What is the relationship between ΔG, ΔH, and ΔS in thermodynamics?

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Discussion Overview

The discussion centers on the relationship between the Gibbs free energy (ΔG), enthalpy (ΔH), and entropy (ΔS) in thermodynamics. Participants explore theoretical implications, clarify concepts, and address specific scenarios related to phase changes and heat transfer in solutions.

Discussion Character

  • Exploratory
  • Technical explanation
  • Conceptual clarification
  • Debate/contested
  • Mathematical reasoning

Main Points Raised

  • One participant suggests that the expression for ΔG simplifies to ΔG = 0, questioning the validity of this conclusion and seeking clarification on the formal proof of free energy.
  • Another participant notes that ΔS_sys = -ΔH_surr/T applies only for reversible processes and states that ΔG = 0 during reversible phase changes.
  • Concerns are raised regarding the treatment of mass when calculating temperature change in a solution, specifically whether to include the mass of dissolved ammonia.
  • A participant corrects the previous claim that ΔG is zero for all reversible processes, providing an example of isothermal expansion of an ideal gas where ΔG = RTln(P2/P1).
  • There is acknowledgment that the heat capacity of the solution changes when ammonia is dissolved, which may affect calculations.

Areas of Agreement / Disagreement

Participants express differing views on the conditions under which ΔG equals zero, particularly regarding reversible processes and specific scenarios like phase changes. The discussion remains unresolved with multiple competing perspectives on the implications of the equations presented.

Contextual Notes

Limitations include assumptions about reversibility, the specific conditions under which ΔG is evaluated, and the potential impact of changing heat capacities in solutions. These factors are not fully resolved in the discussion.

MathewsMD
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If ##ΔG_{sys} = ΔH_{sys} - TΔS_{sys}; ΔS_{sys} = \frac {-ΔH_{surr}}{T} ##

Then, doesn't this expression just simplify to:

##ΔG_{sys} = ΔH_{sys} + ΔH_{surr}## and isn't ##ΔH_{sys} = -ΔH_{surr}##?

So then ##ΔG = 0##...this does not seem correct...could anyone please clarify my mistake and the formal proof of free energy if it differs from the one I have shown?

Also, what is the explanation for why there is no free energy change during phase changes? I was merely told this without any explanation and one would be very helpful.

Finally, just a related question:

If you have 1 gram of ammonia and it dissolves in 50 grams of water to release 1000 J (just hypothetical). When calculating the temperature change of the water, using q = mcΔT, is m = 50g or 51g since the ammonia is now aqueous and inseparable from the water. Yet, it has slightly different properties now. I am unsure if it is treated just like a normal sample of water or not.
 
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ΔS_sys = -ΔH_surr/T only for reversible processes, and it is true that ΔG = 0 for any reversible process.

If the phase changes are occurring reversibly (e.g. melting at the melting point, boiling at the boiling point), then ΔG = 0 for the reason above.

For the last question, if you are really worried about an exact answer, you would also have to take into account that the heat capacity of the solution changes when you dissolve ammonia in it.
 
Ygggdrasil said:
ΔS_sys = -ΔH_surr/T only for reversible processes, and it is true that ΔG = 0 for any reversible process.

If the phase changes are occurring reversibly (e.g. melting at the melting point, boiling at the boiling point), then ΔG = 0 for the reason above.

For the last question, if you are really worried about an exact answer, you would also have to take into account that the heat capacity of the solution changes when you dissolve ammonia in it.
ΔG is not equal to zero for any arbitrary reversible process. For example, in the isothermal expansion of an ideal gas, ΔG=RTln(P2/P1).
 
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Chestermiller said:
ΔG is not equal to zero for any arbitrary reversible process. For example, in the isothermal expansion of an ideal gas, ΔG=RTln(P2/P1).

You are right, I also should have specified any isobaric (constant pressure) reversible process. Chemists usually take the isobaric assumption for granted since most of our chemical reactions are performed at constant (atmospheric) pressure. Thanks for the correction.
 

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