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"In phenol, pulling the $p_z$ electrons from the oxygen atom into the ring causes the hydrogen atom to be more partially positive than it is in aliphatic alcohols. This means it is much more easily lost from phenol than it is from aliphatic alcohols, so phenol has a stronger acidic property than ethanol"

Could someone please explain the link between the $p_z$ electrons of oxygen overlapping with the cloud of delocalised electron of the phenol ring and the increase in positivity of the bonded hydrogen... which in turns allows phenol to lose a proton more easily

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If there's one thing to be learned from the nice question and the answers, it is: Draw, draw, draw :) Keep a pen ready and draw resonance structures on paper, beer mats, etc. –  Klaus Warzecha Mar 10 '14 at 8:37

2 Answers 2

In fact I find more simple reasoning with resonance structure. When phenol lose the $H^{+}$ the phenolate ion is stabilized due the resonance effect. The energy of the dissociated form is lower and so the phenol has more chance to be in the solution dissociated with the phenolate ion. Aliphatic alcohol are not stabilized by resonance so they are not very prone to be dissociated. enter image description here

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+1 for doing what I was to lazy to do before the next coffee: drawing! –  Klaus Warzecha Mar 10 '14 at 8:16

The effect is indeed amazing, if you compare the $pK_a$ of tert-butanol (17.0) with that of phenol (9.95).

Deprotonation is facilitated when the reaction goes downhill (energywise). In order to obtain stabilization of the anion, the negative charge needs to be distributed over a larger number of centres. This distribution (only) is possible if the participating orbitals overlap in space.

So, which orbitals may play a role here? On the one hand, there is the $\pi$ system of the benzene, formed from the $p_z$ orbitals on the carbon atoms. On the other hand, there's the $p_z$ on the oxygen with the same spatial orientation.

Now, can we get comparable molecules, more acidic than phenol itself?

The answer is yes, if we allow further substituents that (a) pull the negative off the oxygen by inductive effects or (b) even allow for a further distribution of the negative charge by additional resonance.

resonance of picric acid

An impressive example for the latter is 2,4,6-trinitrophenol, also known as picric acid with a $pK_a$ of 0.29.

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@GM You are right :) It's indeed Pikrinsäure in German. I corrected the mistake. –  Klaus Warzecha Mar 10 '14 at 8:08
Good to know, I'm trying to learn german! :-) –  G M Mar 10 '14 at 8:14
@GM This is off-topic, but anyway: The Deutsche Welle international broadcasting service had some nice lectures (audio samples and study material) for free. –  Klaus Warzecha Mar 10 '14 at 8:21
Vielen Dank! I will use it! –  G M Mar 10 '14 at 8:29

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