Electrochemistry
CHEM 409
Napoleon III and the King of Siam
Electron Transfer Reactions
These are examples of oxidation-reduction
(or redox) reactions
A chemical reaction can result in the
generation of an electric current (electricity)
Or imposing an electric current can cause a
chemical reaction
Electrochemistry is the name generally
given to this field of Chemistry
Electrochemistry
These types of reactions are important to:
Batteries
Corrosion
Industrial production of chemicals such as Cl2,
NaOH, F2 and Al
Biological redox reactions
Electrochemistry: Definitions
Oxidation
loss of electron(s) by a species
increase in oxidation number
increase in oxygen
Reduction
gain of electron(s)
decrease in oxidation number
decrease in oxygen
increase in hydrogen
Electrochemistry: Definitions
Oxidizing Agent
electron acceptor
species is reduced during reaction
Reducing Agent
electron donor
species is oxidized during reaction
Define direct and indirect
redox reactions
Direct Redox Reaction
Oxidizing and reducing agents in direct
contact, e.g. Zinc (s) in solution of copper
sulfate (aq.):
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
Give examples illustrating direct
and indirect redox reactions:
Indirect Redox Reaction
Reducing and oxidizing agents are kept
separately, e.g. a battery functions by
transferring electrons through an external
wire from the reducing agent to the oxidizing
agent
Electrochemical Cell
An apparatus that allows a redox reaction
to occur by transferring electrons through
an external connector
Product favored reaction - voltaic or
galvanic cell (generates electric current)
Reactant favored reaction - electrolytic cell
(electric current is used to cause a
chemical change)
Use a sketch to illustrate the basic
concepts of an electrochemical cell:
http://www.mhhe.com/physsci/chemistry/essenti
alchemistry/flash/galvan5.swf
Basic Concepts
of Electrochemical Cells
Anode
Cathode
Basic Concepts
of Electrochemical Cells
Zn --> Zn2+ + 2e-
Cu2+ + 2e- Cu
Oxidation
Anode
Negative
Reduction
Cathode
Positive
Anions
Cations
Electrons travel thru external wire
Salt bridge allows anions and cations to move
between electrode compartments
Chemical Change = Electric Current
Zn is oxidized and is the reducing agent:
Zn(s) Zn2+(aq) + 2eCu2+ is reduced and is the oxidizing agent:
Cu2+(aq) + 2e- Cu(s)
Chemical Change = Electric Current
The oxidizing and reducing agents are
separated so that electron transfer
(electrical current) occurs through an
external wire
This is accomplished in a GALVANIC or
VOLTAIC cell - a group of such cells is
called a battery
Battery Technology
Standard Cell Potential (E)
A quantitative measure of the tendency of
reactants to proceed to products when all
are in their standard states at 25 C
Using a table of standard reduction
potentials, show how you could calculate
the standard cell potential (E ) for this
system:
Calculating Cell Voltage
Balanced half-reactions can be added
together to get overall, balanced equation:
Zn(s) Zn2+(aq) + 2eCu2+(aq) + 2e- Cu(s)
Cu2+(aq) + Zn(s) Zn2+(aq) + Cu(s)
Calculating Cell Voltage
If we know E for each half-reaction, we
could get E for net reaction
E (V)
oxidizing
ability of ion
Cu2+ + 2e-
Cu
+0.34
2 H+ + 2e-
0.00
Zn2+ + 2eTo determine an oxidation from
a reduction table, just take the
opposite sign of the reduction!
Zn
-0.76
reducing ability
of element
Calculating Cell Voltage
Zn(s) Zn2+(aq) + 2e- E = +0.76 V
Cu2+(aq) + 2e- Cu(s) E = +0.34 V
Cu2+(aq) + Zn(s) Zn2+(aq) + Cu(s)
E = +1.10 V
GROUP QUESTION:
In the example above, if Cd/Cd2+ replaces
Zn/Zn2+ and Fe/Fe2+ replaces Cu/Cu2+, in
which direction will the REDOX reaction
proceed ?
GROUP QUESTION:
Balance the following REDOX
reaction:
Cu + Ag+ Cu2+ + Ag
Balancing REDOX Equations
1: Divide the reaction into half-reactions, one for
oxidation and the other for reduction
Ox
Cu Cu2+
Red
Ag+ Ag
2: Balance each element for mass
3: Balance each half-reaction for charge by adding
electrons
Ox
Cu Cu2+ + 2eRed
Ag+ + e- Ag
Balancing REDOX Equations
4: Multiply each half-reaction by a factor so that the
reducing agent supplies as many electrons as
the oxidizing agent requires
Reducing agent
Cu Cu2+ + 2eOxidizing agent
2 Ag+ + 2 e- 2 Ag
5: Add half-reactions to give the overall equation.
Cu + 2 Ag+ Cu2+ + 2Ag
Corrosion
Rusting - spontaneous oxidation
Most structural metals have reduction potentials
that are less positive than O2
Fe Fe+2 +2eE= 0.44 V
O2 + 2H2O + 4e- 4OHE= 0.40 V
2Fe+2 + O2 + H2O Fe2O3 + H+
Reactions happens in two places on metal
Corrosion
Salt speeds up process by increasing
conductivity
Water
Fe2+
Rust
eO2 + 2H2O +4e- 4OH-
Iron Dissolves
Fe Fe+2
Fe2+ + O2 + 2H2O Fe2O3 + 8 H+
Electrolysis
The spontaneous direction of a REDOX
reaction can be exploited to generate an
electric current
Electrolysis
Electrolysis is the process of passing an
electric current through an ionic solution or
molten salt to produce a chemical reaction
forcing a REDOX reaction in the nonspontaneous direction
Passive electrolysis is where the electrodes
are chemically inert and merely provide a path
for the electrons
Active electrolysis is when the electrodes are
part of the chemical reaction
Manufacture of Important Inorganic
Compounds
Top Inorganic Chemicals
Sodium Chloride Derivatives
Sodium Hydroxide
Chlorine
Hydrochloric Acid
How is electrolysis used in the
production of chlorine gas and sodium
hydroxide from sodium chloride ?
https://www.youtube.com/watch?v=R-BVMKTlHJg
Membrane Cell Process
Developed in the late 1970s
Brine solution electrolysed
Only sodium ions and water pass through
membrane
Membrane Cell Process
ANODE:
Cl + Cl
Cl2 + 2e
CATHODE:
2H2O + 2e
OVERALL:
2NaCl + 2H2O
H2 + 2HO
Cl2 + H2 + 2NaOH
Diaphragm Cell (Chenier 6.2)
Membrane Cell Process
Mercury Cell (Chenier 6.3)
Aluminum
https://www.youtube.com/watch?v=NW1k4wNEq14
Electrochemistry: Fuel Cells
Fuel cells differ from electrochemical cell
(batteries) in that they consume a reactant,
which must be replenished
The source fuel is converted into an electric
current
A hydrogen fuel cell uses hydrogen as the fuel,
and oxygen (from air)
O2 + H2 H2O
http://en.wikipedia.org/wiki/Fuel_cell
Hydrogen Fuel Cell
Hydrogen Fuel Cell Vehicle
http://www.youtube.com/watch?v=oy8dzOB-Ykg
http://en.wikipedia.org/wiki/Hydrogen_vehicle
The Dangers of Hydrogen
http://www.youtube.com/watch?v=lFptgQ8GA_U
Sources of Hydrogen
Production via steam reforming and coal
gasification using limited fossil resources
such as coal and oil
Formic acid (HCOOH) is one of the major
products formed in biomass processing
(e.g. fermentation) and can undergo
selective decomposition to form hydrogen
and carbon dioxide in the presence of a
catalyst
Hydrogen Storage via Carbon
Dioxide-Formic Acid Conversion
Formic Acid Decomposition
Pathways
Proposed Catalytic Cycle
