Position in The Crystal Structure
A salt with associated water of crystallization is known as a hydrate. The structure of hydrates can be quite elaborate, because of the existence of hydrogen bonds that define polymeric structures. Historically, the structures of many hydrates were unknown, and the dot in the formula of a hydrate was employed to specify the composition without indicating how the water is bound. Examples:
- CuSO4•5H2O - copper(II) sulfate pentahydrate
- CoCl2•6H2O - cobalt(II) chloride hexahydrate
- SnCl2•2H2O - tin(II) (or stannous) chloride dihydrate
For many salts, the exact bonding of the water is unimportant because the water molecules are labilized upon dissolution. For example, an aqueous solution prepared from CuSO4•5H2O and anhydrous CuSO4 behave identically. Therefore, knowledge of the degree of hydration is important only for determining the equivalent weight: one mole of CuSO4•5H2O weighs more than one mole of CuSO4. In some cases, the degree of hydration can be critical to the resulting chemical properties. For example, anhydrous RhCl3 is not soluble in water and is relatively useless in organometallic chemistry whereas RhCl3•3H2O is versatile. Similarly, hydrated AlCl3 is a poor Lewis acid and thus inactive as a catalyst for Friedel-Crafts reactions. Samples of AlCl3 must therefore be protected from atmospheric moisture to preclude the formation of hydrates.
Crystals of the aforementioned hydrated copper(II) sulfate consist of 2+ centers linked to SO42- ions. 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. The cobalt iodide mentioned above occurs as 2+ and I-. In tin chloride, each Sn(II) center is pyramidal (mean O/Cl-Sn-O/Cl angle is 83°) being bound to two chloride ions and one water. The second water in the formula unit is hydrogen-bonded to the chloride and to the coordinated water molecule. 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. In some cases, the majority of the weight of a compound arises from water. Glauber's salt, Na2SO4(H2O)10, is a white crystalline solid with greater than 50% water by weight.
Consider the case of nickel(II) chloride hexahydrate. This species has the formula NiCl2(H2O)6. Crystallographic analysis reveals that the solid consists of subunits that are hydrogen bonded to each other as well as two additional molecules of H2O. Thus 1/3 of the water molecules in the crystal are not directly bonded to Ni2+, and these might be termed "water of crystallization".
Read more about this topic: Water Of Crystallization
Famous quotes containing the words position, crystal and/or structure:
“Because it is not always easy for an adult to predict what inaccurate ideas a child may have, it can help to answer questions first with one of your own: “What do you think?” Once you find out what a child is really asking, you’ll be in a better position to give a helpful answer based on the facts.”
—Joanna Cole (20th century)
“I’m headed for a land that’s far away
Beside the crystal fountains.
So come with me, we’ll go and see
The Big Rock Candy Mountains.”
—Unknown. The Big Rock Candy Mountains (l. 5–8)
“It is difficult even to choose the adjective
For this blank cold, this sadness without cause.
The great structure has become a minor house.
No turban walks across the lessened floors.
The greenhouse never so badly needed paint.”
—Wallace Stevens (1879–1955)