CHEM 409-N05

Ashley Causton 2015

Electrochemistry

Electron transfer reactions are oxidation-reduction or redox reactions

These types of reactions are import to:
o Batteries
o Corrosion
o Industrial production of chemicals such as Cl2, NaOH, F2 and Al
o Biological redox reactions
LEO the lion says GER
OXIDATIONloss of electron(s) by a species; increase in oxidation number; increase in
oxygen
REDUCTIONgain of electron(s); decrease in oxidation number; decrease in oxygen;
increase in hydrogen
OXIDIZING AGENTelectron acceptor; species is reduced
REDUCING AGENTelectron donor; species is oxidized

Define direct and indirect redox reactions:

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/essentialchemistry/flash/galvan5.swf
Chemical Change = Electric Current:
In the example above:
o Zn is oxidized (and is the reducing agent): Zn(s) Zn2+(aq) + 2eo Cu2+ is reduced (and is the oxidizing agent): Cu2+(aq) + 2e- Cu(s)
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
The standard cell potential (E) is a quantitative measure of the tendency of reactants to
proceed to products when all are in their standard states at 25 C
o For Zn/Cu cell, potential is +1.10 V at 25 C and when [Zn2+] and [Cu2+] = 1.0 M
Calculating Cell Voltage the 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)
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CHEM 409-N05

Ashley Causton 2015

Using a table of standard reduction potentials, show how you could calculate the standard cell
potential (E ) for this system:
In the example above, if Cd/Cd2+ replaces Zn/Zn2+ and Fe/Fe2+ replaces Cu/Cu2+, in which
direction will the REDOX reaction proceed ?
Balancing REDOX equations:
Balance the following REDOX reaction: Cu + Ag+ Cu2+ + Ag
Electrolysis:
In the above examples, the spontaneous direction of a REDOX reaction was exploited to
generate an electric current
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
o Passive electrolysis is where the electrodes are chemically inert and merely
provide a path for the electrons
o Active electrolysis is when the electrodes are part of the chemical reaction
Chemicals from Sodium Chloride:
Sodium Hydroxide (#8 at 11 billion kg in 2002)
Chlorine (#10 at 13 billion kg in 2002)
Hydrochloric Acid (#27 at 4.5 billion kg in 2002)

Sodium chloride is a naturally occurring mineral (about 90 billion lbs are processed per
year)
Salt mining is predicted to be as old as humankind
Salt has been worshipped, used as a medium of exchange, used as a political
weapon (highly taxed)
Sodium Chloride is isolated by brine solution, rock salt mining, and the open pan or
grainer process

How is electrolysis used in the production of both chlorine gas and sodium hydroxide starting
from sodium chloride ?
Suggested Reading: Chapter 6 of Survey of Industrial Chemistry (3rd Edition, 2002) by Philip J.
Chenier [Kluwer Academic/Plenum]
Suggested Reading: Chapter 6.19 (pp. 442-458) of "Chemical Technology: An Integral Textbook"
by Andreas Jess & Peter Wasserscheid

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CHEM 409-N05

Ashley Causton 2015

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