Nernst Equation with Pressure Differences

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SUMMARY

The discussion focuses on the application of the Nernst equation, specifically addressing pressure differences in electrochemical reactions. The equation is presented as E = E_t + (RT/nF)ln((P/P_0)^{Δη_G}), where Δη_G represents the change in the number of moles. The user seeks clarification on the stoichiometry of the hydrogen-oxygen reaction, particularly how the value of -1.5 for Δη_G is derived. The conversation highlights the distinction between gaseous and liquid reactants, emphasizing that only gaseous substances impact Δη_G due to their volume changes.

PREREQUISITES
  • Understanding of the Nernst equation and its components
  • Basic knowledge of stoichiometry in chemical reactions
  • Familiarity with gaseous versus liquid reactants in thermodynamics
  • Concept of chemical equilibrium constants Kp and Kc
NEXT STEPS
  • Study the derivation of the Nernst equation in electrochemistry
  • Explore stoichiometric calculations for gas-phase reactions
  • Learn about the relationship between Kp and Kc in chemical equilibria
  • Investigate the impact of pressure on reaction equilibria and volume changes
USEFUL FOR

Chemistry students, electrochemists, and researchers involved in thermodynamics and reaction kinetics will benefit from this discussion.

James Brady
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I'm working with the Nernst equation with pressure differences right now:

## E = E_t + \frac{RT}{nF}ln ((P/P_0)^{\Delta \eta_G})##

I'm assuming pure reactants here so, so I'm omitting the product terms: ##\frac{\Pi_{products} x_i ^{\nu_i}}{\Pi_{reactants} x_i ^{\nu_i}}## which would normally also go in the logarithm.

according to my solutions manual:
##\Delta \eta_G = \nu_P - \nu_R##

##\Delta \eta_G## is referred to as "the change in the number of moles" and it looks like the value should be -1.5. However, I'm not sure how they would get that from the stoichiometry of the hydrogen-oxygen reaction:

##H_2 + \frac{1}{2}O_2 = H_2 O##

##1 H_2 O - (1 H_2 + \frac{1}{2}O_2) = -0.5 ## less moles overall. I'm not sure how they got -1.5. I'm not sure what "nu" is for products and reactants and it's real meaning.
 
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It is the same problem as the difference between Kp and Kc and how to convert between them. \Delta \eta_G takes into account only gaseous substances, as it is related to the change in volume of the reaction mixture (and water, being liquid with volume orders of magnitude lower, can be safely ignored).
 
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Ah gotcha, I guess that makes sense now.
 

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