14.3 Notes

Electrochemistry 14.
3:
Electrolytic Cells
Electrolytic Cell anode is
positive
cathode is
• a cell consisting of negative
2 electrodes, a
single electrolyte
and an external
power source used
to force a
nonspontaneous
redox reaction to
occur
Comparing Voltaic Cells and Electrolytic
Cells
• although the redox reaction in an electrolytic
cell is nonspontaneous, most of the voltaic cell
redox concepts still apply
Cells - Similarities
Voltaic Cell Electrolytic Cell
cathode SOA is reduced SOA is reduced
anode SRA is oxidized SRA is oxidized
direction of
electron anodecathode anodecathode
movement
direction of anionsanode anionsanode
ion movement cationscathode cationscathode
Cells - Differences
Voltaic Cell Electrolytic Cell
spontaneity spontaneous nonspontaneous
standard cell
potential (Ecell) positive negative
cathode positive electrode negative electrode
anode negative electrode positive electrode

Potassium Iodide Electrolytic Cell
• The steps for determining reaction equations

and cell potential are the same as for voltaic
cells. Determine the entities and the cell
notation for a potassium iodide electrolytic
cell that uses two carbon electrodes.
Entities: OA SOA
K (aq) I (aq) H2O(l)
+ -
SRA RA
Cell Notation: C(s) I-(aq) C(s)

Cathode: 2 H2O(l) + 2e-  H2(g) + 2 OH-(aq)
Anode: 2 I-(aq)  I2(s) + 2e-
Net Cell Reaction:

2 H2O(l) + 2 I-(aq)  H2(g) + 2 OH-(aq) + I2(s)
Calculate the minimum voltage needed to
operate the cell.
Eºcell = Eºr  Eºr

cathode anode
Eºcell =  0.83  (+0.54) =  1.37 V
The minimum voltage needed to operate

the cell is 1.37 V.
Practice 1
• Determine the cathode, anode and net cell
reaction for C(s) CuSO4(aq) C(s).
Entities: SOA OA OA
Cu2+(aq) SO42-(aq) H2O(l)
SRA
Cathode: 2(Cu2+(aq) + 2e-  Cu(s) )
Anode: 2 H2O(l)  O2(g) + 4 H +
(aq) + 4e -
Net Reaction:
2 Cu2+(aq) + 2 H2O(l)  2 Cu(s) + O2(g) + 4 H+(aq)
Practice 1
Calculate the minimum voltage needed to
operate the cell.

cathode anode
Eºcell = + 0.34  (+1.23) =  0.89 V

the cell is 0.89 V.
Practice 1
Draw and label the electrolytic cell.
The Chloride Anomaly
There is one exception to the rule that says the
SRA undergoes oxidation at the anode of an
electrolytic cell.
During the electrolysis of aqueous electrolytes
containing the chloride ion (Cl-(aq)), water will
be replaced by chloride ion as the strongest
reducing agent.
This results in chlorine gas (Cl2(g)) being
produced at the anode instead of oxygen gas.
Example – Chloride Anomaly
• Determine the minimum voltage to operate an
electrolytic cell composed of inert carbon
electrodes and an aqueous electrolyte of
nickel(II) chloride.
SOA OA
Entities: Ni2+(aq) Cl-(aq) H2O(l)
SRA RA RA
exception to
the SRA rule
Example – Chloride Anomaly
Cathode: Ni2+(aq) + 2e-  Ni(s) Eºr =  0.26 V

Anode: 2 Cl -
(aq)  Cl 2 (g) + 2e -
Eºr = +1.36 V
Net Reaction:
Ni2+(aq) + 2 Cl-(aq)  Ni(s) + Cl2(g)
cathode anode
Eºcell =  0.26  (+1.36) =  1.62 V
the cell is 1.62 V.
Applications of Electrolytic Cells
1. Production of elements
• most metals occur naturally as a compound
and not as pure metal elements
• metals can be produced by the electrolysis of

ionic solutions
• Problems with using electrolysis to form
metals:
• Some ionic compounds can’t dissolve to form
an aqueous electrolyte
• Water is a stronger OA than many metal
cations so oxygen would be produced instead
of pure metals
• Solution to the “water” problem:
• Melt the ionic compound to form a molten
electrolyte.
• Molten cations can be forced to gain electrons
at the cathode.
• Molten anions are oxidized at the anode of a
molten electrolytic cell.
• Ex/ The electrolysis of molten lithium
chloride.
SOA
Entities: Li+(l) Cl-(l)
SRA
Cathode: 2( Li+(l) + e-  Li(l) )

Anode: 2 Cl-(l)  Cl2(g) + 2e-
Net Reaction:
2 Li+(l) + 2 Cl-(l)  2 Li(l) + Cl2(g)
• Another solution to the “water” problem:
• Use a solvent other than water to dissolve the
ionic compound.
• Ex/ Aluminum oxide is dissolved in cryolite to
produce aluminum through electrolysis.
SOA
Entities: Al3+(cryolite) O2-(cryolite)
SRA
Cathode: 4( Al3+(cryolite) + 3e-  Al(l) )
Anode: 3(2 O2-(cryolite)  O2(g) + 4e- )
Net Reaction:
4 Al3+(cryolite) + 6 O2-(cryolite)  4 Al(l) + 3 O2(g)
1. Production of
elements
• Chlorine and
sodium hydroxide
are produced by the
Chlor-Alkali
process. Brine
(aqueous sodium
chloride) is a
starting material.
• Ex/ Chlor-Alkali Process
OA SOA
Entities: Na +
(aq)Cl -
(aq) H2O(l)
SRA RA
chloride anomaly RA
Cathode: 2 H2O(l) + 2e-  H2(g) + 2 OH-(aq) Eºr = 0.83 V
Anode: 2 Cl-(aq)  Cl (g) + 2e- Eºr = +1.36 V
2
Net Reaction:
2 H2O(l) + 2 Cl-(aq)  H2(g) + 2 OH-(aq) + Cl2(g)
Eºcell = 0.83  (+1.36) = 2.19 V
The minimum voltage required is 2.19 V.
2. Refining of Metals
• Metals containing impurities can be purified
by using the impure metal as the anode in an
electrolytic cell and reducing the metal ions at
the cathode (electrorefining).
2. Refining of Metals
• Copper, iron and zinc are
oxidized to ions and dissolved at
the anode. Only copper is
reduced at the cathode.
• Other impurities in the anode
such as silver, gold and platinum
do not react and fall to the
bottom of the cell as sludge.
2. Refining of copper contaminated with zinc, iron and
silver using sulfuric acid and copper (II) sulfate.
• Entities:
SOA
Cu(s) Zn(s) Fe(s) Ag(s) H+(aq) Cu2+(aq) SO42-(aq) H2O(l)
RA SRA RA RA RA
first reaction:
Cathode: Cu2+(aq) + 2e-  Cu(s)
Anode: Zn(s)  Zn2+(aq) + 2e-
Net Reaction:
Cu2+(aq) + Zn(s)  Cu(s) + Zn2+(aq)
2. Refining of copper contaminated with zinc, iron and
silver using sulfuric acid and copper (II) sulfate.
Second reaction: https://www.youtube.com/watch?v=wwN8lwpQVLk
Cathode: Cu2+(aq) + 2e-  Cu(s)
Anode: Fe(s)  Fe2+(aq) + 2e-
Net Reaction: Cu2+(aq) + Fe(s)  Cu(s) + Fe2+(aq)
Third reaction:
Cathode: Cu 2+
(aq) + 2e -
 Cu(s)
Anode: Cu(s)  Cu2+(aq) + 2e-
Net Reaction: Cu2+(aq) + Cu(s)  Cu(s) + Cu2+(aq)
3. Electroplating
• An object is covered with a thin layer of metal
by using the object as the cathode in an
electrolytic cell.
3. Electroplating
• Electroplating an object in zinc.
Cathode: Zn2+(aq) + 2e-  Zn(s)

Anode: Zn(s)  Zn2+(aq) + 2e-
Net Reaction: Zn(s) + Zn2+(aq)  Zn2+(aq) + Zn(s)

14.3 Notes

Uploaded by

Copyright:

Available Formats

14.3 Notes

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

14.3 Notes

Uploaded by

Copyright:

Available Formats

Electrochemistry 14.

anode negative electrode positive electrode

• The steps for determining reaction equations

Cell Notation: C(s) I-(aq) C(s)

Cathode: 2 H2O(l) + 2e-  H2(g) + 2 OH-(aq)

Anode: 2 I-(aq)  I2(s) + 2e-

Net Cell Reaction:

Eºcell = Eºr  Eºr

Eºcell =  0.83  (+0.54) =  1.37 V

The minimum voltage needed to operate

Eºcell = Eºr  Eºr

Eºcell = + 0.34  (+1.23) =  0.89 V

The minimum voltage needed to operate

Cathode: Ni2+(aq) + 2e-  Ni(s) Eºr =  0.26 V

• metals can be produced by the electrolysis of

Cathode: 2( Li+(l) + e-  Li(l) )

Cathode: Zn2+(aq) + 2e-  Zn(s)

You might also like