2. 1 Electron Transfer Reactions: CH 19: Oxidation-reduction or redox reactions. Results in generation of an electric current (electricity) or caused by imposing an electric current.Results in generation of an electric current (electricity) or caused by imposing an electric current. In previous chapter energy was in form of heat, here it is electricity.In previous chapter energy was in form of heat, here it is electricity. Therefore, this field of chemistry is often called ELECTROCHEMISTRY.Therefore, this field of chemistry is often called ELECTROCHEMISTRY.

3. 2 Terminology for Redox Reactions OXIDATION—loss of electron(s) by a species; increase in oxidation number; increase in oxygen.OXIDATION—loss of electron(s) by a species; increase in oxidation number; increase in oxygen. REDUCTION—gain of electron(s); decrease in oxidation number; decrease in oxygen; increase in hydrogen.REDUCTION—gain of electron(s); decrease in oxidation number; decrease in oxygen; increase in hydrogen. OXIDIZING AGENT—electron acceptor; species is reduced.OXIDIZING AGENT—electron acceptor; species is reduced. REDUCING AGENT—electron donor; species is oxidized.REDUCING AGENT—electron donor; species is oxidized. OXIDATION—loss of electron(s) by a species; increase in oxidation number; increase in oxygen.OXIDATION—loss of electron(s) by a species; increase in oxidation number; increase in oxygen. REDUCTION—gain of electron(s); decrease in oxidation number; decrease in oxygen; increase in hydrogen.REDUCTION—gain of electron(s); decrease in oxidation number; decrease in oxygen; increase in hydrogen. OXIDIZING AGENT—electron acceptor; species is reduced.OXIDIZING AGENT—electron acceptor; species is reduced. REDUCING AGENT—electron donor; species is oxidized.REDUCING AGENT—electron donor; species is oxidized.

4. 3 You can’t have one… without the other! Reduction (gaining electrons) can’t happen without an oxidation to provide the electrons. You can’t have 2 oxidations or 2 reductions in the same equation. Reduction has to occur at the cost of oxidation LEO the lion says GER! Another way to remember. GER! OIL RIG

5. 4 Activity Series For metals, the higher up the chart the element is, the more likely it is to be oxidized. This is because metals like to lose electrons, and the more active a metallic element is, the more easily it can lose them.metals For nonmetals, the higher up the chart the element is, the more likely it is to be reduced. This is because nonmetals like to gain electrons, and the more active a nonmetallic element is, the more easily it can gain them.

6. 5 Metal Activity Metallic elements start out with a charge of ZERO, so they can only be oxidized to form (+) ions. The higher of two metals MUST undergo oxidation in the reaction, or no reaction will happen. The reaction 3 K + FeCl 3  3 KCl + Fe WILL happen, because K is being oxidized, and that is what the activity series says should happen. The reaction Fe + 3 KCl  FeCl 3 + 3 K will NOT happen. 3 K 0 + Fe +3 Cl -1 3 REACTION Fe 0 + 3 K +1 Cl -1 NO REACTION

7. 6 Electrochemical Cells Allows a redox reaction to occur by transferring e- through an external connector.Allows a redox reaction to occur by transferring e- through an external connector. Product favored reaction --> voltaic or galvanic cellProduct favored reaction --> voltaic or galvanic cell Converts chemical energy from a spontaneous redox rxtn into electrical energy. Reactant favored reaction --> electrolytic cell.Reactant favored reaction --> electrolytic cell. Converts chem. energy to electrical energy using a nonspontaneous redox rxtn & an electrical energy source. Batteries are voltaic cells

8. 7 CHEMICAL CHANGE ---> ELECTRIC CURRENT With time, Cu plates out onto Zn metal strip, and Zn strip “disappears.” Zn is oxidized and is the reducing agent Zn(s) ---> Zn 2+ (aq) + 2e-Zn is oxidized and is the reducing agent Zn(s) ---> Zn 2+ (aq) + 2e- Cu 2+ is reduced and is the oxidizing agent Cu 2+ (aq) + 2e- ---> Cu(s)Cu 2+ is reduced and is the oxidizing agent Cu 2+ (aq) + 2e- ---> Cu(s)

9. 8 To obtain a useful current, we separate the oxidizing and reducing agents so that electron transfer occurs thru an external wire.To obtain a useful current, we separate the oxidizing and reducing agents so that electron transfer occurs thru an external wire. CHEMICAL CHANGE ---> ELECTRIC CURRENT This is accomplished in a GALVANIC or VOLTAIC cell. A group of such cells is called a battery. http://www.mhhe.com/physsci/chemistry/essentialchemistry/flash/galvan5.swf

10. 9 Anode: half cell where oxidation occurs Cathode: half cell where reduction occurs Basic Concepts of Electrochemical Cells Electrons travel thru external wire. Salt bridge allows anions and cations to move between electrode compartments, without mixing of metal atoms.

11. 10 Notation: Anode I Anode product I Salt I Cathode ICathode product Zn (s) I Zn 2+ (aq, 1 M) I NaNO 3 I Cu 2+ (aq, 1 M) I Cu (s) Notation: Anode I Anode product I Salt I Cathode ICathode product Zn (s) I Zn 2+ (aq, 1 M) I NaNO 3 I Cu 2+ (aq, 1 M) I Cu (s) Zn --> Zn 2+ + 2e- Cu 2+ + 2e- --> Cu <--AnionsCations--> Oxidation Anode Negative Oxidation Anode Negative Reduction Cathode Positive Reduction Cathode Positive RED CAT An OX

12. 11 Terms Used for Voltaic Cells Electrode: metal connected by an external circuit

13. 12 CELL POTENTIAL, E cell EMF:electromotive force For Zn/Cu cell, potential is +1.10 V at 25 ˚C and when [Zn 2+ ] and [Cu 2+ ] = 1.0 M.For Zn/Cu cell, potential is +1.10 V at 25 ˚C and when [Zn 2+ ] and [Cu 2+ ] = 1.0 M. This is the STANDARD CELL POTENTIAL, E oThis is the STANDARD CELL POTENTIAL, E o —a quantitative measure of the tendency of reactants to proceed to products when all are in their standard states at 25 ˚C.—a quantitative measure of the tendency of reactants to proceed to products when all are in their standard states at 25 ˚C.

14. 13 Calculating Cell Voltage Balanced half-reactions can be added together to get overall, balanced equation.Balanced half-reactions can be added together to get overall, balanced equation. Zn(s) ---> Zn 2+ (aq) + 2e- Cu 2+ (aq) + 2e- ---> Cu(s) -------------------------------------------- Cu 2+ (aq) + Zn(s) ---> Zn 2+ (aq) + Cu(s) Zn(s) ---> Zn 2+ (aq) + 2e- Cu 2+ (aq) + 2e- ---> Cu(s) -------------------------------------------- Cu 2+ (aq) + Zn(s) ---> Zn 2+ (aq) + Cu(s) If we know E o for each half-reaction, we could get E o for net reaction.

15. 14 TABLE OF STANDARD REDUCTION POTENTIALS the standard for measuring is SHE: Standard Hydrogen Electrode 2 E o (V) Cu 2+ + 2e- Cu+0.34 2 H + + 2e- H0.00 Zn 2+ + 2e- Zn-0.76 oxidizing ability of ion reducing ability of element To determine an oxidation from a reduction table, just take the opposite sign of the reduction!

16. 15 Zn/Cu Electrochemical Cell Ox: Zn(s) ---> Zn 2+ (aq) + 2e-E o = +0.76 V Red:Cu 2+ (aq) + 2e- ---> Cu(s)E o = +0.34 V --------------------------------------------------------------- Cu 2+ (aq) + Zn(s) ---> Zn 2+ (aq) + Cu(s) E o = +1.10 V E o = +1.10 V Cathode, positive, sink for electrons Anode, negative, source of electrons +

17. 16

18. 17 Cd --> Cd 2+ + 2e- or Cd 2+ + 2e- --> Cd Fe --> Fe 2+ + 2e- or Fe 2+ + 2e- --> Fe E o for a Voltaic Cell All ingredients are present. Which way does reaction proceed?

19. 18 From the table, you see Fe is a better reducing agent than CdFe is a better reducing agent than Cd Cd 2+ is a better oxidizing agent than Fe 2+Cd 2+ is a better oxidizing agent than Fe 2+ E o for a Voltaic Cell Eo = Eo reduction (reduction process-cathode )– Eo reduction (oxidation process- anode) Positive value indicates spontaneous process. Negative value indicates nonspontaneous. Steps for prediction spontaneity: 1.Write the reaction as oxidation and reduction half reactions. 2.Plug standard reduction potentials in the equation given above. 3.Check for the spontaneity by a positive or negative value.

20. 19 More About Calculating Cell Voltage Assume I - ion can reduce water. 2 H 2 O + 2e- ---> H 2 + 2 OH - Cathode 2 I - ---> I 2 + 2e- Anode ------------------------------------------------- 2 I - + 2 H 2 O --> I 2 + 2 OH - + H 2 2 H 2 O + 2e- ---> H 2 + 2 OH - Cathode 2 I - ---> I 2 + 2e- Anode ------------------------------------------------- 2 I - + 2 H 2 O --> I 2 + 2 OH - + H 2 Assuming reaction occurs as written, E˚ = E˚ cat + E˚ an = (-0.828 V) + (- +0.535 V) = -1.363 V Minus E˚ means rxn. occurs in opposite direction (the connection is backwards or you are recharging the battery)

21. 20 Charging a Battery When you charge a battery, you are forcing the electrons backwards (from the + to the -). To do this, you will need a higher voltage backwards than forwards. This is why the ammeter in your car often goes slightly higher while your battery is charging, and then returns to normal. In your car, the battery charger is called an alternator. If you have a dead battery, it could be the battery needs to be replaced OR the alternator is not charging the battery properly.

22. 21 Dry Cell Battery Anode (-) Zn ---> Zn 2+ + 2e- Cathode (+) 2 NH 4 + + 2e- ---> 2 NH 3 + H 2

23. 22 Alkaline Battery Nearly same reactions as in common dry cell, but under basic conditions. Anode (-): Zn + 2 OH - ---> ZnO + H 2 O + 2e- Cathode (+): 2 MnO 2 + H 2 O + 2e- ---> Mn 2 O 3 + 2 OH -

24. 23 H 2 as a Fuel Cars can use electricity generated by H 2 /O 2 fuel cells. H 2 carried in tanks or generated from hydrocarbons

25. 24 Balance the following in acid solution— VO 2 + + Zn ---> VO 2+ + Zn 2+ VO 2 + + Zn ---> VO 2+ + Zn 2+ Step 1:Write the half-reactions OxZn ---> Zn 2+ RedVO 2 + ---> VO 2+ Step 2:Balance each half-reaction for mass. OxZn ---> Zn 2+ Red Step 3:Balance half-reactions for charge. OxZn ---> Zn 2+ + 2e- Rede- + 2 H + + VO 2 + ---> VO 2+ + H 2 O Step 4:Multiply by an appropriate factor. OxZn ---> Zn 2+ + 2e- Red 2e- + 4 H + + 2 VO 2 + ---> 2 VO 2+ + 2 H 2 O Step 5:Add balanced half-reactions Zn + 4 H + + 2 VO 2 + ---> Zn 2+ + 2 VO 2+ + 2 H 2 O VO 2 + ---> VO 2+ + H 2 O 2 H + + Add H 2 O on O- deficient side and add H + on other side for H-balance.