Does ΔG° for reactions vary by temperature?

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Discussion Overview

The discussion revolves around the variation of Gibbs free energy (ΔG°) with temperature, particularly in the context of a chemistry assignment requiring calculations at 90°C. Participants explore the implications of temperature on ΔG° and its relationship to standard conditions.

Discussion Character

  • Debate/contested
  • Conceptual clarification
  • Exploratory

Main Points Raised

  • Some participants assert that ΔG° is defined at standard conditions, typically at 25°C, leading to confusion about its variability with temperature.
  • Others question whether ΔG° is indeed temperature independent or if it can vary, especially when considering calculations at different temperatures.
  • One participant suggests that the superscript "°" might not encompass all standard conditions, proposing that it could refer only to standard pressure.
  • Another participant speculates that internal energy (ε) might not vary with temperature, which could influence the interpretation of ΔG°.
  • A later reply discusses the relationship between ΔG and equilibrium constants (K), suggesting that ΔG° must vary with temperature based on the equation ΔG = ΔG° + R*T*ln(K).
  • One participant clarifies the distinction between internal energy and Gibbs free energy, emphasizing their different roles in thermodynamics.

Areas of Agreement / Disagreement

Participants express differing views on whether ΔG° is constant at standard conditions or if it varies with temperature. There is no consensus on the implications of these variations or the definitions involved.

Contextual Notes

Participants note potential ambiguities in definitions and the implications of temperature on Gibbs free energy and internal energy, but these remain unresolved within the discussion.

Nikitin
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I thought it was only ΔG which varied by temperature,with the equation ΔG = ΔH - TΔS ?

It makes no sense to me why ΔG° (= change of gibbs free energy at standard conditions during a reaction) should vary with temperature, but I've gotten an assignment here to calculate ε° for a reaction at 90°C (ε is a function of ΔG), which suggests that ΔG° does indeed vary!

How can this be? I thought Gibbs free energy at standard conditions was always constant, with the temperature being 25°C?
 
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ΔG° at 90°C, when ΔG° is defined for 25°C - something doesn't add in what you wrote.
 
Is ΔG° for a reaction defined at 25 degrees, or is it temperature independent? This is what I am unsure about..
 
Nikitin said:
Is ΔG° for a reaction defined at 25 degrees, or is it temperature independent?

Defined at 25°C if you ask me.

Not that I am always right when it comes to thermodynamics.
 
Nikitin said:
I thought it was only ΔG which varied by temperature,with the equation ΔG = ΔH - TΔS ?

It makes no sense to me why ΔG° (= change of gibbs free energy at standard conditions during a reaction) should vary with temperature, but I've gotten an assignment here to calculate ε° for a reaction at 90°C (ε is a function of ΔG), which suggests that ΔG° does indeed vary!

How can this be? I thought Gibbs free energy at standard conditions was always constant, with the temperature being 25°C?

Conjectures:
1) Maybe the superscript "°" doesn't represent all "standard conditions." Maybe "°" in this case it only represents "standard pressure".

Maybe ε° is the internal energy at standard pressure. Maybe the temperature is allowed to vary for internal energy.

2) Maybe in your system the internal energy, ε, doesn't vary with temperature. Maybe it only varies with pressure.

Just because ΔG varies with both temperature and pressure doesn't mean that the internal energy has to vary with both temperature and pressure. The variation with temperature may be subtracted out.

I admit number 2 is a bit of more speculative then the other one. It would take a strange equation of state to make the internal energy NOT vary with temperature. Number 1 is just a matter of convention. Not everyone is careful with the use of subscripts.

By the way: I am used to seeing internal energy designated by "ΔU", not "ΔG". I had to go through Wikipedia to find out that ε sometimes represents internal energy.
 
Maybe the exact text of the assignment would be helpful.
 
It was asking for the emf° (=ε°) at 90°C for a certain reaction. ε is the international sign for emf in chemistry, right?

Anyway, I think delta G does indeed vary by temperature. According to this equation, (ΔG = ΔG°+R*T*ln(K), at equilibrium ΔG° = -R*T*ln(K). This implies ΔG°=0 when K=1 at equilibrium, thus ΔG° must vary with temperature (since it can be both 0 and other values, depending on K). Can anyone see the flaw in my reasoning?

Indeed, when K=1 then all the substances in the equilibrium have an activity of 1. This means that ΔG = ΔG° only when that is the case (or if T=0).

Darwin123: Internal energy (=U) and G are two entirely different things. Internal energy represents the energy of the molecules (=1.5*R*T for an ideal gas), G represents energy free to do work during reversible processes. Enthalpy is a function of U. H = U + P*V. Gibbs free energy is a function of H, T and S. G = H - T*S
 
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