Oxidation number and its

significance
Dr. Shinomol George K
• An oxidation number is a positive or negative number that is assigned to an atom to
indicate its degree of oxidation or reduction.
• The term oxidation state is often used interchangeably with oxidation number.
• A partial electron transfer is a shift in the electron density near an atom as a result
of a change in the other atoms to which it is covalently bonded.
• That charge shift is based on the relative electronegativities of the atoms involved in
the bond.
• Overall, the oxidation number of an atom in a molecule is the charge that the
atom would have if all polar covalent and ionic bonds resulted in a complete
transfer of electrons from the less electronegative atom to the more
electronegative one.
Oxidation numbers can be assigned using the set of rules outlined below.
• The oxidation number of an atom in a neutral free element is zero.
A free element is considered to be any element in an uncombined state, whether monatomic or polyatomic.
Eg: the oxidation number of each atom in Fe, Li, N2, Ar, and P4 is zero.
• The oxidation number of a monatomic (composed of one atom) ion is the same as the charge of the ion.
Eg: the oxidation numbers of K+K+, Se2−Se2−, and Au3+ are +1, −2, and +3, respectively.
• The oxidation number of oxygen in most compounds is −2.
• The oxidation number of hydrogen in most compounds is +1.
• The oxidation number of fluorine in all compounds is −1. Other halogens usually have an oxidation number of −1 in
binary compounds, but can have variable oxidation numbers depending on the bonding environment.
• In a neutral molecule, the sum of the oxidation numbers of all atoms is zero.
Eg:  H2O, the oxidation numbers of H and O are +1 and −2, respectively. Because there are two hydrogen atoms in the
formula, the sum of all the oxidation numbers in H2O is 2(+1)+1(−2)=0.
• In a polyatomic ion, the sum of the oxidation numbers of all atoms is equal to the overall charge on the ion.
Eg:  SO2, the oxidation numbers of S and O are +6 and −2, respectively. The sum of all oxidation numbers in the sulfate ion
would be 1(+6)+4(−2)=−2, which is the charge of the ion.
• An examination of the rules for assigning oxidation numbers reveals that there are many elements for which there are no
specific rules, such as nitrogen, sulfur, and chlorine. These elements, as well as some others, can have variable oxidation
numbers depending on the other atoms to which they are covalently bonded in a molecular compound
• Oxidation numbers for the atoms in a binary ionic compound are easy
to assign because they are equal to the charge of the ion (rule 2).
• In FeCl3, the oxidation number of iron is +3, while the oxidation
number of chlorine is −1−1.
• In Ca3P2, the calcium is +2, while the phosphorus is −3.
• This is because an ionic compound is in the form of a crystal lattice
that is actually composed of these ions.
• Assigning oxidation numbers for molecular compounds is trickier.
• The key is to remember rule 6: that the sum of all the oxidation
numbers for any neutral species must be zero.
• Make sure to account for any subscripts which appear in the formula.
• As an example, consider the compound nitric acid, HNO3.
• According to rule 4, the oxidation number of hydrogen is +1.
According to rule 3, the oxidation number of oxygen is −2.
There is no rule regarding nitrogen, but its oxidation number can be calculated as follows.
• Determining Oxidation States
• Counting the number of electrons transferred is an inefficient and time-consuming way of
determining oxidation states.These rules provide a simpler method:
• The oxidation state of an uncombined element is zero. This applies regardless of the structure of the
element: Xe, Cl2, S8, and large structures of carbon or silicon each have an oxidation state of zero.

• The sum of the oxidation states of all the atoms or ions in a neutral compound is zero.

• The sum of the oxidation states of all the atoms in an ion is equal to the charge on the ion.

• The more electronegative element in a substance is assigned a negative oxidation state. The less
electronegative element is assigned a positive oxidation state. Remember that electronegativity is
greatest at the top-right of the periodic table and decreases toward the bottom-left.
• Exceptions:
• Hydrogen in the metal hydrides: Metal hydrides include compounds like sodium hydride, NaH. Here the
hydrogen exists as a hydride ion, H-. The oxidation state of a simple ion like hydride is equal to the charge on the
ion—in this case, -1.

• Alternatively, the sum of the oxidation states in a neutral compound is zero. Because Group 1 metals always
have an oxidation state of +1 in their compounds, it follows that the hydrogen must have an oxidation state of -1
(+1 -1 = 0).

• Oxygen in peroxides: Peroxides include hydrogen peroxide, H2O2. This is an electrically neutral compound, so
the sum of the oxidation states of the hydrogen and oxygen must be zero.
• Because each hydrogen has an oxidation state of +1, each oxygen must have an oxidation state of -1 to balance
it.

• Oxygen in F2O: The deviation here stems from the fact that oxygen is less electronegative than fluorine; the
fluorine takes priority with an oxidation state of -1. Because the compound is neutral, the oxygen has an
oxidation state of +2.

• Chlorine in compounds with fluorine or oxygen: Because chlorine adopts such a wide variety of oxidation
states in these compounds, it is safer to simply remember that its oxidation state is not -1, and work the correct
state out using fluorine or oxygen as a reference.
• An oxidation number is a number that is assigned to an atom in a
substance.
• The oxidation number could be positive, negative, or zero, and it
indicates if electrons are lost or gained.
• In other words, the oxidation number is a number that helps us keep
track of electrons in an atom.
 Here, the oxidation number of calcium is +2 and the oxidation number of oxygen is -2.
 If the oxidation number is positive, then this means that the atom loses electrons, and if it is negative, it means the
atom gains electrons. If it is zero, then the atom neither gains nor loses electrons.
 Calcium has a +2 charge, which means it lost two electrons. Oxygen has a -2 charge, which means it gained two
electrons.
 If an atom loses electrons, its oxidation number is positive, so we can say that this atom undergoes oxidation. If an
atom gains electrons, its oxidation number is negative, so we can say that the atom undergoes reduction.
 OIL RIG: Oxidation Is Loss (of electrons); Reduction Is Gain (of electrons).
• Rule 1: In its pure elemental form, an atom has an oxidation number
of zero
• What exactly is a pure element? A pure element is an atom that is not
combined with any other elements. This table shows examples of
atoms in their pure elemental form:

Even though the element has subscripts like the 2 in O2 and the
8 in S8, these are still considered pure elements because they
are not combined with any other elements.
• Rule 2: The oxidation number of an ion is the same as its charge
• An ion is an atom with a charge due to the gain or loss of electrons. The charge is
indicated as the superscript after the atom. If an atom has this, then this means
that it is an ion. For example, the potassium ion has a +1 charge, so the oxidation
number is +1. For the bromine ion, the charge is -1, so the oxidation number is -1.
It is important to note that if only a positive (+) or negative (-) is shown, the
charge is assumed to be +1 or -1.

The barium ion has a +2 charge, so the oxidation number is +2.

For the sulfur ion, the charge is -2, and the oxidation number is
-2.
• Rule 3: The oxidation number of metals is +1 in Group 1 and +2 in
Group 2
• Unless it is in pure elemental form, the oxidation number of a metal is
+1 in Group 1 and +2 in Group 2. It is important to note that although
hydrogen is in Group 1, hydrogen is not a metal, so hydrogen is not
included in this rule. In the following illustration, the metals for Group
1 and 2 are indicated.
So, the oxidation number for lithium is +1 because it is a metal that belongs in Group 1, and the
oxidation number of magnesium is +2 because it is a metal that belongs in Group 2
• Rule 4: Hydrogen has two possible oxidation numbers: +1 and -1
• Hydrogen has an oxidation number of +1 when it is bonded to nonmetals, which are highlighted
on the right side of the following periodic table.
• For the compound hydrochloric acid, hydrogen is bonded to chlorine, a nonmetal, so the
oxidation number of hydrogen is +1.

 Hydrogen has an
oxidation number of -1
when it is bonded to a
metal.
 For the compound sodium
hydride, hydrogen is
bonded to sodium, which
is a metal, so the
oxidation number of
hydrogen is -1
Rule 5: Oxygen has three possible oxidation numbers: +2, -2 and -1
In general, oxygen has an oxidation number of -2. The only exceptions are peroxides, where
oxygen has an oxidation number of -1, and in the compound of oxygen difluoride, where it has an
oxidation number of +2.
Rule 6: The oxidation number of fluorine in any compound is -1
A few examples of fluorine-containing compounds are hydrogen fluoride or hydrofluoric acid,
sulfur hexafluoride, and sodium fluoride. The oxidation number of fluorine in each of these
compounds is -1.
Rule 7: For the other halogens (Cl, Br, I), the usual oxidation number is -1, except when they are
combined with oxygen or fluorine.
In the compound sodium chloride, the oxidation number of chlorine is -1. In the compound
hypochlorous acid, the oxidation number of chlorine is +1; and in the compound perchloric acid,
the oxidation number of chlorine is +7.
Rule 8: The sum of the oxidation numbers in a neutral compound is equal to zero
Here are a few examples of neutral compounds:
• Eg:
• Here we have the molecule hydrogen fluoride, which is a neutral compound, so its
oxidation number is 0. To determine the oxidation numbers of the elements hydrogen
and fluorine in this compound, we multiply the number of hydrogen atoms by the
oxidation number of hydrogen. Then, multiply the number of fluorine atoms by the
oxidation number of fluorine.
Hydrogen has an oxidation number of +1, and we have 1 hydrogen atom:
1 * (1) = 1
Fluorine has an oxidation number of -1, and we have 1 fluorine atom:
1 * (-1) = -1
(-1) + 1 = 0
 SIGNIFICANC
E
• Oxidation no. helps to identify the nature of compound or molecule
• It shows how reactions are taking place
• It also shows the valency of a compound
• Understanding and being able to assign oxidation numbers is necessary for:
 going from formulas to names and vice-versa for compounds of metals with
multiple oxidation states (most transition metals).
 recognizing oxidation reduction reactions and identifying the oxidizing and reducing
agents. They can also be helpful in balancing the equations for such reactions.
 This concept can be utilized in solving redox equations, explaining the reactions in
electrochemistry, finding the compound in analytical chemistry 
• Oxidation number of an atom is the ability to donate or accept electrons to satisfy
octet rule. It may be positive, negative or zero. An atom by accepting or donating
electrons makes bond with another atoms and form molecule. So oxidation states
will give you numbers of bonds an atom can form in a molecule.