Examining the Equilibrium Constant for an Ideal Gas Mixture

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SUMMARY

The discussion focuses on deriving the equilibrium constant K(T) for the reaction AB <--> A + B in an ideal gas mixture. The relationship established is n_{AB}/(n_A n_B) = V (f_{AB}/(f_A f_B)), where V is the system volume and f_i are the single-particle partition functions. The Helmholtz free energy is mentioned as a critical component, but its application in this context is unclear to some participants. The solution involves using the grand canonical partition function to express n_A in terms of the chemical potential and partition function.

PREREQUISITES
  • Understanding of ideal gas laws and gas mixtures
  • Familiarity with partition functions in statistical mechanics
  • Knowledge of Helmholtz free energy and its significance
  • Concept of chemical potential in thermodynamics
NEXT STEPS
  • Study the derivation of the grand canonical partition function
  • Explore the application of Helmholtz free energy in equilibrium systems
  • Learn about the law of mass action in chemical reactions
  • Investigate examples of calculating equilibrium constants for gas reactions
USEFUL FOR

This discussion is beneficial for students and researchers in physical chemistry, particularly those studying thermodynamics and statistical mechanics, as well as anyone involved in chemical reaction dynamics and equilibrium analysis.

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Homework Statement


Consider an ideal-gas mixture of atoma A, atoms B and molecules AB, undergoing the reaction AB <---> A+B. If n_A, n_B, and n_{AB} denote their respective concentrations, then show that, in equilibrium

\frac{n_{AB}}{n_A n_B} = V \frac{f_{AB}}{f_A f_B} = K(T)

(the law of mass action)

Here, V is the volume of the system while the f_i are the respective single-particle partition functions; the quantity K(T) is generally referred to as the equilibrium constant of the reaction.


Homework Equations





The Attempt at a Solution



I got the partition function of the system and I got the Helmholtz free energy. The problem is that I just don't know what to do with the Helmholtz free energy i.e. do I minimize it, mazimize it, set it equal to something? Why? Pathria and my other textbook do little more than define it. They never say what to do with it or give any example of how it is useful!
 
Last edited:
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anyone?
 
Sorry for the slow reply. You should be able to show

n_A = e^{\mu_A\beta}\frac{f_A}{V}

straight from the grand canonical partition function (taking the appropriate derivative of \ln \mathcal Z). The desired result then follows from showing the chemical potentials cancel out.
 

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