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CHRIS25
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[*] posted on 1-5-2014 at 08:19
Aluminium Hydroxide experiment


I am just at the beginning of being able to interpret reactions using electron transfers and ionic equations. But I now have a question.

OBJECT: Elemental Aluminium and 5M NaOH to produce 1 mole of Aluminium hydroxide. I expected a gelatinous precipitate upon addition of Sulphuric acid.

RESULTS: Gelatinous Aluminium Hydroxide precipitaed, but upon pouring off excess liquid the gelatinous precipitate dissolved into white crystalline precipitate which is now very mushy and drying outside.

EXTRA OBSERVATION: I used 3 moles of NaOH to 1 mole of Al, I should have used a 1:1 ratio but I originally did this stupid equation: 3NaOH + Al = Al(OH)3 + 3Na I forgot that the water changed this whole equation to produce NaAl(OH)4- and so is in a negatively charged state until the sulphuric acid makes it a completely neutral Ion. So I have excess Sodium Hydroxide I know.

Question: Excess Na+OH- re-dissolves Al(OH)3 into Al(OH)4- . As does an excess of H2SO4. However the addition of NH4OH precipitates Al(OH)3 but an excess does not re-dissolve it. Has this something to do with the fact that Ammonium Hydroxide deprotonates in water but not the sodium hydroxide? Just want to understand the re-dissolving from the gelatinous state, to the white crystaline state to absolutely dissolved back into solution.

(Assuming that I have understood things correctly so far)



[Edited on 1-5-2014 by CHRIS25]




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[*] posted on 1-5-2014 at 09:11


Ammonia (it's not actually ammonium hydroxide) is a weak base, and a solution of it will have a much lower concentration of hydroxide than a solution of sodium hydroxide.

When aluminum hydroxide dissolves in a basic solution, the reaction is Al(OH)3(s) + OH-(aq) <=> Al(OH)4-(aq). In a solution of sodium hydroxide, there's enough hydroxide around to drive the equilibrium to the right, dissolving the aluminum hydroxide. In a solution of ammonia, there isn't, and the reaction stays on the left.




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CHRIS25
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[*] posted on 1-5-2014 at 09:44


"""and a solution of it will have a much lower concentration of hydroxide"""" thankyou Draconic, this explains it.

Thought I would add that I will be reacting the left over 2 moles of NaOH and Al(OH)4 in solution, precipitating this and melting to get the aluminium oxide.

[Edited on 1-5-2014 by CHRIS25]




‘Calcination… is such a Separation of Bodies by Fire, as makes ‘em easily reducible into Powder; and for that reason ‘tis call’d by some Chymical Pulverization.’ (John Friend, Chymical Lectures London, 1712)

Right is right, even if everyone is against it, and wrong is wrong, even if everyone is for it. (William Penn 1644-1718)

The very nature of Random, Chance development precludes the existence of Order - strange that our organic and inorganic world is so well defined by precision and law. (me)
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blogfast25
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[*] posted on 1-5-2014 at 11:02


Aluminium hydroxide from Al is best prepared the other way around: dissolve Al in required amount of dilute (about 30 % I'd say) sulphuric acid, plus 20 % excess, acc:

2 Al(s) + 3 H2SO4(aq) === > Al2(SO4)3(aq) + 3 H2(g)

Then neutralise with NH3 solution to precipitate Al(OH)3:

Al2(SO4)3(aq) + 6 NH3(aq) + 6 H2O(l) === > 2 Al(OH)3(s) + 3 (NH4)2SO4(aq)

Weak and strong bases:

The difference between a weak base (e.g. NH3) and a strong base (e.g. alkali hydroxides MOH) can be further illustrated as follows.

When a strong base dissolves in water the following happens:

MOH(s) === > M<sup>+</sup>(aq) + OH<sup>-</sup>(aq).

This dissociation is almost 100 % complete and as a result [OH<sup>-</sup>] almost equals the nominal concentration of the base.

But when ammonia dissolves in water an equilibrium is established:

NH3(aq) + H2O(l) < === > NH4+(aq) + OH-(aq)

Acc. acid/base theory:

K<sub>B</sub> = ([NH4+]] x [OH-]) / [NH3] with K<sub>B</sub> the base equilibrium constant for NH3.

A little reworking yields the following approximate formula for dilute weak bases:

[OH-] = SQRT (K<sub>B</sub> x C<sub>NH3</sub>;) with C<sub>NH3</sub> the nominal concentration of the NH3 solution.

So let’s crunch some numbers for C<sub>NH3</sub> = 0.1 M. We know that K<sub>B</sub> = 10<sup>-4.75</sup> (literature), so [OH-] = √( K<sub>B</sub> x C<sub>NH3</sub>;) = √ ( 10<sup>-4.75</sup> x 0.1 ) = √ (10<sup>-5.75</sup>;) = 1.33 x 10<sup>-3</sup> = 0.00133 M

For a comparative solution of NaOH 0.1 M, we’d have [OH-] ≈ 0.1 M or about 75 times higher!



[Edited on 1-5-2014 by blogfast25]




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[*] posted on 1-5-2014 at 11:18


Oh the advantages of common sense.... this is brilliant. Thankyou.

And for this extra information, just seen it. 5M NaOH took 2 hours to dissolve 27g Al pipe found on the beach without any heat at all except the exothermic generated, using sulphuric acid is so much slower I see and I have to heat it, even now it looks like it will be quite some hours, a much slower reaction, and cleaner.

[Edited on 2-5-2014 by CHRIS25]




‘Calcination… is such a Separation of Bodies by Fire, as makes ‘em easily reducible into Powder; and for that reason ‘tis call’d by some Chymical Pulverization.’ (John Friend, Chymical Lectures London, 1712)

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[*] posted on 3-5-2014 at 07:27


You can see here the mess up I made: 1.5moles of sulphuric acid and 1mole aluminium. Only needed 85mLs But used 105mLs of 17.6M acid mixed in with 300mLs water to make a 5M solution, I later added another 50mLs water. (I know that concentrated sulphuric acid is a strong oxidizer and would not dissolve the metal). I left the reaction on gentle heat and returned to check - as you see here I have aluminium sulphate precipitated, and although I have not weighed it I have well over 3/4 of undissolved aluminium. I really did not expect this at all since the reaction was on heat yesterday for three hours and hardly anything dissolved, I thought going away for two hours would not matter since there was still 400mLs of solution in the beaker. It's not been a successful few days for me, though I do have lovely Tin chloride crystals now.

IMG_1384.jpg - 146kB
Ok, should have checked solubility of the sulphate, that explains it, 300 not enough especially on cooling, so add more water.

[Edited on 3-5-2014 by CHRIS25]




‘Calcination… is such a Separation of Bodies by Fire, as makes ‘em easily reducible into Powder; and for that reason ‘tis call’d by some Chymical Pulverization.’ (John Friend, Chymical Lectures London, 1712)

Right is right, even if everyone is against it, and wrong is wrong, even if everyone is for it. (William Penn 1644-1718)

The very nature of Random, Chance development precludes the existence of Order - strange that our organic and inorganic world is so well defined by precision and law. (me)
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[*] posted on 3-5-2014 at 10:39


Chris25:

What has happened there is perfectly normal. Aluminium sulphate is highly soluble but also forms a very high hydrate, something silly like 18 H2O! When that starts crystallising it takes with it lots of water and the whole thing tends to solidify. Been there, done that.

So you need to use simply more water and more H2SO4. A stoichiometric amount of acid will always cause the reaction to stall at some point because the acid concentration become very low after a while.

I've dissolved 'tons' of Al scrap in H2SO4 solutions, w/o problems, to prepare alum (the potassium aluminium sulphate double salt.

Of course you can just add water to redissolve the aluminium sulphate you now have and filter off the unreacted metal.




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[*] posted on 3-5-2014 at 11:23


Yes so happy that I am not the only one, yes I read about that hydrated state After this happened. I prepared also the Potassium Aluminium sulphate for a crystal garden from the same source of Al pipe. Sp anyway, now I know. Thanks Blogfast. Out of curiosity, since you have prepared so much alum, what do you do with it if I may ask?



‘Calcination… is such a Separation of Bodies by Fire, as makes ‘em easily reducible into Powder; and for that reason ‘tis call’d by some Chymical Pulverization.’ (John Friend, Chymical Lectures London, 1712)

Right is right, even if everyone is against it, and wrong is wrong, even if everyone is for it. (William Penn 1644-1718)

The very nature of Random, Chance development precludes the existence of Order - strange that our organic and inorganic world is so well defined by precision and law. (me)
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[*] posted on 3-5-2014 at 12:13


Quote: Originally posted by CHRIS25  
Out of curiosity, since you have prepared so much alum, what do you do with it if I may ask?


I used to sell it. Now I prepare it from aluminium sulphate and potassium sulphate: dissolve both together in the right ratio in boiling water, allow to cool, it then crystallises beautifully. Pronto, Alum's your uncle!

Alum is one of the oldest Al compounds known to man and used since MA as a dye mordant. Some miles away from where I live there used to be the 'alum works' (alum found in shallow underground). But no more forest because they used all the wood to fire the boilers!

[Edited on 3-5-2014 by blogfast25]




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CHRIS25
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[*] posted on 3-5-2014 at 13:08


I think I will try that and see how different they come out from the jar that I already have. Hey have you seen this: http://www.youtube.com/watch?v=l_USYub3djY



‘Calcination… is such a Separation of Bodies by Fire, as makes ‘em easily reducible into Powder; and for that reason ‘tis call’d by some Chymical Pulverization.’ (John Friend, Chymical Lectures London, 1712)

Right is right, even if everyone is against it, and wrong is wrong, even if everyone is for it. (William Penn 1644-1718)

The very nature of Random, Chance development precludes the existence of Order - strange that our organic and inorganic world is so well defined by precision and law. (me)
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blogfast25
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[*] posted on 3-5-2014 at 13:13


Nice crystal! (Understatement of the week)

To compare homemade alum with commercial grade, recrystallize the homemade. Take two parts of alum and dissolve it in one part of deionised water. Heat and stir until all is fully dissolved. Then allow to cool overnight. Better purity that way...

[Edited on 3-5-2014 by blogfast25]




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