Chapter 19.

Electrochemistry
19.1 Pulling the Plug on the Power Grid
• Know that electrical power comes from a power grid, a distribution system of electricity in the
country.
• Know that fuel cell technology can replace the power source for an automobile or a home.
• Know that the oxidation and reduction reactions that combine hydrogen and oxygen to water
can power a fuel cell

19.2 Balancing the Oxidation–Reduction Equations

• Know the definition of oxidation and reduction and that paired reactions occur by combinations
of these.
• Balance aqueous redox equations for reactions in acidic solution by using the half-reaction
method. [in ACID: use H+ as source of Hydrogen and H2O as source of Oxygen when balancing]

 STEPS to BALANCING
1. Write reactant being oxidized into its product
a. Mass balance only element being oxidized
b. If either side is deficient in hydrogen, add H+ as source of Hydrogen, (100%) only
to that one side [balancing in acid]
c. If either side is deficient in oxygen, add H2O as source of Oxygen, (33%) only to
that one side
d. Add electrons to the product side only to charge balance the oxidation half reaction.
2. Write reactant being reduced into its product
a. Mass balance only element being reduced
b. If either side is deficient in hydrogen, add H+ as source of Hydrogen, only to that
one side [balancing in acid]
c. If either side is deficient in oxygen, add H2O as source of Oxygen, only to that one
side
d. Add electrons to the reactant side only to charge balance the reduction half reaction
3. Add the two half reactions like simultaneous equations ensuring that the number of
electrons generated by the oxidation half reaction are equivalent the number consumed by
the reduction half reaction. If necessary, multiply one or both of the half reactions by a
coefficient to make the electrons cancel out from the overall reaction. DO NOT MULTIPLY
THE Eo BY THIS COEFFICIENT – Eo IS AN INTENSIVE PROPERTY
4. Check the mass balance and the charge balance (same charge total on left & right)

• Balance aqueous redox equations for reactions in basic solution by using the half-reaction
method. [in BASE: use H2O as source of Hydrogen (66%) and OH- as source of oxygen (50%)
when balancing]
OR: balance in ACID first as above and add one OH- for every H+ ON BOTH SIDES, combine OH-
and H+ into H2O and collect terms]

 oxidation: loss of electrons (gain of oxygen, loss of hydrogen, increase in oxidation number)
 reduction: gain of electrons (loss of oxygen, gain of hydrogen, decrease in oxidation number)
Examples 19.1 Half-Reaction Method of Balancing Aqueous Redox Equations in Acidic Solution
Balance the following reaction in acid:

Examples 19.2 Half-Reaction Method of Balancing Aqueous Redox Equations in Acidic Solution
Balance the following reaction in acid:
Example 19.3 Balance the following reaction in Base

19.3 Voltaic (or Galvanic) Cells: Generating Electricity from Spontaneous

Chemical Reactions
• Know that paired redox reactions are carried out in an electrochemical cell (a.k.a. voltaicor
galvanic cell) and understand that these cells can generate an electrical current.
• Know that electrolytic cells use electrical current to drive nonspontaneous chemical reactions.
• Know and understand that electrochemical reactions are a combination of half-cell reactions—
oxidation occurring at an anode, and reduction occurring at a cathode.
• Know and understand the components of a voltaic cell including the half-cells, electrodes, salt
bridge, and the potential difference generated.
• Understand electrochemical cell notation.
 Outline
1. Electrolytic (non-spontaneous cell – recharging or electrolysis)
2. Electrochemical cell (a.k.a. spontaneous cell,voltaic, galvanic, +emf)
a. properties
i. electrical current (ampere, A) 1A=1C/s
ii. potential difference (volts, V) 1V=1J/C [a.k.a. cell potential, emf]
b. components
i. half-cell (oxidation half reaction/reduction half reaction)
ii. electrodes
1. anode: oxidation
2. cathode: reduction
3. inert: platinum (if gases are used to provide surface for reaction &
conduction)
iii. salt bridge (no electrons allowed – only spectator anion & cations which migrate to
maintain electrical neutrality so cell doesn’t short circuit from charge build-up)

19.4 Standard Reduction Potentials

• Understand standard reduction potentials and use them to generate electrochemical cells.
• Calculate standard potentials for electrochemical cells from standard reduction potentials of the
half-reactions.
• Calculate standard potentials and predict spontaneous redox reactions.
• Understand how to predict whether a metal will dissolve in acid using emf tables
Outline
a. Standard half-cell
a. standard hydrogen electrode SHE
i. reaction
ii. half-cell potential
iii. use as reference
b. Standard reduction potentials
a. measured vs. reference(s) like SHE
i. E°cell = E°cat - E°an (both written as reductions from EMF table

(or E°cell = E°red + E°ox where the oxidation reaction is inverted & the sign of its
EMF changed accordingly)

b. table of values
i. sign and value convention
c. predicting spontaneous direction (the redox combination that produces the larges most
positive E°cell )
d. metals dissolving in acid
i. To dissolve in a binary acid (like HCl or HI) the metal must have a positive E°ox
relative to the SHE (more active metals like Mg react with HCl)
ii. More stable metals (less active) like Cu only don’t react with HCl but require a more
oxidizing acid like HNO3. This reaction will occur if the E°cell is positive when the
metals oxidation reaction is added to the reduction of HNO3 to H2
Example 19.4 Use tabulated standard electrode potentials to calculate the standard cell
potential for the reaction occurring in an electrochemical cell at 25 ○C. (The equation is balanced.)

Example 19.5 Without calculating E○cell, predict whether each redox reaction is spontaneous.
If the reaction is spontaneous as written, make a sketch of the electrochemical cell in which the
reaction could occur. If the reaction is not spontaneous as written, write an equation for the
spontaneous direction in which the reaction would occur and make a sketch of the spontaneous
electrochemical cell (a.k.a. galvanic or voltaic cell) in which the spontaneous reaction would occur.
In your sketches, make sure to label the anode, the cathode, and the direction of electron flow.

Show the standard cell notation for the galvanic cell:

19.5 Cell Potential, Free Energy, and the Equilibrium Constant
• Calculate and interconvert among the standard free energy ΔG°, standard potential for an
electrochemical cell E°cell, and equilibrium constant K.
C J J C
Faraday or F ¿ 96485 −¿ and C= so V = and Amp=
mol e ¿ V C s

a. Recall from Chapter 17 that If ΔG = 0 the system is at equilibrium (no more chemical
potential – a dead battery), Q becomes K and then this equation ∆ G❑ o
rxn =∆ G rxn + RTlnQ
becomes G° = –RT ln Keq
b. Similarly, the chemical potential relates to the cell’s voltage as ΔGo = – nFE°cell (where n=
the number of electrons in the balanced reduction reaction)
c. The Equilibrium constant K can then be related to both E°cell and ΔGo

G° = –RT ln Keq ΔGo = –nFE°cell then Eo cell= 0.0592 V logK

n

Example19.6 Use the tabulated electrode potentials to calculate ΔG○ for the reaction

Example 19.7 Use the tabulated electrode potentials to calculate K for the oxidation of
copper by H+:
19.6 Cell Potential and Concentration
• Calculate and interconvert between the cell potential and reaction quotient Q using the standard
potential and the Nernst equation.
• Know and understand how a concentration cell works.
° RT ° 0.0592V
Ecell =Ecell − lnQ∨at 25 ℃ E cell=E cell− logQ
nF n

Example 19.8 An electrochemical cell is based on these two half-reactions: What is the measured
voltage? Is the cell electrolytic or galvanic?

What is the reduction potential for this half reaction at 25oC when [Cu2+] = 2.5 M and [Cu+] = 0.10 M?
The Eo for this half reaction is 0.161 volts. + ¿¿
−¿→ Cu ¿
¿
Cu2+¿+e

What is the anode reaction in the galvanic cell based on the two half reactions below?
o
−¿ E =2.87 V ¿
−¿ →2 F ¿
F 2+2 e
o
−¿→ NaE =−2.71 V¿
+¿+e ¿
Na
19.7 Batteries: Using Chemistry to Generate Electricity

 Know the basic information about dry-cell, lead storage, NiCad, lithium ion, and other types of
batteries.
 Know and understand how a fuel cell works and some information about common ones like the
hydrogen–oxygen fuel cell.

19.8 Electrolysis: Driving Nonspontaneous Chemical Reactions with Electricity

 Know and understand how an electrolytic cell works and some common examples like electrolysis
of water and silver plating.
 Calculate and interconvert amps and time with grams and moles for an electrolysis process.
 Given possible reactions that could occur at anode and cathode in a non-spontaneous electrolytic
cell; predict the major products of electrolysis by noting that the oxidation half reaction with the
smallest or least negative emf will occur at the anode and the reduction half reaction with the
smallest or least negative emf will occur at the cathode. Often this is an undesirable reaction when
attempting to perform preparative electrolysis in aqueous solution, only achieving the electrolysis
of water, rather that the desired reactants.

Gold can be plated out of a solution containing Au3+ according to the half-reaction:
What mass of gold (in grams) is plated by the flow of 5.5 A of current for 25 minutes?

Would it require more or less current to reduce Au+ to the element under the same conditions?

Predict the half-reaction occurring at the anode and cathode for the electrolysis NaBr(aq)

in the electrolysis of an aqueous salt, Br2(l) + 2 e−  2 Br−(aq) E°= 1.09 V

the anion or water (or electrode) is O2(g) + 4 e + 4H (aq)  2 H2O(l)
− +
E°= 0.82 V
oxidized, and the cation or water is Na+(aq) + 1 e−  Na(s) E°= −3.04 V
reduced 2 H2O(l) + 2 e  H2(g) + 2 OH (aq) E°= −0.41 V
− −

use the values of E° of the half- ox: 2 Br−(aq)  Br2(s) + 2 e− E°= −1.09 V
reactions as a guide to determine 2 H2O O2 + 4e− + 4H+ E°= −0.82 V
which half-reaction is easiest red: Na+(aq) + 1 e−  Na(s) E°= −3.04 V
2 H2O + 2 e  H2 + 2 OH
− −
E°= −0.41 V

oxidation occurs at the anode and anode: 2 H2O(l)  O2(g) + 4 e− + 4H+(aq)

reduction at the cathode cathode: 2 H2O(l) + 2 e−  H2(g) + 2 OH−(aq)
 Predict the half-reaction occurring at the anode and cathode for the electrolysis LiI(aq)

in the electrolysis of an aqueous salt, I2(s) + 2 e−  2 I−(aq) E°= 0.54 V

theanion or water (or electrode) is Li (aq) + 1 e  Li(s)
+ −
E°= −3.04 V
oxidized, and the cation or water is 2 H2O + 2 e−  H2 + 2 OH− E°= −0.83 V
reduced O2 + 4e− + 4H+  2 H2O E°= 1.23 V

use the values of E° of the half- ox:

reactions as a guide to determine
which half-reaction is easiest
red:

oxidation occurs at the anode and

reduction at the cathode anode:

cathode:

19.9 Corrosion: Undesirable Redox Reactions

 Know that corrosion generally refers to the oxidation reactions of metals.
 Know the components and steps by which iron rusts.
 Know some strategies for preventing corrosion (sacrificial anode, anodizing, galvanizing)
 CHE 122 EXAM 3 FORMULAE 20 20
H° = vpHf°(products) – vrHf°(reactants) 23
6.022 x 10 atoms
G °= H°– TS° No=
1 mole
So= vpS°(products) – vrS°(reactants) C J
F=96485 C=
mol V
G° = vpGf°(products) – vrGf°(reactants) J C
V= Amp=
C s
❑ o J
∆ Grxn =∆ Grxn + RTlnQ R=8.314
mol ∙ K
° 0.0592V
G° = –nFE°cell Ecell = log K eq
G° = –RT ln Keq n

° RT ° 0.0592V
Ecell =Ecell − lnQ∨at 25 ℃ E cell=E cell− logQ
nF n
° ° °
Ecell =Ered + E ox
2 8 −27
E=∆ m c c=2.99792 x 10 m/ s 1 amu=1.66054 x 10 kg
2
kg ∙ m
1J= 2
s
0.693
First order k =t 1 first order ln [ A ] t =ln [ A ] 0−kt
2