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Finding Half Reactions

Keep in mind that not all electrochemical reactions will be a simple two-reactant, two product system.
From a cell drawing or line diagram, you should look for elements in two oxidation states to write the half reactions; e.g.:
Cu(s) | Cu(EDTA)2- (aq) || C 2O 2 4 (aq) | Cd(s) | Cd(C 2 O 4 )(s)

Equilibrium Constants and Electrochemistry


The spontaneous reaction from a galvanic cell occurs because the system is not at equilibrium
E for the net reaction can thus be related to K
aA + ne- cC
E+

Cu(EDTA)2- + 2e - Cu ( s ) + EDTA 4
Cd(C2O4 )(s) + 2e- Cd( s) + C 2O 2 4

dD + ne dD E- c .05916 [C] E .05916 log [B]b log a E = E+ E = E+ n n [A] [D]d


E = E
c d

.05916 .05916 [C] [D] log a b = E log K @25C n n [A] [B]

K = 10

nE 0.05916

@25 C

Equilibrium Constant Example


Find the equilibrium constant:
2Bi3+ + 3Cr ( s) 2Bi( s) + 3Cr 2+

There are two types of equilibria associated with a galvanic cell:


Equilibrium between two half-cells Equilibrium within each half-cell
In the right cell, the following reaction can take place:
AgCl( s) Ag+ (aq) + Cl (aq)

Cells as Probes

This can be divided into two half reactions:


2Bi3+ + 6e 2Bi( s) 3Cr 2+ + 6e - 3Cr ( s )
E+ = 0.308 V E - = 0.89 V

E = E+ E = 0.308 (0.89) = 1.198 V

The Ksp reaction in the half-cell is in equilibrium The cell can be thought of as an analytical probe for H+, since it is the only species we do not have a concentration for.

K = 10

nE 0.05916

= 10

(6)(1.198) ( 0.05916 )

= 3 10121!

Tough Problems
You can have some tough problems (the book calls them brainbusters) involving electrochemistry, equilibrium, solubility, and acid-base chemistry. I havent assigned those, but in case you were to face this, you should know generally how to tackle them
1) Write half-reactions and potentials 2)Write Nernst equation for the net reaction and put in all the knowns. 3) Solve for that unknown and plug it into the equilibrium equation for the problem

Redox Reactions in Biochemistry


Many redox reactions are important in biochemistry, especially in respiration Biochemists use a the term of formal potential, meant to define potentials under conditions of biochemistry Formal potential is given the abbreviation E

Important Biochemical Reactions

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