Ion exchange and stability constants

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Discussion Overview

The discussion revolves around a homework problem involving ion exchange and stability constants, specifically focusing on the binding of fulvic acid to calcium in natural water. Participants explore the calculations needed to determine the fraction of fulvic acid bound to calcium, considering various chemical equilibria and constants.

Discussion Character

  • Homework-related
  • Mathematical reasoning
  • Technical explanation

Main Points Raised

  • One participant outlines the problem and initial calculations regarding the concentrations of calcium and fulvic acid binding sites, expressing confusion about the relevance of certain reactions.
  • Another participant points out that the conditional stability constant is likely applicable at pH 5.0 and suggests that the dissociation constant for fulvic acid may not be necessary for the calculations.
  • There is a discussion about the notation used for fulvic acid and its dissociated forms, with some participants suggesting that Org- and A- may refer to the same species.
  • One participant expresses uncertainty about whether to calculate hydrogen ion concentration and whether the focus should be solely on the ratio of calcium fulvic acid complex to total fulvic acid.
  • A participant calculates the stability constant but finds that the resulting concentration of the calcium-fulvic acid complex exceeds the total binding sites, indicating a potential error in their approach.
  • Another participant advises considering the mass balance of fulvic acid and suggests rearranging the stability constant expression to isolate the desired ratio.

Areas of Agreement / Disagreement

Participants express varying levels of understanding regarding the necessary calculations and the relevance of certain constants. There is no consensus on the correct approach to the problem, and multiple viewpoints on the necessary steps remain evident.

Contextual Notes

Participants note the potential confusion arising from the notation and the assumptions regarding the dissociation of fulvic acid. The discussion highlights the complexity of the chemical equilibria involved and the need for clarity in the definitions used.

Who May Find This Useful

This discussion may be useful for students studying chemistry or environmental science, particularly those interested in ion exchange processes and stability constants in natural water systems.

Maharg
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Homework Statement


In natural water containing 0.9 mmol/L calcium and 12 ug/L fulvic acid, determine the
fraction of the fulvic acid that is bound to calcium (i.e. the ratio between the concentration of Ca-FA and total concentration of FA binding sites), assuming that calcium is the only metal presentin a significant concentration.

The pH of the water is 5.0, the conditional stability constant Kf (Ca-FA) is 1.2x103 and the
binding sites on FA is 5 mmol/g.

Homework Equations



FA = H+ + Org-

Org- + Ca2+ = Org-Ca2+

H2O = H+ OH-

Told to find ratio Ca-Org-/Org-

The Attempt at a Solution



Found concentration of FA binding sites = 60 umol/L
then concentration H+ = 50 umol/L
and Ca2+ = 900 umol/L

The professor told us we'll need those reactions but I'm unsure why we need the Water reaction.

Also confused how to get A- as we don't know the equilibrium constant for Fa = H+ + Org- and I've looked it up to see if fulvic acid is strong to find out if it dissociates completely. I don't the next step. If someone could just suggest how I properly do the next step.

I think I have to eventually do Kf = Org-Ca2+/[Org-][Ca2+]
 
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Your notation is hard to follow, as it is inconsistent (FA, Org-, A- - I can guess what you mean, but it distracts).

You are given conditional stability constant - most likely for a pH 5.0. If so, you don't need information about fulvic acid dissociation constant.

--
 
The reactions I listed were given by my professor when I asked him for help and it left me a bit more confused. I assumed he just meant Org- is same as A-.

Do I need to calculate H+? I am just looking for Ca2+Fa/Fa right?\

DO I just calculate Kf = Ca2+FA/[FA][Ca2+]

I also want to thank you Borek you've helped me a few times in the past before and I appreciate it.
 
Maharg said:
I assumed he just meant Org- is same as A-.

Probably.

Do I need to calculate H+? I am just looking for Ca2+Fa/Fa right?

DO I just calculate Kf = Ca2+FA/[FA][Ca2+]

That's my bet - go from here, ignoring pH and fulvic acid protonation. Just take care:

Maharg said:
Found concentration of FA binding sites = 60 umol/L

That's not the number I got.

I also want to thank you Borek you've helped me a few times in the past before and I appreciate it.

You are welcome.
 
My answer isn't making sense.

I did the calculations. So I had

Kf = [CaFA]/[Ca2+][FA]

1.2E3 = [CaFA]/ (0.9E-3)(6E-8)

= 6.5E- 5 mol/L

But this is higher than my FA value. Somehow I'm coming up with more Ca-FA binds then total binding sites. What step am I missing?
 
You are not taking into account mass balance of fulvic acid.

But you don't have to calculate concentration of neither complex nor free fulvic acid! See if you can rearrange Kf expression to get ratio on one side.

--
 

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