Why Is Magnesium Precipitated from Sea Water Using Calcium Hydroxide?

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Discussion Overview

The discussion revolves around the precipitation of magnesium from seawater using calcium hydroxide, specifically exploring the underlying reasons for the reaction and its thermodynamic favorability. Participants delve into qualitative and quantitative explanations, solubility considerations, and the implications of competing salts in solution.

Discussion Character

  • Exploratory
  • Technical explanation
  • Debate/contested
  • Mathematical reasoning

Main Points Raised

  • Some participants propose that magnesium can be precipitated as magnesium hydroxide when calcium hydroxide is added, questioning the thermodynamic favorability of this reaction.
  • Others suggest considering thermodynamic factors such as entropy and free energy changes to explain why the reaction occurs.
  • A participant emphasizes the need for a qualitative explanation rather than a quantitative one, indicating a desire for a more conceptual understanding.
  • Discussion includes solubility product constants (Ksp) for magnesium and calcium hydroxides, with some participants noting the significant difference in solubility between the two compounds.
  • Concerns are raised about discrepancies in calculated Ksp values and the implications of calcium hydroxide's solubility being higher than predicted.
  • Some participants assert that when two weakly soluble salts compete for ions, the reaction will favor the formation of the less soluble salt, which in this case is magnesium hydroxide.
  • There is a suggestion to consider the energy changes associated with the dissolution of calcium hydroxide and the formation of magnesium hydroxide to understand the reaction's favorability.

Areas of Agreement / Disagreement

Participants express differing views on the explanations for the reaction's occurrence, with no consensus reached on the qualitative versus quantitative aspects of the thermodynamic reasoning. The discussion remains unresolved regarding the implications of solubility and Ksp values.

Contextual Notes

Limitations include the dependence on solubility product constants and the assumptions made about the saturation of seawater with respect to magnesium and calcium ions. The discussion also highlights unresolved mathematical steps in calculating Ksp values.

jaumzaum
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For we to obtain metallic magnesium from sea water we can precipitate it in the form of magnesium hydroxide if we add calcium hydroxide:

Mg2+ + Ca(OH)2 → Mg(OH)2 + Ca2+

Why does this reaction happen?
 
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Have you checked the usual suspects? Such as being favored thermodynamically or an increase in entropy?
 
Woopydalan said:
Have you checked the usual suspects? Such as being favored thermodynamically or an increase in entropy?
Hi Woopydalan.
Actually I would like a more qualitative explanation, not a quantitative one. If you had no numbers like the entalpy/entropy/gibbs energy of the substances, how would you explain that a reaction like this would happen?
 
The qualitative answer is that it is favored by thermodynamics to happen or there is an increase in entropy. Whether or not you had the values at your disposal would not really matter. That is how you would explain it happening. I know you are looking for another answer, but simply that is the reason reactions occur.

It's like asking ''Why is a banana yellow?'' the answer would be ''It doesn't absorb wavelengths between 570-590 nm'' but then you say ''well what if I don't know the wavelength of yellow light, then how do I explain it?'' then my response would follow ''It doesn't absorb yellow light.''
 
Try looking up the solubility (specifically, the solubility product constant Ksp) for each of these substances.
 
Ygggdrasil said:
Try looking up the solubility (specifically, the solubility product constant Ksp) for each of these substances.

I thought the solubility could have something to do with it, but I still cannot explain it. Actually the calcium hydroxide is much more soluble than the magnesium one.

Solubility of magnesium hydroxide is 1.4mg/L while solubility of calcium hydroxide is 1.73g/L at 20 °C
The Ksp are 1.5 10-11 for magnesium and 4.68 10-6 for calcium

How can I explain it now, knowing that Mg(OH)2 is much less soluble than Ca(OH)2
 
Calculate concentrations of Ca2+ and OH- in the saturated solution of Ca(OH)2.

Introduce any magnesium salt in such an amount concentration of Mg2+ becomes the same as concentration of Ca2+.

What will happen now?
 
Borek said:
Calculate concentrations of Ca2+ and OH- in the saturated solution of Ca(OH)2.

Introduce any magnesium salt in such an amount concentration of Mg2+ becomes the same as concentration of Ca2+.

What will happen now?

Actually when I was trying to find the concentration of Ca2+ I've got another doubt.

When I try to find the Ksp from the solubility, I get an absurd result.

solubility of calcium hydroxide is 1.85g/L at 0°C, that is 2.5 10-2M
Ca(OH)2 → Ca2+ + 2OH-
2.5 10-2-----0-------0------
---0-----2.5 10-2----5. 10-2

Ksp = 4 (2.5 10-2)3 = 6.25 10-5 that is different from the Ksp0°C = 8 10-6

Why does this happen?

And answering your question. Mg2+ would precipitate as it it less soluble than Ca2+. But what does this have to do with the first question?
 
Solubility of Ca(OH)2 is higher than that predicted by Ksp alone, as Ca2+ gets complexed by OH-.

jaumzaum said:
And answering your question. Mg2+ would precipitate as it it less soluble than Ca2+. But what does this have to do with the first question?

And you still don't see that it means the reaction proceeds to the right?
 
  • #10
Borek said:
Solubility of Ca(OH)2 is higher than that predicted by Ksp alone, as Ca2+ gets complexed by OH-.



And you still don't see that it means the reaction proceeds to the right?

Not yet, haha :(
Could you explain it to me? (I'm not very good in chemistry...)
 
  • #11
To be honest, I have no idea how to help you further. You have came to the right conclusion that when there are two weakly soluble salts competing for an anion (or cation, doesn't matter), reaction will proceed in such a way that the less soluble salt will be the main product. That's exactly what is happening here.
 
  • #12
Borek said:
To be honest, I have no idea how to help you further. You have came to the right conclusion that when there are two weakly soluble salts competing for an anion (or cation, doesn't matter), reaction will proceed in such a way that the less soluble salt will be the main product. That's exactly what is happening here.

But sea water isn't saturated of calcium, it is saturated of magnsium. And we are not adding Mg(OH)2, we are adding CaOH2

I don't see the equivalence
 
  • #13
Will writing the reaction as

Mg2+ + 2OH- -> Mg(OH)2

help?
 
  • #14
Perhaps it is helpful to think of things in terms of energy as Woopydalan suggested. Based on the Ksp values, you require 28 kJ/mol of free energy to break Ca(OH)2 into Ca2+ and two OH-, but forming Mg(OH)2 from Mg2+ and two OH- releases 57 kJ/mol of free energy (under standard conditions). Therefore, breaking apart calcium hydroxide and using the hydroxide ions to form magnesium hydroxide gives an overall decrease in the free energy of the system, and therefore, the reaction is thermodynamically favorable.
 

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