Why is the standard entropy of aqueous ions negative?

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The standard entropy of aqueous ions, such as PO32- (aq) with an entropy of -220 J/K·mol, is defined relative to the entropy of hydrogen ions (H+), which is set to zero. This negative value arises because ions in solution exhibit fewer microstates compared to a perfect crystal at 0 K, leading to a lower entropy state. The convention for standard entropies of ions contrasts with that of electrically neutral substances, which are defined relative to their crystalline state at absolute zero. The sign of standard entropy does not correlate with the signs of standard Gibbs free energy (ΔGf) or standard enthalpy (ΔHf).

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Nikitin
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Why is the standard entropy of aqueous ions negative? I thought it could be no less than 0, which represents a perfect crystal at 0 K?

Is it negative so that calculations can be performed properly? Or is it because it because ions solutes actually have less entropy than a perfect crystal?
 
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Nikitin said:
Or is it because it because ions solutes actually have less entropy than a perfect crystal?

This, I think. Remember what entropy is about (things not wanting to be "pure", basically).
what's the problem statement, anyway?
 
Nikitin said:
Why is the standard entropy of aqueous ions negative?

Do you mean the standard entropy of hydration?
Maybe you could refer to the source of the values you are considering?
 
No, the standard entropy.

For example, PO32- (aq) has an entropy of -220J/K*mol. it's the same with many other ions in aqueous solutions. Why? Is it because ions floating in water are extremely restricted in their number of micro-states?
 
I am not familiar to the concept of standard entropies for ions. Maybe you can give a reference?
 
Standard entropies for ions are defined by convention as relative the the hydrogen as taken to be zero.

Standard entropies for electrically neutral substances are defined to be relative to the crystal state at 0°K

so S* for common hydrogen related species is

H2 130.6
H 114.6
H2O 188.7
OH 183.6
H+ 0
OH- -10.8

all in J/degreee K moles
Hf
Note also that the sign of S* does not follow that of ΔGf or ΔHf, the standard energies of formation, which may also be positive or negative.
 
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