Chapter 19: Electrochemistry: 19.1 Voltaic Cells

CHEM 1442
Chapter 19: Electrochemistry

Brief Overview of Electrochemical Cells
 Electrochemistry- the study of the relationship between chemical reactions and electrical energy.
o All electrochemical reactions are redox reactions. They involve the transfer of electrons.
 There are two kinds of electrochemical cells:
o Voltaic Cells, a.k.a. Galvanic Cells.
 In them, a spontaneous redox reaction is used to generate electrical energy.
 Their Gibbs energy change is negative, their equilibrium is greater than 1, and their cell
potential is positive.
o Electrolytic Cells
 Electrical energy is used to drive a non-spontaneous reaction.
 Their Gibbs energy change is positive, their equilibrium is less than 1 but greater than
zero, and their cell potential is negative.
 In both types of cells:
o Oxidation occurs at the anode; anions migrate toward the anode
o Reduction occurs at the cathode; cations migrate toward the cathode.
19.1 Voltaic Cells

 Observe the redox reaction of solid Zinc is placed in aqueous Copper Sulfate:
REMEMBER THE REACTION IS SPONTANEOUS!

 This redox reaction can be written as two half-reactions:
 Half-cells can be created based on the half-reactions above, placing both the oxidized and reduced
forms of a substance in physical contact with each other.
o These two half-cells can be electrically connected with an external wire and a salt bridge, which
will allow the redox reaction to occur, forming what is called a voltaic, or galvanic cell.
 Why is a “salt bridge” needed?

o A salt bridge will complete the electrical circuit necessary for the reaction to occur.
o It prevents the two solutions from mixing by providing a way for the electrons to migrate from
one substance to the other without physical touch.
 Remember that all that happens in a redox reaction is the transfer of electrons. This
reaction can happen as long as the electrons have a way to get from one substance to
the other; they do not necessarily need to be in physical contact.
 This also maintains electrical neutrality in each half cell.
 Cell Notation
o A voltaic cell can be described using the following cell notation:
anode| anode electrolyte|| cathode electrolyte| cathode
 The single vertical bar represents phase boundaries (anode/ cathode are solid,
electrolytes are in aqueous solution).
 The double vertical bar represents the salt bridge.
0
19.2 Standard Cell Potential ( E ¿ ¿ cell )¿
 Standard Cells: electrochemical cells in which all substances, including reactants and products, are in
their standard states.
 You know that redox reactions are spontaneous, but the driving force behind their spontaneity is the
electromotive force, or e.m.f.
o This e.m.f. is an archaic and misleading name. It is not a force at all, but rather the difference in
potential between the two half-cells.
o In modernity, this is called electrochemical cell potential, cell voltage, or Ecell , measured in Volts
(V), which is defined as Joules per Coulomb(J/C).
o The cell potential under standard conditions, E0cell , is a useful value that can help us predict the
behavior of a voltaic cell.
 Standard Reduction Potentials, E0¿ , are defined relative to the standard hydrogen potentials. These can
be used to compare the relative strengths of oxidizing and reducing agents.
o The more positive E0¿ is, the stronger the oxidizing agent.
o The more negative the E0¿ , the stronger the reducing agent on the right side of the half-reaction.
0
 The E0¿ values for the cathode and anode of a substance can be used to calculate Ecell for a voltaic cell:
E0cell =E0¿ ( cathode ) −E0¿ (anode )
 GUIDING PRINCIPLE: electrons always spontaneously flow from the half-cell with the more negative E0¿
(anode) to the one with the more positive E0¿ (cathode).
19.3 Nonstandard Conditions: The Nernst Equation

 The Nernst Equation can be used to determine the cell potential under nonstandard conditions.
o At 25 degrees C, the Nernst equation is:
0.0592
E=E0− log ⁡(Q)
n
o Where:
 E=cell potential∈nonstandard conditions,∈V
 E0 =standard cell potential ,∈V
 n=number of moles of electrons transferred ∈balanced equation.
 Q=reactionquotient
19.4 Cell Potential, Gibbs Energy, and Equilibrium
 The relationship between standard cell potential, standard Gibbs energy, and equilibrium are expressed
in the following relationships:
∆ G0 =−nFE 0
0.0592
E0 = log ⁡(K )
n
o Where:
 n=number of moles of electrons transferred ∈balanced equation.
C (Coulombs)
 F=Farada y ' s Constant=96,485
mol e−¿ ¿
19.5 Electrolysis
 In electrolysis, electrical energy is used to force a nonspontaneous redox reaction to occur.
o Electroplating is an electrolytic process resulting in a neutral metal being deposited on the
surface of the cathode.
 The Table of Standard Reduction Potentials can be used to predict what will be oxidized and what will be
reduced when an electric current is applied to a mixture of substances.
o In general:
 The strongest oxidizing agent present will be reduced
 The strongest reducing agent present will be oxidized
o Exceptions to this generalization can arise when gases are produced at metal electrodes.
 A large activation energy is involved in the formation of a gas, so more voltage may be
required than what can be predicted by standard electrode potential.
 This higher amount of voltage is called overvoltage.
19.6 Electrochemical Stoichiometry

 Most electrochemical stoichiometry problems focus on the relationship between electrical current,
time, and the amount of metal plated out during electrolysis.
 Every electrochemical stoichiometry problem can be solved by focusing on two important relationships:
o The definition of electrical current:
q ( charge )
I ( current )=
t (time)
o The charge of one mole of electrons:
C (Coulombs)
F=Farada y ' s Constant=96,485
mol e−¿ ¿
 The key feature of any electrochemical stoichiometry problem is that the appropriate mole-to-mole
must be used. That means knowing the number of moles of electrons transferred per mole of reactant
or product.

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CHEM 1442

Chapter 19: Electrochemistry

19.1 Voltaic Cells

REMEMBER THE REACTION IS SPONTANEOUS!

 Why is a “salt bridge” needed?

anode| anode electrolyte|| cathode electrolyte| cathode

E0cell =E0¿ ( cathode ) −E0¿ (anode )

19.3 Nonstandard Conditions: The Nernst Equation

19.6 Electrochemical Stoichiometry

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