How Do You Calculate E°cell Values for Galvanic Reactions?

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Discussion Overview

The discussion revolves around calculating the standard cell potential (E°cell) for a galvanic reaction involving iodate (IO3-) and iron (Fe2+). Participants explore the half-reactions, the values of standard reduction potentials, and the relationship between Gibbs free energy and cell potential. The scope includes theoretical calculations and the derivation of E° values from known reactions.

Discussion Character

  • Technical explanation
  • Mathematical reasoning
  • Debate/contested

Main Points Raised

  • One participant presents the unbalanced reaction and calculates E°cell using the formula E°cell = Ecathode - Eanode, identifying half-reactions for Fe3+/Fe2+ and IO3-/I2.
  • Another participant questions how the E° value of +1.19 V for the IO3- to I2 reaction was obtained, noting that it was found online and not in standard tables.
  • A detailed derivation is provided by a participant, showing how to relate the E° of the desired reaction to other known reactions, including the use of Gibbs free energy equations.
  • Some participants express confusion about the validity of relating ΔG values from different reactions and seek clarification on the operations used to derive the final equation.
  • There is a discussion about the correctness of summing reactions and how to simplify them to arrive at the final balanced equation.

Areas of Agreement / Disagreement

Participants do not reach a consensus on the derivation of the E° value for the IO3- to I2 reaction, and there are differing views on the validity of the mathematical operations used to relate ΔG values from different reactions.

Contextual Notes

Some participants express uncertainty regarding the assumptions made in the derivation process, particularly about the relationship between ΔG values and how to correctly sum reactions. The discussion highlights the dependence on specific definitions and the need for clarity in the mathematical steps involved.

salman213
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I needed to find the E°cell (always positive for a galvanic cell), based on the following (unbalanced) reaction:

IO3-(aq) + Fe2+(aq) --> Fe3+(aq) + I2(s)

So E°cell = Ecathode - Eanode

I made the half reactions

Fe3+ (aq) ---> Fe2+(aq)
EØ = +0.77 V (i found this reaction in my table)

IO3-(aq) ---> I2(s)
balanced the 2nd one to

12 H + 2IO3 + 5e- ---> I2 + 6H2O
EØ = I cannot find this value in that table
I FOUND IT ONLINE ON A WEBSITE TO BE EØ = +1.19V, HOW DID THEY GET THIS VALUE! Anyone know?
 
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salman213 said:
I needed to find the E°cell (always positive for a galvanic cell), based on the following (unbalanced) reaction:

IO3-(aq) + Fe2+(aq) --> Fe3+(aq) + I2(s)

So E°cell = Ecathode - Eanode

I made the half reactions

Fe3+ (aq) ---> Fe2+(aq)
EØ = +0.77 V (i found this reaction in my table)

IO3-(aq) ---> I2(s)
balanced the 2nd one to

12 H + 2IO3 + 5e- ---> I2 + 6H2O
EØ = I cannot find this value in that table
I FOUND IT ONLINE ON A WEBSITE TO BE EØ = +1.19V, HOW DID THEY GET THIS VALUE! Anyone know?
2IO3-(aq) + 10Fe2+(aq) + 12H+ --> 10Fe3+(aq) + I2(s) + 6H2O;
E° = +1.19 - 0.77 = +0.42V.

About the reaction:

(1) 2IO3-(aq) + 12 H+ + 10e- ---> I2(s) + 6H2O

You can find its E° if you know the E° of other similar reactions from which you can get that one, for example:

(2) IO3-(aq) + 6H+ +6e- --> I- + 3H2O;_______>E°(2) = +1.08V
(3) I2(s) + 2e- --> 2I- ;____________________>E°(3) = +0.53V

Reaction (1) is given by: 2*Reaction(2) - Reaction(3) and so:

Delta G°(1) = 2*Delta G°(2) - Delta G°(3)

Now you use the equation: Delta G° = -nF*Delta E° where n is the number of electrons of the reaction, so you have:

-10F*Delta E°(1) = 2*[-6F*Delta E°(2)] - [-2F*Delta E°(3)]

10*Delta E°(1) = 12*Delta E°(2) - 2*Delta E°(3)

Delta E°(1) = (1/10)[12*Delta E°(2) - 2*Delta E°(3)] =

= (1/5)[6*Delta E°(2) - Delta E°(3)] =

= (1/5)[6*1.08 - 0.53] = +1.19V.
 
Last edited:
wowi would never have that of that...:S


how is the delta G of the first equation equal to the delta G if the second and third with those operations. Like how do we know to relate delta G?
 
salman213 said:
wowi would never have that of that...:S


how is the delta G of the first equation equal to the delta G if the second and third with those operations. Like how do we know to relate delta G?

Do you agree on the fact that Reaction (1) is given by 2*Reaction(2) - Reaction(3) ?

2*Reaction(2) = 2IO3-(aq) + 12H+ +12e- --> 2I- + 6H2O

- Reaction(3) = 2I- --> I2(s) + 2e-

Now you sum them:

2IO3-(aq) + 12H+ +12e- + 2I- --> 2I- + 6H2O + I2(s) + 2e-

you simplify canceling 2I- and 2e- on both members:

2IO3-(aq) + 12H+ +10e- --> 6H2O + I2(s).


About summing ΔG: if you have

(1) A --> B you know that ΔG(1) = G(B) - G(A)

(2) C --> D you know that ΔG(2) = G(D) - G(C)

(3) A + C --> B + D you know that ΔG(3) = G(B + D) - G(A + C)

But G(B + D) - G(A + C) = G(B) + G(D) - G(A) - G(C) =

= G(B) - G(A) + G(D) - G(C) = ΔG(1) + ΔG(2)
 

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