What is the relationship between temperature and Gibbs free energy?

In summary, the equation \Delta G = \Delta H - T \Delta S is used to describe the free energy change of a reaction. An endothermic reaction with a positive \Delta S_{system} can be spontaneous at higher temperatures because T\Delta S out-competes the enthalpy term and makes \Delta G negative. However, the temperature cannot change the sign of \Delta G. The equation also assumes that the reaction is spontaneous and that the heat transfer is reversible. Therefore, varying T to test for spontaneity is not possible.
  • #1
Ahmed Abdullah
203
3
[tex]\Delta G = \Delta H - T \Delta S [/tex]

I don't understand this equation satisfactorily.
I have learned so far that endothermic reaction having a positive [tex]\Delta S_{system}[/tex] is spontaneous at higher temperature because [tex]T\Delta S[/tex] out-compete the enthalpy term and make the free energy change negative.
But I don't understand why [tex]T\Delta S _{sorrounding}[/tex] should not increase with temperature as [tex]T\Delta S _{system}[/tex] does.
Clearly [tex]\Delta H[/tex] =[tex]-T\Delta S _{sorrounding}[/tex]
so we can rewrite the gibbs free energy equation
[tex]\Delta G= -T\Delta S _{sorrounding} - T\Delta S _{system}[/tex]
[tex]\Delta G = -T ( \Delta S _{sorrounding} + \Delta S _{system})[/tex]

if [tex]\Delta S _{sorrounding}[/tex] and [tex]\Delta S _{system}[/tex] both are constant then the sign of [tex]\Delta G[/tex] is independent of temperature. If [tex]\Delta G[/tex] is positive increasing temperature just make it more positive and If [tex]\Delta G[/tex] is negative increasing temperature just make it more negative. Temperature cannot change the sign.
I know I must be missing something. Please help!

A[tex]^{ }_{A}[/tex]
 
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  • #2
When you use the equation to describe isolated system you don't have to worry about the rest of the Universe.
 
  • #3
Borek said:
When you use the equation to describe isolated system you don't have to worry about the rest of the Universe.

But I need to know why?
Isn't Del H = -T*Del S (sorrounding)? Clearly it is a function of T, then why it would be unaltered by temperature {but T*Del S (system) is altered}?
 
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  • #4
Ahmed Abdullah said:
Clearly [tex]\Delta[/tex] H = -T[tex]\Delta[/tex]S[tex]^{ }_{sorrounding}[/tex]

Not clearly. That equation only holds if you have a very large heat bath surrounding the system with the same temperature T, so that all heat transfer is reversible. It's important to make this distinction.

But that is a side point. The key issue is this: if you're writing [itex]\Delta H=T\Delta S^\mathrm{surr}[/itex], you're already assuming that the reaction is spontaneous; otherwise energy would not be transferred. And when you write [itex]\Delta G= -T\Delta S^\mathrm{surr} - T\Delta S^\mathrm{sys}[/itex], you're assuming that it's barely spontaneous, that [itex]\Delta G=0[/itex]. Otherwise more energy would be present from the spontaneous forward reaction.

So you can no longer vary T and ask whether the reaction is spontaneous!
 

Related to What is the relationship between temperature and Gibbs free energy?

What is Gibb's free energy?

Gibb's free energy is a thermodynamic property that measures the amount of energy available to do useful work in a system at a constant temperature and pressure.

How is Gibb's free energy related to spontaneity?

Gibb's free energy is related to spontaneity through the equation ΔG = ΔH - TΔS. If ΔG is negative, the reaction or process is spontaneous. If ΔG is positive, the reaction or process is non-spontaneous. If ΔG is zero, the reaction or process is at equilibrium.

What is the difference between ΔG and ΔG°?

ΔG is the change in Gibb's free energy for a reaction under non-standard conditions, while ΔG° is the change in Gibb's free energy for a reaction under standard conditions (1 atm pressure, 25°C temperature, 1 M concentration). ΔG° is often used as a reference point to determine the spontaneity of a reaction.

Why is Gibb's free energy sometimes confused with entropy?

Gibb's free energy and entropy are both related to the spontaneity of a reaction, but they measure different things. Gibb's free energy takes into account both the enthalpy and entropy of a system, while entropy only measures the disorder or randomness of a system. This can lead to confusion, as a reaction may have a positive ΔS (more disorder) but a negative ΔG (spontaneous).

Can Gibb's free energy be negative at a non-standard temperature and pressure?

Yes, Gibb's free energy can be negative at non-standard conditions if the reaction has a negative ΔH and a positive ΔS. This means that the reaction may not be spontaneous under standard conditions, but at a different temperature and pressure, the change in enthalpy and entropy may favor a spontaneous reaction.

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