Redox & Oxidation number

Term 1: Week 4

The bronze statue of Great Buddha in Kamakura, Kanagawa, Japan

Outline Oxidation and reduction Strength of oxidizing and reducing agents Ionic equations Oxidation number

Oxidation and Reduction Reactions in Daily Life

Oxidation with hydrogen peroxide

Batteries

Combustion

Corrosion

Oxidation of apple

Oxidation and reduction in biology

2n CO2 + 2n DH2 + photons 2(CH2O)n + 2n DO

Carbon dioxide + electron donor + light energy carbohydrate + oxidized electron donor

Oxidation and reduction in medicine

Oxidation is linked with the effects of aging of humans. To forestall the effects of oxidation, doctors recommend antioxidants - natural reducing agents such as vitamin C and vitamin E.

Jacob Tsiperovich

Oxidation and Reduction

Originally oxidation meant addition of oxygen and reduction meant removal of oxygen. REDOX a contraction of reduction-oxidation It implies that two processes always act together
Fe2O3 loses oxygen and is reduced Fe2O3 (s) + 3 CO (g) 2Fe (s) + 3 CO2 (g)

CO gains oxygen and is oxidized

Oxidation and Reduction

2Na0 + Cl20
2Na Cl2 + 2

2Na+Cl-

2Na+ + 2 2Cl-

Oxidation is the loss of electrons. Reduction is the gain of electrons.

Memory aid

Oxidizing and reducing agents

2 C(s) + O2(g) CO(g)

Oxidizing and reducing agents

2Na0 + Cl20 2Na Cl2 + 2 2Na+Cl2Na+ + 2 2Cl-

Sodium is oxidized it is the reducing agent

Chlorine is reduced it is the oxidizing agent

Oxidizing and reducing agents

Active metals: Lose electrons easily Are easily oxidized Are strong reducing agents Active nonmetals: Gain electrons easily Are easily reduced Are strong oxidizing agents

Oxidizing agents
1. Free (elemental) nonmetals become negative ions: F2 + 2 2FO2 + 4 2O22. Positive (usually metal) ions become neutral: Ag+ + Ag 3. Higher oxidation states become lower: 8H+ + MnO4- + 5 Mn2+ + H2O Fe3+ + Fe2+

Strong Oxidizing Agents

Metal Oxyacids Chromium Reagents (H2CrO4; K2Cr2O7 + H2SO4; CrO3 + H2SO4) Manganese reagents (KMnO4) Osmium Tetroxide (OsO4) Nitric Acid and Nitrous Acid (HNO3, HNO2) Halogens (F2 > Cl2 > Br2 > I2) Forms of Oxygen and Peroxides (O3, H2O2)

Acids as Oxidizing Agents

Hydrogen ion in hydrochloric acid can be an oxidizing agent because it can be reduced to H2.

HCl H+(aq) + Cl-(aq) 2H+(aq) + Zn(s) Zn2+(aq) + H2(g)

In nitric acid solution, the nitrate ion is a more powerful oxidizing agent than the hydrogen ion.

HNO3 H+(aq) + NO3-(aq) Cu(s)+4H+(aq)+2NO3-(aq) Cu2+(aq)+2NO2(g)+2H2O(l)

Reducing agents
1. Active metals forms ions plus electrons: Zn Zn2+ + 2 Na Na+ + 2. Nonmetals combine with other nonmetals, such as F and O, which they take from compounds with metals: C + [O2-] CO + 2 3C + Fe2O3 3 CO + 2 Fe 3. Lower oxidation states become higher: NO + 2 H2O NO3- + 4H+ + 3

Activity Series
Best oxidizing agent
F2(g) + 2 2 F- (aq)

Worst reducing agent

Fe3+ (aq) + Fe2+(aq) Cu2+(aq) + 2 Cu(s) 2H+(aq) + 2 H2(g) Ni2+(aq) + 2 Ni(s) Fe2+(aq) + 2 Fe(s) Zn2+(aq) + 2 Zn(s)

Al3+(aq) + 3 Al(s)
Worst oxidizing agent Li+(aq) + Li(s)

Best reducing agent

Comparing oxidizing and reducing strength

2H+(aq) + Zn(s) Zn2+(aq) + H2(g)

The formation of hydrogen gas in the reaction of a metal with an acid is a special case of a more general phenomenon one element displacing (pushing out) another element from a compound by means of a redox reaction.

Fe2+(aq) + Cu(s) Fe(s) + Cu2+(aq)

In which direction will reaction go spontaneously?
18

Fe2+(aq) + Cu(s) Fe(s) + Cu2+(aq)

Best oxidizing agent Activity Series
Worst reducing agent F2(g) + 2 2 F- (aq)

Cu2+(aq) + 2 Cu(s) 2H+(aq) + 2 H2(g) Fe2+(aq) + 2 Fe(s) Zn2+(aq) + 2 Zn(s) Worst oxidizing agent

Best reducing agent Fe is a stronger reducing agent than Cu. Fe + Cu2+ Fe2+ + Cu

Li+(aq) +

Li(s)

Fe(s) + Cu2+(aq)

Fe2+(aq) + Cu(s)

Electron transfer
Zn

CuSO4(aq)

ZnSO4(aq)

Cu

Zn(s) + Cu2+(aq) Zn(s)

Zn2+(aq) + Cu(s)

Zn2+(aq) + 2
Cu(s)

Cu2+(aq) + 2

Example of oxidation: corrosion

The rusting of iron is an electrochemical process that begins with the transfer of electrons from iron to oxygen. Fe Fe2+ + 2 e Redox reaction in the presence of water: 4 Fe2+ + O2 4 Fe3+ + 2 O2 Rust formation: Fe2+ + 2 H2O Fe(OH)2 + 2 H+ Fe3+ + 3 H2O Fe(OH)3 + 3 H+ Dehydration: Fe(OH)2 FeO + H2O Fe(OH)3 FeO(OH) + H2O 2FeO(OH) Fe2O3 + H2O

Corrosion
Corrosion is even faster in the presence of salts and acids, because these materials make electrically conductive solutions that make electron transfer easy. Zinc is added to any metal that will be submerged in water and exposed to stray currents to provide protection against galvanic corrosion. Fe2+ + Zn Fe + Zn2+

Corrosion
Gold and platinum are called noble metals because they are resistant to losing their electrons by corrosion. Other metals may lose their electrons easily, but are protected from corrosion by the oxide coating on their surface, such as aluminum oxide.

Ionic equations
To make the essential processes of redox reactions clearer ionic equations are employed. ions in solution are written separately only species that change are shown (not spectator ions)
SnCl2(aq) + Fe2(SO4)3(aq) FeSO4(aq) + SnCl4(aq)

Sn2+(aq) + Fe3+(aq)

Fe2+(aq) + Sn4+(aq)

Half Equations
Ag+ (aq) + Cu(s) Ag(s) + Cu2+ (aq)

Ag+ (aq) + Ag(s) Ag+ gains electrons, is reduced, and is the oxidizing agent. Cu(s) Cu2+ (aq) + 2 Cu loses electrons, is oxidized, and is the reducing agent.

Balancing Half Equations

Oxidation: Cu(s) Cu2+ (aq) + 2 Reduction: Ag+ (aq) + Ag(s) 2

2Ag+ (aq) + 2 Net: Cu(s) + 2Ag+ (aq)

2Ag(s) 2Ag(s) + Cu2+ (aq)

What if there is NO complete electron transfer from one substance to another?

C(s) + O2(g)

CO2(g)

To overcome this problem, the concept of OXIDATION NUMBER (ON) was introduced.

Oxidation number (ON)

Oxidation number is a number assigned to atom or an ion to describe its relative state of oxidation or reduction.

H2O ((H+)2O-2)

ON of H in H2O = +1 ON of O in H2O = -2

HCl (H+Cl-)

ON of H in HCl = +1 ON of Cl in HCl = -1

Dont misunderstand!
Oxidation number has no structural or physical significance. It is not a charge of atom! Oxidation number is relative value of oxidation, which can be equal to the charge.

Advantages of Oxidation Numbers

useful in balancing equations
Oxidation: Reduction: Cu(s) Cu2+ (aq) + 2 Ag+ (aq) + Ag(s) 2 2Ag+ (aq) + 2 2Ag(s) Cu(s) + 2Ag2+ (aq) 2Ag(s) + Cu2+ (aq)

used in systematic nomenclature

HClO FeSO4 Fe2(SO4)3 Recommended name chloric (I) acid iron (II) sulphate iron (III) sulphate Common (trivial) name hypochloric acid

Guidelines for Determining Oxidation Numbers

1. The algebraic sum of oxidation numbers in neutral compound must be zero; in a polyatomic ion, the sum must be equal to the ion charge (Al2O3 or MnO4-)

Guidelines for Determining Oxidation Numbers

2. Each atom in a pure element has an oxidation number of zero (Cu, I2 or S8)

Guidelines for Determining Oxidation Numbers

3. Elements of Group 1A 3A form monoatomic ions with positive charge and the oxidation number is equal to the group number.

Example

K: 1s2 2s2 2p6 3s2 3p6 4s1

K+: 1s2 2s2 2p6 3s2 3p6 4s0 K+: [Ar] octet stability

Guidelines for Determining Oxidation Numbers

4. The oxidation number of H is +1 and fluorine is always -1 in compounds with other elements.
Exceptions: When H forms a binary compound with a metal, the metal forms positive ion and H becomes a hydride ion H-

Guidelines for Determining Oxidation Numbers

5. The oxidation number of O is -2 in most compounds
Exceptions: Oxygen can have an oxidation number -1 in a class of compounds called peroxides

Guidelines for Determining Oxidation Numbers

6. Cl, Br and I are always -1 in compounds except when combined with oxygen and fluorine
( Cl has an oxidation number -1 in NaCl, but in the ion ClO- has an oxidation number +1)

Guidelines for Determining Oxidation Numbers

7. When there is a conflict between two of these rules or an ambiguity in assigning an oxidation number, apply the rule with the lower number and ignore the conflicting rule.
1. The algebraic sum of oxidation numbers in neutral compound must be zero; in a polyatomic ion, the sum must be equal to the ion charge 2. Each atom in a pure element has an oxidation number of zero 3. Elements of Group 1A 3A form monoatomic ions with positive charge and the oxidation number is equal to the group number 4. The oxidation number of H is +1 and fluorine is always -1 in compounds with other elements 5. The oxidation number of O is -2 in most compounds 6. Cl, Br and I are always -1 in compounds except when combined with oxygen and fluorine

Example
1. The algebraic sum of oxidation numbers in neutral compound must be zero; in a polyatomic ion, the sum must be equal to the ion charge 2. Each atom in a pure element has an oxidation number of zero 3. Elements of Group 1A 3A form monoatomic ions with positive charge and the oxidation number is equal to the group number 4. The oxidation number of H is +1 and fluorine is always -1 in compounds with other elements 5. The oxidation number of O is -2 in most compounds 6. Cl, Br and I are always -1 in compounds except when combined with oxygen and fluorine

Mg(NO3)2 (+2)+2(ON(N)+3(-2))=0 ON(N) = +5

Exercise
H3PO4
(+1)3 + ON(P) + (-2)4 = 0

ON (P) = +5 ON (Cr) = +6
ON (C) = +3 ON (Cl) = +5

Cr2O722ON(Cr) + (-2)7 = -2

H2C2O4 NaClO3
(+1) + ON(Cl) + (-2)3 = 0

(+1)2 + 2ON(C) + (-2)4 = 0

WELL DONE!!!

October's MONTHLY QUIZ is at 8 a.m. Wednesday. Groups F and G in 2/302 D, E, H, I in 5/103 A, B, C in 3/143 Turn up in good time with calculator, pencil and ruler. Periodic tables will be provided.

When the student is ready, the master appears.

Buddhist Proverb