ptlmayank
Harmless
Posts: 5
Registered: 17-11-2010
Member Is Offline
Mood: No Mood
|
|
method to check PH of methanol
what is the method to check the pH of methanol
|
|
|
madscientist
|
Thread Moved
17-11-2010 at 03:54 |
not_important
International Hazard
Posts: 3873
Registered: 21-7-2006
Member Is Offline
Mood: No Mood
|
|
A pH meter.
|
|
|
unionised
International Hazard
Posts: 5126
Registered: 1-11-2003
Location: UK
Member Is Offline
Mood: No Mood
|
|
Why do you want to check the pH of methanol?
Just for a start, pure methanol does not have a pH of 7.
True pH measurements in non aqueous media are an absolute pain, using a pH meter is more likely to damage the pH probe than to give you the right
answer..
|
|
|
1281371269
Hazard to Others
Posts: 312
Registered: 15-5-2009
Member Is Offline
|
|
If you know the concentration of the MeOH in M and can find the Ka online then you can calculate it.
|
|
|
BromicAcid
International Hazard
Posts: 3246
Registered: 13-7-2003
Location: Wisconsin
Member Is Offline
Mood: Rock n' Roll
|
|
How precise do you need the pH? Neutral litmus paper will give you a quick 'is it acidic or is it basic' heads up.
|
|
|
Ozone
International Hazard
Posts: 1269
Registered: 28-7-2005
Location: Good Olde USA
Member Is Offline
Mood: Integrated
|
|
Quantitatively mix in some water, and titrate the stuff. This will give you "titrable acidity" rather than "pH" (which is only defined in water,
anyway). [H+] can be back-calculated.
Keep in mind that, in pure MeOH, the pKa of the hydroxyl proton which will be the limiter, e.g. a strong enough base is required to make the alkoxide
or a strong enough acid is required to protonate the hydroxyl. This may yield a base, for example NaOMe, which is far stronger base than the
corresponding NaOH created by quenching the mixture in water.
This is however, routine protocol for catalyst prep (and determination of free fatty acids in used food-oils) in the manufacture of biodiesel, etc.
Cheers,
O3
-Anyone who never made a mistake never tried anything new.
--Albert Einstein
|
|
|
Nicodem
Super Moderator
Posts: 4230
Registered: 28-12-2004
Member Is Offline
Mood: No Mood
|
|
The pKa of methanol is quite close to that of water, so for diluted aqueous solutions of methanol you can safely assume the pH is still very close to
neutral (pH 7). With very accurate measurements you should see some difference, perhaps on at the second decimal point, but then even plain distilled
water hardly gives an exact pH 7.00 measurement as any little contaminant can very easily alter that. For higher concentrations of methanol you can
not truly speak of pH any more, because the pH is defined for aqueous solutions only (for example, a "70% aqueous solution of methanol" is not really
aqueous any more).
Quote: Originally posted by Ozone  | | Keep in mind that, in pure MeOH, the pKa of the hydroxyl proton which will be the limiter, e.g. a strong enough base is required to make the alkoxide
or a strong enough acid is required to protonate the hydroxyl. This may yield a base, for example NaOMe, which is far stronger base than the
corresponding NaOH created by quenching the mixture in water. |
Contrary to popular belief, this is not true. In water, the methoxide ion is a very slightly weaker base than hydroxide (though admittedly the
difference is small - hydroxide is only 1.6-times more basic than methoxide). However, in methanol/ethanol the hydroxide ion is substantially more
basic than the methoxide/ethoxide (there is a thread in the General section where a paper on exact measurements was posted). Also in general, in most
organic solvents, due to the obvious solvation and polarizability reasons, the alkoxide ions of primary alcohols are always less basic than the
hydroxide ion.
[Edited on 20/11/2010 by Nicodem]
…there is a human touch of the cultist “believer” in every theorist that he must struggle against as being
unworthy of the scientist. Some of the greatest men of science have publicly repudiated a theory which earlier they hotly defended. In this lies their
scientific temper, not in the scientific defense of the theory. - Weston La Barre (Ghost Dance, 1972)
Read the The ScienceMadness Guidelines!
|
|
|
unionised
International Hazard
Posts: 5126
Registered: 1-11-2003
Location: UK
Member Is Offline
Mood: No Mood
|
|
' "pH" (which is only defined in water, anyway)'
"For higher concentrations of methanol you can not truly speak of pH any more, because the pH is defined for aqueous solutions only "
Why do people think that the log of the reciprocal of the hydrogen ion activity is only defined in aqueous solutions?
It's a pig to measure in, for example, methanol, but it's not impossible.
|
|
|
spirocycle
Hazard to Others
Posts: 197
Registered: 29-9-2010
Member Is Offline
Mood: No Mood
|
|
why is this?
methanol isn't particularly corrosive
|
|
|
Ozone
International Hazard
Posts: 1269
Registered: 28-7-2005
Location: Good Olde USA
Member Is Offline
Mood: Integrated
|
|
This discussion makes it clear that "simple"concepts such as pH are not "clear" at all. I have attached a nice paper which, at least, clearly defines
the problem.
[Nicodem]The pKa of methanol is quite close to that of water, so for diluted aqueous solutions of methanol you can safely assume the pH is still very
close to neutral (pH 7). With very accurate measurements you should see some difference, perhaps on at the second decimal point, but then even plain
distilled water hardly gives an exact pH 7.00 measurement as any little contaminant can very easily alter that.
Correct, distilled/deionized water will abscond with ions from wherever, e.g. particles in the air, etc. The lack of ions canalso "confuse" a standard
pH probe. Mine (18 MO) reads acidic at
6.8, or so, but has essentially zero buffering capacity (a topic for a separate discussion).
[Nicodem]For higher concentrations of methanol you can not truly speak of pH any more, because the pH is defined for aqueous solutions only (for
example, a "70% aqueous solution of methanol"
is not really aqueous any more).
I did point out that pH is defined in aqueous solution. This is why I recommended that it be diluted, eg. 1:1. I then recommended titration because I
don't like the use of "pH" with respect to non-aqueous solvents; "titrable acidity" is a normalizing metric. However, in methanol, in particular (as
you point out, see discussion below), the pH probe will likely suffice. This is not so true, though, in other solvents that may destabilize anions
leading to much greater
basicity, e.g. DMSO.
I should have taken greater care to point out that, from
http://en.wikipedia.org/wiki/Acid_dissociation_constant :
"When a compound has limited solubility in water it is common practice (in the pharmaceutical industry, for example) to determine pKa values in a
solvent mixture such as water/dioxane or water/methanol, in which the compound is more soluble.[27] In the example shown at the right, the pKa value
rises steeply with increasing percentage of dioxane as the dielectric constant of the
mixture is decreasing.
A pKa value obtained in a mixed solvent cannot be used directly for aqueous solutions. The reason for this is that when the solvent is in its standard
state its activity is defined as one. For example, the standard state of water:dioxane 9:1 is precisely that solvent mixture, with no added solutes.
To obtain the pKa value for use with aqueous solutions it has to be extrapolated to zero co-solvent concentration from values obtained from various
co-solvent mixtures."
Which was the extrapolated correction I was alluding to earlier. At least the hydrolysis of methoxide, if it exists in that mixture, will normalize
(mole-wise) to hydroxide in water, which we can measure with some confidence, despite the required correction.
[Nicodem]Contrary to popular belief, this is not true. In water, the methoxide ion is a very slightly weaker base than hydroxide (though admittedly
the difference is small - hydroxide is only 1.6-times more basic than methoxide). However, in methanol/ethanol the hydroxide ion is substantially more
basic than the methoxide/ethoxide (there is a thread in the General section where a paper on exact measurements was posted). Also in general, in most
organic solvents, due to the obvious solvation and polarizability reasons, the alkoxide ions of primary alcohols are always less basic than the
hydroxide ion.
Oops. Yes, this is true (my reference cites 1.8 times and pKa water = 15.7, MeOH = 15.5).
The definition of a superbase(http://en.wikipedia.org/wiki/Superbase ) can get you into trouble
and even advanced organic chemistry neglects to mention hydroxide in non-aqueous environments, it's simply, "strong base", of which methoxide is the
simplest case.
Methoxide cannot exist in water (that I know of) because it hydrolizes to yield NaOH. Thus, the practical comparison of basicity of MeO- to -OH in
water is moot.
So, I'll agree that if hydroxide can exist, in the dissociated state, in Methanol [which it appears to do, albeit in small concentrations (I can't
find a decent reference for this), which appear relative to a very small amount of contaminating water], it would be a greater base than methoxide.
I'll posit, then, that the basicity (or acidity) is limited by the concentration and activity of the active species in the media in which it is
measured, so long as it can exist in measurable concentration.
At any rate, for methanol dilute (greater than 40 mol %--from attached paper) with water and use a probe or titrate. Correct [H+] for dilution and
recalculate "pH".
Thanks,
O3
Attachment: Abrash 2001.pdf (84kB)
This file has been downloaded 1053 times
-Anyone who never made a mistake never tried anything new.
--Albert Einstein
|
|
|
unionised
International Hazard
Posts: 5126
Registered: 1-11-2003
Location: UK
Member Is Offline
Mood: No Mood
|
|
Well, since it almost certainly won't work it's more likely to damage it than to work.
The glass membrane that acts as a sensing medium for most pH probes is designed to be used wet with water. That's why you shouldn't let them dry out.
Putting it in methanol will dry it very quickly.
Also, all this discussion about dilute solutions of methanol is probably off-topic since the original question was about methanol, not water with a
bit of methanol in it.
|
|
|
![[*]](images/xpblue/default_icon.gif){kind=icon}
