1. Electro Chemistry
Unit 5 Chemistry 12

2. Introduction
Electro chemistry is concerned with the conversion of chemical energy to electrical energy and visa versa.
Electrochemical reactions involve the movement of electrons;one reagent gains electrons, the other reagent looses electrons
Like acid/base reactions you can think of electrochemical reactions as a combination of 2 half reactions

3. Acids/Bases (In the rearview mirror)
Arrhenius: Acid donates H+ ions
Base donates OH- ions
Bronstead-Lowery : Acid proton donor
Base proton accepter
Lewis : Acid is an electron pair accepter
Base an electron pair donor

4. Electro Chemical Reactions
2 types (oxidation and reduction)
Oxidation 1/2 reaction in which the reacting species looses an electro
Reduction 1/2 reaction in which the reacting species gains an electron

5. Memory Trick “LEO the lion says GER”
LEO: loss of electrons = oxidation
GER: Gain of electrons = reduction
We say Fe2+ is oxidized
We say Cr3+was reduced

6. More Definitions
Oxidizing Agent: is the species that gets reduced (because it is what causes the other species to loose electrons)
Reducing Agent: is the species that gets oxidized (because it is what causes the other species to gain electrons)

7. Identification of oxidized/reduced species
Species that have been oxidized become more positive, because they have lost electrons (** the oxidized species is the reducing agent)
Species that have been reduced become more negative, because they have gained electrons. (** the reduced species is the oxidizing agent)

8. Predictions Positive species will likely undergo reduction
Negative species will likely undergo oxidation
Neutral species will either undergo oxidation or reduction depending on their electron negativity.

9. Oxidation numbers
Oxidation number: is the charge that an atom would posses if the species containing the atom were made up of ions
Oxidation numbers are a useful way of deciding if a species has undergone oxidation or reduction
If the oxidation number of a species increases, then the species was oxidized
If the oxidation number of a species decreases, then the species was reduced.

10. Guidelines for Assigning Oxidation Numbers
For ionic compounds (including acids/bases) the oxidation number is the charge on the ion
Group 1 have an oxidation # of plus 1 (hydrogen is sometimes an exception)
Group 2 have an oxidation # of plus 2.
Group 17 usually have an oxidation # of -1.
Group 16 usually have an oxidation # of -2.
THE SUM OF +VE and -VE CHARGES MUST BE EQUAL TO THE OVERALL CHARGE ON THE SPECIES.

11. Strengths of Reducing/oxidizing Agent
The relative strength of reducing/oxidizing agents are measured against the Standard Hydrogen 1/2 cell (often called the SHE electrode)
Standard potential tables are written from a reduction perspective

12. Spontaneity of Redox Reactions
For reagents to under go a redox reactions they must be on opposite sides of the std. reduction potential datasheet. (ie. One reagent must be able to under oxidation and the other reduction)
The reaction will be spontaneous if the reduction 1/2 cell is above the oxidation 1/2 cell in the reduction potential tables
The potential (voltage) of a spontaneous rx is always positive

13. Balancing Redox Reactions
Break the reaction into the two 1/2 cells
Balance each 1/2 cell
Use a stiochiometric ratio so that Total electrons gained=Total electrons lost
Add the two half reactions together canceling out species that appear on both sides of the reaction

14. Balancing 1/2 Cells (acid) MAJOR OH-
Balance Major ions first
Balance oxygen by adding H2O’s
Balance the hydrogen by adding H+
Balance the charge by adding e-

15. Balancing 1/2 Cells (basic) MAJOR OH-(+water)
Balance Major ions first
Balance oxygen by adding H2O’s
Balance the hydrogen by adding H+
Balance the charge by adding e-
Use the dissociation of water to convert H+ into OH-

16. Preferred Redox Reactions
If more than one redox reaction is possible, the reaction which has the highest voltage potential will occur first. ( Farthest apart on the standard tables using “DISCO RULE”)
Example Rust protection using Zinc as a “sacrificial anode”
Zn -> Zn+2 +2e
Fe -> Fe+2 +2e
1/2 O2(aq) + 2H+(10-7) +2e -> H2O

17. Galvanic/Voltaic/Electrochemical Cells
An-Ox Ca-red
An-OX Ca-Red

18. Electrolysis
Definition: is the process of supplying electrical energy to a molten ionic compound or ionic solution to produce a chemical change. Electrolysis supplies energy to non-spontaneous electro chemical reactions in which E0 is < O

19. Electrolytic or Electrolysis Cell
Electrolyte is a molten salt or ionic solution
For Electrolytic cells, The Redox reaction with the least negative voltage will occur first

20. Electrowinning
Electrowinning: Is an electrolytic cell that causes the electro deposition of metal from metallic ore/ liquid leach solution. The metal is deposited on the cathode. Usually oxygen is produced at the anode.

21. Electro-plating
Electro-plating is a process in which a metallic ion is reduced or “plated out” onto a cathode of a different material
The Electrolyte contains the metallic ion to be plated out.
The anode can be an inert electrode or the same material as the cathode

22. Electrorefining
Electrorefining is an electrolytic process in which impure metal is purified by oxidizing the impure metal at the anode and reduce the metallic ion produced at a cathode this process is voltage regulated such that only the reduction of the metal being purified plates out

23. Gottchas
Non-standard potentials
Aqeous solutions vs. molten salts