PH of weak acid/weak base salts

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Discussion Overview

The discussion revolves around the pH of solutions formed from salts of weak acids and weak bases, specifically focusing on calcium carbonate (CaCO3). Participants explore the behavior of calcium ions and carbonate ions in water, comparing their contributions to the acidity or basicity of the solution.

Discussion Character

  • Technical explanation
  • Debate/contested
  • Mathematical reasoning

Main Points Raised

  • One participant argues that CaCO3 is basic due to the behavior of Ca2+ and CO32- in water, suggesting that the equilibrium of the carbonate reaction will dominate.
  • Another participant challenges the first reaction proposed, stating that calcium hydroxide is fairly soluble and that Ca2+ acts as a spectator ion, thus questioning the relevance of the first equation.
  • A third participant disputes the correctness of both proposed reactions, asserting that the first reaction incorrectly implies that a strong base would produce H3O+, and presents an alternative equilibrium involving hydrated calcium ions.
  • Further contributions include specific pK values for calcium hydroxide and carbonic acid, as well as a calculated pH for a saturated CaCO3 solution, indicating a basic nature.
  • One participant notes that the final pH will vary due to the increased solubility of CaCO3 influenced by hydrolysis, although they suggest that the contribution from Ca2+ can be neglected.

Areas of Agreement / Disagreement

Participants express differing views on the behavior of calcium ions and the validity of the proposed reactions. There is no consensus on the correctness of the reactions or the implications for the pH of the solution.

Contextual Notes

Participants reference specific pK values and solubility data, but there are unresolved assumptions regarding the behavior of calcium ions in solution and the applicability of the proposed reactions.

dumuzi
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I'm trying to show my students that [itex]CaCO_3[/itex] is basic.
[itex]Ca^2^+[/itex] comes from [itex]Ca(OH)_2[/itex], which is a weak base due to it's low solubility. [itex]CO_3^2^-[/itex] comes from the weak acid [itex]HCO_3^-[/itex]. To compare the two we compare:

1) [itex]Ca^2^+ + H_2O --> Ca(OH)_2 + H_3O^+[/itex]

and

2) [itex]CO_3^2^- + H_2O --> HCO_3^- + OH^-[/itex]

We want to compare the K values. It is clear that equation 2 will have a significantly larger K value and the solution will be basic, but where can a person find a K value for something like equation 1?
Are there charts for the Ka of metal ions?
What order of magnitude is it? I imagine Ka for 1 is <<< Kw
 
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I don't think equation 1 will occur appreciably, calcium hydroxide is fairly soluble in water so you can reasonably neglect it; thus calcium is a spectator ion (solubility of calcium hydroxide is .18g/100mL).
 
The first reaction isn't even correct and frankly I don't know why you think that a strong base like calciumhydroxide would create an acidic particle like [tex]H3O^+[/tex].

This reaction would occur:
[tex]Ca(H_2O)_6^{2+}(aq)+H_2O(l) \rightleftharpoons CaOH(H_2O)_5^+(aq)+H_3O^+(aq)[/tex] Which explains why a solution of [tex]CaCl_2[/tex] is acidic.

The second reaction is also incorrect since it's an equilibrium:
[tex]CO_3^{2-}(aq) + H_2O(l) \rightleftharpoons HCO_3^-(aq) + OH^-(aq)[/tex]
 
[tex]Ca(OH)_2[/tex]
pKb1 = 2.43
pKb2 = 1.40
(http://ifs.massey.ac.nz/resources/chemistry/dissociation/inorgbases.htm )

[tex]H_2CO_3[/tex]
pKa1 = 6.37
pKa2 = 10.25

[tex]CaCO_3[/tex]
pKso = 8.3

So the concentration of saturated [tex]CaCO_3[/tex] solution is [tex]7.1\cdot10^{-5}[/tex]

pH calculated using BATE is 9.73.

(see http://www.chembuddy.com/?left=pH-calculation&right=pH-salt-solution for general approach to pH calculation of salt solution).

In fact final pH will be different, as you should take into account increased solubility of [tex]CaCO_3[/tex] (due to [tex]Ca^{2+}[/tex] and [tex]CO_3^{2-}[/tex] hydrolysis - although the first can be neglected, as [tex]Ca^{2+}[/tex] is dominant at 99.9% of total calcium concentration).
 
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