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Separation of ions that spontaneously convert to each other

Posted: Thu Sep 05, 2019 6:20 pm
by Telesforo Bruni
Is an ionic chromatograph able to separate ionic species that are in equilibrium with each other?
What exactly happens when an ion that is in equilibrium with other ionic species (e.g. hydrogen phosphate with dihydrogen phosphate, chromate with dichromate) moves through a separation column?

Re: Separation of ions that spontaneously convert to each other

Posted: Fri Sep 06, 2019 4:54 am
by Markus Laeubli, Metrohm
Dear Telesforo Bruni

It is not possible to separate e.g. hydrogen phosphate and dihydrogen phosphate or similar.
These ionic forms depend on the pH of the solution. When the sample is injected to the eluent, the eluent's pH defines the ratio of the two species. Elution takes place according to the "charge" of the ion (i.e. 1.5 if the ratio is 1:1).

Re: Separation of ions that spontaneously convert to each other

Posted: Sat Sep 07, 2019 10:16 am
by Telesforo Bruni
Thus the same ion while it is in one form runs through the column at a certain speed, while it is in the other form at another speed, but the result at the end is that all the species in equilibrium with each other come out at the same time and produce only a single peak.
The rate of the ion mixture is given by the mean, weighed on the concentrations at the pH of the eluent, of the rates at which the individual ionic forms flow.
If the ion is in equilibrium with a non-ionic form (e.g. completely protonated acid), then this molecule has the same velocity as the eluent, being without charge.

Is that right?

Re: Separation of ions that spontaneously convert to each other

Posted: Sat Sep 07, 2019 7:57 pm
by tom jupille
To phrase it in a slightly different way: in effect, a compound at its own pKa spends half the time ionized and half the time neutral, but because the rate of interconversion is orders of magnitude faster than the rate of migration through the column, it behaves as though it has a fractional charge.

Re: Separation of ions that spontaneously convert to each other

Posted: Sat Oct 05, 2019 1:26 am
by jimhart
You can't separate e.g. hydrogen phosphate and dihydrogen phosphate or similar.
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Re: Separation of ions that spontaneously convert to each other

Posted: Fri May 08, 2020 10:36 pm
by LuisM
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