sign up

Chemistry Stack Exchange log in

Questions Tags Users Badges Unanswered Ask

Read this post in our app!

8 Why is methanol more acidic than water?

acid-base water

Methanol is slightly more acidic than water. Their pKa values, in water, are
15.5 and 15.7, respectively. All other aliphatic alcohols, however, are less
acidic than water.
Is the following reasoning correct? This is my best rationalization; is there
anything better or anything that can be added?

In both hydroxide and methoxide, we have an O bearing negative charge. In

the former, we have a hydrogen attached to the O. In the latter, we have a
carbon attached to the O. Carbon is more electronegative than hydrogen,
therefore, carbon should be able to better withdraw electron density via
induction from the O. This is a stabilizing interaction.

We often think of methyl groups as inductively donating, but that's molecular

proling. They can inductively donate to a carbocation, partly because a
carbocation is highly electronegative, so the carbocation pulls the electrons
toward itself pretty well (so there's both pushing and pulling of electrons going
on). When you have a methyl group attached to an O, however, the methyl
group is often inductively withdrawing. NMR data supports this.

Now the question is why aren't other aliphatic alcohols more acidic than water?
In longer-chain aliphatic alkoxides, you don't just have a methyl group
attached to the O bearing the negative charge - you have a bunch of methyl
groups strung together. These lessen the amount of inductive withdrawal that
the alpha carbon can do. EachCH2 unit attached to the alpha CH2 is
somewhat inductive donating to the alpha CH2 .

share improve this question

Dissenter Asked
4,626 5 35 128 Dec 21 '15 at 6:24

ringo Edited
9,544 2 25 59 May 4 at 7:36

3 The pKa of water is 14.0 so it is more acidic than methanol.

chemwiki.ucdavis.edu/Organic_Chemistry/Fundamentals/ MaxW Dec 21 '15 at
6:34
 @MaxW - well, that opens up a whole new can of worms because I do see the 15.7
value cited a lot. ;) Time for another question? Dissenter Dec 21 '15 at 6:53

1 There are also a lot of reports that aliens have attacked Earth. Doesn't make it so...
MaxW Dec 21 '15 at 7:18

[H+ ][OH ]
14 14.0 is log([H+ ][OH ]); 15.7 is log . Ivan Neretin Dec 21 '15 at
[H2 O]
7:45

@IvanNeretin but can we say that the activity of water is its concentration? That is,
we are determining the pka of water in water-so shouldn't we use the activity of
water? Aditya Anand Dec 21 '15 at 16:19

add a comment

1 Answer Order By Votes

 The relative acidities of these molecules in the aqueous solution[1][2]
6 is:

methanol > water > ethanol > isopropanol > t-butanol

The relative acidities of these molecules in DMSO[3] is:

methanol > ethanol > isopropanol > t-butanol > water

The problem with only considering the acidities of these molecules in
aqueous solution is that it assumes only one explanation for acidity.
The inversion of the order of acidity in DMSO indicates that there are
multiple factors at play.

The acidity trend in DMSO is explained by polarizability and the

anionic hyperonjugation eect[4] of the conjugate bases of the
molecules. The larger size of the alkyl substituents in the conjugate
bases allows for increased distribution of negative charge over a
larger volume. This reduces the charge density, and thereby the
Coulombic repulsion between the conjugate base and the solvent. In
DMSO, water is much less acidic than even methanol, which is also
consistent with the relative polarizability of a methyl group and a
hydrogen atom, but fails to explain the relative acidity of t-butanol
and methanol.

The trend in alcohol acidity is explained by anionic hyperconjugation,

which is weakened in larger alkyl substituents.

For methanol and the methoxide anion, the primary interaction occurs
between a lled lone-pair (n) orbital on oxygen and an unoccupied Me

orbital of the methyl group, resulting in a two-electron stabilizing eect.

Deprotonation of the alcohol leads to an increase in the energy of the n

orbitals on oxygen, and a decreased energy separation between the
, and hence a greater stabilizing
interacting orbitals n and Me
interaction[5]
share improve this answer

ringo Answered
9,544 2 25 59 May 4 at 5:28

Edited
May 4 at 19:02

2 Water is a complicated substance. Water molecules solvated by water are

anomalously acidic due to unusual stabilization of the conjugate base ( OH ) by very
strong hydrogen bonds. Water in a non-aqueous solvent (especially aprotic solvents)
suers a decrease in acidity by many orders of magnitude more than one might
expect. Here is a relevant past answer of mine, with a nice source. Nicolau Saker
Neto May 4 at 12:26

add a comment

Your Answer

log in

or

Name

Email

By posting your answer, you agree to the privacy policy and Post Your Answer
terms of service.

meta chat tour help blog privacy policy legal contact us full site
Download the Stack Exchange Android app
2016 Stack Exchange, Inc