OXIDATION NUMBERS The following rules predict the oxidation number for each of the atoms/ions in a compound or ion.

General Rules (Always applicableNo exceptions) 1. For any uncombined element, the oxidation number is zero. Examples: Fe, Xe, O2, H2 (0 for all of these) 2. For any monatomic ion, the oxidation number is equal to the charge on the ion. Examples: Fe2+, F-, O2-, H+ (+2, -1, -2, and +1 respectively) 3. For any compound, the sum of the oxidation numbers must be zero. Examples: NaCl = Na+ + Cl- = +1 + (-1) = 0 MgF2 = Mg2+ + 2 F- = +2 + 2(-1) = 0 Fe2(Cr2O7)3 = 2 Fe3+ + 6 Cr6+ + 21 O2= 2(+3) + 6(+6) + 21(-2) = 0 4. For any ion, the sum of the oxidation numbers must equal the charge on the ion. Examples: NO31- = N5+ + 3 O2- = +5 + 3(-2) = -1 C2H3O21- = 2C0 + 3H+ + 2O2- = 2(0) + 3(+1) + 2(-2) = -1 Special Rules These rules only apply to certain columns on the Periodic Table. They often combine with General Rules 3 and 4. Note: Rules 1-8 apply to the main group elements. Different Periodic Tables label these in different ways, so two types of numbers are given. The currently accepted method is to use the numbers 1-2 and 13-18 for the representative elements. Older tables used IA-VIIIA (or IBVIIIB). Each of the rules will use both of these methods with the newer method of labeling given in parentheses. Note: These are the most common/stable oxidation numbers. There are exceptions in addition to the ones given below. Note: These values refer to these elements in compounds. General Rule 1 still applies to the elements in the elemental state.

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1. Column IA (1) 2. Column IIA (2)

+1 (Except H with a metal, then H = -1) +2

3. Column IIIA (13) +3 (Normally, however +1 possible near the bottom of the table) 4. Column IVA (14) +4 to -4 5. Column VA (15) +5 to -3

6. Column VIA (16) +6 to -2 (Oxygen is -2 except when combined with F, or in O22- or O2-) 7. Column VIIA (17) +7 to -1 (Fluorine is -1 in compounds) 8. Column VIIIA (18) +8 to 0 (Usually only 0) 9. Transition Metals IIIB-IIB (3-12) If the B designation is used the values may range from +2 to the group number. If the other designation is used, the values may range from +2 to the group number for columns 3-8 and to the group number minus 10 for groups 11 and 12 (treat columns 9 and 10 as if they were 7 and 6 respectively). Exceptions: Hg22+ (Hg = +1) and Au3+ (Au = +3) When an element may have a positive or negative oxidation number, it will normally be negative if it is to the upper right, on the Periodic Table, with respect to the other elements in the compound or ion. When it is negative, under these circumstances, it will probably have the most negative of the possible values noted in the rules above. Note that in Special Rules 4-8 the range of possible values is always eight. With these elements, the more probable oxidation states may be determined by counting from highest to lowest by twos. In naming compounds containing a metal with a variable oxidation number (most of the transition metals and those around lead on the Periodic Table), Stock Numbers should be used in the name. Older nomenclature systems used different names to designate variations in the oxidation number (for example, ferrous and ferric). We will not do so in this class. In this class, do not use Stock Numbers except with a metal.

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Examples: Cr Cl F C Pb NaH BaO2 Cl2O7 CuS Hg2Cl2 HgCl2 Pb3O4 H2SO4 MoO3 possible values: possible values possible values possible values possible values Na+ Ba2+ Cl7+ Cu2+ Hg+ Hg2+ Pb8/3+ H+ Mo6+ HOO2S2ClClO2S6+ O20, +2, +3, +4, +5, +6 -1, 0, +1, +2, +3, +4, +5, +6, +7 (underlined preferred) -1, 0 -4, -3, -2, -1, 0, +1, +2, +3, +4 0, +2, +4 (even though Pb and C are in the same column, Pb only has positive values since it is a metal.) (barium peroxide)

(actually 2 Pb2+ + 1 Pb4+) O2-

At one time different names were used for different oxidation states for a few elements. These are no longer proper names, however they are still seen for a few elements (iron, copper and tin), and appear as trivia for others. These names are not acceptable on a lecture exam. These names were devised so that the lower oxidation state of an element ended in -ous, and the higher oxidation state ended in -ic. In general, the more likely elements to use this method were p and d block metals and metalloids with names based upon a Latin root instead of an English root. Some examples are included in the following table. Name (lower state) Antimonous Aurous Cerous Chromous Cobaltous Cuprous Ferrous Manganous Mercurous Nickeleous Platinous Plumbous Stannous Stibonious Thallous Titanous Vanadous Charge Sb3+ Au+ Ce3+ Cr2+ Co2+ Cu+ Fe2+ Mn2+ Hg22+ Ni2+ Pt2+ Pb2+ Sn2+ Sb3+ Tl+ Ti3+ V2+ Name (higher state) Antimonic Auric Ceric Chromic Cobaltic Cupric Ferric Manganic Mercuric Nickelic Platinic Plumbic Stannic Stibonic Thallic Titanic Vanadic Charge Sb5+ Au3+ Ce4+ Cr3+ Co3+ Cu2+ Fe3+ Mn3+ Hg2+ Ni3+ Pt4+ Pb4+ Sn4+ Sb5+ Tl3+ Ti4+ V3+

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