Influence of temperature on spontaneous process

A spontaneous process is a chemical reaction in which a system releases free energy (most often as heat) and moves to a lower, more thermodynamically stable, energy state. The sign convention of changes in free energy follows the general convention for thermodynamic measurements, in which a release of free energy from the system corresponds to a negative change in free energy, but a positive change for the surroundings.

Thus, for a reaction at constant temperature and pressure where

ΔG = ΔH - TΔS
a negative ΔG would depend on the sign of the changes in enthalpy (ΔH), entropy (ΔS), and the magnitude of the absolute temperature (in kelvins). Changes in the sign of ΔG cannot be changed directly by temperature, because it can never be less than zero.

When ΔS is positive and ΔH is negative, a process is spontaneous

When ΔS is positive and ΔH is positive, a process is spontaneous at high temperatures, where exothermicity plays a small role in the balance.

When ΔS is negative and ΔH is negative, a process is spontaneous at low temperatures, where exothermicity isimportant.

When ΔS is negative and ΔH is positive, a process is not spontaneous at any temperature, but the reverse process is spontaneous.

1 comment:

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