Atomic models

There has been a variety of atomic models throughout history of atomic physics that refers mainly to a
period from the beginning of 19th century to the first half of 20th century, when a final model of atom which
is being used nowadays (or accepted as the most accurate one) was invented. Although the awareness of
atom existence goes way back to the antique period of the world history (Greek conception of atom), this
article will be mainly about five basic atomic models, from which each one has somehow contributed to how
we percept the structure of atom itself - Dalton´s Billiard Ball Model, J.J Thomson's "plum pudding"
model, Rutherford's Planetary model, Bohr's Atomic model, Electron Cloud Model/Quantum
Mechanics Model.

John Dalton’s atomic model

John Dalton was an English scientist, who came up with an idea that all matter is composed of very small
things. It was the first complete attempt to describe all matter in terms of particles. He called these particles
atoms and formed an atomic theory. In this theory he claims that:

 All matter is made of atoms. Atoms are indivisible and indestructible

 All atoms of a given element are identical in mass and properties
 Compounds are formed by a combination of two or more different kinds of atoms
 A chemical reaction is a rearrangement of atoms

Parts of his theory had to be modified based on the discovery of subatomic particles and isotopes. We now
also know that atoms are not indivisible, because they are made up of neutrons, electrons and protons.

Plum pudding model

After discovery of an electron in 1897, people realised that atoms are made up of even smaller particles.
Shortly after in 1904, J. J. Thomson proposed his famous “plum pudding model”. In this model, atoms were
known to consist of negatively charged electrons, however the atomic nucleus had not been discovered yet.
Thomson knew that atom had an overall neutral charge. He thought that there must be something to
counterbalance the negative charge of an electron. He came up with an idea that negative particles are
floating within a soup of diffuse positive charge. His model is often called the plum pudding model, because
of his similarity to a popular English dessert.

Rutherford’s model of the atom

Rutherford was first, who suggested that Thomson’s plum pudding model was incorrect. His new model
introduces nucleus to the atom theory. Nucleus contains relatively high central charge concentrated into very
small volume. This small volume also contains the bulk of the atomic mass of the atom. Nucleus is
surrounded by lighter and negatively charged electrons. His model is sometimes known as the planetary
model of the atom. However, there were still some major problems with this model. For example Rutherford
could not explain why atoms only emit light at certain frequencies. This problem was solved later by a
Danish physicist Niels Henrik David Bohr.

Bohr’s model of the atom

Bohr model describes the atom as a positively charged nucleus, which is surrounded by electrons. Electrons
travel in circular orbits, attraction is provided by electrostatic forces. Normally occupied
energy level of the electron is called the ground state. The electron can move to the less –
stable level by absorbing energy. This higher – energy level is called excited state. The
electron can return to its original level by releasing the energy. All in all, when electron
jumps between orbits, it is accompanied by an emitted or absorbed amount of energy (hν).
Electron Cloud Model/Quantum Mechanics Model of Atom
Quantum Mechanics Model of Atom is nowadays being taught as the most "realistic" atomic model that
describes atomic mechanisms as how present science presumes they work. It came to exist as a result of
combination of number of scientific assumptions:

1. All particles could be perceived as matter waves with a wavelength. (Louis de Broglie)
2. Resulting from the previous assumption, atomic model which treats electrons also as matter waves
was proposed. (Erwin Schrödinger, quantum mechanical atomic model emerged from the solution of
Schrödinger's equation for electron in central electrical field of nucleus.)
3. Principle of uncertainty states that we can't know both the energy and position of an electron.
Therefore, as we learn more about the electron's position, we know less about its energy, and vice
versa. (Werner Heisenberg)
4. There exists more than one energy level of electron in the atom. Electrons are assigned certain atomic
orbitals that can differ from one another in energy. (Niels Bohr)
5. Electrons have an intrinsic property called spin, and an electron can have one of two possible spin
values: spin-up or spin-down. Any two electrons occupying the same orbital must have opposite
spins. (the Stern-Gerlach Experiment)
Basic description of the quantum mechanical atomic model:
Quantum mechanics physics propose that electrons are moving around the nucleus not on specifically
defined electron paths (as we have seen e.g. in Rutherford's planetary atomic model), but in a certain three
dimensional space (atomic orbital), in which their own occurrence has a certain probability, meaning their
position cannot be calculated with 100% accuracy.

Four numbers, called quantum numbers, were introduced to describe the characteristics of electrons and their
orbitals.
Quantum numbers
Principal quantum number: n
 Describes the energy level of the electron in an atom (it also describes the average distance of the
orbital from nucleus)
 It has positive whole number values: 1, 2, 3, 4, ( theoretically speaking the numbers could go to
infinite, practically there are 7 known energy levels), it can be seen sometimes described in capital
letters instead of numbers, beginning with K (K, L, M, N...)
 The n value describes the size of the orbital

Angular momentum quantum number: l

 Describes basically the shape of the orbital
 This number is limited by the principal quantum number. Its value goes from 0 to n-1. For example,
for orbitals with principal quantum number n=2 there can by 2 different shapes of orbitals (2
different values l=0 and l=1)
 For every number exists a letter describing the shape of the orbital as shown in the table below
 Value of l (subshell) Letter

Value of l (subshell) Letter

0 s
1 p
2 d
3 f
4 g

Orbital shapes and their orientation for different angular momentum and magnetic numbers
Magnetic quantum number: ml
 Describes how different shapes of orbitals are oriented in space. Its value can be from -l to 0 to +l.
For example, for value l=1 there exists 3 values m= -1, 0, +1, meaning that the shape of that orbital
can be oriented in 3 different ways in space.

Value of l Values of ml

0 0

1 -1,0,+1

3 -3,-2,-1,0,+1,+2,+3

Spin quantum number: ms

 Describes in which direction is an electron spinning in a magnetic field . That can be either clockwise
or counter clockwise and as a result, there are only 2 values allowed: -1/2 and +1/2.
 One consequence of electron spin is that a maximum of two electrons can occupy any given orbital,
and the two electrons occupying the same orbital must have opposite spin. This is also called the
Pauli Exclusion Principle.

Principles of atom structure

Based on knowledge of quantum numbers, we are now able to build an electron configuration of an atom
that describes electron arrangement in an atom. Apart from Pauli Exclusion Principle, there are 2 other rules
that we must follow:

 Aufbau principle: Each electron occupies the lowest energy orbital available.
 Hund's rule: a single electron with the same spin must occupy each orbital in a sublevel before they
pair up with an electron with an opposite spin.

Hund's Rule of Maximum Spin Multiplicity

Examples of atoms described by quantum numbers

The importance of quantum mechanical atomic model has 2 main aspects. First, being able to build an
electron structure of atoms of specific substances helps us to understand how the atoms interact in
molecules; therefore we are one step closer to a more detailed description of attributes of those substances.
Second, it leaves an open door to more potential theories which could expand our knowledge and perception
of the world and universe surrounding us.
The Pauli exclusion principle is the quantum mechanical principle which states that two or
more identical fermions (particles with half-integer spin) cannot occupy the same quantum state within
a quantum system simultaneously. This principle was formulated by Austrian physicist Wolfgang Pauli in
1925 for electrons, and later extended to all fermions with his spin–statistics theorem of 1940.
In the case of electrons in atoms, it can be stated as follows: it is impossible for two electrons of a poly-
electron atom to have the same values of the four quantum numbers: n, the principal quantum number, ℓ,
the azimuthal quantum number, mℓ, the magnetic quantum number, and ms, the spin quantum number. For
example, if two electrons reside in the same orbital, then their n, ℓ, and mℓ values are the same, therefore
their ms must be different, and thus the electrons must have opposite half-integer spin projections of 1/2 and
−1/2.
Types of bonds
A covalent bond is a chemical bond that involves the sharing of electron pairs
between atoms. These electron pairs are known as shared pairs or bonding pairs,
and the stable balance of attractive and repulsive forces between atoms, when
they share electrons, is known as covalent bonding.
Ionic bonding is a type of chemical bonding that involves the electrostatic
attraction between oppositely charged ions, or between two atoms with sharply
different electronegativities.
A coordinate covalent bond, also known as a dative bond, dipolar bond, or
coordinate bond is a kind of two-center, two-electron covalent bond in which
the two electrons derive from the same atom.
 Metallic bonding is a type of chemical bonding that arises from the electrostatic
attractive force between conduction electrons and positively charged metal ions.
It may be described as the sharing of free electrons among a structure of
positively charged ions.

In chemistry, orbital hybridisation (or hybridization) is the concept of mixing atomic orbitals into new
hybrid orbitals (with different energies, shapes, etc., than the component atomic orbitals) suitable for the
pairing of electrons to form chemical bonds in valence bond theory.

1930 Heitler and London

BF3

 Step -1: Formation of excited state:

 Step = 2: Mixing and recasting of atomic orbitals:
 Step – 3: Proper Orientation of the Hybrid Orbitals in Space:
Hybridization is very useful and an important topic while studying inorganic chemistry. It helps us to
understand the formation of chemical bonds; the way atoms overlap with each other to form a molecule.
At the same time it lets you know about the shape, geometry, bond angle, no of bond pairs, no of lone
pairs in a molecule.
Hybridization may be defined as the phenomenon of mixing of atomic orbitals of nearly equivalent energy,
involving redistribution of energy, to form new orbitals of equal energy known as hybrid orbitals.

The number of hybrid orbitals is equal to the number of the orbitals hybridized.

The properties of the hybrid orbitals are in between the properties of the orbitals which are hybridized.
L.P. –L. P. > L.P.- B.P. > B.P-B.P.
The valence bond theory was proposed by Heitler and London to explain the formation of covalent bond
quantitatively using quantum mechanics. Later on, Linus Pauling improved this theory by introducing the
concept of hybridization.

The main postulates of this theory are as follows:

* A covalent bond is formed by the overlapping of two half -filled valence atomic orbitals of two different
atoms.

* The electrons in the overlapping orbitals get paired and confined between the nuclei of two atoms.

* The electron density between two bonded atoms increases due to overlapping. This confers stability to the
molecule.

* Greater the extent of overlapping, stronger is the bond formed.

* The direction of the covalent bond is along the region of overlapping of the atomic orbitals i.e., covalent
bond is directional.

* There are two types of covalent bonds based on the pattern of overlapping as follows:

(i) σ-bond: The covalent bond formed due to overlapping of atomic orbital along the inter nucleus axis is
called σ-bond. It is a stronger bond and cylindrically symmetrical.

Depending on the types of orbitals overlapping, the σ-bond is divided into following types:
σs-s bond:

σp-p bond:

σs-p bond:

(ii) π-bond: The covalent bond formed by sidewise overlapping of atomic orbitals is called π- bond. In this
bond, the electron density is present above and below the inter- nuclear axis. It is relatively a weaker bond
since the electrons are not strongly attracted by the nuclei of bonding atoms.

Note: The 's' orbitals can only form σ-bonds, whereas the p, d & f orbitals can form both σ and π-bonds.

1) H2 molecule:

* The electronic configuration of hydrogen atom in the ground state is 1s1.

* In the formation of hydrogen molecule, two half filled 1s orbitals of hydrogen atoms overlap along the
inter-nuclear axis and thus by forming a σs-s bond.

2) Cl2 molecule:

* The electronic configuration of Cl atom in the ground state is [Ne]3s2 3px2 3py2 3pz1.

* The two half filled 3pz atomic orbitals of two chlorine atoms overlap along the inter-nuclear axis and thus
by forming a σp-p bond.
3) HCl molecule:

* In the ground state, the electronic configuration of hydrogen atom is 1s1.

* And the ground state electronic configuration of Cl atom is [Ne]3s2 3px2 3py2 3pz1.

* The half filled 1s orbital of hydrogen overlap with the half filled 3pz atomic orbital of chlorine atom along
the inter-nuclear axis to form a σs-p bond.

4) O2 molecule:

* The electronic configuration of O in the ground state is [He] 2s2 2px2 2py1 2pz1.

* The half filled 2py orbitals of two oxygen atoms overlap along the inter-nuclear axis and form σp-p bond.

* The remaining half filled 2pz orbitals overlap laterally to form a πp-p bond.

* Thus a double bond (one σp-p and one πp-p) is formed between two oxygen atoms.

5) N2 molecule:

* The ground state electronic configuration of N is [He] 2s2 2px1 2py1 2pz1.

* A σp-p bond is formed between two nitrogen atoms due to overlapping of half filled 2px atomic orbitals
along the inter-nuclear axis.

* The remaining half filled 2py and 2pz orbitals form two πp-p bonds due to lateral overlapping. Thus a triple
bond (one and two) is formed between two nitrogen atoms.
However the old version of valence bond theory is limited to diatomic molecules only. It could not explain
the structures and bond angles of molecules with more than three atoms.

E.g. It could not explain the structures and bond angles of H2O, NH3 etc.,

However, in order to explain the structures and bond angles of molecules, Linus Pauling modified the
valence bond theory using hybridization concept.

What is hybridization?

The intermixing of two or more pure atomic orbitals of an atom with almost same energy to give same
number of identical and degenerate new type of orbitals is known as hybridization.

The new orbitals formed are also known as hybrid orbitals.

What is intermixing?

The intermixing or hybridization of atomic orbitals is a mathematical concept based on quantum mechanics.
During this process, the wave functions, Ψ of atomic orbitals of same atom are combined to give new wave
functions corresponding to hybrid orbitals.

What are the requirements for atomic orbitals to undergo hybridization?

* The atomic orbitals of same atom with almost same energy can only participate in the hybridization.

* The full filled or half-filled or even empty orbitals can undergo hybridization provided they have almost
equal energy.

Do the orbitals of different atoms undergo hybridization?

No! The hybridization is the mixing of orbitals of same atom only. The combination of orbitals belonging to
different atoms is called bonding.

What are hybrid orbitals? And what are its characteristics?

* The new orbitals that are formed due to intermixing of atomic orbitals are also known as hybrid orbitals,
which have mixed characteristics of atomic orbitals.

* The shapes of hybrid orbitals are identical. Usually they have one big lobe associated with a small lobe on
the other side.

* The hybrid orbitals are degenerate i.e., they are associated with same energy.

How many hybrid orbitals are formed?

* The number of hybrid orbitals formed is equal to the number of pure atomic orbitals undergoing
hybridization.
E.g. If three atomic orbitals intermix with each other, the number of hybrid orbitals formed will be equal to
3.

How do the electrons are going to be filled in the hybrid orbitals?

* The hybrid orbitals are filled with those electrons which were present in the pure atomic orbitals forming
them.

* The filling up of electrons in them follows Pauli's exclusion principle and Hund's rule.

What is the use of hybrid orbitals?

* The hybrid orbitals participate in the σ bond formation with other atoms.

Why atomic orbitals in a given atom undergo hybridization?

* The hybrid orbitals are oriented in space so as to minimize repulsions between them. This explains why the
atomic orbitals undergo hybridization before bond formation.

The reason for hybridization is to minimize the repulsions between the bonds that are going to be formed by
the atoms by using hybrid orbitals.

Remember that the hybridization is the process that occurs before bond formation.

And finally:

* The bond angles in the molecule are equal to or almost equal to the angles between the hybrid orbitals
forming the σ bonds. The shape of the molecule is determined by the type of hybridization, number of bonds
formed by them and the number of lone pairs.

What is sp hybridization?

* Intermixing of one 's' and one 'p' orbitals of almost equal energy to give two identical and degenerate
hybrid orbitals is called 'sp' hybridization.

* These sp-hybrid orbitals are arranged linearly at by making 180o of angle.

* They possess 50% 's' and 50% 'p' character.

What is sp2 hybridization?

* Intermixing of one 's' and two 'p' orbitals of almost equal energy to give three identical and degenerate
hybrid orbitals is known as sp2 hybridization.

* The three sp2 hybrid orbitals are oriented in trigonal planar symmetry at angles of 120o to each other.

* The sp2 hybrid orbitals have 33.3% 's' character and 66.6% 'p' character.
What is sp3 hybridization?

* In sp3 hybridization, one 's' and three 'p' orbitals of almost equal energy intermix to give four identical and
degenerate hybrid orbitals.

* These four sp3 hybrid orbitals are oriented in tetrahedral symmetry with 109o28' angle with each other.

* The sp3 hybrid orbitals have 25% ‘s’ character and 75% 'p' character.

What is sp3d hybridization?

* In sp3d hybridization, one 's', three 'p' and one 'd' orbitals of almost equal energy intermix to give five
identical and degenerate hybrid orbitals, which are arranged in trigonal bipyramidal symmetry.

Among them, three are arranged in trigonal plane and the remaining two orbitals are present above and
below the trigonal plane at right angles.

* The sp3d hybrid orbitals have 20% 's', 60% 'p' and 20% 'd' characters.

What is sp3d2 hybridization?

* Intermixing of one 's', three 'p' and two 'd' orbitals of almost same energy by giving six identical and
degenerate hybrid orbitals is called sp3d2 hybridization.

* These six sp3d2 orbitals are arranged in octahedral symmetry by making 90o angles to each other. This
arrangement can be visualized as four orbitals arranged in a square plane and the remaining two are oriented
above and below this plane perpendicularly.
 Postulates of Valence Bond Theory
The important postulates of the valence bond theory are listed below.

 Covalent bonds are formed when two valence orbitals (half-filled) belonging to two different atoms
overlap on each other. The electron density in the area between the two bonding atoms increases as a
result of this overlapping, thereby increasing the stability of the resulting molecule.
 The presence of many unpaired electrons in the valence shell of an atom enables it to form multiple
bonds with other atoms. The paired electrons present in the valence shell do not take participate in
the formation of chemical bonds as per the valence bond theory.
 Covalent chemical bonds are directional and are also parallel to the region corresponding to the
atomic orbitals that are overlapping.
 Sigma bonds and pi bonds differ in the pattern that the atomic orbitals overlap in, i.e. pi bonds are
formed from sidewise overlapping whereas the overlapping along the axis containing the nuclei of
the two atoms leads to the formation of sigma bonds.

 It can be noted that sigma bonds involve the head-to-head overlapping of atomic orbitals whereas pi
bonds involve parallel overlapping.

Number of Orbitals and Types of Hybridization

According to VBT theory the metal atom or ion under the influence of ligands can use its (n-1)d, ns,
np, or ns, np, nd orbitals for hybridization to yield a set of equivalent orbitals of definite geometry
such as octahedral, tetrahedral, square planar and so on. These hybrid orbitals are allowed to overlap
with ligand orbitals that can donate electron pairs for bonding.

Distribution of
Coordination Type of
Hybrid Orbitals
Number Hybridisation
in Space
4 sp3 Tetrahedral
4 dsp2 Square planar
Trigonal
5 sp3d
bipyramidal
6 sp3d2 Octahedral
6 d2sp3 Octahedral

Applications of Valence Bond Theory

 The maximum overlap condition which is described by the valence bond theory can explain the
formation of covalent bonds in several molecules.
 This is one of its most important applications. For example, the difference in the length and strength
of the chemical bonds in H2 and F2 molecules can be explained by the difference in the overlapping
orbitals in these molecules.
 The covalent bond in an HF molecule is formed from the overlap of the 1s orbital of the hydrogen
atom and a 2p orbital belonging to the fluorine atom, which is explained by the valence bond theory.

Limitations of Valence Bond Theory

The shortcomings of the valence bond theory include

 Failure to explain the tetra-valency exhibited by carbon

 No insight offered on the energies of the electrons.
 The theory assumes that electrons are localized in specific areas.
 It does not give a quantitative interpretation of the thermodynamic or kinetic stabilities of
coordination compounds.
 No distinction between weak and strong ligands.
 No explanation for the colour exhibited by coordination compounds.
1. Concentration in Parts Per Million (ppm)
The parts of a component per million parts (106) of the solution.

ppm(A)=1/106

2. Mass Percentage (w/w):

When the concentration is expressed as the percent of one component in the solution by mass it is called
mass percentage (w/w). Suppose we have a solution containing component A as the solute and B as the
solvent, then its mass percentage is expressed as:

Mass % of A = Mass of component A in the solution/Total mass of the solution×100

3. Volume Percentage (V/V):

Sometimes we express the concentration as a percent of one component in the solution by volume, it is then
called as volume percentage and is given as:

volume % of A = Volume of component A in the solution/Total volume of the solution×100

For example, if a solution of NaCl in water is said to be 10 % by volume that means a 100 ml solution will
contain 10 ml NaCl.

4. Mass by Volume Percentage (w/V):

This unit is majorly used in the pharmaceutical industry. It is defined as the mass of a solute dissolved per
100mL of the solution.

5. Molarity (M):
One of the most commonly used methods for expressing the concentrations is molarity. It is the number of
moles of solute dissolved in one litre of a solution. Suppose a solution of ethanol is marked 0.25 M, this
means that in one litre of the given solution 0.25 moles of ethanol is dissolved.

The number of atoms or molecules in one mole of a substance, equal to 6.023 × 1023.
NaOH= 23 + 16 + 1=40g dissolved in 1000ml of solution = 1M NaOH

NaOH + HCl = NaCl + H2O

Ca(OH)2= 40 + 2 x(16 + 1) =74g

Ca(OH)2 + 2HCl = CaCl2 + 2 H2O

74 /2 =37

100mL 0.05 M NaOH solution

1M=40g in 1000mL solution

0.5M = 20g in 1000mL solution

0.05M =2g in 1000mL solution

0.05M = 0.2g in 100mL solution

0.05M = 200mg in 100mL solution

N=(Weight of solute in grams/Equivalent mass )×Volume in liter

100mL 0.05 N NaOH solution

0.05M =2g in 1000mL solution

0.05M =2g in 1000mL solution

2 /40 x 1= 0.05N

1g = 1000mg

6. Molality (m):
Molality represents the concentration regarding moles of solute and the mass of solvent. It is given by moles
of solute dissolved per kg of the solvent. The molality formula is as given-

Molality(m)=Moles of solute/Mass of solvent in kg

7. Normality
It is the number of gram equivalents of solute present in one liter of the solution and it is denoted by N.

N=(Weight of solute in grams/Equivalent mass )×Volume in liter

The relation between normality and molarity.

 N x Eq.Wt = Molarity x Molar mass

 N = Molarity x Valency
 N = Molarity x Number of H+ or OH– ion.

8. Formality
It is the number of gram formula present in one litre of solution. It is denoted by F.

F=Weight of solute in gramFormula wt×Volume in liter

It is applicable in the case of ionic solids like NaCl.

9. Mole Fraction:
If the solution has a solvent and the solute, a mole fraction gives a concentration as the ratio of moles of one
component to the total moles present in the solution. It is denoted by x. Suppose we have a solution
containing As a solute and B as the solvent. Let nA and nB be the number of moles of A and B present in the
solution respectively. So mole fractions of A and B are given as:

xA=nAnA+nB
xB=nBnA+nB

The above-mentioned methods are commonly used ways of expressing the concentration of solutions. All
the methods describe the same thing that is, the concentration of a solution, each of them has its own
advantages and disadvantages. Molarity depends on temperature while mole fraction and molality are
independent of temperature. All these methods are used on the basis of the requirement of expressing the
concentrations.

Solutions of Solids in Liquids

1. A saturated solution is a solution that remains in contact with an excess of solute.
2. The amount of solute dissolved per 100g of solvent in a saturated solution at a specific temperature
represents the solubility of the solute.
3. For exothermic substances such as KOH, CaO, Ca(OH)2, M2CO3, M2SO4, etc, solubility is inversely
proportional to temperature.
4. For endothermic substances such as NaCl, KNO3, NaNO3, glucose, etc., solubility is directly
proportional to temperature.

Solubility of Gases
The solubility of gases is mostly expressed in terms of the absorption coefficient, k that is the volume of the
gas dissolved by unit volume of solvent at 1 atm pressure and a specific temperature.

The solubility of a gas in a liquid depends upon

1. Temperature solubility is inversely proportional to temperature as the dissolution of gas is

exothermic in most cases.
2. Nature of gas – Gases having a higher value of van der Waals force of attraction that is gases that are
more easily liquefied are more soluble. For example, SO2 and CO2 are more soluble in water than O2,
N2, and H2.
3. Nature of solvent – Gases which can ionize in aqueous solution are more stable in water as compared
to the other solvents.

Equivalent weight, in chemistry, the quantity of a substance that exactly reacts with, or is equal to the
combining value of, an arbitrarily fixed quantity of another substance in a particular reaction.
Substances react with each other in stoichiometric, or chemically equivalent, proportions, and a common
standard has been adopted.
For an element the equivalent weight is the quantity that combines with or replaces 1.00797 grams (g) of
hydrogen or 7.9997 g of oxygen; or, the weight of an element that is liberated in an electrolysis (chemical
reaction caused by an electric current) by the passage of 96,500 coulombs of electricity.
The equivalent weight of an element is its gram atomic weight divided by its valence (combining power).
Some equivalent weights are:
silver (Ag), 107.868 g;
magnesium (Mg), 24.312/2 g;
aluminum (Al), 26.9815/3 g;
sulfur (S, in forming a sulfide), 32.064/2 g.
 For compounds that function as oxidizing or reducing agents (compounds that act as acceptors or donors
of electrons), the equivalent weight is the gram molecular weight divided by the number of electrons lost
or gained by each molecule;
e.g., potassium permanganate (KMnO4) in acid solution, 158.038/5 g;

4KMnO4 + 6H2SO4 → 4MnSO4 + 2K2SO4 + 5O2 + 6H2O

8 H++ MnO−4 + 5 e− → Mn2+ + 4 H2O

In an acidic solution, permanganate(VII) is reduced to the pale pink +2 oxidation state of the manganese(II)
(Mn2+) ion.

8 H++ MnO−4 + 5 e− → Mn2+ + 4 H2O

In a strongly basic solution, permanganate(VII) is reduced to the green +6 oxidation state of the manganate
ion, MnO2−4.
MnO−4 + e− → MnO2−4

In a neutral medium, however, it gets reduced to the brown +4 oxidation state of manganese dioxide MnO2.

2 H2O + MnO−4 + 3 e− → MnO2 + 4 OH−

potassium dichromate (K2Cr2O7), 294.192/6 g;

and sodium thiosulfate (Na2S2O3·5H2O), 248.1828/1 g.
For all oxidizing and reducing agents (elements or compounds) the equivalent weight is the weight of the
substance that is associated with the loss or gain of 6.023 × 1023 electrons.
The equivalent weight of an acid or base for neutralization reactions or of any other compound that acts
by double decomposition is the quantity of the compound that will furnish or react with or be equivalent
to 1.00797 g of hydrogen ion or 17.0074 g of hydroxide ion;
e.g., hydrochloric acid (HCl), 36.461 g;
sulfuric acid (H2SO4), 98.078/2 g;

sodium hydroxide (NaOH), 40 g;

sodium carbonate (Na2CO3), 105.9892/ 2 g.
The equivalent weight of a substance may vary with the type of reaction it undergoes.
Thus, potassium permanganate reacting by double decomposition has an equivalent weight equal to its
gram molecular weight, 158.038/1 g;
as an oxidizing agent under different circumstances it may be reduced to the manganate ion (MnO 42-), to
manganese dioxide (MnO2), or to the manganous ion (Mn2+), with the equivalent weights of 158.038/1 g,
158.038/3 g, and 158.038/5 g, respectively.
The number of equivalent weights of any substance dissolved in one litre of solution is called the
normality of that solution.

Oxidation and reduction in terms of oxygen transfer

The terms oxidation and reduction can be defined in terms of the adding or removing oxygen to a
compound. while this is not the most robust definition, as discussed below, it is the easiest to remember.
Oxidation and Reduction with respect to Oxygen Transfer

 Oxidation is the gain of oxygen.

 Reduction is the loss of oxygen.

For example, in the extraction of iron from its ore:

Because both reduction and oxidation are occurring simultaneously, this is

known as a redox reaction.

An oxidizing agent is substance which oxidizes something else. In the above

example, the iron(III) oxide is the oxidizing agent. A reducing agent reduces
something else. In the equation, the carbon monoxide is the reducing agent.

 Oxidizing agents give oxygen to another substance.

 Reducing agents remove oxygen from another substance.

Oxidation and reduction in terms of hydrogen transfer

These are old definitions which are no longer used, except occasionally in
organic chemistry.

Oxidation and Reduction with respect to Hydrogen Transfer

 Oxidation is the loss of hydrogen.

 Reduction is the gain of hydrogen.

Notice that these are exactly the opposite of the oxygen definitions (#1).

For example, ethanol can be oxidized to ethanal:

An oxidizing agent is required to remove the hydrogen from the ethanol. A

commonly used oxidizing agent is potassium dichromate(VI) solution acidified
with dilute sulfuric acid. Ethanal can also be reduced back to ethanol by adding
hydrogen. A possible reducing agent is sodium tetrahydridoborate, NaBH 4.
Again the equation is too complicated to consider at this point.
More precise definitionsof oxidizing and reducing agents are

 Oxidizing agents add oxygen to another substance or remove hydrogen

from it.
 Reducing agents remove oxygen from another substance or add hydrogen
to it.

Oxidation and reduction in terms of electron transfer

Oxidation and Reduction with respect to Electron Transfer

 Oxidation is loss of electrons

 Reduction is gain of electrons

Remembering these definitions is essential, and easily done using this

convenient acronym:

Example 1

The equation below shows an obvious example of oxygen transfer in a simple

redox reaction:

CuO+Mg→Cu+MgO(1)

Copper(II) oxide and magnesium oxide are both ionic compounds. If the above
is written as an ionic equation, it becomes apparent that the oxide ions are
spectator ions. Omitting them gives:

In the above reaction, magnesium reduces the copper(II) ion by transferring

electrons to the ion and neutralizing its charge. Therefore, magnesium is a
reducing agent. Another way of putting this is that the copper(II) ion is
removing electrons from the magnesium to create a magnesium ion. The
copper(II) ion is acting as an oxidizing agent.

Summary
Confusion can result from trying to learn both the definitions of oxidation and
reduction in terms of electron transfer and the definitions of oxidizing and
reducing agents in the same terms.

The following thought pattern can be helpful:

  An oxidizing agent oxidizes something else.
 Oxidation is loss of electrons (OIL RIG).
 Therefore, an oxidizing agent takes electrons from that other substance.
 Therefore, an oxidizing agent must gain electrons.

Here is another mental exercise:

 An oxidizing agent oxidizes something else.

 Therefore, the oxidizing agent must be reduced.
 Reduction is gain of electrons (OIL RIG).
 Therefore, an oxidizing agent must gain electrons.
0.05N 1000ml =x g

284g sodium thiosulphate 1000ml = 1N

28.4 sodium thiosulphate 1000ml = 0.1N

14.2g sodium thiosulphate 1000ml = 0.05N

1.42g sodium thiosulphate 100ml = 0.05N