What Is the Standard Potential for Tl2S Reduction?

AI Thread Summary
The discussion centers on calculating the standard potential for the reduction of Tl2S to Tl and S^2-. The initial attempt used the Nernst equation but raised confusion regarding the correct concentration terms and logarithmic calculations. Participants clarified that the K_sp value should be applied correctly, emphasizing the need to solve for [Tl+] in relation to [S^2-]. After several iterations, the final calculation yielded a standard potential of approximately -0.984 V, although there was ongoing debate about the signs and logarithmic arguments used in the Nernst equation. Ultimately, the conversation highlighted the importance of precise algebra and understanding of electrochemical principles in solving such problems.
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Homework Statement



From the standard potential Tl^+ + e^- -----> Tl (solid) E^o= -0.336 V

Determine the standard potential of
Tl_2S (solid) + 2e^- -----> 2Tl (solid) + S^2^-

Given that the K_sp for Tl_2S is 1.2x10^-22

***I cannot get latex to put the -22 in the exponent. The Ksp is 1.2 * 10 ^-22

Homework Equations



Nernst Equation

E = E^o -(0.05916/n) log(concentration)

The Attempt at a Solution




E = -0.336 -(0.05916/2) log (1.2x10^-22)

E = +0.312

Im wondering if the log (1.2x10^-22) should be log (1/1.2x10^-22)
because the concentration is the products over the reactants. Can someone point me in the right direction? Thanks
 
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10^{-22} = 10^{-22}

Write Kso formula for Tl2S and solve for [Tl+].
 
Borek said:
10^{-22} = 10^{-22}

Write Kso formula for Tl2S and solve for [Tl+].

OK BOREK! You have given me some insight. Thank you! Products over reactants. and because the reactants are solid, they will be in the denominator as the number 1. Ok I was able to come up with the following calculation. I would be much appreciated if someone could confirm for me the accuracy. Thanks!

Calculate the standard potential (E_{total}) of

Tl_2S (solid) + 2 e^- = 2Tl (solid) + S^{2-}

given that the K_{sp} of Tl_2S is 1.2x10^{-22}

E_{total} = E_{Tl^+/Tl} + E_{ksp} = -0.336 + (0.05916/2) * log(1.2x10^{-22})

E_{total} = -0.336 + (-0.648) = -0.984

so my answer is -0.98 when using significant figures due to the Ksp being 2 sig figs...right?
Look good?
 
No. Do what I told you to do.
 
Borek said:
10^{-22} = 10^{-22}

Write Kso formula for Tl2S and solve for [Tl+].

Kso formula

Tl_2S = 2Tl^+ (aq) + S^- (aq)

1.2x10^{-22} = {[Tl^+]^2[S^-]}/[{Tl_2S}]

Tl_2S is a solid so we can remove it from the equation giving me

1.2x10^{-22} = {[Tl^+]^2[S^-]}

So this is where I get confused... is the correct way to do it this:

1.2x10^{-22} = {[x]^2[x]}

x = 4.9 x 10^{-8}
 
Solve for Tl+. Not for some x, you are not trying to find out concentration of saturated solution (which you did wrong BTW - concentrations are different, not identical), but concentration of Tl+ as a function of Kso and [S2-].
 
Borek said:
Solve for Tl+. Not for some x, you are not trying to find out concentration of saturated solution (which you did wrong BTW - concentrations are different, not identical), but concentration of Tl+ as a function of Kso and [S2-].

Borek thank you so much for your help on this problem and that other problem I posted. Borek I am going to level with you... I am very confused. I thought I knew what a Kso was (something to do with solubility) but I don't know much more than that. In post # 3 (my first reply) I did something similar to what a TA did on a similar problem and I was following his steps. I am guessing that the problem is where i am taking the log but I really am not positive.

Can you give me a little bit more of a bump in the right direction please? Thanks.
 
Looks like you have problems with simple algebra.

K_{so} = [Tl^+]^2[S^{2-}]

Solving for [Tl+]:

[Tl^+]=\sqrt \frac {K_{so}} {[S^{2-}]}

Now put [Tl+] concentration into the original equation. As the question asks about standard potential, sulfide activity is 1.
 
Borek said:
Looks like you have problems with simple algebra.

K_{so} = [Tl^+]^2[S^{2-}]

Solving for [Tl+]:

[Tl^+]=\sqrt \frac {K_{so}} {[S^{2-}]}

Now put [Tl+] concentration into the original equation. As the question asks about standard potential, sulfide activity is 1.
Ok ok ok...

<br /> E_{total} = E_{Tl^+/Tl} + E_{ksp} = -0.336 + (0.05916/2) * log(\sqrt {1.2x10^{-22}})<br /> ?

This would give
E_{total} = -0.66 ?
 
  • #10
Electrode reaction is still Tl+ + e- -> Tl...
 
  • #11
Borek said:
Electrode reaction is still Tl+ + e- -> Tl...

omg did i do that honestly


E_{total} = E_{Tl^+/Tl} + E_{ksp} = -0.336 + (0.05916) * log(\sqrt {1.2x10^{-22}})

= -0.984

Look good now?
 
  • #12
Better, but still wrong. What sign in Nernst equation if it contains concentration of oxidized form?
 
  • #13
Borek said:
Better, but still wrong. What sign in Nernst equation if it contains concentration of oxidized form?

It would make it negative wouldn't it?

E_{total} = E_{Tl^+/Tl} + E_{ksp} = -0.336 + (\frac {.05916}{-1}) * log(\sqrt {1.2x10^{-22}})

= 0.312 volts

with sig figs making the answer 0.31 volts

This has to be correct this time. (btw thanks you have been unknowingly teaching me latex as well!)
 
  • #14
Oops, sorry. You have been juggling signs and log argument and at about 1 a.m. you've lost me. -0.984 was OK. Still, your original Nernst equation

ssb said:
E = E^o -(0.05916/n) log(concentration)

is incorrect, as long as it doesn't state concentration of what.

E = E_0 + \frac {RT} {nF} ln {\frac {[Ox]} {[Red]}}

if reduced form is solid, it simplifies to

E = E_0 + \frac {RT} {nF} ln {[Ox]}

or

E = E_0 + \frac {0.05916} {n} log {[Ox]}
 
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