Using entropy to solve for Free Gibbs energy

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SUMMARY

The discussion centers on calculating Gibbs free energy (dG) for a perfect gas undergoing isothermal expansion from 5.00 atm to 1.00 atm. The user calculated dG as -3.99 kJ using the equation dG = dH - TdSsys, but the expected answer is +3.98 kJ. The confusion arises from the use of dSsur instead of dSsys in the Gibbs free energy equation for reversible processes. The correct approach confirms that dG should indeed be calculated using dSsys, leading to the conclusion that the user’s calculation is incorrect due to a misunderstanding of the thermodynamic definitions involved.

PREREQUISITES
  • Understanding of thermodynamic principles, specifically Gibbs free energy.
  • Familiarity with the concepts of entropy (dSsys and dSsur).
  • Knowledge of isothermal processes and their characteristics.
  • Ability to perform calculations involving the ideal gas law and related equations.
NEXT STEPS
  • Review the derivation and application of the Gibbs free energy equation in thermodynamics.
  • Study the differences between system and surroundings entropy in thermodynamic processes.
  • Learn about isothermal expansion and its implications on work (w) and heat (q) in thermodynamic systems.
  • Explore examples of reversible and irreversible processes to solidify understanding of entropy changes.
USEFUL FOR

Students studying thermodynamics, particularly those preparing for exams in physical chemistry or related fields, as well as educators looking to clarify concepts of Gibbs free energy and entropy.

jtruth914
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1.00 mol of perfect gas at 25 C is expanded isothermally from an initial pressure of 5.00 atm to a final pressure of 1.00 atm in two ways:(a) reversibly (b) against a constant external pressure of 1.00 atm. Calculate the values for q, w, dU, dH, dG, dSsys, dSsur, dStot for each path.
(I pretty much know how to calculate all of them, but for Gibbs free energy for part (a) I got a different answer. I got -3.98kJ, but the answer is +3.98kJ. The only way I can get that is if I plug in dSsur in the dG equation instead of dSys. Do you use dSsur to get dG for an isothermal reversible process? I thought dG= dH-TdSsys Please explain.) Thanks.

This is what I did to solve for (a)

w= -nRT ln Vf/Vi
w= -3.98 kJ

q= -w for isothermal process b/c dU is equal to 0 so q=+3.98kJ

dU=0
dH= dU + d(nRT), for isothermal process T=0
Thus, dH=0

dSsys= q/T= 3.98kJ/298 K= +13.39 J/K

dSsur= -13.39 J/K

This is where my problem is

dG= dH-TdS
dG= 0-(298K)(13.39J/K)
dG= -3.99 kJ <----- this is what I got, but my professor's answer to this problem is positive. I think he used dSsur, but I don't understand why? Isn't Gibbs free energy in regards to the "system" ?
 
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Haha maybe you are in my class because I have an exam tomorrow and I was just working on this problem and also cannot figure out how he got a positive answer for G in part a either. I am hoping he made a mistake because I really don't understand why it would be positive.
 

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