Discussion:
Transition metal carbonates
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Permafacture
2009-07-04 06:04:27 UTC
Permalink
Hi all,

I had some chemistry in college but am trying to get a more intuitive
grasp on the subject now that I am graduated.

I've heard of using sodium/potassium/calcium hydroxide solutions as an
absorbent of carbon dioxide, since the carbonate salt is insoluble.
These salts are not easily decomposed however. using a metal with a
less energetic reaction would be more easily reversible. For
instance, Copper carbonate or silver carbonate are easily decomposed
by heat.

The most obvious ways I can think of using copper or silver ions to
absorb gaseous co2 is 1) to have the reaction happen at low temp and
high pressure, such that the carbonium ion causes some acidity and the
metal oxide is somewhat dissolved, and then reacts to form the
carbonate or 2) to use the nitrate salt of these metals.

in the second case, The precipitation of the carbonate would cause the
solution to become acidic (nitric acid)? (Is this true?) Transition
metal carbonates are soluble in acid, and so the reaction would reach
an equilibrium well before all the transition metal ions are
consumed. But I'm confused about how to set this up to figure out at
what point (pH) will the carbonate stop precipitating, or become so
slow as to be not worth while. It isn't a common ion situation, as
N03^- does not appear in the precipitation equation:

M^+ + CO3^2- -> MCO3 (s)

How do I go about this?

In practice, leaving some unreacted metal oxide (silver or Copper(I)
in this case) in the container would counter act this, adding more M+
as the solution becomes more acidic so that an arbitrary ammount of
CO2 gas could be sequestered with a given amount of nitrate salt. is
this true? (i guess that's a synthesis between my two possible
approaches).


Also, to get an idea of what pressure of CO2 could be developed in a
closed, heated container of this salt, i believe I would use the Gibbs
free energy. i tried doing this for calcium carbonate but did not
figure it out. is this the right path? If so i'll just keep plugging
away at it, perhaps check a different textbook. Any pointers to a
good reference would be appreciated.

much thanks,
elliot
JJ beans
2011-06-03 21:40:32 UTC
Permalink
If you just want a carbon dioxide scrubber use sodium hydroxide. It is
much more effective and cheap. Do not over think this one. It has
nothing to do with solubility either. The crusty stuff that builds up
on the strong hydroxide solutions containers is the
carbonate/bicarbonates.
LeChatlies principle is why carbon dioxide screws up basic solutions
and not acidic - acidcs solutions are much more pH tolerant to
atmospheric Carbon dioxide. The driving force is the dissolution of
carbon dioxide into water forming carbonic acid - not favored at all
in acidic solutions - basic solutions love it
If you really want to ratchet it up use cesium.
On Fri, 3 Jul 2009 23:04:27 -0700 (PDT), Permafacture
Post by Permafacture
Hi all,
I had some chemistry in college but am trying to get a more intuitive
grasp on the subject now that I am graduated.
I've heard of using sodium/potassium/calcium hydroxide solutions as an
absorbent of carbon dioxide, since the carbonate salt is insoluble.
These salts are not easily decomposed however. using a metal with a
less energetic reaction would be more easily reversible. For
instance, Copper carbonate or silver carbonate are easily decomposed
by heat.
The most obvious ways I can think of using copper or silver ions to
absorb gaseous co2 is 1) to have the reaction happen at low temp and
high pressure, such that the carbonium ion causes some acidity and the
metal oxide is somewhat dissolved, and then reacts to form the
carbonate or 2) to use the nitrate salt of these metals.
in the second case, The precipitation of the carbonate would cause the
solution to become acidic (nitric acid)? (Is this true?) Transition
metal carbonates are soluble in acid, and so the reaction would reach
an equilibrium well before all the transition metal ions are
consumed. But I'm confused about how to set this up to figure out at
what point (pH) will the carbonate stop precipitating, or become so
slow as to be not worth while. It isn't a common ion situation, as
M^+ + CO3^2- -> MCO3 (s)
How do I go about this?
In practice, leaving some unreacted metal oxide (silver or Copper(I)
in this case) in the container would counter act this, adding more M+
as the solution becomes more acidic so that an arbitrary ammount of
CO2 gas could be sequestered with a given amount of nitrate salt. is
this true? (i guess that's a synthesis between my two possible
approaches).
Also, to get an idea of what pressure of CO2 could be developed in a
closed, heated container of this salt, i believe I would use the Gibbs
free energy. i tried doing this for calcium carbonate but did not
figure it out. is this the right path? If so i'll just keep plugging
away at it, perhaps check a different textbook. Any pointers to a
good reference would be appreciated.
much thanks,
elliot
Bodo Mysliwietz
2011-06-04 09:36:55 UTC
Permalink
Post by Permafacture
I had some chemistry in college but am trying to get a more intuitive
grasp on the subject now that I am graduated.
I've heard of using sodium/potassium/calcium hydroxide solutions as an
absorbent of carbon dioxide, since the carbonate salt is insoluble.
Sodium and potassium carbonate/hydrocarbonate are high soluble in water.
Calcium carbonate is low soluble but forms, depending on pressure and
temperature, calcium hydrogen carbonate.

When you just need to develop a CO2-scrubber I recommend to think about
molecular sieve's (zeolite). Zeolite are easily refreshable by heat.
--
Glück Auf - Bodo Mysliwietz
----------------------------------------
http://www.labortechniker.de/
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