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Author: Subject: Gibbs free energy
guy
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[*] posted on 20-2-2006 at 13:15
Gibbs free energy


I am trying to find the ΔG for Zn --> Zn2+ + 2e- at 298K.
ΔH for Zn(s) = 0 kJ/mol
ΔS for Zn(s) = 41.63 J/K

ΔH for Zn2+ = -153.9 kJ/mol
ΔS for Zn2+ = -112.1 J/mol

I plugged the values in the equation ΔG = ΔH - TΔS
ΔG = (-153.9-0) - 298(-112.1-41.63)(1/1000)
ΔG = -108.1 kJ

The problem is that the real value is -147.6 kJ.

I cannot find what I am doing wrong. Any help is appreciated.




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Darkblade48
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[*] posted on 20-2-2006 at 14:39


Instead of using ΔG = ΔH - TΔS (you cannot use this equation), you must use

ΔG = -nFE instead (where F is Faraday's Constant and E is the potential).

You can find E for Zn --> Zn2+ + 2e- in any standard reduction potential table.
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guy
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[*] posted on 20-2-2006 at 14:44


Yeah I am aware of that equation too. That's where I got the real value from. The point is I wanna see if they match.



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[*] posted on 20-2-2006 at 22:07


I'm with you guy. I don't know why they don't agree.

I agree that the value calculated from the half-cell voltage is correct since it agrees with the Gibb's free energy of formation for Zn2+.

I tried this with Cu --> Cu2+ + 2e- . Same problem here. :o




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Darkblade48
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[*] posted on 20-2-2006 at 22:42


Does it have something to do with having to find H and S for electrons? When you are using the G = H - TS formula, you don't take into account the electrons?
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guy
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[*] posted on 20-2-2006 at 23:46


Yeah, I think there is SOMETHING missing here. Could be electrons, or ionization energy, etc.

Do people usually find Eo by calculations or experiement anyways?

[Edited on 2/21/2006 by guy]




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[*] posted on 28-2-2006 at 10:30


Yes that is some problem that stumped me some time ago.

Half cell EMF is relative to the standard H electrode, so it will not agree with Gibb's free energy. If you subtract two half cell potentials it should work (but don' forget about the number of electrons!)

S and H are not straightforward either as H is relative to a standard state (element 298 K 1 bar) and S is absolute (zero for a perfect crystal at zero kelvin).
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