Gibbs free energy and entropy inconsistency

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Discussion Overview

The discussion centers around the relationship between Gibbs free energy (ΔG), entropy (ΔS), and enthalpy (ΔH) in the context of a specific chemical reaction. Participants explore the implications of calculated values for these thermodynamic quantities at a given temperature, addressing questions of spontaneity and the conditions under which reactions occur.

Discussion Character

  • Homework-related
  • Technical explanation
  • Conceptual clarification
  • Debate/contested

Main Points Raised

  • The original poster calculated ΔG, ΔS, and ΔH for a reaction at 298.15 K and noted a contradiction regarding the signs of ΔG and ΔS in terms of spontaneity.
  • Some participants suggest that reactions can be driven by either entropic or enthalpic factors, indicating that the relationship between ΔG and ΔS is not straightforward.
  • One participant clarifies that ΔS in the Gibbs free energy equation reflects only the change in entropy of the system, not the surroundings, which may explain the observed results.
  • A later reply emphasizes the importance of temperature units, noting that for thermodynamic equations, temperature should be in Kelvin.

Areas of Agreement / Disagreement

Participants express differing views on the relationship between ΔG and ΔS, with some arguing that the signs should be opposite while others provide explanations for why they may not be. The discussion remains unresolved regarding the implications of these calculations for spontaneity.

Contextual Notes

There is an assumption that the temperature must be in Kelvin for the calculations, but this is not universally agreed upon without explicit clarification from the source of the empirical equation.

Who May Find This Useful

This discussion may be useful for students and practitioners in chemistry and thermodynamics who are grappling with the concepts of Gibbs free energy, entropy, and enthalpy, particularly in the context of reaction spontaneity and temperature considerations.

MexChemE
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Homework Statement


For a certain reaction, ΔG = 13580 + 16.1 T log10(T) - 72.59 T. Find ΔS and ΔH for the reaction at 298.15 K.

Homework Equations


ΔG = ΔH - TΔS
\left[\frac{\partial (\Delta G)}{\partial T} \right]_P = - \Delta S

The Attempt at a Solution


For the sake of this thread's length I won't write too much details, I'm having a very specific question about the solutions of this problem.

First I calculated ΔG plugging T = 298.15 K into the given function and got ΔG = 3815.11 cal. Now, this result is telling me the reaction is non-spontaneous. Fine.

Then I calculated ΔS by differentiating the ΔG function and plugged T = 298.15 K in order to get ΔS = 25.76 cal K-1. This result is telling me the reaction is spontaneous. Both results are given by the textbook and are correct. I also plugged the numeric values of ΔS and ΔG into ΔH = ΔG + TΔS and got ΔH = 11495.45 cal, which is also a correct solution according to the textbook.

Aren't the signs of ΔG and ΔS supposed to be opposite, according to the spontaneity criteria? Thanks in advance for any input!
 
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MexChemE said:
signs of ΔG and ΔS supposed to be opposite
A reaction can be "entropically driven," or, it may be "enthalpically driven." No big deal. Entropically driven examples, vaporization, solution, mmmm ---- what else? Enthalpically driven, oxidation, solidification, anything that gets hot. Throw sulfuric acid into water and watch enthalpy and entropy at work. Dilute a concentrated sodium chloride solution and watch entropy at work and enthalpy opposing the process (it cools, at room T).
 
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A reaction is spontaneous if it results in an increase in the entropy of the universe (i.e. the system and its surroundings). The ΔS in the equation reflects only the change in entropy of the system. For a reaction at constant temp and pressure, the enthalpy will be proportional to the change in entropy of the surroundings (with more negative ΔH leading to a larger increase in entropy). Thus, if a reaction increases the entropy of the system at the expense of the entropy of the surroundings (by converting thermal energy into chemical potential energy), the reaction can still be non-spontaneous overall.
 
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Ygggdrasil said:
The ΔS in the equation reflects only the change in entropy of the system.

I was ignoring this little detail, now I can be at peace again. Thank you both!
 
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In my question the temperature given is 27°C.. should I just go ahead with the same temperature or should I convert it into Kelvin?
 
If you are given an empirical equation like this:
MexChemE said:
ΔG = 13580 + 16.1 T log10(T) - 72.59 T.
the source should tell you whether T is in °C or K. Sometimes it's one, sometimes the other. If the question asks "Find ΔS and ΔH for the reaction at 298.15 K" then presumably T is in K for this equation.
For fundamental thermodynamic equations like ΔG = ΔH - TΔS, T is always in K.
 

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