How to Calculate Ksp for Ag2SO4 Using Electrochemistry?

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SUMMARY

The calculation of the solubility product constant (Ksp) for Ag2SO4 using electrochemical principles involves a lead (Pb) and silver (Ag) electrode setup. The standard reduction potentials are E(Ag+/Ag) = 0.8V and E(Pb2+/Pb) = -0.13V. The Nernst equation is applied to determine the Ksp, resulting in an erroneous concentration of [Ag+] = 65.9M, indicating a miscalculation in the setup or assumptions. The discussion emphasizes the need to correctly identify the anode and cathode and to consider the system's equilibrium state before adding solid Ag2SO4.

PREREQUISITES
  • Understanding of electrochemical cells and their components
  • Familiarity with the Nernst equation and its application
  • Knowledge of standard reduction potentials
  • Basic concepts of solubility product constants (Ksp)
NEXT STEPS
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  • Learn about the principles of electrochemical cell design and function
  • Research the solubility product constant (Ksp) calculations for different salts
  • Explore the effects of concentration changes on electrochemical equilibrium
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Chemistry students, electrochemists, and anyone involved in analytical chemistry or materials science who seeks to understand the calculations related to solubility and electrochemical systems.

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Homework Statement



An electrochemical cell is made up of a Pb and an Ag electrode:
Ag+ + e --> Ag(s) E = 0.8V
Pb2+ + 2e --> Pb(s) E = -0.13V

Calculate the Ksp for Ag2SO4(s).
"Note that to obtain ions in the right compartment, excess silver sulfate solid was addded and a small amount of it dissoved"
There is a picture of the cell, showing the Pb electrode on the left and the Ag on the right, a voltage of 0.83V and a concentration of 1.8 M Pb2+


Homework Equations



Ksp = [Ag+]^2 * [SO42-]
E = E(ox) + E(red)
E = Eo + (RT/nF)lnQ

The Attempt at a Solution



lead should be the anode, silver the cathode, so E = +0.93V

0.83V = 0.93V + (8.314*298/(2*96,485) ln(1.8/[Ag+]^2)
*no temperature was given, so 298 K was used*
ln(1.8/[Ag+]^2) = -7.789
[Ag+] = 65.9M

this is way too big, so something must be wrong in the of this solution

making lead the cathode and silver the anode doesn't seem to work

it seems that the reason that there is a voltage is that the system went from being at an equilibrium concentration of Ag+ ions (with no voltage) to a voltage of 0.83V when the solid was added, and the Ag+ concentration went up. there is no data on this initial state, but the ratio of Pb to Ag ions can be found...
 
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Write separate Nernst equations for both half cells.
 
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