Electrochemistry

Compiled by: E.S. Espiritu

https://www.youtube.com/watch?v=teTkvUt
W4SA
 Electrochemistry
18.1 Balancing Oxidation–Reduction Reactions
18.2 Galvanic Cells
18.3 Standard Reduction Potentials
18.4 Cell Potential, Electrical Work, and Free Energy
18.5 Dependence of Cell Potential on Concentration
18.6 Batteries
18.7 Corrosion
18.8 Electrolysis
18.9 Commercial Electrolytic Processes
Redox Reactions
• Examples of Redox Reactions:
Zn(s) + CuSO4(aq)  ZnSO4(aq) + Cu(s);
Zn(s) + Cu2+(aq)  Zn2+(aq) + Cu(s)

Cu(s) + 2AgNO3(aq)  CuSO4(aq) + 2Ag(s);

Cu(s) + 2Ag+(aq)  Cu2+(aq) + 2Ag(s)

-
MnO4 (aq) + 5Fe2+(aq) + 8H+(aq) 
Mn2+(aq) + 5Fe3+(aq) + 4H2O
 What is electrochemistry
• Electrochemistry is the science that unites electricity and
chemistry. It is the study of the transfer of electrons. If a
chemical reaction is driven by an external applied
voltage, as in electrolysis, or if a voltage is created by a
chemical reaction, as in a battery, it is an electrochemical
reaction.
What is voltage/charge/current
• An electric potential difference is called as voltage. The SI unit of
voltage is volts.
• Electric charge is that which causes electrons and ions to attract
each other, and repel the particles of the same kind. Coulomb is
the unit used to measure electric charge.
• Current is the flow of charge per unit of time. Ampere is the SI unit of
electric current , equal to 1C/s.
• One joule of energy is used when 1C moves across a potential of 1V.
• Energy (J)= potential (V) х Charge(C)
Oxidation Numbers (O.N.)

• 1. Pure element O.N. is zero

• 2. Monatomic ion O.N. is charge

• 3. Neutral compound: sum of O.N. is zero

• Polyatomic ion: sum of O.N. is ion’s charge

• *Negative O.N. generally assigned to more electronegative element

Redox
• Oxidation is loss of e-
• causes reduction
• “reducing agent”

• Reduction is gain of e-
• causes oxidation
• “oxidizing agent”
Redox Reactions
• Examples of Redox Reactions:
Zn(s) + CuSO4(aq)  ZnSO4(aq) + Cu(s);
Zn(s) + Cu2+(aq)  Zn2+(aq) + Cu(s)

Cu(s) + 2AgNO3(aq)  CuSO4(aq) + 2Ag(s);

Cu(s) + 2Ag+(aq)  Cu2+(aq) + 2Ag(s)

-
MnO4 (aq) + 5Fe2+(aq) + 8H+(aq) 
Mn2+(aq) + 5Fe3+(aq) + 4H2O
Balancing Redox Equations
• Review of Terms:
• Oxidation–reduction (redox) reaction – involves a transfer of electrons from the
reducing agent to the oxidizing agent
• Oxidation – loss of electrons
• Reduction – gain of electrons
• Reducing agent – electron donor
• Oxidizing agent – electron acceptor
Oxidation Numbers (O.N.)
• 4. Hydrogen
• assigned +1
• (metal hydrides, -1)
• 5. Oxygen
• assigned -2
• (peroxides, -1; OF2, +2)
• 6. Fluorine
• always -1
 Balancing Redox Equations
• Half–Reactions Method:
• The overall reaction is split into two half–reactions, one involving
oxidation and one reduction.
8H+ + MnO4 + 5Fe2+  Mn2+ + 5Fe3+ + 4H2O

Reduction: 8H+ + MnO4 + 5e  Mn2+ + 4H2O

Oxidation: 5Fe2+  5Fe3+ + 5e
Balancing Redox Equations

• The Half–Reaction Method for Balancing

Equations for Oxidation–Reduction Reactions
Occurring in Acidic Solution
1. Write separate equations for the oxidation and reduction half–
reactions.
2. For each half–reaction:
A. Balance all the elements except H and O.
B. Balance O using H2O.
C. Balance H using H+.
D. Balance the charge using electrons.
 Balancing Redox Equations:
The Half-Reaction Method
1. Write separate equations for oxidation and
reduction half–reactions.
2. For each half–reaction:
Balance all the elements except H and O.
Balance O using H2O.
Balance H using H+.
Balance the charge using electrons.
3. If necessary, multiply one or both balanced half–
reactions by an integer to make the number of
electrons in both half–reactions equal.
4. Add half–reactions and cancel identical species.
Balancing Redox Equations

Example:

Cr2O72-(aq) + HSO3-(aq)  Cr3+(aq) + HSO4-(aq)

•How can we balance this equation?

•First Steps:
Separate into half-reactions.
Balance elements except H and O.
Balancing Redox Equation:
The Half-Reaction Method
• Cr2O72-(aq)  2Cr3+(aq)
• HSO3-(aq)  HSO4-(aq)

• How many electrons are needed to balance the charge in each half-
reaction?
Balancing Redox Equation:
The Half-Reaction Method

•Adding electrons:
• 6e- + Cr2O72-(aq)  2Cr3+(aq)
• HSO3-(aq)  HSO4-(aq) + 2e-

• How can we balance the oxygen atoms?

Balancing Redox Equation:
The Half-Reaction Method

•6e- + Cr2O72-(aq)  Cr3+(aq) + 7H2O

•H2O + SO32-(aq)  + SO42-(aq) + 2e-
• How can we balance the hydrogen atoms?
Balancing Redox Equation:
The Half-Reaction Method

•This reaction occurs in an acidic solution.

• 14H+ + 6e- + Cr2O72-  2Cr3+ + 7H2O
• H2O + HSO3-  HSO4- + 2e- + 2H+

•How can we balance the electrons?

Balancing Redox Equation:
The Half-Reaction Method
• 14H+ + 6e- + Cr2O72-  2Cr3+ + 7H2O
• 3[H2O + HSO3-  HSO42- + 2e- + 2H+]

• The final balanced equation:

Cr2O72- + 3HSO3- + 8H+  2Cr3+ + 3HSO4- + 4H2O

Sample Exercises

Balance the following redox reactions in acidic solution.

1) Br–(aq) + MnO4–(aq)  Br2(l) + Mn2+(aq)

2) Cr2O72-(aq) + H2O2(aq)  Cr3+(aq) + H2O(l) + O2(g)

 Electrochemistry
• Electrochemical reactions are oxidation-reduction reactions.
• The two parts of the reaction are physically separated.
• The oxidation reaction occurs in one cell.
• The reduction reaction occurs in the other cell.

23
Electrochemistry

There are two kinds electrochemical cells.

1. Electrochemical cells containing in nonspontaneous chemical
reactions are called electrolytic cells.
2. Electrochemical cells containing spontaneous chemical reactions
are called voltaic or galvanic cells.

24
A Galvanic Cell
Galvanic Cell
• A device in which chemical energy is converted to electrical energy.
• It uses a spontaneous redox reaction to produce a current that can be
used to generate energy or to do work.
 In Galvanic Cell:
• Oxidation occurs at the anode.
• Reduction occurs at the cathode.
• Salt bridge or porous disk allows ions to flow without extensive mixing
of the solutions.
 Salt bridge – contains a strong electrolyte held in a gel–like matrix.
 Porous disk – contains tiny passages that allow hindered flow of ions.
 Electrical Conduction
• Metals conduct electric currents well in a process called metallic
conduction.
• In metallic conduction there is electron flow with no atomic motion.
• In ionic or electrolytic conduction ionic motion transports the electrons.
• Positively charged ions, cations, move toward the negative electrode.
• Negatively charged ions, anions, move toward the positive electrode.

28
https://www.youtube.com/watch?v=J1ljxodF9_g
Designation of Anode and Cathode

• Write balanced net ionic equation for the

spontaneous cell reaction.
• The oxidizing agent (one with the more positive or
less negative reduction potential E°) will be the
cathode and the other will be the anode.
• Oxidation occurs in anode half-cell and reduction in
cathode half-cell.
• Anode is negative(-) and cathode is positive(+).
Cell Potential
• A galvanic cell consists of an oxidizing agent (in
cathode half-cell) and a reducing agent (in anode
half-cell).
• Electrons flows through a wire from the anode half-
cell to the cathode half-cell.
• The driving force that allows electrons to flow is
called the electromotive force (emf) or the cell
potential (Ecell).
 The unit of electrical potential is volt (V).
 1 V = 1 J/C of charge transferred.
 Cell Potential
•Cell Potential / Electromotive Force (EMF):

• The “pull” or driving force on electrons

• Measured voltage (potential difference)
 17_363

e– e–

e– e–
Ecell = +1.10 V

+ +
Zn 2 Cu 2
– –
SO 4 2 SO 4 2
Zn(s) Cu(s)
+ 2+
1.0 M Zn 2 1.0 M Cu
solution solution

Anode Cathode
Standard Electrode Potential

• To measure relative electrode potentials, we must

establish an arbitrary standard.
• That standard is the Standard Hydrogen Electrode
(SHE).
• The SHE is assigned an arbitrary voltage of 0.000000… V

35
Standard Electrode Potential

36
 Standard Reduction Potentials
• Values of E° in standard table of half-cell potentials
are for reduction half-cell reactions
 1 M, 1 atm, 25°C
• When a half-reaction is reversed, the algebraic sign of
E° changes.
• When a half-reaction is multiplied by an integer, the
value of E° remains the same.
• A galvanic cell runs spontaneously in the direction that
gives a positive value for E°cell
Standard Reduction Potentials
• E0 values for reduction half-reactions with solutes at 1M and gases at 1
atm

•Cu2+ + 2e  Cu
• E0 = 0.34 V vs. SHE

•SO42 + 4H+ + 2e  H2SO3 + H2O

• E0 = 0.20 V vs. SHE
 Standard Reduction Potentials
• Values of E° in standard table of half-cell potentials are
for reduction half-cell reactions
 Table 18.1 (or 17.1)
 1 M, 1 atm, 25°C
• When a half-reaction is reversed, the algebraic sign of
E° changes.
• When a half-reaction is multiplied by an integer, the
value of E° remains the same.
• A galvanic cell runs spontaneously in the direction that
gives a positive value for E°cell
Uses of Standard Electrode Potentials

• Use standard electrode potentials to predict whether an

electrochemical reaction at standard state conditions will occur
spontaneously.
• Example 21-3: Will silver ions, Ag+, oxidize metallic zinc to Zn2+ ions,
or will Zn2+ ions oxidize metallic Ag to Ag+ ions?
• Steps for obtaining the equation for the spontaneous reaction.

43
Uses of Standard Electrode Potentials

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.
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.

44
Uses of Standard Electrode Potentials

E0
Reduction 2(Ag + + e -  Ag 0 ) + 0.7994 V
Oxidation 1(Zn  Zn 2+ + 2 e - ) - (-0.7628 V)
Cell reaction 2Ag + + Zn 0  2Ag 0 + Zn 2+ E 0cell = +1.5662 V

45
Example: Fe3+(aq) + Cu(s)  Cu2+(aq) +
Fe2+(aq)

• Half-Reactions:
 Fe3+ + e–  Fe2+ E° = 0.77 V
 Cu2+ + 2e–  Cu E° = 0.34 V
• To balance the cell reaction and calculate the cell potential, we must
reverse reaction 2.
 Cu  Cu2+ + 2e– – E° = – 0.34 V
• Each Cu atom produces two electrons but each Fe3+ ion accepts only one
electron, therefore reaction 1 must be multiplied by 2.
 2Fe3+ + 2e–  2Fe2+ E° = 0.77 V
 Standard Cell Potential
2Fe3+ + 2e–  2Fe2+ ; E° = 0.77 V (cathode)

Cu  Cu2+ + 2e– ; – E° = – 0.34 V (anode)

• Balanced Cell Reaction:
Cu + 2Fe3+  Cu2+ + 2Fe2+

• Cell Potential: E

°
E cell = E°(cathode) – E°(anode)
°
E cell = 0.77 V – 0.34 V = 0.43 V
Calculating Standard Cell Potential

• Given the following reduction potentials:

• Ag+(aq) + e-  Ag(s); E° = 0.80 V
• Zn2+(aq) + 2e-  Zn(s); E° = -0.76 V

• Calculate the cell potential for the following

reaction and predict whether the reaction will take
place:
• Zn(s) + 2Ag+(aq)  Zn2+(aq) + 2Ag(s)
Example: Fe3+(aq) + Cu(s)  Cu2+(aq) + Fe2+(aq)
• Half-Reactions:
 Fe3+ + e–  Fe2+ E° = 0.77 V
 Cu2+ + 2e–  Cu E° = 0.34 V
• To balance the cell reaction and calculate the cell potential, we must
reverse reaction 2.
 Cu  Cu2+ + 2e– – E° = – 0.34 V
• Each Cu atom produces two electrons but each Fe3+ ion accepts only one
electron, therefore reaction 1 must be multiplied by 2.
 2Fe3+ + 2e–  2Fe2+ E° = 0.77 V
 Standard Cell Potential
2Fe3+ + 2e–  2Fe2+ ; E° = 0.77 V (cathode)

Cu  Cu2+ + 2e– ; – E° = – 0.34 V (anode)

• Balanced Cell Reaction:
Cu + 2Fe3+  Cu2+ + 2Fe2+

• Cell Potential: E

°
E cell = E°(cathode) – E°(anode)
°
E cell = 0.77 V – 0.34 V = 0.43 V
Calculating Standard Cell Potential

• Given the following reduction potentials:

• Ag+(aq) + e-  Ag(s); E° = 0.80 V
• Zn2+(aq) + 2e-  Zn(s); E° = -0.76 V

• Calculate the cell potential for the following reaction

and predict whether the reaction will take place:
• Zn(s) + 2Ag+(aq)  Zn2+(aq) + 2Ag(s)
Standard Cell Potentials

• Given the following reduction potentials:

• Cu2+(aq) + 2e-  Cu(s); E° = 0.34 V
• Ni2+(aq) + 2e-  Ni(s); E° = -0.23 V

• Predict whether the following reaction will take

place:
• Cu(s) + Ni2+(aq)  Cu2+(aq) + Ni(s)
Standard Cell Potentials

• Given the following reduction potentials:

• Cu2+(aq) + 2e-  Cu(s); E° = 0.34 V
• Ni2+(aq) + 2e-  Ni(s); E° = -0.23 V

• Predict whether the following reaction will take

place:
• Cu(s) + Ni2+(aq)  Cu2+(aq) + Ni(s)
 Cell Notations for Galvanic Cells
• Used to describe electrochemical cells.
• Anode components are listed on the left.
• Cathode components are listed on the right.
• Separated by double vertical lines.
• The concentration of aqueous solutions should be
specified in the notation when known.
• Example: Mg(s)|Mg2+(aq)||Al3+(aq)|Al(s)
 Mg  Mg + 2e
2+ – (anode)

 Al3+ + 3e  Al
– (cathode)
 Description of a Galvanic Cell
• The cell potential is always positive for a galvanic cell,
where E°cell = E°(cathode half-cell) – E°(anode half-cell) (as given in
the table of half-cell potentials)
• Anode is the negative terminal and cathode is the
positive terminal.
• Electron flows from the anode (-) to cathode (+).
• Current flows from cathode(+) to anode(-).
• Positive ions flows from anode to cathode half-cells
and negative ions flows from cathode to anode
though the “salt bridge”.
 Cell Notations for Galvanic Cells
• Used to describe electrochemical cells.
• Anode components are listed on the left.
• Cathode components are listed on the right.
• Separated by double vertical lines.
• The concentration of aqueous solutions should be
specified in the notation when known.
• Example: Mg(s)|Mg2+(aq)||Al3+(aq)|Al(s)
 Mg  Mg + 2e
2+ – (anode)

 Al3+ + 3e  Al
– (cathode)
 Description of a Galvanic Cell
• The cell potential is always positive for a galvanic cell,
where E°cell = E°(cathode half-cell) – E°(anode half-cell) (as given in
the table of half-cell potentials)
• Anode is the negative terminal and cathode is the
positive terminal.
• Electron flows from the anode (-) to cathode (+).
• Current flows from cathode(+) to anode(-).
• Positive ions flows from anode to cathode half-cells
and negative ions flows from cathode to anode though
the “salt bridge”.
Designation of Anode and Cathode

• Write balanced net ionic equation for the

spontaneous cell reaction.
• The oxidizing agent (one with the more positive or
less negative reduction potential E°) will be the
cathode and the other will be the anode.
• Oxidation occurs in anode half-cell and reduction in
cathode half-cell.
• Anode is negative(-) and cathode is positive(+).
 Effect of Concentrations (or Partial
Pressures) on Electrode Potentials

The Nernst Equation

• Standard electrode potentials, those compiled in appendices, are
determined at thermodynamic standard conditions.
• Reminder of standard conditions.
1.00 M solution concentrations
1.00 atm of pressure for gases
All liquids and solids in their standard thermodynamic states.
Temperature of 250 C.

60
Concentration Cells

•. . . a cell in which both

compartments have the same
components but at different
concentrations
17_366

e– e–

e– Porous e–
disk
Ag Ag

0.1 M Ag + 1 M Ag +
– –
0.1 M NO 3 1 M NO 3

Anode Cathode
Nernst Equation
• At 25oC.

0.0591
E = E  log Q 
n

0.0591
E= log  K 
n
 The Nernst Equation
• For this half-reaction:

Cu 2+ 
 e  Cu
-  0
E = +0.153 V
• The corresponding Nernst equation is:

0.05920
Cu   +

 
E=E - log 2
1 Cu

65
 The Nernst Equation
• Substituting E0 into the above expression gives:

0.0592 Cu   +

 
E = 0.153 V - log 2
1 Cu
• If [Cu2+] and [Cu+] are both 1.0 M, i.e. at standard conditions, then E = E0
because the concentration term equals zero.

0.0592 1
E = 0.153 V - log
1 1
66
The Nernst Equation

67
 The Nernst Equation
• Example 21-6: Calculate the potential for the Cu2+/ Cu+ electrode at 250C
when the concentration of Cu+ ions is three times that of Cu2+ ions.

Cu 2+ + e - 
 Cu 
Cu   3 Cu   3
+ 2+
Q=
Cu  Cu 
2+ 2+

68
 The Nernst Equation
• Example 21-6: Calculate the potential for the Cu2+/ Cu+ electrode at 250C
when the concentration of Cu+ ions is three times that of Cu2+ ions.

0.0592
E = E0 - log Q
1
0.0592
E = 0.153 V - log 3
1

69
 The Nernst Equation
• Example 21-6: Calculate the potential for the Cu2+/ Cu+ electrode at 250C
when the concentration of Cu+ ions is three times that of Cu2+ ions.

0.0592
E = E0 - log Q
1
0.0592
E = 0.153 V - log 3
1
E = 0.153V - 0.05920.477  V
E = 0.153 - 0.0282  V
E = 0.125 V
70
The Nernst Equation

71
 The Nernst Equation
• Example 21-7: Calculate the potential for the Cu2+/Cu+ electrode at 250C
when the Cu+ ion concentration is 1/3 of the Cu2+ ion concentration.

Cu 2+ 
+ e  Cu
- 

Cu  + 1 Cu 2 +
3
 
  0.333
Q=
Cu  2+
Cu 
2+

You do it!

72
 The Nernst Equation
• Example 21-7: Calculate the potential for the Cu2+/Cu+
electrode at 250C when the concentration of Cu+ ions
is 1/3 that of Cu2+ ions.
0 0.0592
E=E - log Q
1
0.0592
E = 0.153 V - log 1
1 3

73
The Nernst Equation

0 0.0592
E=E - log Q
1
0.0592
E = 0.153 V - log 1
1 3
E = 0.153V - 0.0592- 0.477  V
E = 0.153 + 0.0282  V
E = 0.181 V 74
The Nernst Equation

• The Nernst equation can also be used to calculate

the potential for a cell that consists of two
nonstandard electrodes.
• Example 21-9: Calculate the initial potential of a cell
that consists of an Fe3+/Fe2+ electrode in which
[Fe3+]=1.0 x 10-2 M and [Fe2+]=0.1 M connected to a
Sn4+/Sn2+ electrode in which [Sn4+]=1.0 M and
[Sn2+]=0.10 M . A wire and salt bridge complete the
circuit.

75
 The Nernst Equation
• Calculate the E0 cell by the usual procedure.

E0
Reduction 
2 Fe 3+ + e  Fe 2+  0.771 V
Oxidation 1Sn 2+
 Sn 4+ + 2 e -  - 0.15 V
Cell reaction 2 Fe 3+  Sn 2+  2 Fe 2+  Sn 4+ E 0cell  0.62 V

76
The Nernst Equation

• Substitute the ion concentrations into Q to calculate

Ecell.
0.0592
E cell = E 0cell - log Q
2

= 0.62 V -
0.0592
log
 Fe  
2 2
Sn 4

  Sn 
2
2 Fe3 2

E cell = 0.62 V -
0.0592
log
 .  10
010 . 
2

2 .  10
10 
2 2
010
.  

77
The Nernst Equation

E cell = 0.62 V -
0.0592
log
0.10  1.0 
2

2   2

1.0  10 0.10 
2

E cell  0.62 V -
0.0592
3.00
2
E cell  0.62  0.09 V
E cell = 0.53 V

78
Batteries

• https://www.youtube.com/watch?v=9OVtk6G2TnQ
Primary Voltaic Cells

• As a voltaic cell discharges, its chemicals are consumed.

• Once the chemicals are consumed, further chemical action is
impossible.
• The electrodes and electrolytes cannot be regenerated by reversing
current flow through cell.
• These cells are not rechargable.

80
Nonalkaline Dry Cell
 The Dry Cell
• One example of a dry cell is flashlight, and radio,
batteries.
• The cell’s container is made of zinc which acts as an
electrode.
• A graphite rod is in the center of the cell which acts as
the other electrode.
• The space between the electrodes is filled with a
mixture of:
1. ammonium chloride, NH4Cl
2. manganese (IV) oxide, MnO2
3. zinc chloride, ZnCl2
4. and a porous inactive solid.

82
 The Dry Cell
• As electric current is produced, Zn dissolves and goes
into solution as Zn2+ ions.
• The Zn electrode is negative and acts as the anode.

83
 The Dry Cell

• The anode reaction is:

Zn  Zn 0 2+
+2 e -
• The graphite rod is the positive electrode (cathode).
• Ammonium ions from the NH4Cl are reduced at the cathode.

2 +
NH 4  2 e  2 NH 3 g   H 2 g 
-

84
The Dry Cell

• The cell reaction is:

Anode reaction Zn 0  Zn 2 + + 2 e -
Cathode reaction 2 NH +4 + 2 e -  2 NH 3g   H 2 g 
Cell reaction Zn 0 + 2 NH +4  Zn 2 +  2 NH 3g   H 2 g 

85
 The Dry Cell
• The other components in the cell are included to remove the
byproducts of the reaction.
• MnO2 prevents H2 from collecting on graphite rod.

H 2  g   2 MnO 2  s  2 MnO(OH)  s
• At the anode, NH3 combines with Zn2+ to form a soluble
complex and removing the Zn2+ ions from the reaction.

 4 NH 3  Zn 
2+ 2
Zn NH 3 4
86
The Dry Cell

87
The Dry Cell

• Alkaline dry cells are similar to ordinary dry cells

except that KOH, an alkaline substance, is added to
the mixture.
• Half reactions for an alkaline cell are:
Anode reaction Zn 0s  + 2 OH -  Zn OH 2 s   2 e 
Cathode reaction 2 MnO 2 s   2 H 2 O + 2 e -  2 MnO(OH) s  + 2 OH -
Cell reaction Zn 0s  + 2 MnO 2 s   2 H 2 O  Zn OH 2s   2 MnO(OH) s 
E 0cell  1.5 V

88
The Dry Cell

• Alkaline dry cells are similar to ordinary dry cells

except that KOH, an alkaline substance, is added to
the mixture.
• Half reactions for an alkaline cell are:

89
Mercury Battery
Secondary Voltaic Cells

• Secondary cells are reversible, rechargeable.

• The electrodes in a secondary cell can be regenerated by the
addition of electricity.
• These cells can be switched from voltaic to electrolytic cells.
• One example of a secondary voltaic cell is the lead storage
or car battery.

91
The Lead Storage Battery

• In the lead storage battery the electrodes are two sets of lead
alloy grids (plates).
• Holes in one of the grids are filled with lead (IV) oxide, PbO2.
• The other holes are filled with spongy lead.
• The electrolyte is dilute sulfuric acid.

92
Lead Storage Battery
 The Lead Storage Battery

• Diagram of the lead storage battery.

94
 The Lead Storage Battery
• As the battery discharges, spongy lead is oxidized to lead ions and the
plate becomes negatively charged.

Pb0s   Pb 2 +  2 e -
This is the anode reaction.
The anode is the negative battery post during discharge.
• The Pb2+ ions that are formed combine with SO42- from sulfuric acid to form
solid lead sulfate on the Pb electrode.

Pb 2+
 2-
SO 4  PbSO 4  s
95
 The Lead Storage Battery
• The net reaction at the anode during discharge is:

0
Pb s  2-
SO 4  PbSO 4  s + 2 e -

• Electrons are produced at the Pb electrode.

• These electrons flow through an external circuit (the wire and starter)
to the PbO2 electrode.
• PbO2 is reduced to Pb2+ ions, in the acidic solution.
• The Pb2+ ions combine with SO42- to form PbSO4 and coat the PbO2
electrode.
• PbO2 electrode is the positive electrode (cathode).

96
 The Lead Storage Battery

• As the cell discharges, the cathode reaction is:

PbO 2  s + 4 H + + SO 2-
4 + 2 e -
 PbSO 4  s + 2 H 2 O
• The cell reaction for a discharging lead storage battery is:
Anode reaction Pb s   SO 24-  PbSO 4 s   2 e -
Cathode reaction PbO 2 s  + 4 H + + SO 24- + 2 e -  PbSO 4 s  + 2 H 2 O
Cell reaction Pb s   PbO 2 s  + 4 H + + SO 24-  2 PbSO 4 s  + 2 H 2 O

97
 The Lead Storage Battery

• As the cell discharges, the cathode reaction is:

PbO 2  s + 4 H + + SO 2-
4 + 2 e -
 PbSO 4  s + 2 H 2 O
• The cell reaction for a discharging lead storage battery is:

98
 The Lead Storage Battery
• What happens at each electrode during recharging?
• At the lead (IV) oxide, PbO2, electrode, lead ions are oxidized to
lead (IV) oxide.

PbSO 4 s   2 H 2 O  PbO 2 s   4 H +  SO 24-  2 e -

• The concentration of the H2SO4 decreases as the cell discharges.
• Recharging the cell regenerates the H2SO4.


Pb s   PbO 2 s  + 4H + 2SO    PbSO  2H O
discharge
+ 2-
4  
charge 4 s  2

99
 The Lead Storage Battery
• What happens at each electrode during recharging?
• At the lead (IV) oxide, PbO2, electrode, lead ions are oxidized to
lead (IV) oxide.

PbSO 4 s   2 H 2 O  PbO 2 s   4 H +  SO 24-  2 e -

• The concentration of the H2SO4 decreases as the cell discharges.
• Recharging the cell regenerates the H2SO4.

100
 The Nickel-Cadmium (Nicad) Cell
• Nicad batteries are the rechargeable cells used in calculators, cameras,
watches, etc.
• As the battery discharges, the half-reactions are:

Anode Cd s   2 OH -  Cd(OH) 2  2 e -
Cathode NiO 2 s  + 2 H 2 O + 2 e -  Ni(OH) 2s  + 2 OH -
Cell rxn Cd s   NiO 2s  + 2 H 2 O  Cd(OH) 2 s  + Ni(OH) 2s 
E 0  1 .4 V

101
Fuel Cell
The Hydrogen-Oxygen Fuel Cell

• Fuel cells are batteries that must have their reactants continuously
supplied in the presence of appropriate catalysts.
• A hydrogen-oxygen fuel cell is used in the space shuttle
• The fuel cell is what exploded in Apollo 13.
• Hydrogen is oxidized at the anode.
• Oxygen is reduced at the cathode.

103
The Hydrogen-Oxygen Fuel Cell


Anode reaction 2 H 2 g   2 OH -(aq)  2 H 2 O (  )  2 e - 
Cathode reaction O    2 H O
2 g 2 ()  4 e -
 4 OH -
(aq) 
Cell reaction 2 H 2 g   O 2 g   2 H 2 O  
• Notice that the overall reaction is the combination of
hydrogen and oxygen to form water.
• The cell provides a drinking water supply for the astronauts
as well as the electricity for the lights, computers, etc. on
board.
• Fuel cells are very efficient.
• Energy conversion rates of 60-70% are common!

104
Corrosion
• The process that returns metals to their oxidized state.
• Involves oxidation of the metal.
Electrochemical Corrosion of Iron
Corrosion Prevention

•Apply coating (such as paint or metal

plating)
Galvanizing
•Alloying
•Cathodic Protection
Protects steel in buried fuel tanks and
pipelines.
Cathodic Protection
Electrolytic Cells

• Electrical energy is used to force nonspontaneous chemical

reactions to occur.
• The process is called electrolysis.
• Two examples of commercial electrolytic reactions are:
1. The electroplating of jewelry and auto parts.
2. The electrolysis of chemical compounds.

109
 Electrolytic Cells
• Electrolytic cells consist of:
1. A container for the reaction mixture.
2. Two electrodes immersed in the reaction mixture.
3. A source of direct current.

110
Electrolysis
• A process that forces a current through a cell to produce a chemical
change for which the cell potential is negative.
Electrolysis
• Consider a solution containing 0.10 M of each of the
following: Ni2+, Cu2+, Zn2+, Sn2+, and Pb2+.

• Predict the order in which the metals plate out as the

voltage is applied.

• Do the metals form on the cathode or the anode?

Explain.
Commercial Electrolytic Processes

• Production of aluminum
• Purification of metals
• Metal plating
• Electrolysis of sodium chloride
• Production of chlorine and sodium hydroxide
The Hall-Heroult Process for Al Production
Electroplating/Silver Plating a Spoon
The Downs Cell for the Electrolysis of Molten
Sodium Chloride
The Electrolysis of Molten Sodium Chloride

• Liquid Sodium is produced at one electrode.

• Indicates that the reaction Na+() + e-  Na(s) occurs at this electrode.
• Is this electrode the anode or cathode?
• Gaseous chlorine is produced at the other electrode.
• Indicates that the reaction 2 Cl-  Cl2(g) + 2 e- occurs at this electrode.
• Is this electrode the anode or cathode?

117
 The Electrolysis of Molten Sodium Chloride

Diagram of this electrolytic cell.

118
The Electrolysis of Molten Sodium Chloride

• The nonspontaneous redox reaction that occurs is:

Anode reaction 2 Cl  Cl 2(g)  2 e

- -

 
Cathode reaction 2 Na  e  Na  -

Cell reaction 2 Cl -  2 Na   Cl 2 g   2 Na  

119
The Electrolysis of Molten Sodium Chloride

• In all electrolytic cells, electrons are forced to flow from the positive
electrode (anode) to the negative electrode (cathode).

120
The Electrolysis of Aqueous Sodium Chloride

• In this electrolytic cell, hydrogen gas is produced at one electrode.

• The aqueous
Anode solution becomes
reaction 2 Cl -
basic nearCl 
this electrode.
• What reaction is occurring at this electrode? 2(g)
2
You do it!
e -

• Gaseous chlorine is produced at the other- electrode.

Cathode reaction
• What reaction is occurring2atH 2O
this  2 e You
electrode? doHit!2 g   2 OH -

• These experimental facts lead us to the following nonspontaneous

Cell reaction 2 Cl  2 H O  H  Cl  2 OH
electrode reactions: -
2 2 g 
-
2 g 

K  is a spectator ion. Note that water is electrolyzed!

121
The Electrolysis of Aqueous Sodium Chloride

Cell diagram

122
The Mercury Cell for Production of
Chlorine and Sodium Hydroxide