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reducing agent = species that is oxidized oxidizing agent = species that is reduced

Some redox processes, however, do not involve the transfer of electrons. Consider, for example, a reaction similar to the one yielding NaCl:

H 2 ( g ) + Cl 2 ( g ) 2 HCl( g )

The product of this reaction is a covalent compound, so transfer of electrons in the explicit sense is not involved. To clarify the similarity of this reaction to the previous one and permit an unambiguous definition of redox reactions, a property called oxidation number has been defined. The oxidation number    (or oxidation state ) of an element in a compound is the charge its atoms would possess if the compound was ionic . The following guidelines are used to assign oxidation numbers to each element in a molecule or ion.

  1. The oxidation number of an atom in an elemental substance is zero.
  2. The oxidation number of a monatomic ion is equal to the ion’s charge.
  3. Oxidation numbers for common nonmetals are usually assigned as follows:
    • Hydrogen: +1 when combined with nonmetals, –1 when combined with metals
    • Oxygen: –2 in most compounds, sometimes –1 (so-called peroxides, O 2 2− ), very rarely 1 2 (so-called superoxides, O 2 ), positive values when combined with F (values vary)
    • Halogens: –1 for F always, –1 for other halogens except when combined with oxygen or other halogens (positive oxidation numbers in these cases, varying values)
  4. The sum of oxidation numbers for all atoms in a molecule or polyatomic ion equals the charge on the molecule or ion.

Note: The proper convention for reporting charge is to write the number first, followed by the sign (e.g., 2+), while oxidation number is written with the reversed sequence, sign followed by number (e.g., +2). This convention aims to emphasize the distinction between these two related properties.

Assigning oxidation numbers

Follow the guidelines in this section of the text to assign oxidation numbers to all the elements in the following species:

(a) H 2 S

(b) SO 3 2−

(c) Na 2 SO 4

Solution

(a) According to guideline 1, the oxidation number for H is +1.

Using this oxidation number and the compound’s formula, guideline 4 may then be used to calculate the oxidation number for sulfur:

charge on H 2 S = 0 = ( 2 × +1 ) + ( 1 × x ) x = 0 ( 2 × +1 ) = −2

(b) Guideline 3 suggests the oxidation number for oxygen is –2.

Using this oxidation number and the ion’s formula, guideline 4 may then be used to calculate the oxidation number for sulfur:

charge on SO 3 2– = −2 = ( 3 × −1 ) + ( 1 × x ) x = −2 ( 3 × −2 ) = +4

(c) For ionic compounds, it’s convenient to assign oxidation numbers for the cation and anion separately.

According to guideline 2, the oxidation number for sodium is +1.

Assuming the usual oxidation number for oxygen (–2 per guideline 3), the oxidation number for sulfur is calculated as directed by guideline 4:

charge on SO 4 2− = −2 = ( 4 × −2 ) + ( 1 × x ) x = −2 ( 4 × −2 ) = +6

Check your learning

Assign oxidation states to the elements whose atoms are underlined in each of the following compounds or ions:

(a) K N O 3

(b) Al H 3

(c) N ¯ H 4 +

(d) H 2 P _ O 4

Answer:

(a) N, +5; (b) Al, +3; (c) N, –3; (d) P, +5

Using the oxidation number concept, an all-inclusive definition of redox reaction has been established. Oxidation-reduction (redox) reactions are those in which one or more elements involved undergo a change in oxidation number. (While the vast majority of redox reactions involve changes in oxidation number for two or more elements, a few interesting exceptions to this rule do exist [link] .) Definitions for the complementary processes of this reaction class are correspondingly revised as shown here:

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Source:  OpenStax, Ucd bis2a intro to biology v1.2. OpenStax CNX. Sep 22, 2015 Download for free at https://legacy.cnx.org/content/col11890/1.1
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