CH302 UNIT 8 Electrochemistry notes part 1 Electrochemical reactions are oxidation-reduction reactions.

OXIDATION IS a LOSS of electrons REDUCTION IS a GAIN of electrons Reduction and oxidation often take place in two different places. Cell Types: electrolytic cell: cell containing a nonspontaneous chemical reaction. The reaction is forced to occur by applying an electrical potential. voltaic or galvanic cell: cell containing a spontaneous chemical reaction These cells can be used as a source of energy. Electrodes: REMEMBER RED CAT This convention for electrodes is correct for either electrolytic or voltaic cells: Reduction ALWAYS occurs at the cathode Oxidation ALWAYS occurs at the anode Electrode SIGN varies with cell type: The anode is positive in electrolytic cells and negative in voltaic cells. The cathode is negative in electrolytic cells and positive in voltaic cells. Voltaic or Galvanic Cells A spontaneous chemical reaction produces electrical energy. Two half cells are physically separated so that electrons from the redox reaction are forced to travel through wires and create a potential difference. Examples include auto batteries, Flashlight batteries, Computer, cellphone and calculator batteries

Anode reaction Cathode reaction

Zn 0 Zn 2+ + 2e Cu 2+ + 2e Cu 0

Overall cell reaction Zn 0 + Cu 2+ Zn 2+ + Cu 0 This is a spontaneous reaction with E 0 cell = +1.10V

A commonly used short hand notation for ALL cells can be used:
species (and concentrations) in contact with electrode surfaces

Zn/Zn2+(1.0 M) || Cu2+(1.0 M)/Cu salt bridge electrode surfaces

Anode reaction Cathode reaction

Cu 0 Cu 2+ + 2e 2 Ag + + e - Ag 0

Overall cell reaction Cu 0 + 2 Ag + Cu 2+ + 2 Ag 0 This is a spontaneous reaction with E 0 cell = +0.46 V

Strengths of Reducing and Oxidizing Agents In the Zn-Cu cell Cu is the cathode: Overall Cu2+ oxidizes metallic Zn to Zn2+. In the the Cu-Ag cell Cu is the anode: Overall Ag+ oxidizes metallic Cu to Cu 2+. Listing in order of increasing strengths: Zn2+ < Cu2+ < Ag+ strength as oxidizing agent Zn0 > Cu0 > Ag0 strength as reducing agent (as all are metals, this means Zn is more reactive than Ag) Standard Reduction Potentials We measure the relative potentials of different species against a Standard Hydrogen Electrode (SHE). The SHE is assigned an arbitrary voltage of zero V. The reactions are: 2H+(aq) + 2e- H2(g) or H2(g) 2H+(aq) + 2e-

E0 Anode reaction Zn 0 Zn 2+ + 2 e Cathode reaction 2 H + 2 e H 2(g )

+ -

0.763 V 0.000 V

Cell reaction Zn 0 + 2H + Zn 2 + + H 2 (g ) E 0 cell = 0.763 V

The cathode is the Standard Hydrogen Electrode. Zn reduces H+ to H2. The anode is Zn metal. Zn metal is oxidized to Zn2+ ions.

E0 Anode reaction H 2(g ) 2 H + + 2 e Cathode reaction Cu

2+

0.000 V 0.337 V
0

+ 2e Cu
2+

Cell reaction H 2(g ) + Cu

2H + Cu
+

0 cell

= +0.337 V

In this cell the SHE is the anode The Cu2+ ions oxidize H2 to H+. The Cu is the cathode. The Cu2+ ions are reduced to Cu metal.

Standard Reduction Potentials (E0) Electrodes that force the SHE to act as an anode are assigned positive standard reduction potentials. Electrodes that force the SHE to act as the cathode are assigned negative standard reduction potentials. Standard (electrode) reduction potentials show the tendencies of reduction half-reactions to occur. The more positive the value of Eo, the greater the tendency for the reduction reaction to occur. Uses of Standard Electrode Potentials + 0 The half-reaction for the reduction of potassium is: K + e K E 0 = -2.925 V The large negative value shows this reaction will occur only under extreme conditions. The half-reaction for the reduction of fluorine is :

F20 + 2 e- 2 F-

E 0 = +2.87 V

The large positive value denotes this reaction occurs readily as written. We use standard electrode potentials to predict whether an electrochemical reaction at standard state conditions (1M concentrations) will occur spontaneously. Method: 1. Choose the appropriate half-reactions from a table of standard reduction potentials. 2. Write the equation for the half-reaction with the more positive E0 value first, along with its E0 value. 3. Write the equation for the other half-reaction as an oxidation with its oxidation potential, i.e. reverse the tabulated reduction half-reaction and change the sign of the tabulated E0. 4. Balance the electron transfer by multiplying the half reactions. DO NOT MULTIPLY THE REDUCTION POTENTIALS!! 5. Add the reduction and oxidation half-reactions and their potentials. This produces the equation for the reaction for which E0cell is positive, which indicates that the forward reaction is spontaneous. NOTE: Some redox reactions such as Fe2+ Fe3+ + e- do not involve the element. They can still be found in the table of E0 values. In these cells, the electrode is typically the Pt inert electrode mentioned previously. Example: Will Ag+, oxidize Zn to Zn2+, or will Zn2+ oxidize Ag to Ag+ ions?

Example 2: Will permanganate ions, MnO4-, oxidize iron (II) ions to iron (III) ions, or will iron (III) ions oxidize manganese(II) ions to permanganate ions in acidic solution?

Example 3: Will nitric acid, HNO3, oxidize arsenous acid, H3AsO3, in acidic solution? The reduction product of HNO3 is NO in this reaction.