2O base
Na2O + H2O 2 NaOH
d. nonmetallic oxide + H2O acid
SO2 + H2O H2SO3
2. Decomposition Reaction (AB A + B)
a. metal oxide metal + O2

HgO Hg + O2
b. metal carbonates metal oxide + CO2

Na2CO3 Na2O + CO2

c. metal bicarbonates metal carbonate + CO2 + H2O

2 NaHCO3 Na2CO3 + CO2 + H2O

d. metal nitrates metal nitrite + O2

KNO3 KNO2 + O2

e. metal oxyhalides metal halide + O2

2 KClO3 2 KCl + 3 O2

3. Single Replacement (AB + C CB + A)

a. Halogen Replacement (according to halogen activity series)
2 KI + Cl2 2 KCl + I2
2 KCl + I2 no reaction
b. Hydrogen Displacement Reaction (according to metal activity series)
HCl(aq) + Zn(s) ZnCl2(aq) + H2(g)
HCl(aq) + Au(s) no reaction
Activity Series of Metals (arranged in decreasing activity)
Li K Na Ca Mg Al Mn Zn Cr Fe Ni Sn Pb H Cu Bi Sb Hg Ag Pt Au

B - 11
Activity Series of Halogens (arranged in decreasing activity)
F2 Cl2 Br2 I2

4. Double Replacement or Metathesis Reaction

a. Precipitation Reaction. Reaction that involves formation of precipitate or
insoluble solid in aqueous solution
AgNO3(aq) + NaCl(aq) AgCl(s) + NaNO3(aq)
b. Neutralization Reaction. Reaction of an acid and a base forming salt and
water
HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)

B.1.16 Molar Mass and Avogadros Number

The atomic mass is a relative scale for mass of elements. One atomic mass unit (amu) is
equal to one-twelfth of the mass of one carbon (C12) atom. The atom in one mole of C-
12 atom or 12 grams of C-12 atom is 6.022 x 10 23, known as the Avogadros number. The
molecular mass of a molecule is the sum of the atomic masses of elements making up the
molecule. The relationship between masses, number of moles and number of atoms can
be obtained as follows:
divide multiply

MASS MOLES Atoms

Molecules
multiply divide

MOLAR AVOGADROS
NUMBER
MASS

B.1.17 Solutions
Many chemical reactions take place between ions and molecules dissolved in water or in
any other solvents. Numerous reactions in nature takes place in water solutions like in
rivers, lakes and oceans. Aqueous solutions are of great interest to scientists since water is
considered to be a universal solvent.
This section includes properties of solutions, methods of expressing concentration of
solutions and reactions in solutions. Colligative properties of solutions are also included
in this section both for solutions of electrolyte and non-electrolyte.

B.1.18 Types of Solutions

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Solutions can be classified based on their capacity to dissolve a solute. A saturated
solution is a solution that contains the maximum amount of solute dissolved in a given
amount of solvent. This maximum amount of solute a solvent can hold is known as the
solubility and is a fixed value for a given temperature. An unsaturated solution contains
less amount of solute a given solvent can dissolve. A supersaturated solution contains
more than the maximum amount of solute a solvent can hold. This type of solution is
unstable and dissolved solute crystallizes out of the solution.

B.1.19 Mechanism of Dissolution

When a solute dissolves in a solvent, its particles disperse throughout the solvent. The
ease of dissolution is dependent on the strength of solute-solvent interactions, solute-
solute interactions and solvent-solvent interactions. The separation of solute and solvent
molecules requires energy to break intermolecular forces between them. The combination
of solute and solvent molecules can either require (endothermic) or release (exothermic)
some amount of energy. The dissolution is said to be exothermic if the solute-solvent
interaction overcomes the solvent-solvent and solute-solute interactions and is therefore
favorable.

B.1.20 Concentrations of Solutions

Concentration of a solution is the measure of the amount of solute dissolved in a given
solvent or solution. The following are common methods of expressing this amount of
solute in solutions or solvents:
1. Weight percent, %w/w
wt solute
% wt solute 100% (3)
wt solution
2. Weight by volume percent, %w/v
wt solute (gram)
% wt solute 100% (4)
vol solution (mL)
3. Volume Percent, %v/v
vol solute
% vol solute 100% (5)
vol solution
4. Mole Fraction, X
mol solute
X solute 100% (6)
mol solute mol solvent
5. Molarity, M
mol solute
M (7)
vol solution (L)
6. Molality, m

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 mol solute
m 100% (8)
wt solvent (kg)
7. Normality, N
equiv solute
N (9)
vol solution (L)

B.1.21 Colligative Properties of Solutions

These properties depend on the amount of solute present on the solution and the nature of
the solvent used. The following properties are as follows:
1. Boiling Point Elevation/Rise
TB TB,solution - TB,solvent K B m (10)
where TB boiling point elevation/rise
KB ebullioscopic constant / molal boiling point constant
m molality
2. Freezing Point Depression
TB TF, solvent - TF, solution K F m (11)
where TF freezing point depression
KB cryoscopic constant / molal freezing point constant
m molality
3. Vapor Pressure Lowering
P solvent - Psolution solvent X solute (12)
where P vapor pressure lowering
vapor pressure
X mole fraction of solute in solution
4. Osmotic Pressure. The pressure to prevent osmosis. Osmosis is the
MRT (13)
where osmotic pressure
M molarity, mol/L
R universal gas constant, 0.08205 L-atm / K-mol
T temperature of solution, K

The colligative properties of an aqueous solution can best viewed using a phase diagram
of both water and solution.

Figure B.4 Phase Diagram of Water and an Aqueous Solution

P
H2O
L
solution

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 1 atm

T
TF TB

B.1.22 Ideal Gases

Matter can exist in three forms namely solid, liquid and gases. Water exists as solid ice,
liquid water or even water vapor. Elements that exist as gases at standard ambient
condition include the noble gases, and the diatomic molecules such as H2, O2, N2, F2, and
Cl2. The physical characteristics of a gas include:
1. It assumes the volume and shape of its container
2. It has lower density compared to solids and liquids
3. It is compressible and mixes completely with other gases in a container

In this section, ideal gases and mathematical expressions describing its behavior are
discussed.

B.1.23 Kinetic Molecular Theory

James Maxwell and Ludwig Boltzmann proposed that the physical properties of gases
could be correlated to the motion of individual molecules. Such observations lead to
some generalizations about the behavior of gases called kinetic molecular theory of
gases. Gases that behave according to the kinetic molecular theory are called ideal gases.
The assumptions are given as follows:
1. Gases are composed of molecules separated from each other at a distance very
much greater than its size. It has mass but negligible volume.
2. Gas molecules move in random motion and collide with each other. The collision
is said to be perfectly elastic. This type of collision results in the conservation of
momentum and kinetic energy.
3. The individual gas molecules neither exert attractive nor repulsive forces with one
another.
4. The average kinetic energy of molecules varies directly to the absolute
temperature.

B.1.23 Ideal Gas Laws

B - 15
Based from experiments on the physical properties of gases, several generalizations was
made to explain the macroscopic behavior of ideal gases as temperature, volume,
pressure and its amount in moles are varied.
1. At constant temperature (isothermal condition), the pressure of a gas varies
inversely to its volume. Robert Boyle using a U-tube filled with mercury observed
this relationship of pressure-volume as the temperature of a gas is fixed.
P1V1 = P2V2
(14)
Boyles Law
2. At constant pressure (isobaric condition), Jacques Charles and Joseph Louis Gay-
Lussac proposed that the volume of a fixed amount of gas varies directly to its
temperature in Kelvin.
V1 V2

T1 T2 (15)
Charles Law
3. At constant volume (isochoric condition), the pressure of a fixed amount of gas
increases as the temperature increases. This study was done by Guillaume
Amonton.
P1 P
2
T1 T2 (16)
Amontons Law
4. At constant pressure and temperature, volume of a gas is directly proportional to
the number of moles of the gas. At 1 atm and 0C, one mole of a gas occupies
22.414 L. The mathematical expression of Avogadros Law is
V1 V2

n1 n2 (17)
Avogadros Law

Combining these laws, the relationship of pressure, volume, temperature, and the amount
of gas in moles can be expressed as
PV nRT (18)
The values of the universal gas constant, R is given in Table B.1

Table B.2 Universal Gas Constant

m 3 Pa m 3 bar
8.314 0.08314
gmol K gmol K
L atm L mm Hg
0.08205 62.36
gmol K gmol K

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 cal ft 3 psia
1.987 10.73
gmol K lbmol R

For mixture of ideal gases at constant temperature and volume, the total pressure of an
ideal gas mixture is equal to the sum of the partial pressures of the individual gases in the
mixture. This is a statement of the Daltons Law of Partial Pressure. Consider a mixture
of three ideal gases with nA, nB and nC number of moles at temperature, T and occupying
a volume V
PT PA PB PC (19)
nA nA
PA PT PT y A PT (20)
nA nB nC nT
Similarly at constant temperature and pressure (Amagats Law of Partial Volume)
VA
yA (21)
VT
For the diffusion of gases, Thomas Graham in 1830 states that rates of diffusion of two
gases is inversely proportional to the square root of their densities. Since the density of an
ideal gas is directly proportional to its molecular weight, Grahams Law of Diffusion can
be expressed as:
rA B MWB
(22)
rB A MWA

B.1.24 Nuclear Chemistry

A special type of reaction that involves the change of atoms to different types of atoms is
a called a nuclear reaction. A branch of chemistry that deals with the study of changes
occurring in radioactive substances is Nuclear Chemistry. A radioactive element is one
that spontaneously emits radiation. Most of the radioactive elements are not found free in
nature but are made synthetically. Of the 3000 nuclides, 280 are stable and the rest are
unstable and said to change to a different nuclide. Such change is known as radioactive
decay. Table B.2 summarizes different emitted particle or radiation in a radioactive decay.

Table B.3 Types of Emitted Particle/Radiation

PARTICLE CHARGE SYMBOL
beta particle / electron -1 0
1 or 0
1 e
positron +1 0
1 or 0
1 e
1 1
proton or a hydrogen nucleus +1 1 p or H
1
1
neutron 0 0 n

B - 17
 gamma ray 0
0
0
alpha particle or helium nucleus +2 4
2 or 4
2 He

B.1.25 Types of Radioactive Decay

There are three emissions characteristic of most radioactive decay. These are alpha (),
beta () and gamma () emission. Typical examples of radioactive decay are as follows:
1. Alpha Emission
211
83 Bi 207
81 Tl 4
2
2. Beta Emission
10
4 Be 10
5 B 0
-1
3. Electron Capture
50
23 V 0
-1 e 50
22Ti X - ray
4. Gamma Ray Emission
211
83 Bi 207
81 Tl 4
2 0
0
5. Neutron Emission
87
36 Kr 86
36 Kr 1
0 n
6. Positron Emission
54
27 Co 54
26 Fe 0
1

B.1.26 Application of Radioactivity

Radioactive decay follows first order kinetics such that the amount of substance left at
any time, t is given by

A t A o e kt (23)

The specific rate constant, k can be obtained using the half-life of the radioactive
substance.
ln2
k (24)
t 1/2
The half-life of a substance is the time required for 50% of the original amount to decay.
Typical half-life of radioactive materials are given in Table B.4

Table B.4 Half Life of Radioactive Substances and Uses

HalfLife, t Uses
Determination of organic objects to over 70,000 years
C14 5730 yrs
or older

B - 18
U238 4.51 x 109 yrs Estimation of ages of rocks and extraterrestial objects
Used in geochemistry for age of specimens by electron
K40 1.2 x 109 yrs
capture
Used in ionization chambers of smoke-detecting
Am241 433 yrs
devices
Sr90 28 yrs Used as power sources for instruments in space or sea
Cm247 18 yrs explorations
I131 8 days Used for treatment of thyroid cancers
Used for the detection of damaged or malfunctioning
Tl201 74 hrs
cells in the heart or blood vessel cells
Tc99 6 hrs Used in the detection of diseased tissues

B - 19
B.2 Analytical Chemistry
This branch of chemistry involves the study of separation, identification and composition
of matter. It is divided into two: quantitative analysis and qualitative analysis.
Qualitative analysis involves identification of the components of a given sample while
quantitative analysis deals with the determination of the proportions at which the
components are present.

B.2.1 Methods of Analysis

In quantitative analysis, methods are classified as classical and modern methods.
Classical methods include gravimetric methods and volumetric methods. Modern
methods are instrumental methods like electroanalytic and spectroscopic methods.

Gravimetric analysis involves the determination of weight of the substance chemically

related to it. Volumetric analysis deals with the volume of the solution that is chemically
equivalent to the analyte.
Electroanalytic methods, on the other hand, measure the electrical properties of the
sample such as current, potential difference, and resistance. Spectroscopic methods relate
the production of electromagnetic radiation of analytes or their interactions.

A typical analysis starts with the search for an appropriate method that will satisfy the
need for an accurate and economical one. Standard analyses can be obtained from
published journals like Association of Official Analytical Chemists (AOAC). After the
method selection, sampling is done. A laboratory sample is obtained in such a way that it
represents the entire bulk sample. Physical treatment like grinding and crushing is done to
the sample to attain a size fit for the laboratory. Replicate samples are also prepared to
ensure reliability of the analysis. Commonly, analyses are done in solutions. The most
common solvent is water. If the sample is sparingly soluble, acids, bases and fluxing
agents in varying concentrations and application of heat are used to completely dissolve
the sample. In most of the samples, some substances are present that interferes in the
analysis. Precipitation and masking are usually employed to eliminate such interferences.
After these substances are removed, measurement of the analyte is done based on the
methods described. Statistical methods are then finally applied to the data obtained to
check on the accuracy and precision of data.

B.2.2 Gravimetric Analysis

Gravimetric method deals on mass measurement. One type of gravimetric analysis is
precipitation method. In this method, the analyte is converted into a sparingly soluble
precipitate by the addition of a precipitating agent. The precipitate is then filtered, washed
and converted into a product of known composition and weighed. Another type is

B - 20
volatilization method. In this method, the analyte decomposes and the lost of mass of the
sample indicates the amount of product that is chemically related to the analyte. In some
cases, the decomposition product is collected or absorbed and then weighed.

The percentage of the analyte by mass in the sample can be computed using the
gravimetric factor, (GF):
substance weighed GF
% wt analyte 100% (25)
mass of sample
Molar Mass of desired substance (ds) x ds
GF (26)
Molar Mass of substance weighed (sw) y sw

B.2.2.1 Precipitation Method

In dealing with this method, a precipitating agent must be properly selected so that the
precipitate obtained is easily filtered, inert towards the atmosphere and of known
composition after drying or application of a suitable heat treatment. Table B.5 lists the
common inorganic and organic precipitants.

Table B.5 Common Organic and Inorganic Precipitants

Precipitant Element(s) Precipitated Weighed Form

Al Al2O3
NH3 Fe Fe2O3
Cr Cr2O3
Mg Mg2P2O7
(NH4)2HPO4
Zn Zn2P2O7
H2PtCl6 K K2PtCl6
Cl AgCl
AgNO3 Br AgBr
I AgI
BaCl2 SO4= BaSO4
Ni Nickel
dimethylglyoxime
dimethylglyoxime
K+ KB(C6H5)4
NaB(C6H5)4
NH4+ NH4B(C6H5)4

B.2.3 Volumetric Analysis

This method involves the measurement of the volume that will react with the analyte
completely. A standard solution is used to titrate the sample. A standard solution is a

B - 21
solution of known concentration. Methods of expressing concentrations of solutions are
discussed in section B.1.20. For a standard solution, it must be stable, reacts rapidly and
completely with the analyte and its reaction with the analyte can be described by a simple
chemical equation. The concentration of a standard solution is done by standardization
using a primary standard. A primary standard is a compound of high purity, stable
towards air, soluble in water and readily available at a reasonable cost. In this section,
acid-base, precipitation, complex formation, and oxidation-reduction titrations are
discussed with its applications.

B.2.3.1 Acid-Base Titration

Neutralization reaction is a reaction between an acid and a base to form salt and water.
The reaction is almost complete and can be represented through a simple chemical
equation. Definitions of acids and bases are given in Table B.6.

Table B.6 Definitions of Acids and Bases

DEFINITIONS ACIDS BASES
+
Produces H3O Produces HO ions
Arrhenius
ions in solution in solution
BronstedLowry Proton donor Proton acceptor
Electron pair Electron pair
Lewis
acceptor donor

Acids and bases can be classified according to the number of replaceable hydronium ions
or equivalent hydroxide ions or according to their extent of ionization or dissociation in
water. Strong acids/bases ionize completely in water while weak acids/bases partially
ionize in water. Table B.7 summarizes this classification.

Table B.7 Classification of Acids and Bases

According to Extent of Ionization
ACIDS BASES
HCl HNO3
Bases of Group 1A
Strong HBr HClO4
and Group 2A
HI H2SO4*
HNO2 HCN
NH3 and
Weak HF Organic
derivatives
H2SO3 acids

B - 22
 According to Number of Replaceable Hydronium Ion and Equivalent Hydroxide Ion
ACIDS BASES
Monoprotic HNO3 HCN LiOH NH3
Monoequivalent HCl CH3COOH NaOH CH3NH2
Diprotic H2SO4 H2C2O4 Ba(OH)2
Mg(OH)2
Diequivalent H2CO3 H2C4H4O6 Ca(OH)2
Polyprotic H3PO4
H3AsO4 Al(OH)3
Polyequivalent H3PO3

B.2.3.1.1 Strength of Acids and Bases

The strength of an acid and a base is measured through its pH. When the acid is the major
contributor of the hydronium ion (H3O+) in solution, the pH can be calculated as

pH log H 3O (27)
For alkali solutions, the pOH can be a measure of its strength and is computed as
pOH log HO (28)
For solutions at 25C, the pH and pOH are related as follows:
pH pOH 14 (29)
The ionization reactions of acids and bases are summarized as follows:
HCl + H2O H3O+(aq) + Cl(aq) strong acid
HCN + H2O H3O+(aq) + CN(aq) weak acid
NaOH + H2O Na (aq) + HO (aq)
+
strong base
+
NH3 + H2O NH4 (aq) + HO (aq) weak base

Note that for strong acids and bases, reaction goes to completion and the concentration of
the acid or base is equal to the concentration of the hydronium or hydroxide ion. For
weak acids and bases, the extent of ionization is given by their ionization constant, KI.
Table B.8 shows the ionization constant of common weak acids and bases.
Table B.8 Ionization Constant of Common Weak Acids and Bases at 25C
ACID KA BASE KB
Acetic Acid 1.75 10 5
Ammonia 1.75 105
Benzoic Acid 6.28 105 Aniline 3.98 1010
Formic Acid 1.80 104 Methyl amine 4.35 104
Hydrogen cyanide 6.2 1010 Dimethyl amine 5.95 104
Hydrogen fluoride 6.8 104 Trimethyl amine 6.33 105
Nitrous acid 7.1 104 Hydrazine 9.52 107
The pH of acids and bases can be computed using the following equations:

B - 23
 Strong Acid pH log C acid 30
K 2 4K C
acid K A
pH log
A A
Weak Acid 31
2

Strong Base pH log n OH C base 32
K 2 4K C
base K B
pH 14 log
B B
Weak Base 33
2

The extent of ionization can also be expressed in terms of percentage ionization:

% ionization
H O or HO 100%
3
-

34
C acid or C base
Based from the equations presented, the higher the ionization constant, the more acidic or
alkaline the solution is and therefore the higher the percentage ionization. It is also
important to note that pH is applicable to dilute solutions of acids and bases and the
logarithmic function is used solely for convenience thus avoiding very small number
expressed in scientific notation. For acids greater than 1M, the pH is not anymore
applicable. Since the logarithm of real numbers greater than one is positive, the pH value
that can be obtained is negative.

B.2.3.1.2 Standardization of Acids and Bases

Titrimetric methods of analysis measure the volume of solutions of known concentration
that is chemically equivalent to the analyte in the sample. Standardization is the process
of such concentration determination. For acids and bases, several primary standards are
being used that are obtained in such a high purity, greater extent of solubility in water,
high molecular weight and very stable towards air. Table B.9 presents the primary
standards used for acids and bases.
Table B.9 Primary Standards used for Standardization of Acids and Bases
ACID BASE
Sodium Carbonate, Na2CO3 Potassium Hydrogen Phthalate (KHP)
O- K+
Na+ O-
O C Molar Mass = 106 Molar Mass = 204.22
Na+ -O C
HO C
COCH32+2H3O+ 3H2O+CO2
O
C C CH

Tris-hydroxylmethylamino
O HC CH methane
OH
Sulfamic Acid, HSO3NH2
H2C

H2C C NH2

HO
B - 24
H2C
OH
 Molar Mass = 121

Molar Mass = 97.09

Mercuric Oxide, HgO Benzoic Acid, C6H5OH

HO HC CH

Hg ++
O--2
Molar Mass = 122.12
C C CH
Molar Mass = 216.59
O O CH
HC
HgO + 4I + H2O HgI42 + 2HO
2 3O 2H2O
+
HO SHO NH+H Oxalic acid, H2C2O4
O
Sodium
O Tetraborate Decahydrate
C OH
Molar Mass = 90
HO C Na2B4O7 . 10H2O
Molar Mass = 381
O
B4O7 + 2H3O+ + 3H2O 4 H3BO3
2
H2C2O4 + 2HO C2O42 + 2H2O

Note: Primary standards listed reacts in 1:1 ratio with an acid or base otherwise reaction
is specified.

B.2.3.1.3 Indicators for Titration, Titration Curves and Buffer Solutions

When the standard solution added is chemically equivalent to the analyte in the sample,
the equivalence point is attained. Such point in the reaction is detected using an indicator.
These indicators are consisting of weak organic acid or base whose undissociated form
has different color with its conjugate. The point at which there is an observable change in
the solution due to color change of the indicator is known as end point.

Table B.10 AcidBase Indicators

ACID TYPE
pH Color
Name
Transition Range Change
Bromothymol blue 6.2 7.6 yellow to blue
Phenolphthalein 8.3 10.0 colorless to pink
Bromocresol green 3.8 5.4 yellow to blue

B - 25
 BASE TYPE
Methyl orange 3.1 4.4 red to yellow
Methyl red 4.2 6.3 red to yellow
Methyl yellow 2.9 4.0 Red to yellow

When the acid reacts completely with the base, salt and water is formed. The nature of
the salt dictates the pH of the solution thus the indicator to be used for titration.
At equivalence point, only the salt is responsible for the relative acidity or alkalinity of
the solution. For titration of a strong acid with a strong base, the pH at equivalence point
is 7 or nuetral. A concrete example is the titration of HCl and NaOH.
HCl + NaOH NaCl + H2O
For titration of a weak acid with a strong base, the salt formed is basic and therefore the
pH at equivalence point is greater than 7. Titration of acetic acid with sodium hydroxide
is a typical example.
CH3COOH + NaOH CH3COONa + H2O
(pH at equivalence point > 7.0)
When the salt is formed, it may undergo hydrolysis. As a general rule, salt coming from
weak acids or weak bases hydrolyzes in water. For sodium acetate, the hydrolysis
reaction is
CH3COO + H2O CH3COOH + HO
The pH at equivalence point can be calculated as:
K 2 4K C K
pH 14 log
h h salt h
35
2

K W 110 14
Kh , hydrolysis constant 36
KA KA

For titration of a weak base with a strong acid, the resulting solution is acidic. Titration of
ammonia with HCl gives the reaction:
HCl + NH3 NH4Cl
The hydrolysis reaction for NH4Cl is
NH4+ + H2O H3O+ + NH3
The pH of the solution is calculated as follows:
K 2 4K C K
pH log
h h salt h
37
2

The titration of weak acid with a weak base is not commonly used in volumetric analysis.
This is because there is no sharp endpoint observed and no indicator can be used to signal

B - 26
the end of titration. However, the pH at equivalence point can be calculated using the
equation:
KWKA
pH 1 2 log 38
KB
For the reaction,
NH4OH + CH3COOH NH4OOCH3 + H2O
The ionization constants for acetic acid and ammonia are used to calculate the pH at
equivalence point and KW is the ionization constant for water at 25C having a value of 1
x 1014. The self-ionization or autoprotolysis of water is given by the reaction:
H2O + H2O H3O+ + HO

Titration curves are being used to identify the indicator fit for a given combination of
acids and bases. Table B.11 are examples of titration curves.

Table B.11 Titration Curves

Titration Curve of 0.1 M CH3COOH with 0.1 M NaOH

14
13
12
11
10
9
8
pH

7
6
5
4
3
2
1
0
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56 58 60

Volum e of Base Added

B - 27
 Titration Curve of 0.1 M HCl with 0.1 M NaOH

14
13
12
11
10
9
8
pH

7
6
5
4
3
2
1
0
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56 58 60

Volum e of Base Added

Note that in the titration of a weak acid with a strong base, a region wherein the addition
of base has a little effect on the pH of solution. This region is known as the buffer region.
In this region, the solution contains the unreacted weak acid and its conjugate salt. The
solution formed is known as buffer solution. At this point in titration, the pH of the buffer
solution formed can be computed using the HendersonHasslebalch Equation given as
follows:
pH pK A log
acidic component
39
basic component
If a buffer solution containing a weak base and its conjugate salt is present, pK A can be
obtained using the relationship:
K
KA W 40
KB

B.2.3.1.4 Applications of AcidBase Titration

Kjeldahl Method. This method is used to determine organic nitrogen content of samples
and can be extended for protein determination. The following steps are followed for this
analysis:
1. Digestion. The sample is oxidized in hot, concentrated sulfuric acid, H2SO4
and turns black. This step is necessary to convert carbon and hydrogen to CO 2
and H2O, amides and amines to NH4+ and azo, azoxy and nitro group to N or
its oxides. Potassium Sulfate (K2SO4) is also used to increase the boiling point
of sulfuric acid and Mercuric Oxide (HgO) as promoter.

B - 28
 2. Distillation. The oxidized solution is cooled and treated with NaOH to liberate
ammonia gas according to the reaction: NH4+ + HO- NH3(g) + H2O
3. Titration. Ammonia due to its high volatility can be collected in two ways:
i. Using an excess amount of hydrochloric acid, HCl. The NH3 liberated
from the sample is collected in an excess amount of standard HCl solution
and the excess is determined by a standard NaOH solution using methyl
red indicator. This type of titration is called back titration. The amount of
nitrogen in the sample is calculated as:
1 mol HCl 1 mol NH 3 1 mol N 14.07 g N
g N M HCl VHCl M NaOH VNaOH 41
1 mol NaOH 1 mol HCl 1 mol NH 3 1 mol N
ii. Using an excess amount of boric acid, H 3BO3. Ammonia is collected in an
excess amount of boric acid solution. The reaction is
NH3 + H3BO3 NH4+ + H2BO3-2
The reaction of ammonia with boric acid produces a strong conjugate
base, H2BO3-2 that is titrated by a standard HCl solution. This type of
titration is called replacement titration. The nitrogen content of the sample
is determined by the equation:
-2
1 mol H 2 BO 3 1 mol NH 3 1 mol N 14.07 g N
g N M HCl VHCl -2
42
1 mol HCl 1 mol H 2 BO 3 1 mol NH 3 1 mol N
To get the nitrogen content of the sample,
gN
% N wt 100% 43
g sample
The protein content of the sample can also be calculated using the following factors:
% CHON = % N * f 44
where f = 6.25 for meat products
f = 6.38 for dairy products
f = 5.70 for cereals

DoubleIndicator Titration. One interesting application of neutralization titration is the

quantitative and qualitative of mixture of acids and bases.

Mixture of Bases. These samples contain sodium carbonate, sodium hydroxide and
sodium bicarbonate, either alone or in compatible combinations. In this method, the
sample is titrated with standard HCl to the phenolphthalein endpoint. When the solution
becomes colorless, methyl red is added and titrated until the solution turns salmon pink.
Table B.12 shows the variation of volume for two endpoints and the corresponding
components of the mixture.

B - 29
Table B.12 Mixture of Bases using Phenolphthalein and Methyl Red
COMPONENT VOLUME OF TITRANT
Na2CO3 and NaOH *V0-Ph > VPh-MR
Na2CO3 and NaHCO3 V0-Ph < VPh-MR
NaOH only VPh-MR = 0
Na2CO3 only V0-Ph = VPh-MR
NaHCO3 only V0-Ph = 0
* All volume terms used in this text are in liters (L)

For a mixture of Na2CO3 and NaOH, the percentage of each component in the sample is
calculated using the following equations:
1 mol Na 2 CO3 106.00 g Na 2 CO3
2 VPh MR ( M HCl )
2 mol HCl 1 mol Na 2 CO3 45
% Na 2 CO 3 100%
mass of sample (gram)
V0Ph - VPh MR (M HCl ) 1 mol NaOH 40.00 g NaOH
% NaOH 1 mol HCl 1 mol NaOH 100% 46
mass of sample (gram)

For a mixture of Na2CO3 and NaHCO3, percentage composition of the sample is

calculated using the following equations:
1 mol Na 2 CO 3 106.00 g Na 2 CO 3
2 V0Ph M HCl
2 mol HCl 1 mol Na 2 CO 3 47
% Na 2 CO 3 100%
mass of sample (gram)
VPh MR - V0Ph M HCl 1 mol NaHCO3 84.01g NaHCO3
1 mol HCl 1 mol Na 2CO 3 48
% NaHCO3 100%
mass of sample (gram)

For samples containing NaOH, Na2CO3 or NaHCO3, the amount of each component in
weight percentage is given as follows:

V0Ph M HCl 1 mol NaOH 40.00 g NaOH

% NaOH 1 mol HCl 1 mol NaOH 100% 49
mass of sample (gram)

VPh MR M HCl 1 mol NaHCO3 84.01 g NaHCO3

1 mol HCl 1 mol Na 2 CO 3 50
% NaHCO3 100%
mass of sample (gram)

B - 30
 1 mol Na 2 CO 3 106.00 g Na 2 CO 3
2 V0Ph M HCl
2 mol HCl 1 mol Na 2 CO 3 51
% Na 2 CO 3 100%
mass of sample (gram)

In some procedures, duplicate samples are titrated with standard HCl, one with
phenolphthalein indicator and the other sample with bromocresol green. Table B.13
shows the volume at phenolphthalein and bromocresol green endpoint for sample of
mixture of bases.
Table B.13 Mixture of Bases using Phenolphthalein and Bromocresol Green
COMPONENT VOLUME OF TITRANT
Na2CO3 and NaOH V0-Ph > V0-BCG
Na2CO3 and NaHCO3 V0-Ph < V0-BCG
NaOH only V0-Ph = V0-BCG
Na2CO3 only V0-Ph = V0-BCG
NaHCO3 only V0-Ph = 0

The amount of the components are calculated as follows:

Mixture of Na2CO3 and NaOH
1 mol Na 2 CO3 106.00 g Na 2 CO3
2 V0BCG - V0Ph (M HCl )
2 mol HCl 1 mol Na 2 CO3 52
% Na 2 CO3 100%
mass of sample (gram)
2V0Ph - V0BCG (M HCl ) 1 mol NaOH 40.00 g NaOH
% NaOH 1 mol HCl 1 mol NaOH 100% 53
mass of sample (gram)
Mixture of Na2CO3 and NaOH
1 mol Na 2 CO 3 106.00 g Na 2 CO 3
2 V0Ph ( M HCl )
2 mol HCl 1 mol Na 2 CO 3 54
% Na 2 CO 3 100%
mass of sample (gram)
V0MR - 2V0Ph (M HCl ) 1 mol NaHCO3 84.01g NaHCO3
1 mol HCl 1 mol Na 2CO3 55
% NaHCO3 100%
mass of sample (gram)

B - 31
For individual samples of NaOH, Na2CO3 and NaHCO3
V0BCG M HCl 1 mol NaOH 40.00 g NaOH
% NaOH 1 mol HCl 1 mol NaOH 100%
56
mass of sample (gram)
Note: V0-BCG = V0-Ph

12 V0BCG M HCl 1 mol Na 2CO 3 106.00 g Na 2 CO 3

2 mol HCl 1 mol Na 2 CO 3
% NaOH 100% 57
mass of sample (gram)
Note: V0-Ph = V0-BCG

V0BCG (M HCl ) 1 mol NaHCO3 84.01 g NaHCO3

1 mol HCl 1 mol Na 2 CO 3 58
% NaHCO3 100%
mass of sample (gram)

Free Fatty Acid (Acid Number). It is expressed as the milligram of KOH needed to
neutralize the free fatty acid released by one gram of oil due to water oxidative
degradation. High value of the acid number implies deterioration of the oil or fat. The
Acid Number is computed as follows:

M KOH VKOH 56.11 g KOH 1000 mg

1 mol KOH 1g 59
Acid Number
mass of oil sample (gram)
Saponification Number (Koettstorfer Number). A measure of the mean molecular weight
of the fatty acid. Expressed as the milligram of KOH required to saponify one gram of fat
or oil. In the analysis, a sample is boiled in a reflux condenser with alcoholic KOH.

M HCl Vblank Vsample HCl 1 mol KOH 56.11 g KOH 1000 mg

1 mol HCl 1 mol KOH 1 g60
Saponification No.
mass of oil sample (gram)

B.2.3.2 Precipitation Titration

In this section, titrations involving the use of AgNO 3 solutions are discussed.
Argentometric titration is used to determine chloride, bromide, cyanide and even silver.
Mohr, Volhard and Fajan Method are included in this section.

B.2.3.2.1 Solubility Product Constant

For a saturated solution of a sparingly soluble salt, equilibrium is established between the
undissolved salt and its ion in the solution. Consider a saturated solution of lead(II)
chloride

B - 32
 PbCl2(s) Pb2+(aq) + 2Cl(aq)
The mathematical expression of this equilibrium is expressed as
[Pb 2 (aq) ] [Cl- (aq) ]2
K eq
[PbCl 2(s) ]
Since the activity of a pure substance is unity and for a solute in dilute solution is the
same as its concentration, the solubility product constant is defined as:
K sp [Pb 2 (aq) ] [Cl (aq) ]2
From this expression, high Ksp value means the salt is more soluble in water. If x, is the
molar solubility of PbCl2, then x moles of lead ion and 2x moles of chloride ion will be
present in solution. Therefore, the Ksp expression for PbCl2 in terms of its molar solubility
is 4x3. Some values of Ksp are given in Table B.14.

Table B.14 Solubility Product Constants at 25C

Salt Ksp Salt Ksp Salt Ksp
AgBr 5.0 10 13
Ag2CrO4 1.2 1012 Ca(OH)2 6.5 106
Hg2Br2 5.6 1023 BaCrO4 2.1 105 AgI 8.3 1017
PbBr2 2.1 106 AgCN 2.2 1016 PbI2 7.9 109
AgCl 1.8 1010 Hg2(CN)2 5.0 1040 Hg2I2 1.1 1028
Hg2Cl2 1.2 1018 CaF2 3.9 1011 Ag2S 8.0 1051
PbCl2 1.7 105 Mg(OH)2 7.1 1012 PbS 3.0 1028
B.2.3.2.2 Common Precipitimetric Methods
The equivalence point of precipitation titrations can be observed through the following:
a. Formation of a secondary colored precipitate (Mohr Method)
b. Formation of a colored complex ion (Volhard Method)
c. Formation of colored adsorption compound (Fajan Method)

Mohr Method. This method is used for the direct determination of chlorides and
bromides. The titration uses a small amount of K2CrO4 (about 1 mL of a 5% wt. K2CrO4)
as indicator. During titration, the solution must be neutral to avoid precipitation of silver
oxide (pH>10) or conversion of the indicator to dichromate (pH<6). The endpoint is
observed through the formation of a red precipitate of Ag 2CrO4. The titration and
indicator reactions are as follows:
Titration Reaction: Ag+ + Cl AgCl(s)
Indicator Reaction: Ag+ + CrO42 Ag2CrO4(s)

Fajan Method. The use of adsorption indicators is used for the direct determination of
chlorides, bromides, iodides and thiocyanates. Fluorescein, dichlorofluorescein and Eosin

B - 33
are used as indicators. In the titration of chloride ion with AgNO3, the addition of excess
silver ion results in the adsorption of this ion to the AgCl precipitate hence acquiring a
positive charge and attracts negative ion to the counter-ion layer. The indicator anion,
initially yellow in color, is then attracted to the counter-ion layer and changes color to
pink, signaling the endpoint of the titration.
Titration Reaction: Ag+ + Cl AgCl(s)
Indicator Reaction: AgClAg+ + DCF AgClAg+:DCF

Volhard Method. This method is used for the direct determination of silver using KSCN
as titrant and ferric ions as indicator. It is also applied for the indirect determination of
halides. Titration is carried out in acidic medium to prevent precipitation of the ferric ion
indicator to its hydrated oxide form. The endpoint is observed by the formation of a red
brown complex of Fe(SCN)2+.
Direct Titration Reaction: Ag+ + SCN AgSCN(s)
Indirect Titration reaction: Ag+ + Cl AgCl(s)
Ag+ + SCN AgSCN(s)
Indicator Reaction: Fe+3 + SCN Fe(SCN)2+

B.2.3.3 ComplexFormation Titration

This type of titration is usually used for the determination of cations. In this section
titration with aminocarboxylic acids and the Liebig Method for cyanides are discussed.

B.2.3.3.1 Titration with EDTA

Most metals react with Bronsted bases to form coordination compounds. Typical
examples of these Bronsted bases are water, ammonia and the halide ions.
Ethylenediamminetetraacetic acid or commonly known as EDTA is used for
compleximetric titration. It is a hexadentate ligand that is capable of bonding with metal
ions. EDTA has six sites available for bonding that include four carboxyl groups and two
amino groups. Commercially, the free acid and the dihydrate disodium salt is available.
The standard solutions of EDTA combine in a 1:1 ratio with any metal ion and titration is
carried out using Eriochrome Black T (EBT) or Calmagite. Calcium carbonate is used as
primary standard dried at 110C and dissolved in concentrated HCl solution.

B - 34
B.2.3.3.2 Displacement Titration with EDTA

In the determination of cations, it is necessary to add metal cations that forms complex
with EDTA and is less stable with the analyte ionEDTA complex. In the determination
of calcium, a small amount of magnesium ion is added using magnesium chloride in an
EDTA solution. In the first stage of the titration, calcium ion displaces the magnesium ion
in the EDTA complex and a red complex of calcium-EDTA is formed. When all calcium
ions are titrated, the magnesium ion combines with the EDTA imparting a blue color
using EBT as indicator thus signals the endpoint of the reaction.

The following reactions are observed in the titration:

Titration Reaction: Ca+2 + MgY2 CaY2 + Mg+2
Mg+2 + In MgIn
red
Endpoint Reaction: MgIn
+ H2Y 2
MgY2 + HIn2 + H+
red blue

B.2.3.3.3 Back Titration with EDTA

Determination of aluminum involves back titration with EDTA. In the analysis, the
solution is buffered to pH=7 to avoid precipitation of aluminum as Al(OH) 3. To ensure
complete formation of the aluminum complex, the solution is boiled and the excess
EDTA is determined by a standard magnesium solution using calmagite as indicator.

B.2.3.3.4 Determination of Cyanides and CyanideHalide Mixture

The dropwise addition of silver nitrate results in the formation of a soluble silver cyanide
complex:
Ag+ + CN Ag(CN)2

The endpoint of the titration is observed through the formation of a faint turbid solution
as shown in the reaction:
Ag(CN)2 + Ag+ Ag[Ag(CN)2]
For a mixture of cyanide and halide, the addition of AgNO 3 causes the precipitation of
CN as soluble Ag(CN)2 complex. Further addition of a measured excess amount of
standard AgNO3 results in the formation of insoluble precipitates of Ag[Ag(CN)2] and
AgCl. The precipitate is filtered and the excess solution is determined by a standard
KSCN. This method is a combination of Liebig and Volhard Method.

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B.2.3.3.5 Determination of Nickel

A sample containing nickel was treated with ammonia solution forming a soluble
hexaamminenickel(II) complex:
Ni+2 + 6NH3 Ni(NH3)6+2
The ammoniacal solution of nickel is treated with excess standard cyanide solution. The
excess cyanide is determined using the Liebig Method.
Ni(NH3)6+3 + 4CN1 + 6H2O Ni(CN)41 + 6NH4OH

B.2.3.3.5 Determination of Mercury

In this analysis, mercury complexes with EDTA and forms a stable complex but cannot
be titrated using Calmagite or EBT indicator. Instead, a solution of MgY2 is added in
excess and the liberated Mg+2 is titrated by EDTA. The reaction proceeds as follows:
Hg+2 + MgY2 HgY2 + Mg+2

B.2.3.4 Oxidation Reduction Titration

Modern methods utilize the electrical properties of materials due to their ability to accept
and donate electrons during reaction. This method of volumetric titration involves
oxidation and reduction reactions wherein reactants undergo changes in its oxidation
state. Oxidation reaction involves an increase in the oxidation number of the substance
by losing electrons. Reduction reaction, on the other hand, results in the decrease of
oxidation number by gaining electrons.

B.2.3.4.1 Permanganate Titration

In this process, potassium permanganate (KMnO4) is used as titrant and can oxidize
various ions of iron, mercury, tin and anions such as oxalate, nitrite and sulfite. It is a
powerful oxidizing agent and reduced to Mn+2 in acidic medium and to MnO2 in weakly
acidic or alkaline and neutral solutions according to the reactions:
MnO41(aq) + 8H+(aq) + 5e Mn2+(aq) + 4H2O(l)
MnO41(aq) + 2H2O(l) + 3e MnO2(s) + 4HO(aq)
The solution of KMnO4 is quite unstable and normally kept in a colored bottle. It is a
very powerful oxidizing agent in which even water is oxidized and wavelengths of light
can actually promote such reaction. The endpoint is observed by a pink color of the
solution due to the excess addition of the titrant. Standardization of KMnO 4 is done using
sodium oxalate and arsenious oxide.

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Sodium oxalate, Na2C2O4 dried at 105C is dissolved in water and sulfuric acid and
titrated with the solution, adding about 140 times the weight of dissolved primary
standard. The solution is then heated from 55-60C and titrated until a faint pink color
persist after 15 minutes of stirring. The titration reaction is as follows:
5H2C2O4 + 2MnO4 + 6H+ 2Mn+2 + 10CO2 + 8H2O

Arsenious oxide, As2O3 dissolved in 6N NaOH is made acidic with HCl and treated with
a dilute solution of KI that serves as a catalyst in the reaction. Titration with KMnO 4 then
proceeds until a faint pink solution is observed. The reactions are:
As2O3 + 6HO 2AsO33 + 3H2O
AsO33 + 6H+ As+3 + 3H2O
5As+3 + 2MnO4 + 12H2O 5H3AsO4 + 2Mn+2 + 9H+

One application of permanganate titration is the determination of iron. In the analysis,

iron-containing sample is dissolved by an appropriate solvent. However, iron was found
to exist in two oxidation states and pre-reduced before the treatment. Several metals like
zinc, silver, lead and aluminum were found to be useful for pre-reduction. A typical
example is the Jones reductor, which is composed of a vertical tube filled with
amalgamated zinc. Another type is the Walden reductor, in which metallic silver is being
used. The reaction involved in the determination of iron is
5Fe+2 + MnO4 + 8H+ 5Fe+3 + Mn+2 + 4H2O

Table B.15 shows other applications of permanganate titration.

Table B.15 Application of Permanganate Titration

Analyte Reaction Treatment
Metal is precipitated as
5H2C2O4 + 2MnO4 + 6H+
Mg, Ca, Ba, Co oxalate and titration is carried
2Mn+2 + 10CO2 + 8H2O
out in acidic medium
5HNO2 + 2MnO4 + H+ Back titration
NO2
2Mn+2 + 5NO3 + 3H2O
5H2O2 + 2MnO4 + 6H+ Titration in acidic medium
H2O2
2Mn+2 + 5O2 + 8H2O
5Sn+2 + 2MnO4 + 16H+ Pre-reduction with Zn is
Sn
2Mn+2 + 5Sn+4 + 8H2O required
3S2 + 8MnO4 + 4H2O 3SO4 Excess alkaline KMnO4 is
H2S 2
+ 8MnO2 + 8HO used

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B.2.3.4.2 Dichromate and Ceric Titration

Dichromate and ceric ions are also used for many redox titrations due to their stability
even at higher temperatures. Potassium dichromate crystals have no water of
crystallization and usually obtained in high purity. Ceric solutions are commonly
obtained from ceric ammonium sulfate or ceric ammonium nitrate. Sodium salt of
diphenylamine sulfonate and ferroin (ferrous complex of phenanthroline) are used as
indicators. The halfcell reaction for these oxidants are:
Cr2O72 + 14H+ + 6e 2Cr+3 + 7H2O
Ce+4 + e Ce+3
Primary standards for K2Cr2O7 and Ce+4 include pure iron, and ferrous sulfate. The half-
cell reactions are:
Fe(s) Fe2+(aq) + 2e
Fe2+(aq) Fe3+(aq) + e

The applications of this type of titration are the same as to that of permanganate. If back
titration is to be employed in the analysis, the excess reagent is determined by a standard
ferrous solution. Such method is used in the determination of chemical oxygen demand,
which is the measure of the oxygen equivalent to the organic matter in the water sample
which can oxidized by K2Cr2O7. In the analysis of COD, the water sample is treated with
excess K2Cr2O7 and refluxed for about two hours. The excess oxidizing agent is
determined by standard FeSO4 solution with ferroin as indicator. The half-cell reactions
involved are:
O2 + 4H+ + 4e 4H2O
Cr2O7 + 14H+ + 6e 2Cr+3 + 7H2O
2

The COD in the water sample is calculated as

1 mol K 2 Cr2 O 7 6 mol e - 1 mol O 2 32 g O 2 1000
(Vblank Vsample blank )( M FeSO4 )
1 mol FeSO4 1 mol K 2 Cr2 O 7 4 mol e 1 mol O 2 1g
COD
volume of sample (L)
B.2.3.4.3 Iodometric and Iodimetric Titration

Direct Titration with Iodine. Iodimetric titration involves a standard solution of iodine
solution in iodide solution forming the triiodide ion, I3 as titrant. Freshly prepared starch
solution is used as indicator and imparts a blue color at the endpoint. The half-cell
reaction for the titrant is
I3 + 2e 3I

B - 38
Indirect Titration with Iodine. Iodometric titration is an indirect method where the sample
is treated and iodine is released. The iodine released is titrated with a standard Na 2S2O3
solution. The reaction is governing the titration is
I2 + 2e 2I
2S2O32 S4O62 + 2e

Standardization of Iodine and Na2S2O3 Solution. Iodine is standardized using sodium

thiosulfate according to the reaction:
I2 + 2S2O32 2I + S4O62
The thiosulfate solution in turn is standardized using potassium bromate (KBrO 3),
potassium iodate (KIO3), potassium dichromate (K2Cr2O7), and metallic copper (Cu). The
primary standard reacts with excess iodine and the iodine liberated is titrated with the
thiosulfate solution The reactions are
BrO3 + 6I + 6H+ Br + 3I2 + 3H2O
IO3 + 5I + 6H+ 3I2 + 3H2O
Cr2O7 + 6I + 14H+ 2Cr+3 + 3I2 + 7H2O
2

2Cu+2 + 4I 2CuI(s) + I2

Table B.16 Applications of Direct and Indirect Titration with Iodine

Analyte Half Cell Reaction Method of Titration
+
As H3AsO3 + H2O H3AsO4 + 2H + 2e Direct titration
2 2 +
SO2 SO3 + H2O SO4 + 2H + 2e Back titration
+
N2H4 N2H4 N2(g) + 4H + 4e Direct titration
+
H2S H2S S + 2H + 2e Back titration

B - 39