Oxidation State

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Oxidation-Reduction (redox) reactions take place in the world at every moment. In fact, they
are directly related to the origin of life. For instance, oxidation of nutrients forms energy and
enables human beings, animals, and plants to thrive. If elements or compounds were
exposed to oxygen, after a series of reactions the oxygen will be converted into carbon
dioxide or water (combustion). To fully understand redox and combustion reactions, we must
first learn about oxidation states (OS).

Introduction
An oxidation state is a number that is assigned to an element in a chemical combination. This number represents the
number of electrons that an atom can gain, lose, or share when chemically bonding with an atom of another element.
The terms oxidation state and oxidation number are often used interchangeably. The transfer of electrons is
described by the oxidation state of the molecule. One might mistaken formal charge for oxidation state but they are
different. Oxidation state is commonly used to determine the changes in redox reactions and is numerically similar
to valence electrons, but different from formal charge. Formal charge determines the arrangement of atoms and the
likelihood of the molecule existing.

Oxidation State Rules

To effectively assign oxidation states to a compound, the seven basic rules must be followed in order. Remember to
use the rule that comes first if two rules conflict with each other. These rules hold true for most compounds..

RULE 1: Any individual atom uncombined with other

elements has the oxidation state of 0 (zero).
Ex.) The OS for Ag is 0. The oxidation state for O (oxygen) or O2 is 0 as long as it is uncombined with any
other element.

RULE 2: The total sum of the oxidation state of all atoms in

any given species is equal to the net charge on that species.
a.) In neutral species, the total sum of the oxidation state of all atoms is 0.
 Ex.) The sum of OS for NaCl is 0 since the OS of Na = +1 and the OS of Cl = -1, therefore NaCl total OS
=0

b.) In ions, the total sum of the oxidation state is the charge of the ion.

Ex.) The OS of Ca2+ (Calcium) is = +2. The total sum of the OS of all atoms in CrO42 (Chromate ion) is -2.
The total sum of the oxidation states of all atoms in CH3COO- (Acetate ion) is -1.

RULE 3: In a compound, the Oxidation state for Group 1(1A)

metal is +1 and for Group 2(2A) metal, the oxidation state is
+
Ex.) In NaCl, Na has the oxidation state of +1 since it is a Group 1 Alkali metal. Cl would have an oxidation
number of -1 to make the sum of the oxidation states 0 (Rule 2). In MgCl 2, Mg has the oxidation state of +2,
since it is a Group 2 Alkaline Earth metal. Cl would have an oxidation state of -1, and since there are 2 Cl
atoms, the overall charge of the species would again be 0 (Rule 2).

RULE 4: The oxidation state of FLOURINE is -1 in a

compound.
Ex.) OS of F is -1 in HF, SF6

RULE 5: The oxidation state of HYDROGEN is +1 in a

compound.
Ex.) OS of H is +1 in HI, CH4, NH4+

RULE 6: The oxidation state of OXYGEN is -2 in a compound.

Ex.) OS of Oxyen is -2 in OH-, H2O, CO32-

RULE 7: In two-element compounds with metals, Group

15(3A) elements have the oxidation state of -3, Group
16(6A) elements have the oxidation state of -2, and Group
17(7A) elements have the oxidation state of -1.
Ex.) In MgBr2, Br has the oxidation state of -1, since it is a Group 17 element. In Li 2S, S has the oxidation
state of -2, since it is a Group 16.
 Example 1

Find the oxidation state of Cr in CrO4-2

SOLUTION

1. From Rule #2, we know that the sum of OS for this compound is -2.
2. From Rule #6, we know that Oxygen in a compound is -2. Since we have four
oxygen, -2 x 4 = -8.
3. With those information, set up an short equation
Cr+(8)=2Cr+(8)=2

So the oxidation state of Cr is +6

Example 2

Find the oxidation state of C in C2H3O2-

SOLUTION

1. From Rule #2, we know that the sum of OS for this compound is -1
2. From Rule #5, we know that Hydrogen in a compound is +1. Since we have
three Hydrogen, +1 x 3 = +3
3. From Rule #6, we know that Oxygen in a compound is -2. Since we have two
oxygen, -2 x 2 = -4
4. With those information, set up an equation
2C+(+3)+(4)=12C+(+3)+(4)=1

Rewrite as

2C+34=12C+34=1

2C=02C=0

C=0/2=0C=0/2=0

The oxidation state for C is 0.

Example 3
 Find the oxidation state of S in S2O32-

SOLUTION

1. From Rule #2, we know that the sum of OS for this compound is -2
2. From Rule #6, we know that Oxygen in a compound is -2. Since we have
three oxygen, -2 x 3 = -6
3. With those information, set up an equation 2S + (-6) = -2
Rewrite as

2S6=22S6=2

2S=42S=4

S=4/2=2S=4/2=2

The oxidation state for S is 2.

Fractional Values for Oxidation States

The oxidation states are usually in whole numbers, but in some cases, they are in fractional numbers.
Consider Fe3O4.

Using rule #2, the sum of the oxidation state of all atoms is 0
Using rule #6, the O has the oxidation state of -2. 4x(-2) = -8
Equation: 3Fe + (-8) = 0
3Fe = 8
Fe = 8/3
In most cases, atoms of the same element in a given compound have the same oxidation states, but each
atom can have a different state than the other. For Fe 3O4, two Fe atoms have an oxidation state of +3 and one of +2,
which makes the total oxidation state of Fe= 8/3.

Instead of averaging the oxidation states, we must keep them separated. This is called fragmenting, which occurs if
there is an ionic compound, and the ions can be separated. The oxidation state of the individual atoms in the
different ions can be determined.

Practice Problems
Determine the oxidation states of the underlined elements in

1) Cl ; 2 2) NaH; 3) H CO;
2 4) S O ;
2 3
2-
5) KMnO .; 6)FeCl ; 7)N ; 8)H SO ;
4 3 2 2 4

9)HClO2; 10)CuSO4;
Transition metal complex

11) [Co(NH3)5CO3]Br

Solutions
1. Using rule #1, Cl isn't combine with any other element other than itself,
therefore the oxidation state for Cl is 0.
2. Using rule #2, we know that the sum of the oxidation states for Na and H is 0
because NaH is a neutral compound. Now, we might be tempted to say H has
the oxidation state of +1 because of rule #5. However, recall that one must
use the rules in order. Because Na is in Group 1A, according to rule #3, the
oxidation state of Na is +1. Thus, H must have the oxidation state of -1 so
that the sum of the oxidation state for Na and H is 0.
3. Using rule #2, the sum of the oxidation state is 0. Using rule #5, H has the
oxidation state of +1, and using rule #6, O has the oxidation state of -2. The
equation for H CO: 2(+1) + C + (-2) = 0. -----> 2 + C - 2 = 0 --------> C = 0
2

4. Using rule #2, the sum of the oxidation state is -2. Using rule #6, O has the
oxidation state of -2. We want to know the oxidation of S, so the equation
forS O : 2S + 3(-2) = -2 ------> 2S -6 = -2 ------> 2S = +4 ------> S = 4/2
2 3
2-

-----> S = 2
5. Using rule #2, the sum of the oxidation state is 0, and using rule #3, the
oxidation state for K is +1. Using rule #6, O has the oxidation state of -2. The
equation for KMnO : 1 + Mn + 4(-2) = 0 -----> Mn = -1 + 8 -----> Mn = 7
4

6. Using rule #2, the sume of oxidation state is 0. Using rule #7, Cl has a -1
charge. The equation for FeCl Fe + 3(-1) = 0 -----> Fe -3 = 0 -----> Fe = 3
3

7. Using rule #1, N isn't combine with any other element other than itself,
therefore the oxidation state for N is 0.
8. Using rule #2, the sum of the oxidation state is 0, and using rule #5, the
oxidation state for H is +1. Using rule #6, O has the oxidation state of -2.
The equation for H SO : 2(1) + S + 4(-2) = 0 -----> S = -2 + 8 -----> S= 6
2 4

9. Using rule #2, the sum of the oxidation state is 0, and using rule #5, the
oxidation state for H is +1. Using rule #6, O has the oxidation state of -2.
The equation for HClO : 1 + Cl + 2(-2) = 0 -----> Cl = -1 + 4 -----> Cl = 3
2

10.Using rule #2, the sum of the oxidation state is 0. Using rule #6, O has the
oxidation state of -2. Cu only have one charge which is +2. The equation
for CuSO : 2 + S + 4(-2) = 0 -----> S = -2 + 8 -----> S = 6
4

11.[Co(NH ) CO ]Br is a transition metal complex, whatever is inside the

3 5 3

bracket [ ] has to balance out with the outside, which is the Br in this case to
make the whole complex = 0.
Lets start off with the outside (Br) first, the OS of Br is -1 (Rule #7).
Everything INSIDE of the bracket must equal to +1. Since Br is -1, the whole
bracket is +1 = 0.
We know that NH have a 0 charge.
3

The charge of CO is -2. 3

The equation for the INSIDE bracket is Co + 0(5) + (-2) = +1

 Co -2 = +1 ----> oxidation state for Co = +3

Video Links
http://www.youtube.com/watch?v=_fNNQfGGYr4
http://www.youtube.com/watch?v=GA88JI4AymY
http://www.youtube.com/watch?v=XITIaylIMM8
http://www.youtube.com/watch?v=9EYRKfWIARA

Oxidation Numbers

It is often useful to follow chemical reactions by looking at changes in the oxidation

numbers of the atoms in each compound during the reaction. Oxidation numbers also
play an important role in the systematic nomenclature of chemical compounds. By
definition, the oxidation number of an atom is the charge that atom would have if the
compound was composed of ions.

1. The oxidation number of an atom is zero in a neutral substance that contains atoms
of only one element. Thus, the atoms in O2, O3, P4, S8, and aluminum metal all have an
oxidation number of 0.

2. The oxidation number of simple ions is equal to the charge on the ion. The
oxidation number of sodium in the Na+ ion is +1, for example, and the oxidation
number of chlorine in the Cl- ion is -1.

3. The oxidation number of hydrogen is +1 when it is combined with a nonmetal as in

CH4, NH3, H2O, and HCl.

4. The oxidation number of hydrogen is -1 when it is combined with a metal as in.

LiH, NaH, CaH2, and LiAlH4.

5. The metals in Group IA form compounds (such as Li 3N and Na2S) in which the
metal atom has an oxidation number of +1.

6. The elements in Group IIA form compounds (such as Mg 3N2 and CaCO3) in which
the metal atom has a +2 oxidation number.
7. Oxygen usually has an oxidation number of -2. Exceptions include molecules and
polyatomic ions that contain O-O bonds, such as O 2, O3, H2O2, and the O22- ion.

8. The elements in Group VIIA often form compounds (such as AlF 3, HCl, and ZnBr2)
in which the nonmetal has a -1 oxidation number.

9. The sum of the oxidation numbers in a neutral compound is zero.

H2O: 2(+1) + (-2) = 0

10. The sum of the oxidation numbers in a polyatomic ion is equal to the charge on
the ion. The oxidation number of the sulfur atom in the SO 42- ion must be +6, for
example, because the sum of the oxidation numbers of the atoms in this ion must
equal -2.

SO42-: (+6) + 4(-2) = -2

11. Elements toward the bottom left corner of the periodic table are more likely to
have positive oxidation numbers than those toward the upper right corner of the table.
Sulfur has a positive oxidation number in SO 2, for example, because it is below
oxygen in the periodic table.

SO2: (+4) + 2(-2) = 0

Practice Problem 6:

Name the following ionic compounds.

(a) Fe(NO3)3

(b) SrCO3

(c) Na2SO3

(d) Ca(ClO)2

Click here to check your answer to Practice Problem 6

 Practice Problem 7:

Assign the oxidation numbers of the atoms in the following compounds.

(a) Al2O3

(b) XeF4

(c) K2Cr2O7

Click here to check your answer to Practice Problem 7

What are oxidation numbers?

Chemists use oxidation numbers (or oxidation states) to keep track of how
many electrons an atom has. Oxidation numbers dont always correspond
to real charges on molecules, and we can calculate oxidation numbers for
atoms that are involved in covalent (as well as ionic) bonding.

Let's make sense of oxidation numbers with a few examples!

Guidelines for determining the oxidation

number
Oxidation numbers are usually written with the sign (+plus or -minus)
first, then the magnitude, which is the opposite of charges on ions.
Chemists use the following guidelines to determine oxidation numbers:

Step 1 Atoms in their elemental state have an oxidation number of 0.

Step 2. Atoms in monatomic (i.e. single atom) ions have an oxidation
number equal to their charge.

Step 3. In compounds: fluorine is assigned a 1 oxidation number;

oxygen is usually assigned a 2 oxidation number (except in peroxide
compounds where it is 1, and in binary compounds with fluorine where it
is positive); and hydrogen is usually assigned a +1+1plus, 1 oxidation
number except when it exists as the hydride ion, H, in which case
rule 2 wins.
[What is a peroxide?]

Step 4.In compounds, all other atoms are assigned an oxidation number
so that the sum of the oxidation numbers on all the atoms in the species
equals the charge on the species.

Determining the oxidation state in H2 and H

2O
When using the guidelines, we usually start with rule 1 and move
downward in the list until we are done. By following that order, we
determine the oxidation states for the easy atoms first, and use the
process of elimination for trickier examples.

Example: What is the oxidation state of the hydrogen atom in H2

and H2O
H2: We can use rule 1here. Since H2 is in its elemental state, it has an
oxidation number of 0.

H2O Rules 1 and 2 dont apply to this situation, so we can skip them.
Rule 3 tells us that hydrogen usually has the oxidation number of +1,
except in hydrides. We dont have a hydride here, but even if we arent
sure if our hydrogen has a +1 or -1 oxidation state, we can use rule 4 to
check.

Rule 4 tells us that all the oxidation numbers in a compound have to add
up to charge on the compound, and rule 3 says that oxygen usually has
an oxidation number of -2. Water is a neutral compound, so we need our
oxidation numbers to add up to 0. If we assign a -1, oxidation number to
hydrogen because we think it might be a hydride, we get for the sum of
oxidation numbers:

(oxidation # of O# of O atoms)+(oxidation # of H# of H
atoms)=(21)+(12)=4
That doesn't look right! If instead we use the oxidation number +1for
hydrogen, we get for the sum: (21)+(+12)=0 which is what we
would expect for a neutral molecule. Thus, using rules 3 and 4 we can
assign the hydrogen in H2O an oxidation state of +1.

Concept check: What is the oxidation state of sulfur in the sulfate

ion, SO42
[Show the answer]

A quick skim of the guidelines tells us that we don't have the

oxidation state of sulfur listed. That means we will have to use
rules 333 and 444 to figure out the oxidation state of sulfur.

Rule333 tells us that the oxidation state of oxygen is -22minus,

2. We can then use rule 444to calculate the oxidation state of
sulfur:

\begin{aligned} \text{Net charge on SO}_4^{2-} &=

(\text{oxidation number of O} \times 4) +
\text{oxidation number of S} \\ -2 &= (-2 \times 4) +
\text{oxidation number of S} \\ -2 &= -8 +
\text{oxidation number of S} \end{aligned}
Net charge on SO4222=(oxidation number of
O4)+oxidation number of S=(24)+oxidation numb
er of S=8+oxidation number of S
Solving the equation for the oxidation number of sulfur, we get the
following answer:

\text{oxidation number of S in } \text{SO}_4^{2-} =

+6oxidation number of S in SO42=+6

Using oxidation numbers: Oxidation and

reduction
Now we can follow instructions to find oxidation numbers. Thats cool, but
why do oxidation states matter? After all, they are practically imaginary!

A thin ribbon of silver magnesium metal burns with white flame to

produce a white-grey solid, magnesium oxide.
When pure magnesium metal is burned, the magnesium gets oxidized to form magnesium
oxide. Photo from Wikimedia Commons, CC BY-SA 3.0

Chemists are usually interested in keeping track of electrons because we

want to know when electrons get transferred from one atom to another. In
the above example, we can see that the oxidation state of the hydrogen is
different in \text H_2H2H, start subscript, 2, end subscript compared
to \text{H}_2 \text OH2OH, start subscript, 2, end subscript, O. If we
compare the oxidation states, a chemist might say that hydrogen in water
has fewer electrons compared to elemental hydrogen.

Here is the reaction to make water from hydrogen gas and oxygen gas:

2\text H_2(g)+ \text O_2(g) \rightarrow 2\text{H}_2 \text O

(l)2H2(g)+O2(g)2H2O(l)2, H, start subscript, 2, end subscript, left
parenthesis, g, right parenthesis, plus, O, start subscript, 2, end subscript,
left parenthesis, g, right parenthesis, right arrow, 2, H, start subscript, 2,
end subscript, O, left parenthesis, l, right parenthesis

We will see that this reaction not only breaks and makes new chemical
bonds, but also involves a loss of electrons from \text H_2H2H, start
subscript, 2, end subscript. Chemists have specific terms to describe
processes that involve the loss or gain of electrons:

Oxidation is the loss of one or more electrons by an atom. When the

oxidation number of an element increases, that means there is a loss of
electrons and that element is being oxidized. In the above reaction, \text
H_2H2H, start subscript, 2, end subscript is being oxidized because it
loses electrons to form \text{H}_2 \text OH2OH, start subscript, 2,
end subscript, O. The loss of electrons is evident from the oxidation
number changing from 000 to +1+1plus, 1: since the hydrogen atom
lost an electron (which has a negative charge), the oxidation number
increased.

Reduction is the gain of one or more electrons by an atom. When the

oxidation number of an element decreases, that means there is a gain of
electrons and that element is being reduced. In the reaction to make
water, \text O_2O2O, start subscript, 2, end subscript is being reduced
because the oxidation number of each oxygen atom decreased
from 000to -22minus, 2 from the gain of 222 negatively charged
electrons.

Some ways to remember oxidation and reduction include:

1.~1. 1, point, spaceOIL RIG: "Oxidation Is Loss" and
"Reduction Is Gain"

2.~2. 2, point, spaceLEO the lion says GER: "Loss of Electron

is Oxidation" and "Gain of Electrons is Reduction"

The terms oxidizing agent and reducing agent are closely related to
oxidation and reduction.

A reducing agent, or reductant, loses electrons and is therefore oxidized

in a chemical reaction. In our example, \text H_2H2H, start subscript, 2,
end subscript is acting as a reducing agent in the reaction since it is
getting oxidized and causing the reduction of \text O_2O2O, start
subscript, 2, end subscript.

An oxidizing agent, or oxidant, gains electrons and gets reduced in a

chemical reaction. \text O_2O2O, start subscript, 2, end subscript is
acting as an oxidizing agent in our reaction because it is responsible for
the oxidation of the reducing agent, \text H_2H2H, start subscript, 2,
end subscript.

For more examples, see this video on oxidation and reduction, and this
video on oxidizing and reducing agents.

Oxidation numbers and redox reactions

Chemical reactions that involve the transfer of electrons are
called oxidation-reduction or redox reactions. Oxidation state changes are
a sign that an electron transfer is occurring. All redox reactions involve
both a reduction and an oxidation.

Many reaction types such as combustion, single replacement, and some

synthesis and decomposition reactions fall into the category of redox
reactions. Oxidation numbers and redox reactions are important concepts
in more advanced chemistry classes as well, such as biochemistry,
electrochemistry, organic chemistry, and inorganic chemistry to name a
few. We aren't going to go into more detail about redox reactions in this
article, but keep in mind being comfortable with oxidation numbers will
come in handy!

Summary
Oxidation numbers are used by chemists to keep track of electrons within
a compound. We can use guidelines to assign oxidation numbers to atoms
in a compound. Changes in oxidation state during a reaction tell us that
there is a transfer of electrons. Reactions that involve the transfer of
electrons are called redox reactions, and they include a reduction (a gain
of electrons) and an oxidation (a loss of electrons). The substance that is
reduced is called the oxidizing agent, and the substance that is oxidized is
called the reducing agent.

Practice Problem 8:

Arrange the following compounds in order of increasing oxidation state for the carbon atom.

(a) CO

(b) CO2

(c) H2CO

(d) CH3OH

(e) CH4