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RULES FOR ASSIGNING OXIDATION STATES

1. The oxidation state (O.S.) of an individual atom in a free element


(uncombined with other elements) is 0.
[Examples: The O.S. of an isolated Cl atom is 0; the two Cl atoms in the
molecule Cl2 both have an O.S. of 0.]
2. The total of the O.S. of all the atoms in:
a. Neutral species, such as isolated atoms, molecules, and formula units,
is 0;
[Examples: The sum of the O.S. of all the atoms in CH3OH and of all the
ions in MgCl2 is 0]
b. An ion is equal to the charge on the ion;
i. In a polyatomic ion, the sum of oxidation numbers of all the
elements in the ion must be equal to the net charge of the ion.
[Example: in the ammonium ion, NH+4 , the oxidation number
of N is -3 and that of H is +1. Thus the sum of the oxidation
numbers is -3+4(+1)=+1, which is equal to the net charge of the
ion.]
ii. In a monatomic ions, the oxidation number is equal to the
charge on the ion.
[Examples: Li+ ion has an oxidation number of +1; Ba2+ ion,

+2; Fe3+ ion, +3; I- ion, -1; O2- ion, -2; and so on.]
3. In their compounds, the group 1 metals (Alkali) have an O.S. of +1 and the
group 2 metals (Alkaline) have an O.S. of +2.
[Examples: The O.S. of K is +1 in KCl and K2CO3; the O.S. og Mg is +2 in
MgBr2 and Mg(NO3)2]
4. In its compounds, the O.S. of fluorine is -1.
[Examples: The O.S. of F is -1 in HF, ClF3 and SF6 ]
5. In its compounds, hydrogen usually has an O.S. of +1.
[Examples: The O.S of H is +1 in HI, H2S, NH3, CH4]

The principal exceptions to rule 5 occur when H is bonded to metals, as in LiH,


NaH, and CaH2 (its oxidation number is -1)

6. In its compounds, oxygen usually has an O.S. of -2.


[Examples: The O.S. of O is -2 in H2O, CO2 and KMnO4.]

Exceptions to rule 6 occur in compounds with O-F bonds, such as OF2, and in
compounds where O atoms are bonded to one another, as in H2O2, and KO2.

7. n binary (two-element) compounds with metals, group 17 elements have


an O.S. of -1; group 16 elements, -2; and group 15 elements, -3.
[Examples: The O.S. of Br is -1 in MgBr2; the O.S. of S is -2 in Li2S; and the O.S.
of N is -3 in Li3N]
8. Oxidation numbers do not have to be integers.
[Example: the oxidation number of O in the superoxide ion, O2- , is -1/2.]

Source:
General Chemestry Petrucci, Chapter 3, page 85
Chang Chemestry, Chapter 4, page 138
2

EXERCISES
P4:

This formula represents a molecule of elemental phosphorus. For an

atom of a free element,the O.S. = 0 (rule 1). The O.S. of P in P4 is 0.


Cr2O72-:
From rule 2 we see that the sum of the oxidation numbers in the
dichromate ion Cr2O72- must be -2. We know that the oxidation number of O is
-2, so all that remains is to determine the oxidation number of Cr, which we call
y. The dichromate ion can be written as:








HNO3:
This is the formula for nitric acid, which yields a H+ ion and a
NO2 ion in solution. From rule 5 we see that H has an oxidation number of +1.
Thus the other group (the nitrate ion) must have a net oxidation number of -1.
Oxygen has an oxidation number of -2, and if we use x to represent the
oxidation number of nitrogen, then the nitrate ion can be written as:









H2O2:
This is hydrogen peroxide. Rule 5, stating that H has an O.S. of
+1, takes precedence over rule 6. The sum of the oxidation states of the two H
atoms is +2 and that of the two O atoms must be -2. The O.S. of O must be -1.
NaH:
This is a formula unit of the ionic compound sodium hydride.
Rule 3 states that the O.S. of Na is +1. Rule 5 indicates that H should also have
an O.S. of +1. If both atoms had a O.S. of +1, the total for the formula unit
would be +2. This violates the rule 2.
Na has an O.S. of +1; the total for the formula unit is 0; and the O.S. of H must
be -1.
Al2O3:

The total of the oxidation states of all the atoms in this formula

unit is 0. The O.S. of oxygen is -2. The total for three O atoms is -6. The total
for two Al atoms is +6. The O.S. of Al is +3.

MnO4-:

This is the formula for permanganate ion. The total of the

oxidation states of all the atoms in the ion is -1. The total for the four O atoms
is -4. The O.S. of Mn is +7.

PF3: Using algebra like in the other compounds I can calclulate the oxidation
states.
F= -1 Rule 4
P + 3(-1) = 0 Rule 2
P=0+3
P = +3

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