4-Bromophenol vs 4-aminophenol pKa in water comparison confusion Recently the other week, I was asked the following question:


  Would you expect 4-aminophenol to have a higher or lower pKa than 4-
  bromophenol when measured in water? 


And I thought about this on the way home, and decided to try and justify this using resonance. 



My feeling was that Nitrogen couldn't handle 4 bonds and an extra lone pair on its atom, so the negative charge won't leave the benzene ring, whereas the Bromine could handle the double bond (I might have been mistaken with the negative charge on the Bromine - if so, do let me know please.)

Using this, I thought that this is the reason why 4-aminophenol would have a higher pKa than 4-bromophenol as its resonance form is not as extended as Bromine's, which is at a lower energy level to be able to handle the extra negative charge, plus all the carbons in the ring have 4 bonds as normal. 

Is this a correct answer and justification?
Answer to this question is, as orthocresol pointed out, simpler than what you think. As you know, $\ce{-Br}$ is deactivate the ring (even though it is o,p-directing) while $\ce{-NH2}$ is great ring activator. What that means is regardless of the mesomeric effect, compared to $\ce{-H}$, $\ce{-Br}$ is overall electron withdrawing and $\ce{-NH2}$ is electron donating (remember, $\ce{-NH2}$ is a Lewis base). 

Said that, I'd say basically, $\mathrm{pH}$ of a phenol ($\mathrm{p}K_\mathrm{a} = 9.95$) is depended on how stable phenolate ion is after it donated $\ce{H+}$. Electron withdrawing groups stabilize phenolate ion (e.g., $\ce{-NO2}$ group, p-nitrophenol: $\mathrm{p}K_\mathrm{a} = 7.1$) while electron donating groups destabilize it (e.g., $\ce{-OCH3}$ group, p-methoxyphenol: $\mathrm{p}K_\mathrm{a} = 10.2$). Thus, one can expect that p-bromophenol should have a lower $\mathrm{p}K_\mathrm{a}$ than that of phenol (meaning more acidic than phenol) while  p-aminophenol should have a higher $\mathrm{p}K_\mathrm{a}$ than that of phenol (meaning more basic than phenol). This is true in reality. Actual $\mathrm{p}K_\mathrm{a}$ values of p-bromophenol  and  p-aminophenol are $9.34$ and $10.3$, respectively ($9.34 \lt 9.95 \lt 10.3$).

Sources for $\mathrm{p}K_\mathrm{a}$ values: Evans pKa Table and Wikipedia.