[Catalist] Buffers Chemistry Query

Fri May 19 21:35:51 AEST 2017

UPDATE: It seems I am out of date. In 2014, Korean authors Choi et al 
(in the journal The Journal of Physical Chemistry Letters 2014(5) 
2568-2572) show that H3O+ moves through solution by proton exchange 
("proton hopping"), while hydroxide ion moves by regular Brownian 
diffusion. Conventional wisdom held that both moved by proton exchange 
up until that time. My training is out of date :)   !!

We teach our students that OH- will react with H2PO4-, as it is the 
highest concentration instead of H3O+. We also teach that as H2PO4- is a 
stronger acid, it will react with OH-. We do not consider that the other 
potential acid, HPO4 2- will react with OH-, as despite being present in 
equimolar amounts as H2PO4-, it is a weaker acid. When you consider what 
it means by weaker acid (ie dissociates less into H3O+), it makes you 
wonder what exactly is reacting with the OH- added. Without taking 
actual measurements, really who knows? Chemical techniques allow us to 
measure concentrations and amounts directly, from which we infer 
reaction rates. It would be hard to measure. Dueterated H2PO4- added to 
a solution of HPO4 - and some sort of NMR measurement as tritiated OH- ? 
Hard to do, and you would need some kind of stopped-flow cell to capture 
the kinetics? I don't know, I am not skilled in this area and have 
little idea of the limits of this sort of technology.

Perhaps in this question we are best to teach what the syllabus 
requires, but in the back of our minds it is probably good to flag this 
one as not yet experimentally determined.

Cheers,
Leon

On 17/05/2017 12:19 PM, leon wrote:
> Hi. In and of itself, you cant tell. Due to the lesser mass of OH- 
> versus H2PO4- , its velocity at a given temp will be higher an hence 
> all others equal you would expect oh to react. Add To this that oh may 
> move through solution fasteR than it can diffuse via "proton hopping" 
> where oh exchanges protons with water and you end up with oh moving 
> close to the speed of the proton diffusion.
>
> Against this, you have higher conc of h2po4- . I think both should be 
> acceptable, as at this level we dont do rate constants, and without 
> them you cant really answer.
>
> And whatever the rate both reactions will occur to at least some 
> extent. cheers leon
>
> Sent from my Samsung Galaxy smartphone.
>
> -------- Original message --------
> From: Karen Johnson <kjohnson at sjgs.wa.edu.au>
> Date: 17/5/17 9:52 am (GMT+08:00)
> To: catalist at lists.stawa.net
> Subject: [Catalist] Buffers Chemistry Query
>
> ATTENTION: Chemistry Teachers
>
> I was wondering if someone could give a clear cut answer on buffers. I 
> have spoken to a couple of experienced Chemistry teachers and they 
> both have validated my concerns with this type of buffer question and 
> informed me to post my concerns. I want to make sure that I am 
> teaching buffers correctly with the concept of adding in hydroxide 
> ions in case is ever comes up in the WACE exam.
>
> Let’s say you have the following buffer below. Can someone explain to 
> me what happens when hydroxide ions are added to this buffer? Does it 
> react more with H_2 PO_4 ^–  (aq)  or H_3 O^+ (aq) and therefore which 
> equation forward or reverse is favoured more? From my understanding, I 
> believe it would react with the H_2 PO_4 ^–  (aq)  as there is a 
> greater concentration of this acid in the buffer compared to H_3 O^+ 
> (aq). Although hydroxide ions can react with hydronium it does this to 
> a lesser extent and has less effect.
>
> *H_2 PO_4 ^–  (aq) +   H_2 O (l)   ⇌   HPO_4 ^2–  (aq) +   H_3 O^+ (aq)*
>
> I have looked through the last 5 years worth of WACE papers and there 
> is literally only this question (see attached 2012 WACE question) that 
> discusses this type of question. Most buffer questions in the WACE 
> exams are the more straight forward ones, in which they ask about how 
> the effect of adding a small amount of acid to a buffer equation that 
> has hydronium ions already. I know that the Essential Chemistry book 
> is stating that the hydroxide ions react with the hydronium ions but 
> take a look at the WACE exam and is begs to differ!!
>
> This question in the 2012 WACE exam does look at it in question (f). I 
> presume that the first equation in (f) links to the first equation in 
> (e). This shows that hydroxide ions react with the acid and not the 
> hydronium ions.
>
> If anyone could give me a clear cut answer to this question so I can 
> make sure I am teaching this correct, it would be greatly appreciated.
>
> Looking forward to your responses.
>
> Kind regards,
>
> Karen
>
> 	
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> Karen Johnson
> Science Teacher
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