Electrochemical Cells

(aka – Galvanic or Voltaic

Cells)
AP Chemistry
Unit 10
Electrochemistry
Chapter 17
 Electrochemical/Galvanic Cells
 Chemical Energy is converted to Electrical
Energy.
 A spontaneous redox reaction that is used
to generate a voltage (Electricity)
 You separate the reactants (oxidizing and
reducing agents) and force the electrons
to travel through a wire.
 Electrochemical Cell
Voltmeter
Salt Bridge
Cathode - Reduction Anode - Oxidation
 Electrochemical Cells
 Anode – The electrode where oxidation
occurs
 Cathode – The electrode where reduction
occurs.
 Salt Bridge – prevents build up of ions
on one side of the cell and balances the
charge.
 No more electricity can flow when the
anode disappears!
 Electrochemical Cell Animation Tutorial Lin
k
 Cell Diagrams
 A voltaic/electrochemical cell may be
represented by the following
 ANODE CATHODE
 Zn(s) Zn2+ (1M) Cu2 (1M) Cu(s)

 The single lines represent phase boundaries

(e.g. solid anode to 1M liquid) and the double
lines represent the salt bridge.
 Standard conditions are 25oC,1 atm and 1M
solutions.
 The Cell Potential
The potential is the ability of a cell to do
electrical work. ξcell is measured in volts.
 1 volt = 1 joule/ coulomb A coulomb
is the quantity of charge passing in 1
second when the current is 1 ampere
 1C= 1A•sec
Standard Reduction Potentials
 Most reference tables for electrochemistry are
written as reductions in a half-reaction format,
with the most negative reduction on the top and
the most positive on the bottom. By definition, all
half reductions are compared to the hydrogen half
reaction that has the standard value of 0.00 V
under standard conditions.
 Standard state: 25oC, 1 atm
 2H+ + 2 e-  H2 ξ0cell = 0.00
 All other reduction potentials are based on this
zero point.
 Standard Reduction Potentials
Strongest
Oxidizing
Agents/
Easily
Reduced

Strongest
Reducing
Agents/
Easily
Oxidized
 Rules for Using Standard Reduction
Potentials
1) Read the half reactions as written
2) The more POSITIVE the reduction potential,
the greater the tendency is for the substance
to be reduced and therefore the better the
oxidizing agent
 (keep the half-reaction with the more POSITIVE
cell potential as written in the table—that is the
reduction reaction)
3) The half-cell reactions ARE reversible. IF you
need to reverse, you MUST change the sign
of the ξ0cell.
4) If you change the stoichiometric
coefficients, ξ0cell remains the same
 Rules for Using Standard Reduction
Potentials
5) Under standard state conditions: any
species on the LEFT of a given half-
reaction will react spontaneously with a
species that is on the RIGHT and ABOVE it
6) The most positive values for ξcell mean
that they are the strongest OXIDIZING
AGENTS and therefore are themselves
reduced.
7) The most negative values for ξcell mean
that they are the strongest REDUCING
AGENTS and therefore are themselves
oxidized.
 The Total Cell Potential
 The total cell potential is the sum of the
half-cell potentials

ξ0cell. = ξ0 ox + ξ0red

 A (+) ξ0cell means the reaction will

happen spontaneously
 A (-) ξ0cell means the reaction will
not happen!
 Determining ξ cell 0

 Example:
 What will be the overall reaction and the ξocell-
total if Br2 is added to a solution containing I2 at
25oC? Assume all species are in their standard
states.
 Half reactions (as found in a standard table):
 I2 (s) + 2 e- 2I– (aq) ξocell = 0.53 V
 Br2 (l)+ 2e-  2Br­(aq) ξored = 1.07 V
 Using the standard reduction potentials, the fact that Br 2
has the more positive potential indicates that the Br2
will be reduced. So, change the sign on the oxidation
reaction and reverse it so that it is written as an
oxidation.

 Br2 (l) + 2e-  2Br­ (aq) ξored = 1.07 V

 2I–(aq)  I2 (s) + 2 e- ξoox = -0.53 V

 Add the reactions:

 Br2 (l) + 2e-  2Br­(aq) ξored = 1.07 V
 2I– (aq)  I2 (s)+2 e- ξoox = -0.53 V

 Br2 (l)+2I–(aq)  2Br ­(aq) + I2(s)

ξocell-total= +0.54 V
 Sample Problem 2

 What will be the overall reaction and the

ξocell-total if Zn(s), a 1M solution of Zn2+,
Cu(s) and a 1M solutions of Cu2+ are
reacted?