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How do copper sulphate and the like change crystal structure on adding water of hydration?
Copper sulphate, in its hydrated form, is crystalline, whereas the anhydrous form is amorphous.
Gypsum has a similar story-- on heating the crystalline dihydrate we get an amorphous hemihydrate. (Gypsum in fact has two different
crystalline forms of the dihydrate, and has an anhydrous form as well).
I've never really grasped how the water makes it crystalline. I suspect it has to do with the relative sizes of the compounds being recompensated by ligands, but I'm not sure. How does the water affect/create the crystalline properties?
inorganic-chemistry

coordination-compounds

crystal-structure

asked May 29 '12 at 5:23

ManishEarth
5,787
3 21

64

2 Answers
I learned something in trying to answer this question since I've never quite understood what the
water was doing in hydrated crystals either. The waters of hydration help to stabilize the crystalline
form by holding the crystal together with hydrogen bonding. Water incorporated into the crystal
allows the negative dipole of the water to partially diffuse the positive charge and the positive dipole
of the water to partially diffuse the negative charge, and would help to minimize repulsive forces
between ions of like charge "close" in the crystal. Speaking of Cu(SO 4 ) 2 5 H2 O...
Copper is surrounded by six oxygen atoms, provided by two different sulfate groups and four
molecules of water. A fifth water resides elsewhere in the framework but does not bind directly
to copper.....Water of crystallization is stabilized by electrostatic attractions, consequently
hydrates are common for salts that contain +2 and +3 cations as well as -2 anions. 1 (Ref)
A more interesting reference that takes some looking at to get the sense of is given below.
Fe (SO ) xH O , with iron with a 3+ charge, forms various hydrates with x = 6, 7, 9, 10.
2
4 3
2
(Disclaimer....actually this is the crystal structure for coquimbite with has an occasional Al for Fe
substitution thrown in, but the principle is the same)

In this picture, the sulfate ions are shown as tetrahedra and the Fe 3+ ions are shown as octahedra
(presumably because Fe 3+ ions have 6-coordination sites). The crystal is formed from "clusters of
6 sulfate tetrahedra and 3 iron octahedra which share only corners" and there are two clusters per
unit cell. Each of the clusters is linked to the others through hydrogen bond provided by the
incorporated water, and parallel chains are held together only through hydrogen bonds.
The individual chain segments are linked through hydrogen bonds only. The geometrical
arrangement of the chains gives rise to "channels," ... which are occupied by water molecules
linked to the chains by hydrogen bonds.
So, you can see how removing the waters of hydration would cause the crystalline structure to

break down and result in an amorphous substance.

Further information from the paper: Coquimbite has 9 H2 O . The crystal structure shows that, of
the 3 Fe found in a cluster, one Fe is associated with 4 oxygens from sulfate groups, the second Fe
is surrounded by 3 oxygens from sulfate groups and 3 water molecules, and the third Fe (or Al) is
surrounded by 6 water molecules, so the octahedral representation does make sense.
edited May 31 '12 at 5:17

answered May 30 '12 at 0:12

Janice DelMar
2,802
12 23

Hmm, interesting. I'll wait a bit and then accept. Any reason why Fe
ions are shown as octahedra? Is it because
there's some coordination compound being formed? (Probably it, the "incorporated water" may be acting as a ligand
3 +

on the Iron side) ManishEarth May 30 '12 at 0:53

Could you incorporate that into your post? Thanks :) ManishEarth May 30 '12 at 9:11

[Manishearth, I'm not sure I'm even answering the right question below. After reading your question
more carefully, I think you were more interested in how water molecules help crystals form, rather
than whether or not the anhydrous forms can form crystals also (versus being strictly amorphous).
So, oops. Maybe some one else has a good answer on the water molecules part?]
I suspect the answer is an issue of process rather than of fundamentals.
That is, if you could find a non-aqueous medium that readily dissolves the anhydrous form of some
salt, my very strong suspicion is that you could grow excellent clear crystals of it that would look
almost nothing like the hydrous crystalline forms.
The problem for metallic-anion salts in particular is that finding a liquid that dissolves the salt
without simultaneously forming strong coordination complexes with it is going to be tricky, since I'm
guessing it's usually the coordination effect that help ionize the units of the material to make it
soluble!
Here's a wild guess: Someone, somewhere, has likely done research on how to grow crystals of
substances such as anhydrous CaSO4 (hmm, why does this phrase "dead burnt plaster" come to
mind? :) or anhydrous CuSO4 by using low-temperature molten solutions of... something or other?
Not sure what!
And what a delightful crystal that would be to have! It would be way out of the ordinary despite
being so very... ordinary?... in one sense in its composition.

Update: Apparently, clear crystals of anhydrous CuSO4 do indeed exist, and are easier to create
than I thought. You just add concentrated sulfuric acid [a] to ordinary copper sulphate pentahydrate
solution and let it evaporate slowly. Since H2 SO 4 is one of the most aggressive drying agents in
existence, my guess is that the CuSO4 just can't compete for the remaining water molecules and
is forced to crystallize without hydration.
[a] Please, never ever attempt to use concentrated H2 SO 4 anywhere except in a real lab with
protections and procedures fully in place. This is a compound that wants water so badly that it willy
synthesize water right out of the hydrogen and oxygen bonded into proteins and carbohydrates,
leaving only charred carbon. Ironically, the actual acidity of concentrated (vs hydrated) H2 SO 4 is
quite moderate, comparable to that of vinegar.

Addenda:
-- Another common-exotic crystal may be lithium fluoride, LiF , although the accuracy of that
seems to depend on who you read. Unique how, you say? Even though lithium was an early result
of the Big Bang, lithium and fluorine are both consumed rapidly by large hot stars, especially
fluorine. Their existence on earth thus appears to depend on processes such as proton irradiation
and possibly even intensive neutrino irradiation tht only occur during the explosion of a supernova
star, rather than being inherited from before the cataclysmic event. Pretty much all of the elements
(except H ) here on Earth are star-forged of course, but the elements in LiF crystals thus may be
remnants of the supernova event itself. That would... cool!)
-- And speaking of unique, wearable crystals: I've always wondered if there's a market out there for
diamond crystals synthesized using carbon that was captured as carbon dioxide during the
cremation of a loved one. If there is, feel free -- that is definitely not my bailiwick!
edited May 29 '12 at 22:47

answered May 29 '12 at 16:53

Terry Bollinger
1,396
4 13

As a possibly useful addition: structures for chalcanthite, the pentahydrate, and chalcocyanite, the anhydrous
copper sulphate. Also, cremation diamonds. (Though, made from ash rather than carbon dioxide.) Aesin May 29
'12 at 18:00
Aesin, that cremation diamonds link is... remarkable! I had that idea longer ago than I care to admit. Clearly a
missed opportunity. And thanks for all the structures, wow. Terry Bollinger May 29 '12 at 22:37
Yeah, I was looking for how it forms a crystal. It's OK, I know about conc H2 SO4 (though others may not). Of

course, in concentrated form it only goes till HSO 4 , making it not that great, but the water thingy is always there.
And the anhydrous crystals concept is interesting--most probably they just retain a brittle structure after
dehydration. ManishEarth May 30 '12 at 0:43
Hmm. You have a solid correct answer now -- I'm inclined just to delete this one as overly irrelevant?...
Terry Bollinger May 30 '12 at 11:22
@TerryBollinger I wouldn't delete it...the suggestion to dehydrate the copper (II) sulfate with sulfuric acid was
interesting I thought. I have no idea what would happen, and I would try it if I still had a lab. Multiple answers
usually give interesting ways to think about things. Janice DelMar May 31 '12 at 1:16