Ksp from electrochemistry setup

In summary, the conversation discusses the calculation of the Ksp for Ag2SO4(s) in an electrochemical cell with a Pb and Ag electrode. The voltage of the cell is 0.83V and the concentration of Pb2+ is 1.8M. The attempt at a solution involves using the Nernst equation and considering the equilibrium concentrations of Ag+ ions. However, discrepancies in the calculations suggest that the initial state of the system may impact the results. Separate Nernst equations are also mentioned for each half cell.
  • #1
roundedcanuck
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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 teh left and the Ag on teh 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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  • #2
Write separate Nernst equations for both half cells.
 
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1. What is Ksp?

Ksp, or solubility product constant, is a measure of the maximum amount of solute that can dissolve in a solvent at a given temperature. It is a measure of the solubility of a compound in a solution.

2. How is Ksp related to electrochemistry setup?

Ksp is related to electrochemistry setup because it can be determined using electrochemical methods. By measuring the potential of a solution containing the solute and its ions, the Ksp value can be calculated.

3. Can Ksp be affected by temperature changes?

Yes, Ksp is highly dependent on temperature. As temperature increases, the solubility of a compound generally increases, resulting in a higher Ksp value.

4. How does Ksp differ from Ksp'?

Ksp and Ksp' are both measures of solubility, but Ksp' is only applicable to slightly soluble compounds, while Ksp is applicable to any compound. Ksp' takes into account the formation of complexes, while Ksp does not.

5. How can Ksp be used to predict the formation of a precipitate?

If the product of the ion concentrations in a solution exceeds the Ksp value, then a precipitate will form. This is because the concentration of the ions is higher than the maximum amount that can dissolve, and so the excess ions will form a solid precipitate.

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