Water of crystallization
{{Short description|Water molecules present inside crystals}}
In chemistry, water(s) of crystallization or water(s) of hydration are water molecules that are present inside crystals. Water is often incorporated in the formation of crystals from aqueous solutions.{{Greenwood&Earnshaw2nd}} In some contexts, water of crystallization is the total mass of water in a substance at a given temperature and is mostly present in a definite (stoichiometric) ratio. Classically, "water of crystallization" refers to water that is found in the crystalline framework of a metal complex or a salt, which is not directly bonded to the metal cation.
Upon crystallization from water, or water-containing solvents, many compounds incorporate water molecules in their crystalline frameworks. Water of crystallization can generally be removed by heating a sample but the crystalline properties are often lost.
Compared to inorganic salts, proteins crystallize with large amounts of water in the crystal lattice. A water content of 50% is not uncommon for proteins.
Applications
Knowledge of hydration is essential for calculating the masses for many compounds. The reactivity of many salt-like solids is sensitive to the presence of water.
The hydration and dehydration of salts is central to the use of phase-change materials for energy storage.{{cite journal|doi=10.1016/j.rser.2007.10.005|title=Review on thermal energy storage with phase change materials and applications|year=2009|last1=Sharma|first1=Atul|last2=Tyagi|first2=V.V.|last3=Chen|first3=C.R.|last4=Buddhi|first4=D.|journal=Renewable and Sustainable Energy Reviews|volume=13|issue=2|pages=318–345|bibcode=2009RSERv..13..318S }}
Position in the crystal structure
File:H-bondingFeSO47aq.tif crystallizes with water of hydration, which interacts with the sulfate and with the {{chem2|[Fe(H2O)6](2+)}} centers.]]
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.{{cite journal | url=http://pubs.acs.org/doi/abs/10.1021/ic025915o | doi=10.1021/ic025915o | title=Novel Hydrogen-Bonded Three-Dimensional Networks Encapsulating One-Dimensional Covalent Chains: [M(4,4′-bipy)(H2O)4](4-abs)2·nH2O (4,4′-bipy = 4,4′-Bipyridine; 4-abs = 4-Aminobenzenesulfonate) (M = Co, n = 1; M = Mn, n = 2) | year=2002 | last1=Wang | first1=Yonghui | last2=Feng | first2=Liyun | last3=Li | first3=Yangguang | last4=Hu | first4=Changwen | last5=Wang | first5=Enbo | last6=Hu | first6=Ninghai | last7=Jia | first7=Hengqing | journal=Inorganic Chemistry | volume=41 | issue=24 | pages=6351–6357 | pmid=12444778 | url-access=subscription }}
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. Per IUPAC's recommendations, the middle dot is not surrounded by spaces when indicating a chemical adduct.{{cite book |last1=Connelly|first1=Neil G.|last2=Damhus|first2=Ture|last3=Hartshorn|first3=Richard M.|last4=Hutton|first4=Alan T. |title=Nomenclature of Inorganic Chemistry, IUPAC Recommendations 2005 (the "Red Book") |date=2005 |isbn= 0-85404-438-8 |page=56 |url=https://iupac.org/wp-content/uploads/2016/07/Red_Book_2005.pdf |access-date=10 January 2023}} Examples:
- {{chem2|CuSO4*5H2O}} – copper(II) sulfate pentahydrate
- {{chem2|CoCl2*6H2O}} – cobalt(II) chloride hexahydrate
- {{chem2|SnCl2*2H2O}} – tin(II) (or stannous) chloride dihydrate
For many salts, the exact bonding of the water is unimportant because the water molecules are made labile upon dissolution. For example, an aqueous solution prepared from {{chem2|CuSO4*5H2O}} and anhydrous {{chem2|CuSO4}} behave identically. Therefore, knowledge of the degree of hydration is important only for determining the equivalent weight: one mole of {{chem2|CuSO4*5H2O}} weighs more than one mole of {{chem2|CuSO4}}. In some cases, the degree of hydration can be critical to the resulting chemical properties. For example, anhydrous {{chem2|RhCl3}} is not soluble in water and is relatively useless in organometallic chemistry whereas {{chem2|RhCl3*3H2O}} is versatile. Similarly, hydrated {{chem2|AlCl3}} is a poor Lewis acid and thus inactive as a catalyst for Friedel-Crafts reactions. Samples of {{chem2|AlCl3}} must therefore be protected from atmospheric moisture to preclude the formation of hydrates.
File:Ca(aq)6 improved image.tif.]]
Crystals of hydrated copper(II) sulfate consist of {{chem2|[Cu(H2O)4](2+)}} centers linked to {{chem2|SO4(2-)}} 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.{{cite book|last1=Moeller|first1=Therald|title=Chemistry: With Inorganic qualitative Analysis|date=Jan 1, 1980|publisher=Academic Press Inc (London) Ltd|isbn=978-0-12-503350-3|page=909|url=https://books.google.com/books?id=uyjjgw_EmXEC&q=dehydration+of+copper(lI)+sulfate+pentahydrate|access-date=15 June 2014}} The cobalt chloride mentioned above occurs as {{chem2|[Co(H2O)6](2+)}} and {{chem2|Cl-}}. In tin chloride, each Sn(II) center is pyramidal (mean {{chem2|O/Cl\sSn\sO/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, {{chem2|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 {{chem2|NiCl2(H2O)6}}. Crystallographic analysis reveals that the solid consists of {{nowrap|[trans-{{chem2|NiCl2(H2O)4]}}}} subunits that are hydrogen bonded to each other as well as two additional molecules of {{chem2|H2O}}. Thus one third of the water molecules in the crystal are not directly bonded to {{chem2|Ni(2+)}}, 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.{{cite journal|author=K. Waizumi |author2=H. Masuda |author3=H. Ohtaki |title=X-Ray Structural Studies of FeBr2·4H2O, CoBr2·4H2O, NiCl2·4H2O, and CuBr2·4H2O. cis/trans Selectivity in Transition Metal(II) Dihalide Tetrahydrate|journal=Inorganica Chimica Acta|year=1992|volume=192|issue=2 |pages=173–181|doi=10.1016/S0020-1693(00)80756-2 }}{{cite journal|author=B. Morosin|title=An X-ray Diffraction Study on Nickel(II) Chloride Dihydrate|journal=Acta Crystallographica |year=1967|volume=23|issue=4 |pages= 630–634|doi=10.1107/S0365110X67003305|bibcode=1967AcCry..23..630M }}
Examples are rare for second and third row metals. No entries exist for Mo, W, Tc, Ru, Os, Rh, Ir, Pd, Hg, Au. AuCl3(H2O) has been invoked but its crystal structure has not been reported.
Hydrates of metal sulfates
Transition metal sulfates form a variety of hydrates, each of which crystallizes in only one form. The sulfate group often binds to the metal, especially for those salts with fewer than six aquo ligands. 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.{{cite journal|last=Baur |first=W. H. |title=On the crystal chemistry of salt hydrates. III. The determination of the crystal structure of FeSO4(H2O)7 (melanterite) |journal=Acta Crystallographica |year=1964 |volume=17 |issue=9 |pages=1167–1174 |doi=10.1107/S0365110X64003000|doi-access=free |bibcode=1964AcCry..17.1167B }} Many of the metal sulfates occur in nature, being the result of weathering of mineral sulfides.{{cite journal |doi=10.1016/j.jseaes.2012.11.027|title=The stability of sulfate and hydrated sulfate minerals near ambient conditions and their significance in environmental and planetary sciences|year=2013|last1=Chou|first1=I-Ming|last2=Seal|first2=Robert R.|last3=Wang|first3=Alian|journal=Journal of Asian Earth Sciences|volume=62|pages=734–758|bibcode=2013JAESc..62..734C}} Many monohydrates are known.
Hydrates of metal nitrates
Transition metal nitrates form a variety of hydrates. The nitrate anion often binds to the metal, especially for those salts with fewer than six aquo ligands. Nitrates are uncommon in nature, so few minerals are represented here. Hydrated ferrous nitrate has not been characterized crystallographically.
Photos
File:Copper sulfate.jpg|Hydrated copper(II) sulfate is bright blue.
File:Copper sulfate anhydrous.jpg|Anhydrous copper(II) sulfate has a light turquoise tint.