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4)
Big-picture perspective:
Oxidation-reduction reactions are integral to many aspects of inorganic chemistry. Building on
your existing knowledge of electrochemistry, we will discuss some fundamental aspects of
inorganic electrochemistry that you may not have previously considered (and therefore make
some new connections to other areas of chemistry) and also introduce and use three diagram-
matic tools that help us to rationalize and predict redox behavior, reactivity, and stability.
Learning goals:
• Balance complex oxidation-reduction reactions by the ion-electron method.
• Understand periodic trends in the activity series and electrochemical series.
• Use the Nernst equation to determine half-cell and cell potentials.
• Derive the stability field of water and use this to rationalize aqueous redox chemistry.
• Construct and be proficient with Latimer diagrams, using them to determine unknown
reduction potential values and to quickly identify stable and unstable species.
• Construct and be proficient with Frost diagrams, using them to identify stable and unstable
species, as well as those that are strong oxidizers.
• Construct and be proficient with Pourbaix diagrams, using them to identify redox and non-
redox reactions, reactions that are and are not pH-dependent, and ultimately to predict and
rationalize stability, reactivity, corrosion, and passivation.
Introduction
Oxidation-reduction phenomena are integral to many aspects of inorganic chemistry
Many elements, including the transition metals, have multiple accessible oxidation
states. The compounds that they form, as well as their chemical properties and
reactivity, are tied intimately to their oxidation states
Many inorganic compounds catalyze, and participate in, redox reactions
(e.g. in industry and biology)
Energy conversion processes (solar, batteries, fuel cells)
rely on inorganic redox reactions
Review and know: Electrochemistry chapter in (any) general chemistry textbook –
assigning oxidation states, balancing redox reactions, using and applying the table of
standard reduction potentials, Nernst equation (important!), and quantitative
relationships among E, G, and K (important!)
Our focus in Chem 310: (a) thermochemical aspects of reduction potentials and their
relationships to redox trends among the elements and (b) diagrammatic tools to help
predict and rationalize electrochemical reactions.
Balancing Redox Reactions
The Ion-Electron Method:
(1) Identify the elements undergoing redox, balance them in half rxns
(2) Add water to balance O
(3) Add H+ to balance H
(4) Add e- to balance charge
(5) Combine half-reactions
(6) For reactions in base, add OH- to neutralize H+
Practice balancing:
In the process, we will investigate three diagrammatic tools, which are familiar
to and used by practicioners of inorganic chemistry – Latimer diagrams, Frost
diagrams, and Pourbaix diagrams.
Fe2+ + 2 e– Fe(s)
Fe3+ + e– Fe2+
Fe3+ + 3 OH– Fe(OH)3(s)
Fe2+ + 2 OH– Fe(OH)2(s)
Fe(OH)3 + e– + 3 H+ Fe2+ + 3 H2O
Pourbaix diagram
Pourbaix diagram: Plot of E vs. pH