Water of crystallization

Nomenclature

In molecular formulas water of crystallization can be denoted in different ways:

"hydrated compound⋅nH₂O" or "hydrated compound×nH₂O"

This notation is used when the compound only contains lattice water or when the crystal structure is undetermined. For example Calcium chloride: CaCl₂·2H₂O

"hydrated compound(H₂O)_n"

A hydrate with coordinated water. For example Zinc chloride: ZnCl₂(H₂O)₄

Both notations can be combined as for example in copper(II) sulfate: [Cu(H₂O)₄]SO₄·H₂O

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 [Cu(H₂O)₄]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 chloride mentioned above occurs as [Co(H₂O)₆]²⁺ and Cl⁻. 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 [trans-NiCl₂(H₂O)₄] 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".

Analysis

The water content of most compounds can be determined with a knowledge of its formula. An unknown sample can be determined through thermogravimetric analysis (TGA) where the sample is heated strongly, and the accurate weight of a sample is plotted against the temperature. The amount of water driven off is then divided by the molar mass of water to obtain the number of molecules of water bound to the salt.

Other solvents of crystallization

Water is particularly common solvent to be found in crystals because it is small and polar. But all solvents can be found in some host crystals. Water is noteworthy because it is reactive, whereas other solvents such as benzene are considered to be chemically innocuous. Occasionally more than one solvent is found in a crystal, and often the stoichiometry is variable, reflected in the crystallographic concept of "partial occupancy." It is common and conventional for a chemist to "dry" a sample with a combination of vacuum and heat "to constant weight."

For other solvents of crystallization, analysis is conveniently accomplished by dissolving the sample in a deuterated solvent and analyzing the sample for solvent signals by NMR spectroscopy. Single crystal X-ray crystallography is often able to detect the presence of these solvents of crystallization as well. Other methods may be currently available.

Table of crystallization water in some inorganic halides

In the table below are indicated the number of molecules of water per metal in various salts.

Hydrates of transition metal sulfates

Transition metal sulfates form mono-, tetra-, and pentahydrates, each of which crystallizes in only one form. The water in these salts typically is coordinated, together with sulfate to the metal center. The sulfates of these same metals also crystallize as both tetragonal and monoclinic hexahydrates, wherein all water is coordinated and the sulfate is a counterion. The heptahydrates, which are often the most common salts, crystallize as monoclinic and the less common orthorhombic forms. In the heptahydrates, one water is in the lattice and the other six are coordinated to the ferrous center. Cr₂(SO₄)₃^.18H₂O