Redox Reactions and

Electrochemistry

1
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 Electrochemical processes are oxidation-reduction reactions
in which:
•  the energy released by a spontaneous reaction is
converted to electricity or
•  electrical energy is used to cause a nonspontaneous
reaction to occur
0 0 2+ 2-
2Mg (s) + O2 (g) 2MgO (s)

2Mg 2Mg2+ + 4e- Oxidation half-reaction (lose e-)

O2 + 4e- 2O2- Reduction half-reaction (gain e-)

2
 Oxidation number
The charge the atom would have in a molecule (or an
ionic compound) if electrons were completely transferred.

1.  Free elements (uncombined state) have an oxidation

number of zero.

Na, Be, K, Pb, H2, O2, P4 = 0

2.  In monatomic ions, the oxidation number is equal to
the charge on the ion.

Li+, Li = +1; Fe3+, Fe = +3; O2-, O = -2

3.  The oxidation number of oxygen is usually –2. In H2O2
and O22- it is –1.
3
4.  The oxidation number of hydrogen is +1 except when
it is bonded to metals in binary compounds. In these
cases, its oxidation number is –1.

5.  Group IA metals are +1, IIA metals are +2 and fluorine is
always –1.

6. The sum of the oxidation numbers of all the atoms in a

molecule or ion is equal to the charge on the molecule
or ion.
HCO3−
Identify the oxidation numbers of O = −2 H = +1
all the atoms in HCO3− ?
3x(−2) + 1 + ? = −1
C = +4 4
 Balancing Redox Equations

The oxidation of Fe2+ to Fe3+ by Cr2O72- in acid solution?

1.  Write the unbalanced equation for the reaction ion ionic form.

Fe2+ + Cr2O72- Fe3+ + Cr3+

2.  Separate the equation into two half-reactions.

+2 +3
Oxidation: Fe2+ Fe3+
+6 +3
Reduction: Cr2O72- Cr3+

3.  Balance the atoms other than O and H in each half-reaction.

Cr2O72- 2Cr3+
5
 Balancing Redox Equations
4.  Add electrons to one side of each half-reaction to balance the
charges on the half-reaction.
Fe2+ Fe3+ + 1e-
6e- + Cr2O72- 2Cr3+
5.  For reactions in acid, add H+ to balance electronic charge and
H2O to balance O atoms and H atoms
6e- +14H+ + Cr2O72- 2Cr3+

6e- + 14H+ + Cr2O72- 2Cr3+ + 7H2O

6.  If necessary, equalize the number of electrons in the two half-
reactions by multiplying the half-reactions by appropriate
coefficients.
6Fe2+ 6Fe3+ + 6e-
6e- + 14H+ + Cr2O72- 2Cr3+ + 7H2O 6
 Balancing Redox Equations
7.  Add the two half-reactions together and balance the final
equation by inspection. The number of electrons on both
sides must cancel.

Oxidation: 6Fe2+ 6Fe3+ + 6e-

Reduction: 6e- + 14H+ + Cr2O72- 2Cr3+ + 7H2O
14H+ + Cr2O72- + 6Fe2+ 6Fe3+ + 2Cr3+ + 7H2O
8.  Verify that the number of atoms and the charges are balanced.
14x1 – 2 + 6 x 2 = 24 = 6 x 3 + 2 x 3
9.  For reactions in basic solutions, add OH- to instead of H+ to
balance electronic charges.
10. Balance the reaction in the molecular form.
7
 Galvanic Cells

anode cathode
oxidation reduction

spontaneous
redox reaction

8
 Galvanic Cells
The difference in electrical
potential between the anode
and cathode is called:
•  cell voltage
•  electromotive force (emf)
•  cell potential
Zn (s) + Cu2+ (aq) Cu (s) + Zn2+ (aq)
[Cu2+] = 1 M and [Zn2+] = 1 M

Cell Diagram

phase boundary
Zn (s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu (s)
anode salt bridge cathode 9
 Standard Reduction Potentials

Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)

Anode (oxidation): Zn (s) Zn2+ (1 M) + 2e-

Cathode (reduction): 2e- + 2H+ (1 M) H2 (1 atm)
Zn (s) + 2H+ (1 M) Zn2+ + H2 (1 atm)
10
 Standard Reduction Potentials

Standard reduction potential (E°) is the voltage associated

with a reduction reaction at an electrode when all solutes
are 1 M and all gases are at 1 atm.

Reduction Reaction

2e- + 2H+ (1 M) H2 (1 atm)

E° = 0 V

11
Standard hydrogen electrode (SHE)
 Standard Reduction Potentials
Ecell
0 = 0.76 V

Standard emf (Ecell

° )

° = E°
Ecell °
cathode - Eanode

Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)

° = E ° + - E ° 2+
Ecell H /H 2 Zn /Zn
° 2+
0.76 V = 0 - EZn /Zn
° 2+
EZn /Zn = -0.76 V

Zn2+ (1 M) + 2e- Zn E° = -0.76 V 12

 Standard Reduction Potentials

Ecell
° = 0.34 V
° = E°
Ecell - E °
cathode anode

Ecell
° = E ° 2+
Cu /Cu – EH +/H2
°

0.34 = ECu
° 2+
/Cu - 0
° 2+
ECu /Cu = 0.34 V

Pt (s) | H2 (1 atm) | H+ (1 M) || Cu2+ (1 M) | Cu (s)

Anode (oxidation): H2 (1 atm) 2H+ (1 M) + 2e-
Cathode (reduction): 2e- + Cu2+ (1 M) Cu (s)
H2 (1 atm) + Cu2+ (1 M) Cu (s) + 2H+ (1 M) 13
•  E° is for the reaction as
written
•  The more positive E° the
greater the tendency for the
substance to be reduced
•  The half-cell reactions are
reversible
•  The sign of E° changes
when the reaction is
reversed
•  Changing the stoichiometric
coefficients of a half-cell
reaction does not change
the value of E° 14
 What is the standard emf of an electrochemical cell made
of a Cd electrode in a 1.0 M Cd(NO3)2 solution and a Cr
electrode in a 1.0 M Cr(NO3)3 solution?

Cd2+ (aq) + 2e- Cd (s) E° = -0.40 V Cd is the stronger oxidizer

Cd will oxidize Cr
Cr3+ (aq) + 3e- Cr (s) E° = -0.74 V
Anode (oxidation): Cr (s) Cr3+ (1 M) + 3e- x 2
Cathode (reduction): 2e- + Cd2+ (1 M) Cd (s) x3
2Cr (s) + 3Cd2+ (1 M) 3Cd (s) + 2Cr3+ (1 M)

° = E°
Ecell °
cathode - Eanode

Ecell
° = -0.40 – (-0.74)

Ecell
° = 0.34 V
15
The electrochemical cell
 The electrochemical cell

Redox reactions can be used to generate electric current

Electrode processes
 Electrode processes
The metallic electrode is dipped into a solution containing a salt of the metal.
Some atoms of the metal can leave the electrode and form the cation in
solution, leaving electrons in the metal. This form a double layer of opposite
charges to the electrode surface. The electrochemical potential of the metal and
its ion should be the same at the equilibrium.

M(s)  Mn+(aq) + ne-

There is the formation of an electric potential proportional at the ion

concentration in solution

+ - - +
+ - - +
+ - - +
+ - - +
+ - - +
+ - - - +
+ + +
Electrode potential
Nernst law
M+(aq) + e-  M(s)

GM = G°M + RTlnaM GM+ = G°M+ + RTlnaM+

ΔG = G°M + RTlnaM - G°M+ + RTlnaM+

ΔG = ΔG° + RTln(aM/aM+)


ΔG = -nFE

-nFE = ΔG° + RTln(aM/aM+)

E = -ΔG°/nF + RT/nF ln(aM+/aM) aM = 1

E = E° + RT/nF ln aM+
 The Nernst equation
The potential of an electrode is expressed by the Nernst law:

2.3RT 0 [Ox]
E=E + log
nF [Re d]
Where Ox and Red are oxidized and reduced forms of
Red-Ox couple in equilibrium:
!
Oxn+ + ne-  Red0

R is the universal gas constant, T is the absolute temperature in Kelvins, n is a number of electrons
transferred in reaction, F is Faraday constant (~ 96500 C)
The electromotive force
•  It is useful to separate the overall redox reaction in two
separated processes: the oxidation and reduction semi-
reaction.

•  In the electrochemical cell we have two electrodes and

we indicate as Cathode the electrode where the
reductions occur and Anode the electrode of oxidation
processes.

•  The electromotive force (EMF) of the cell is the electric

potential difference among the cathode and anode.
 The Standard Hydrogen Electrode

We cannot know the absolute potential of a single electrode (it is not possible to
measure half reaction), so the E° = 0 V was assigned to the semi-reaction

2 H3O+ + 2e-  H2
Reference electrodes: Ag/AgCl and SCE
 Metallic electrodes
3 main groups:
•  First kind - wire of active metal
immersed in solution, contained the ions
of this metal (Cu, Zn, Co, Fe, etc)

Al, Cu, Sn, inox, brass and Fe electrodes

•  Second kind – wire of metal covered by precipitate of hardly soluble salt

or oxide: M/Mn+ (Ag/AgCl for instance)

•  Third kind - inert metallic electrodes (Pt, Au, etc)

Pt electrode
 Electrochemical cell

Minimum 2 electrodes are

required for electrochemical
measurements. Dipped in
electrolyte solution these
electrodes constitute an
electrochemical cell.

INDICATOR (or WORKING) electrode is an electrode responding to a

target analyte
REFERENCE electrode has a stable well defined potential value,
independent on analyzed solution composition
Reference electrodes: Ag/AgCl and SCE
 Spontaneity of Redox Reactions
ΔG = -nFEcell n = number of moles of electrons in reaction

°
J
ΔG° = -nFEcell F = 96,500 = 96,500 C/mol
V • mol
°
ΔG° = -RT ln K = -nFEcell

RT (8.314 J/K•mol)(298 K)
°
Ecell = ln K = ln K
nF n (96,500 J/V•mol)

° 0.0257 V
Ecell = ln K
n
0.0592 V
°
Ecell = log K
n

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Spontaneity of Redox Reactions

°
ΔG° = -RT ln K = -nFEcell

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What is the equilibrium constant for the following reaction
at 25°C? Fe2+ (aq) + 2Ag (s) Fe (s) + 2Ag+ (aq)

° 0.0257 V
Ecell = ln K
n

Oxidation: 2Ag 2Ag+ + 2e-

n=2
Reduction: 2e- + Fe2+ Fe
° 2+ °
E° = EFe /Fe – EAg +/Ag

E° = -0.44 – (0.80)
Ecell
° xn -1.24 V x 2
E° = -1.24 V 0.0257 V 0.0257 V
K=e =e

K = 1.23 x 10-42
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 The Effect of Concentration on Cell Emf
ΔG = ΔG° + RT ln Q ΔG = -nFE ΔG° = -nFE °

-nFE = -nFE° + RT ln Q

Nernst equation

RT
E = E° - ln Q
nF

At 298 K

0.0257 V 0.0592 V
E =E° - ln Q E =E° - log Q
n n

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Will the following reaction occur spontaneously at 250C if
[Fe2+] = 0.60 M and [Cd2+] = 0.010 M?
Fe2+ (aq) + Cd (s) Fe (s) + Cd2+ (aq)

Oxidation: Cd Cd2+ + 2e-

n=2
Reduction: 2e- + Fe2+ 2Fe
° 2+ °
E° = EFe /Fe – ECd 2+/Cd

E° = -0.44 – (-0.40) 0.0257 V

E =E° - ln Q
n
E° = -0.04 V
0.0257 V 0.010
E = -0.04 V - ln
2 0.60
E = 0.013

E>0 Spontaneous
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 Concentration Cells

Galvanic cell from two half-cells composed of the same

material but differing in ion concentrations.

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 Electrolysis

•  Electrolysis is the process in which

electrical energy is used to cause a
nonspontaneous chemical reaction
to occur.

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 Electrolysis
•  Previously our lectures on electrochemistry were
involved with voltaic cells i.e. cells with Ecell > 0
and ΔG < 0 that were spontaneous reactions.
•  Today we discuss electrochemical cells where
Ecell < 0 and ΔG > 0 that are non-spontaneous
reactions and require electricity for the reactions
to take place. We can take a voltaic cell and
reverse the electrodes to make an electrochemical
cell.
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 Electrolytic
Voltaic

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Electrolytic conductors
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Fig. 21.18: Car battery, both voltaic and electrochemical
cell.

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 Increase
oxidizing
power

Increase
reducing
power

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A standard electrolytic cell. A power source forces the
opposite reaction

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Electrolysis

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 (a) A silver-plated teapot.
(b) Schematic of the electroplating of a spoon.

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 Schematic of the
electroplating of a spoon.

AgNO3(aq)

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The electrolysis of water produces hydrogen gas at the
cathode (on the right) and oxygen gas at the anode
(on the left).

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 Electrolysis of water

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 Electrolysis of water
•  At the anode (oxidation):
•  2H2O(l) + 2e-  H2(g) + 2OH-(aq) E= -0.42V

•  At the cathode (reduction):

•  O2(g) + 4H+(aq) + 4e-  2H2O(l) E= 0.82V
•  Overall reaction after multiplying anode reaction by 2,
•  2H2O(l)  2H2(g) + O2(g)
•  Eocell = -0.42 -0.82 = -1.24 V

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Electrolysis: Consider the electrolysis of a solution
that is 1.00 M in each of CuSO4(aq) and NaCl(aq)

•  Oxidation possibilities follow:

•  Cl2(g) + 2e–  2Cl–(aq) E° = +1.358 V
•  S2O82–(aq) + 2e–  2SO42–(aq) E° = +2.010 V
•  O2(g) + 4H+(aq) + 4e–  2H2O E° = +1.229 V

•  Reduction possibilities follow:

•  Na+(aq) + e–  Na(s) E° = –2.713 V
•  Cu2+(aq) + 2e–  Cu(s) E° = +0.337 V
•  2H2O + 2e–  H2(g) + 2OH–(aq) E° = -0.428 V

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 Electrolysis
•  We would choose the production of O2(g) and Cu(s).
•  But the voltage for producing O2(g) from solution is considerably
higher than the standard potential, because of the high activation
energy needed to form O2(g).
•  The voltage for this half cell seems to be closer to –1.5 V in reality.
•  The result then is the production of Cl2(g) and Cu(s).
anode, oxidation: Cl2(g) + 2e–  2Cl–(aq) E° = +1.358 V
•  cathode, reduction: Cu2+(aq) + 2e–  Cu(s) E° = +0.337 V

•  overall: CuCl2(aq)  Cu(s) + Cl2(g) E = –1.021 V

•  We must apply a voltage of more than +1.021 V to cause this reaction
to occur.

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Houghton Mifflin Company and G. 54
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 Stoichiometry of electrolysis: Relation between
amounts of charge and product

•  Faraday s law of electrolysis relates to the amount

of substance produced at each electrode is directly
proportional to the quantity of charge flowing
through the cell (half reaction).
•  Each balanced half-cell shows the relationship
between moles of electrons and the product.

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 Application of Faraday s law
•  1. First balance the half-reactions to find number
of moles of electrons needed per mole of product.
•  2. Use Faraday constant (F = 9.65E4 C/mol e-) to
find corresponding charge.
•  3. Use the molar mass of substance to find the
charge needed for a given mass of product.
–  1 ampere = 1 coulomb/second or 1 A = 1 C/s
–  A x s = C

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 Stoichiometry of Electrolysis
  How much chemical change occurs with the
flow of a given current for a specified time?

•  current and time → quantity of charge →

•  moles of electrons → moles of analyte →
•  grams of analyte

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 Fig. 21.20

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Doing work with
electricity.

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Electrolysis and Mass Changes

charge (C) = current (A) x time (s)

1 mol e- = 96,500 C

60
How much Ca will be produced in an electrolytic cell of
molten CaCl2 if a current of 0.452 A is passed through the
cell for 1.5 hours?

Anode: 2Cl- (l) Cl2 (g) + 2e-

Cathode: Ca2+ (l) + 2e- Ca (s)

Ca2+ (l) + 2Cl- (l) Ca (s) + Cl2 (g)

2 mole e- = 1 mole Ca

C s 1 mol e- 1 mol Ca
mol Ca = 0.452 x 1.5 hr x 3600 x x
s hr 96,500 C 2 mol e-
= 0.0126 mol Ca

= 0.50 g Ca
61
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 Batteries

Dry cell

Leclanché cell

Anode: Zn (s) Zn2+ (aq) + 2e-

Cathode: 2NH4+ (aq) + 2MnO2 (s) + 2e- Mn2O3 (s) + 2NH3 (aq) + H2O (l)

Zn (s) + 2NH4 (aq) + 2MnO2 (s) Zn2+ (aq) + 2NH3 (aq) + H2O (l) + Mn2O3 (s)

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 Alkaline  ba*ery  
•  Electrolyte  is  a  concentrated  
solu5on  of  KOH  
•  The  anode  is  inside  the  
ba*ery  as  a  powder  paste    
•  MnO2  is  pasted  with  graphite  
around  the  Zn  anode  and  
contacted  with  the  external  
steel  electrode  
 Alkaline  ba*ery  
•  Lower  polariza5on  
•  Higher  dura5on  
•  Lower  self  discharge  
 Rechargeable  Alkaline  Ba*ery  
•  Rechargeable  Alkaline  Manganese  (RAM)  
cell  
•  The  interest  is  due  to  the  higher  A:  
Alkaline  manganese  2  –  3  Ah  
Nickel  /  cadmium  0.5  –  1.0  Ah  
Nickel  /  metal  hydride  1  –  1.5  Ah  
The  number  of  charge-­‐discharge  is  lower  than  
usual  Ni/Cd  or  Ni/MH  cells  
 Button Batteries
High energy and stable discharge, ideal for long time operation
with low A

Mercury Battery

(Silver Oxide)

Anode: Zn(Hg) + 2OH- (aq) ZnO (s) + H2O (l) + 2e-

Cathode: HgO (s) + H2O (l) + 2e- Hg (l) + 2OH- (aq)

Zn(Hg) + HgO (s) ZnO (s) + Hg (l)

67
 Batteries

Lead storage
battery

Anode: Pb (s) + SO2-4 (aq) PbSO4 (s) + 2e-

Cathode: PbO2 (s) + 4H+ (aq) + SO2-

4 (aq) + 2e
- PbSO4 (s) + 2H2O (l)

Pb (s) + PbO2 (s) + 4H+ (aq) + 2SO42- (aq) 2PbSO4 (s) + 2H2O (l)

68
 Acidic  ba*eries  
•  Pb  ba*eries  have  been  first  reported  in  1859  
•  Electrode  reac5ons:  
 Pb  +  H2SO4                PbSO4  +  2H+  +  2e-­‐      (  -­‐0.356  V)  
 PbO2  +  H2SO4  +  2H+  +  2e-­‐                PbSO4  +  2H2O  
 (1.685  V)  
 Total  reac5on:  
 Pb  +  PbO2  +  H2SO4                2PbSO4  +  2H2O  (2.041  V)  
 Pb  ba*eries  
•  Advantages:  
 Low  cost  
 Well  known  Technology    
 Good  Ah  
•  Disadvantages:  
 Low  energy  density  
 Deposi5on  of  low  soluble  PbSO4  
 Ni-­‐Cd  
Cd  +  2NiOOH  +  4H2O      Cd(OH)2  +  2Ni(OH)2.H2O  
e.f.m.  =  1.20  V  
 
High  number  of  cycles,  reliable,  low  maintenance  
Energy  density  not  high  
Cd  is  toxic  and  costly  
 Ni-­‐MH  
•  Alterna5ve  to  Ni-­‐Cd  cells  
•  Developed  ader  Ni-­‐H2  cells,  for  military  
applica5ons  
•  Electrode  reac5ons:  
 H2  +  2OH-­‐              2H2O  +  2e    
2NiOOH  +  2H2O  +  2e                2Ni(OH)2  +  2OH-­‐  
e.f.m.  =  1.2  –  1.3  V  
Metallic  hydride  is  used  as  hydrogen  source  
 Li  Ba*ery  

   
•  Lightest  metal;  
   
•  High  nega5ve  standard  poten5al      
 
but:    
   
•  Easy  to  oxidize  
   
•  Unstable  and  not  compa5ble  with  water  
 Li  Ba*ery  
•  Need  non  aqueous  solvents  
•  Advantages:  
•  High  voltage  (  >4V)  
•  Uniform  T    discharge  
•  Long  shelf-­‐life  
•  Loss  of  capacity  <  10%  
•  Wide  range  of  working  T  
 Li  Ba*ery  
•  Cathode  MnO2  

•  Long  self  discharge  (up  to  10  years)  

•  Working  T  around  -­‐40  °C  and  60  °C    
 Batteries

76
Solid State Lithium Battery
Li-­‐ion  Ba*eries  
 Batteries

A fuel cell is an
electrochemical cell
that requires a
continuous supply of
reactants to keep
functioning

Anode: 2H2 (g) + 4OH- (aq) 4H2O (l) + 4e-

Cathode: O2 (g) + 2H2O (l) + 4e- 4OH- (aq)

2H2 (g) + O2 (g) 2H2O (l)

78
 History

•  The fuel cells had been conceived in 1839

by the British scientist Mr. William Grove.

•  Developed practical applications during

years 60 and 70, for NASA.

•  The American astronauts consumed the

water produced for the electric generators
of its ships.

•  These generators had constituted the first

operational use of fuel cells.
 What they are…
•  Electrochemical cell that converts chemical energy into electric
energy;

•  It can have taxes of conversion in the order of 90%;

•  Cathode + anode + electrolyte + catalyst;

•  Ex.: Combustible H2 and oxidant O2

Anode – H2(g) → 2H+(aq) + 2e-
Cathode – 1/2O2(g) + 2H+(aq) + 2e- → H2O(g)

•  It is important the selection of the electrolyte, and the dimensions

of this and the electrodes.
and its operating…
 Types of Fuel Cells
•  Polymer Electrolyte Fuel Cell (PEMFC)
•  Alkaline Fuel Cell (AFC)
•  Phosphoric Acid Fuel Cell (PAFC)
•  Molten Carbonate Fuel Cell (MCFC)
•  Intermediate Temperature Solid Oxide Fuel Cell (ITSOFC)
•  Solid Oxide Fuel Cell (SOFC)
 PEMFC
•  Operating Temperature: 50-100ºC

•  Appropriate for electric vehicles (Automobile

Industry)

•  Anode – Platinum (0.4mg/Pt cm2)

H2(g) → 2H+ + 2e-
•  Cathode – Platinum (0.4 mg/Pt cm2)
1/2O2(g) + 2H+ + 2e- → H2O(aq)

•  Common electrolyte:
- Solid organic polymer poly- perfluorosulfonic
acid;
- Membrane of Nafion.

•  System Output: < 1kW - 250kW

•  Efficiency Electrical:
- 53-58% (transportation) [1] http://www.cogeneration.net/molten_carbonate_fuel_cells.htm
- 25-35% (stationary)
Polymer Electrolyte Fuel Cell (PEMFC)
Applications :

•  Backup power
•  Small distributed generation
•  Portable power
•  Transportation

Advantages :
•  Solid electrolyte reduces corrosion & electrolyte management problems

•  Low temperature

•  Quick start-up

Disadvantages :
•  Requires expensive catalysts

•  High sensitivity to fuel impurities

•  Low temperature waste heat

•  Waste heat temperature not suitable for combined heat and power (CHP)
 AFC

•  Operating Temperature: 90-100ºC

•  Anode – Zn
H2(g) + 2OH-(aq) → 2H2O + 2e-

•  Cathode – MnO2
1/2O2(g) + H2O + 2e- → 2OH-(aq)

•  Common electrolyte:
- Aqueous solution of potassium
hydroxide soaked in a matrix

•  System Output: 10kW - 100kW

•  Efficiency Electrical: 60%

[1] http://www.cogeneration.net/molten_carbonate_fuel_cells.htm
 Alkaline Fuel Cell (AFC)

Applications :
•  Military
•  Space

Advantages :
• Cathode reaction faster in alkaline electrolyte, higher performance.

Disadvantages :

•  Expensive removal of CO2 from fuel and air streams required (CO2 degrades
the electrolyte).
 PAFC

•  Operating Temperature: 150-200ºC

•  Anode – Platinum (0.1 mg/Pt cm2)

H2(g) → 2H+ + 2e-

•  Cathode – Platinum (0.5 mg/Pt cm2)

1/2O2(g) + 2H+ + 2e- → H2O(aq)

•  Common electrolyte:
- Liquid phosphoric acid soaked in a matrix

•  System Output: 50kW – 1MW (250kW module

typical)

•  Efficiency Electrical: 32-38%

[1] http://www.cogeneration.net/molten_carbonate_fuel_cells.htm
Phosphoric Acid Fuel Cell (PAFC)

Applications :
•  Distributed generation

Advantages :

•  Higher overall efficiency with CHP

•  Increased tolerance to impurities in hydrogen

Disadvantages :

•  Requires expensive platinum catalysts

•  Low current and power

•  Large size/weight
 MCFC
•  Operating Temperature: 600-700ºC

•  Anode: Nickel
H2(g) + CO32- → H2O(g) + CO2(g) + 2e-

•  Cathode: Nickel
•  1/2O2(g)+CO2(g)+2e-→ CO32-

•  Common electrolyte:
- Carbonate salt

•  System Output: < 1kW – 1MW (250kW

module typical)

•  Efficiency Electrical: 45-47%

[1] http://www.cogeneration.net/molten_carbonate_fuel_cells.htm
Molten Carbonate Fuel Cell (MCFC)
Applications :
•  Electric utility
•  Large distributed generation

Advantages :
•  High efficiency
•  Fuel flexibility
•  Can use a variety of catalysts
•  Suitable for CHP

Disadvantages :

•  High temperature speeds corrosion and breakdown of cell components

•  Complex electrolyte management

•  Slow start-up
 TSOFC

•  Operating Temperature: 800 -1000ºC

•  Anode: Co-ZrO2 or Ni-ZrO2 cermet

•  H2(g) + O2- → H2O(l) + 2e-

•  Cathode: Sr-doped LaMnO3

•  1/2O2(g) + 2e- → O2-

•  Common electrolyte:
- Solid zirconium oxide to which a small
amount of Yttria is added

•  System Output: 5kW – 3MW

•  Efficiency Electrical: 35-43%

[2] http://www.treehugger.com/files/2007/06/biogas-powered_fuel_system.php
Solid Oxide Fuel Cell (SOFC)
Applications :
•  Auxiliary power
•  Electric utility
•  Large distributed generation

Advantages :
•  High efficiency
•  Solid electrolyte •  Suitable for CHP
•  Fuel flexibility
reduces electrolyte •  Hybrid/GT cycle
•  Can use a variety of catalysts management problems

Disadvantages :
•  High temperature enhances corrosion and breakdown of cell components

•  Slow start-up
•  Brittleness of ceramic electrolyte with thermal cycling
 ITSOFC
•  Operating Temperature: 600-800ºC

•  Anode: Co-ZrO2 or Ni-ZrO2 cermet

•  H2(g) + O2- → H2O(l) + 2e-

•  Cathode: Sr-doped LaMnO3

•  1/2O2(g) + 2e- → O2-

•  Lower temperatures ⇒ increase the internal

resistance of the cell

•  Common electrolyte:
- Solid zirconium oxide to which a small
amount of Yttria is added

•  System Output: 5kW – 3MW

•  Efficiency Electrical: 35-43%

[1] http://www.cogeneration.net/molten_carbonate_fuel_cells.htm
Applications
 Corrosion  
Corrosion  is  a  spontaneous  and  irreversible    electrochemical  process,  which  
results  in  the  degrada5on  of  a  metallic  material,  upon  interac5on  with  the  
environment.  
 
The  corrosion  could  occur  in  the  presence  or  in  the  absence  of  water:  
The  first  one  is  called  wet  corrosion,  the  second  dry  corrosion  
 
As  for  all  the  chemical  processes,  the  corrosion  depends  on  both  
thermodynamic  (spontaneous  or  not  process)  and  kine5c  (rate  of  the  
process)  factors  
   
The  interac5on  with  the  environment  could  lead  to:  
 
1. The  corrosion  of  the  metal  (ac5ve  condi5on):  the  process  
is  both  thermodynamic  and  kine5c  favored.    ΔE  >  0  

2. The  forma5on  of  a  protec5ve  film  (passive  condi5on):  the  

process  is  favored  by  thermodynamic  but  kine5cally  
inhibited  

3. No  modifica5on  of  the  metal:  :  the  process  is  not  

thermodynamic  favored.  ΔE  <  0  
The  corrosion  is  an  electrochemical  process,  where  a  cathode  and  an  anode  
are  formed  
The  metal  is  oxidized  in  the  anodic  region  and  leaves  the  electrons  that  
migrate  to  the  cathodic  region,  the  corrosive  region,  where  molecular  oxygen  
is  reduced  

Anodic  process:  
 
Me    Men+  +  ne-­‐  
 

Cathodic  process:  
 
O2  +  2H2O  +  4e-­‐    4OH-­‐  
 

or  
 
O2  +  4H+  +  4e-­‐    2H2O  
 
 
 
The  molecular  oxygen  is  more  concentrated  at  the  surface  than  in  
the  bulk  of  the  droplet,  leading  to  a  concentra5on  cell.  The  
oxygen  reduc5on  produces  the  hydroxide  ions  that  lead  to  the  
rust  forma5on      

This  effect  produces  the  ring  morphology  for  the  metal  corrosion  
  The  corrosion  can  be:  
 
 
Generalized:  the  anodic  zone  is  big,  while  the  cathodic  zone  is  small  
 
 
Localized:  is  the  reverse  case  of  the  generalized  corrosion.  It  is  the  
most  dangerous      
 Generalized  corrosion  
 
This  corrosion  interests  all  the  metallic  surface  and  leads  to  a  
reduc5on  of  the  metal  thickness  

Uniform  
 
 
 
Not  uniform  
Localized  corrosion  
 
This  corrosion  interests  only  small  parts  of  the  metal  surface  and  it  is  the  most  
dangerous  because  it  is  impossible  
to  evaluate  the  gravity  of  the  
corrosive  a*ack  from  an  external  
inspec5on.  
Temporal  evolu5on  of  the  corrosion  
 
Constant  process:  ex.  Fe  in  HCl  
 
Self-­‐cataly5c  process:  the  hydrolysis  of  iron  in  the  presence  of  Cl-­‐  ion  
produces  protons  in  the  anodic  zone  that  increases  the  corrosion  rate  
 
Self-­‐inhibi5ng  process:    the  forma5on  of  carbonate  salts  in  the  alkaline  
region  can  produce  low  soluble  salts  that  par5ally  protect  the  metal  
surface  from  the  oxygen  reduc5on  
 
Passiva5ng  process:  the  forma5on  in  the  anodic  zone  of  a  compact  
oxide  film  that  protect  the  metal:  ex.  Al  
Galvanic  corrosion  
 
The  corrosion  is  produced  by  a  junc5on  of  two  metals  having  
different  E:  the  metal  with  lower  E  is  oxidized.  
Lower  the  ra5o  of  the  zone  anode/cathode,  higher  and  more  
penetra5ng  the  dissolu5on  of  the  less  noble  metal.  
Example  of  corrosion:  the  brass  
 
The  brass  is  an  alloy  of  copper  and  zinc:  the  zinc  is  oxidized  and  
copper  forms  the  characteris5c  colored  powder  
Protec5on  methods  
 
Cathodic  protec5on:  cathodic  current  or  sacrificial  anode  
 
Appica5on  of  films  resistant  to  corrosion:  metallic,    
non-­‐metallic,  polymers  
Cathodic Protection of an Iron Storage Tank

107
Protec5on  with  metallic  films  
 
Hot  deposi5on:  immersion  or  spray  coa5ng  
 
Galvanic  deposi5on:  electrochemical  deposi5on  (problems:  not  
homogeneous  thickness)  
 
Chemical  deposi5on:  deposi5on  of  the  film  by  redox  reac5on    
Protec5on  with  non-­‐metallic  films  
 
Conver5on  layers:  the  film  is  formed  in  situ  by  forma5on  of  chemical  
bond  with  the  metal  surface  
 
Ex.:  chromature  
 

Protec5on  with  organic  layers  

 
 
Thick  films:  gums  or  polymers  
 
Thin  films:  paints