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CHEM1104 Lab Electrochemistry
CHEM1104 Lab Electrochemistry
CHEM1104 Lab Electrochemistry
Example:
in BaCl2 EACH Ba has an oxidation state of 2+
in Ca3(PO4)2 EACH Ca has an oxidation state of 2+.
A free Mg+2 has an oxidation state of 2+.
RULES FOR ASSIGNING OXIDATION STATES
(Review)
Example:
a Fe+3(aq) ion has an oxidation state of 3+.
RULES FOR ASSIGNING OXIDATION STATES
(Review)
K = +1 (Rule 1) = +1
O = -2 (Rule 2) = 4(-2)
Mn = ? (Rule 10) = X .
total = 0
Mn - +1 + 4(-2) + X = 0 (solve for X)
+1 + (-8) + X =0
(-7) + X = 0
X = 7 , Mn = +7
Electrochemistry
• Electrochemistry is the study of chemical
processes that cause electrons to move. This
movement of electrons is called electricity,
which can be generated by movements of
electrons from one element to another in a
reaction known as an oxidation-reduction
("redox") reaction.
Redox Reaction
• A redox reaction is a reaction that involves
a change in oxidation state of one or more
elements.
• When a substance loses an electron, its
oxidation state increases; thus, it is
oxidized. When a substance gains an
electron, its oxidation state decreases, thus
being reduced. For example, for the redox
reaction
Redox Reactions
• Examples of Redox Reactions:
Zn(s) + CuSO4(aq) ZnSO4(aq) + Cu(s);
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
• Half–Reactions Method:
• The overall reaction is split into two half –
reactions, one involving oxidation and one
reduction.
8H+ + MnO4 + 5Fe2+ Mn2+ + 5Fe3+ + 4H2O
Example:
• Cr2O72-(aq) 2Cr3+(aq)
• HSO3-(aq) HSO4-(aq)
• Adding electrons:
• 6e- + Cr2O72-(aq) 2Cr3+(aq)
• HSO3-(aq) HSO4-(aq) + 2e-
Electrolytic 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.
A Galvanic Cell
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.
Galvanic Cell
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.
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
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
• Cell Potential: E
E°cell = E°(cathode) – E°(anode)
E°cell = 0.77 V – 0.34 V = 0.43 V
Calculating Standard Cell Potential
• 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 Mercury Cell for Production of
Chlorine and Sodium Hydroxide
The Downs Cell for the Electrolysis of Molten
Sodium Chloride
Difference between galvanic
and electrolytic cell
Electrochemical Energy Storage
Electrochemical energy storage is a method
used to store electricity under a chemical
form. This storage technique benefits from
the fact that both electrical and chemical
energy share the same carrier, the
electron. This common point allows to limit
the losses due to the conversion from one
form to another
Battery
Three categories of batteries
The half reactions are essentially the same, but the use
of the KOH eliminates the ammonia gas build up and
maintains the Zn electrode.
Alkaline Battery
Hg & Ag Button Batteries
• Both use a zinc container
as the anode in a basic medium
• Mercury battery employs HgO
as oxidizing agent while Ag2O
for silver battery and both use a steel can around
the cathode.
Cathode (reduction)
HgO (s) + H2O + 2e- Hg(ℓ) + 2OH- (aq)
Ag2O + H2O + 2e- 2Ag(s) + 2OH- (aq)
Cathode (reduction):
NiO(OH)(s) + H2O(ℓ) Ni(OH)2(s) + OH-
Ecell= 1.4 V
Lithium-Ion Battery
• The anode is Li and the atoms lie between sheets of graphite
(designated LixC6) while the cathode is lithium metal oxide,
such as LiMn2O4 or LiCoO2 and a typical electrolyte is 1M
LiPF6 in an organic solvent, such as mixture of dimethyl
carbonate and methylethyl carbonate.