Chapter 3
Oxidation and Reduction

Oxidation-Reduction
Concepts

Electrochemical Cells
Voltaic Cell
Electrolytic Cell

Pre...
Electrochemistry
• Electrochemistry
– The study of the relationship between chemical change
(reactions) and the flow of el...
Electrochemical Cells
 Voltaic (Galvanic) Cells
• Use spontaneous reaction ( G < 0) to generate
electrical energy
• Diffe...
Electrochemical Cells
 Electrolytic Cells
• Uses electrical energy to drive nonspontaneous
reaction ( G > 0)
• Electrical...
Electrochemical Cells
Voltaic (Galvanic) Cells
 Voltaic (Galvanic) Cells
• Zinc metal (Zn) in solution of Cu2+ ions
Zn(s)
Zn 2+ (aq) + 2eCu 2+ ...
v

Theodore L.
Brown , H. Eugene
Lemay , Bruce E.
Bursten , Catherine
J. Murphy ,David
P. White,
Chemistry the
central sci...
Voltaic (Galvanic) Cells

Oxidation Half-Cell

Reduction Half-Cell

•

•

Anode

Compartment

– Oxidation of Zinc
•

Zinc ...
Voltaic (Galvanic) Cells
• Relative Charges on the Anode/Cathode electrodes
 Electrode charges are determined by the sour...
Voltaic (Galvanic) Cells
 Purpose of Salt Bridge
• Electrons from oxidation of Zn leave neutral ZnSO4 solution
producing ...
Voltaic (Galvanic) Cells
 Cell notation is used to describe the structure of a
voltaic (galvanic) cell
• For the Zn/Cu ce...
Voltaic (Galvanic) Cells
• Active vs Inactive Electrodes
 Active Electrodes
• Electrodes in Zn/Cu2+ cell are active
• Zin...
Voltaic Cell
with
Inactive Graphite
Electrodes
Each half-cell consists of
inactive electrodes immersed in
an electrolyte s...
Practice Problem
Write the cell notation for a voltaic cell with the
following cell reaction
Ni(s) + Pb 2+ (aq)

Ans:

Ni ...
Practice Problem
A mercury battery, used for hearing aids and
electric watches, delivers a constant voltage (1.35
V) for l...
Summary
• A voltaic cell consists of oxidation (anode) and
reduction (cathode) half-cells, connected by a wi re to
conduct...
Week 6.2   voltaic cells
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Week 6.2 voltaic cells

  1. 1. Chapter 3 Oxidation and Reduction Oxidation-Reduction Concepts Electrochemical Cells Voltaic Cell Electrolytic Cell Prepared by: Mrs Faraziehan Senusi PA-A11-7C Corrosion & Prevention David P. White Prentice Hall © 2003
  2. 2. Electrochemistry • Electrochemistry – The study of the relationship between chemical change (reactions) and the flow of electrons (electrical work) • Electrochemical Systems – Voltaic/Galvanic – Release of free energy from a spontaneous reaction to produce electricity (Batteries) – Electrolytic – Work done by absorbing free energy from a source (passage of an electrical current through a solution) to drive a nonspontaneous reaction
  3. 3. Electrochemical Cells  Voltaic (Galvanic) Cells • Use spontaneous reaction ( G < 0) to generate electrical energy • Difference in Chemical Potential energy between higher energy reactants and lower energy products is converted to electrical energy to power electrical devices • Thermodynamically - The system does work on the surroundings
  4. 4. Electrochemical Cells  Electrolytic Cells • Uses electrical energy to drive nonspontaneous reaction ( G > 0) • Electrical energy from an external power supply converts lower energy reactants to higher energy products • Thermodynamically – The surroundings do work on the system • Examples – Electroplating and recovering metals from ores
  5. 5. Electrochemical Cells
  6. 6. Voltaic (Galvanic) Cells  Voltaic (Galvanic) Cells • Zinc metal (Zn) in solution of Cu2+ ions Zn(s) Zn 2+ (aq) + 2eCu 2+ (aq) + 2eZn(s) + Cu 2+ (aq) Cu(s) [oxidation] [reduction] Zn 2+ + Cu(s)  Construction of a Voltaic Cell • The oxidizing agent (Zn) and reducing agent (Cu2+) in the same beaker will not generate electrical energy • Separate the half-reactions by a barrier and connect them via an external circuit (wire) • Set up salt bridge between chambers to maintain neutral charge in electrolyte solutions
  7. 7. v Theodore L. Brown , H. Eugene Lemay , Bruce E. Bursten , Catherine J. Murphy ,David P. White, Chemistry the central science.
  8. 8. Voltaic (Galvanic) Cells Oxidation Half-Cell Reduction Half-Cell • • Anode Compartment – Oxidation of Zinc • Zinc metal in solution of • Copper bar in solution of Cu2+ electrolyte (CuSO4) Zn is reactant in oxidation • half-reaction • Compartment - Reduction of Copper Zn2+ electrolyte (ZnSO4) • Cathode Copper metal is product in reduction half-cell reaction Conducts released electrons • (e-) out of its half-cell Conducts electrons into its half-cell Zinc-Copper Voltaic Cell
  9. 9. Voltaic (Galvanic) Cells • Relative Charges on the Anode/Cathode electrodes  Electrode charges are determined by the source of the electrons and the direction of electron flow  Zinc atoms are oxidized (lose 2 e-) to form Zn2+ at the anode • Anode – negative charge (e- rich)  Released electrons flow to right toward cathode to be accepted by Cu2+ to form Cu(s) • Cathode – positive charge (e- deficient)
  10. 10. Voltaic (Galvanic) Cells  Purpose of Salt Bridge • Electrons from oxidation of Zn leave neutral ZnSO4 solution producing net positive charge • Incoming electrons to CuSO4 solution would produce net negative charge in solution as copper ions are reduced to copper metal • Resulting charge imbalance would stop reaction • Salt bridge provides “liquid wire” allowing ions to flow through both compartments completing circuit • Salt bridge constructed of an inverted “U-tube” containing a solution of non-reacting Na+ & SO42- ions in a gel
  11. 11. Voltaic (Galvanic) Cells  Cell notation is used to describe the structure of a voltaic (galvanic) cell • For the Zn/Cu cell, the cell notation is: Zn(s) Zn2+(aq) Cu2+(aq) Cu(s) = phase boundary (solid Zn vs. Aqueous Zn2+) = salt bridge • Anode reaction (oxidation) is left of the salt bridge (AnOx) • Cathode reaction (reduction) is right of the salt bridge (RedCat) • Half-cell components usually appear in the same order as in the half-reactions (Zn(s) + 2eZn2+). • Zinc solid loses 2e- (oxidized) to produce zinc(II) at the negative ANODE • Copper(II) gains 2e- (reduced) to form copper metal at positive CATHODE
  12. 12. Voltaic (Galvanic) Cells • Active vs Inactive Electrodes  Active Electrodes • Electrodes in Zn/Cu2+ cell are active • Zinc & Copper bars are components of the cell reactions • Mass of Zn bar decreases as Zn2+ ions in cell solution increase • Mass of Copper bar increases as Cu2+ ions accept electron to form more copper metal  Inactive Electrodes • In many Redox reactions, one or the other reactant/product is not capable of serving as an electrode,so inactive electrodes are used. • Inactive electrodes - Graphite or Platinum – Can conduct electrons into and out of half-cells – Cannot take part in the half-reactions
  13. 13. Voltaic Cell with Inactive Graphite Electrodes Each half-cell consists of inactive electrodes immersed in an electrolyte solution that contains all the reactant species involved in that half reaction. ~ Anode : I– ions oxidized to solid I2. ~ e– released flow into graphite anode, through the wire, and into graphite cathode. ~ e– are consumed by MnO4–, which reduced to Mn2+ ions. graphite I– (aq) I2 (s) H+(aq), MnO4–(aq),Mn2+(aq) graphite
  14. 14. Practice Problem Write the cell notation for a voltaic cell with the following cell reaction Ni(s) + Pb 2+ (aq) Ans: Ni 2+ (aq) + Pb(s)
  15. 15. Practice Problem A mercury battery, used for hearing aids and electric watches, delivers a constant voltage (1.35 V) for long periods. The half reactions are given below. Which half reaction occurs at the Anode and which occurs at the Cathode? What is the overall cell reaction? HgO(s) + H2O(l) + 2eZn(s) + 2 OH-(aq) Hg(l) + 2 OH-(aq) Zn(OH)2(s) + 2e-
  16. 16. Summary • A voltaic cell consists of oxidation (anode) and reduction (cathode) half-cells, connected by a wi re to conduct electrons and a salt bridge to maintain charge neutrality as the cell operates. • Electrons move from anode (left) to cathode (right), while cations move from the salt bridge into the cathode half-cell and anions from the salt bridge into the anode half-cell. • The cell notation shows the species and their phases in each half-cell, as well as the direction of current flow.
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