Redox Reactions and
Electrochemistry
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Textbook: Chapter 18
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Electrochemical processes
Electrochemical processes are
oxidation-reduction reactions in which:
- the energy released by a spontaneous
reaction is converted to electricity
or
- electrical energy is used to cause
nonspontaneous reaction to occur
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Electrochemical process
Electrochemical process involve Red-Ox reactions
occuring with the variation of the oxidation number
0 0 2+ 2-
2Mg (s) + O2 (g) 2MgO (s)
0
Oxidation 2Mg 2Mg2+ + 4e-
half-reaction (lose e-)
0
Reduction O2 + 4e- 2O2-
half-reaction (gain e-)
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Oxidation number
The charge the atom would have in a molecule (or an
ionic compound) if electrons were completely transferred.
1. Free elements (uncombined state) have an oxidation
number of zero.
Na, Be, K, Pb, H2, O2, P4 = 0
2. In monatomic ions, the oxidation number is equal to
the charge on the ion.
Li+, Li = +1; Fe3+, Fe = +3; O2-, O = -2
3. The oxidation number of oxygen is usually –2. In H2O2
and O22- it is –1.
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Oxidation number
4. The oxidation number of hydrogen is +1 except
when it is bonded to metals in binary
compounds, hydrides. In these cases, its
oxidation number is –1.
+1 -1 +1 -1 +1 -1
KH, LiH, NaH
5. Group IA metals are +1, IIA metals are +2 and fluorine
is always –1.
6. The sum of the oxidation numbers of all the atoms in a
molecule or ion is equal to the overall charge of the
molecule or ion.
Identify the oxidation numbers of all the atoms in HCO3− ?
HCO3− We know: O = −2 and H = +1
For all anion: 3x(−2) + 1 + x = −1
x = +4 C = +4
HNO2 HNO3 K2MnO4 CrCl3
H2SO3 HSO4-
H2S Ca(HSO3)2 Na2Cr2O7 CrPO4
MgH2 CaCl2
Balancing Redox Equations
The oxidation of Fe2+ to Fe3+ by Cr2O72- in acid solution?
ferrous ferric
FeCl2 + K2Cr2O7+ HCl à FeCl3 + CrCl3 + KCl + H2O
1. Write the unbalanced equation for the reaction ion ionic form.
Fe2+ + Cr2O72- Fe3+ + Cr3+
2. Separate the equation into two half-reactions.
+2 +3
Oxidation: Fe2+ Fe3+
+6 +3
Reduction: Cr2O72- Cr3+
Balancing Redox Equations
The oxidation of Fe2+ to Fe3+ by Cr2O72- in acid solution?
ferrous ferric
1. Write the unbalanced equation for the reaction ion ionic form.
Fe2+ + Cr2O72- Fe3+ + Cr3+
2. Separate the equation into two half-reactions.
+2 +3
Oxidation: Fe2+ Fe3+
+6 +3
Reduction: Cr2O72- Cr3+
3. Balance the atoms other than O and H in each half-reaction.
Cr2O72- 2Cr3+
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Balancing Redox Equations
4. Add electrons to one side of each half-reaction to balance the
charges on the half-reaction.
Fe2+ Fe3+ + 1e-
6e- + Cr2O72- 2Cr3+
Balancing Redox Equations
4. Add electrons to one side of each half-reaction to balance the
charges on the half-reaction.
Fe2+ Fe3+ + 1e-
6e- + Cr2O72- 2Cr3+
5. For reactions in acid, add H+ to balance electronic charge and
H2O to balance O atoms and H atoms
6e- +14H+ + Cr2O72- 2Cr3+
6e- + 14H+ + Cr2O72- 2Cr3+ + 7H2O
Balancing Redox Equations
4. Add electrons to one side of each half-reaction to balance the
charges on the half-reaction.
Fe2+ Fe3+ + 1e-
6e- + Cr2O72- 2Cr3+
5. For reactions in acid, add H+ to balance electronic charge and
H2O to balance O atoms and H atoms
6e- +14H+ + Cr2O72- 2Cr3+
6e- + 14H+ + Cr2O72- 2Cr3+ + 7H2O
6. If necessary, equalize the number of electrons in the two half-
reactions by multiplying the half-reactions by appropriate
coefficients.
6Fe2+ 6Fe3+ + 6e-
6e- + 14H+ + Cr2O72- 2Cr3+ + 7H2O 12
Balancing Redox Equations
7. Add the two half-reactions together and balance the final
equation by inspection. The number of electrons on both
sides must cancel.
Oxidation: 6Fe2+ 6Fe3+ + 6e-
Reduction: 6e- + 14H+ + Cr2O72- 2Cr3+ + 7H2O
14H+ + Cr2O72- + 6Fe2+ 6Fe3+ + 2Cr3+ + 7H2O
Balancing Redox Equations
7. Add the two half-reactions together and balance the final
equation by inspection. The number of electrons on both
sides must cancel.
Oxidation: 6Fe2+ 6Fe3+ + 6e-
Reduction: 6e- + 14H+ + Cr2O72- 2Cr3+ + 7H2O
14H+ + Cr2O72- + 6Fe2+ 6Fe3+ + 2Cr3+ + 7H2O
8. Verify that the number of atoms and the charges are balanced.
14x1 – 2 + 6 x 2 = 24 = 6 x 3 + 2 x 3
Balancing Redox Equations
7. Add the two half-reactions together and balance the final
equation by inspection. The number of electrons on both
sides must cancel.
Oxidation: 6Fe2+ 6Fe3+ + 6e-
Reduction: 6e- + 14H+ + Cr2O72- 2Cr3+ + 7H2O
14H+ + Cr2O72- + 6Fe2+ 6Fe3+ + 2Cr3+ + 7H2O
8. Verify that the number of atoms and the charges are balanced.
14x1 – 2 + 6 x 2 = 24 = 6 x 3 + 2 x 3
9. For reactions in basic solutions, add OH- to instead of H+ to
balance electronic charges.
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Balancing Redox Equations
7. Add the two half-reactions together and balance the final
equation by inspection. The number of electrons on both
sides must cancel.
Oxidation: 6Fe2+ 6Fe3+ + 6e-
Reduction: 6e- + 14H+ + Cr2O72- 2Cr3+ + 7H2O
14H+ + Cr2O72- + 6Fe2+ 6Fe3+ + 2Cr3+ + 7H2O
8. Verify that the number of atoms and the charges are balanced.
14x1 – 2 + 6 x 2 = 24 = 6 x 3 + 2 x 3
9. For reactions in basic solutions, add OH- to instead of H+ to
balance electronic charges.
10. Balance the reaction in the molecular form:
6FeCl2 + K2Cr2O7+ 14HCl à 6FeCl3 + 2CrCl3 + 2KCl + 7H2O 16
Balancing Redox Equations
HCl + Na2Cr2O7 + NaCl à NaClO + CrCl3 + H2O
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Balancing Redox Equations
Na2S2O3 + I2 + NaOH à Na2SO4 + H2O + NaI
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Balancing Redox Equations
Re + HNO3 à HReO4 + H2O + NO
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Balancing Redox Equations
S + NaOH à Na2S + Na2S2O3 + H2O
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Balancing Redox Equations
As2S3 + H2O + HNO3 à H3AsO4 + H2SO4 + NO
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