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Inorganic Chemistry

Hydrate Isomers

Definition and meaning of Hydrate Isomers in chemistry.

Hydrate isomers are coordination compounds sharing the same overall formula that differ in whether water molecules occupy the metal ion's inner coordination sphere or exist instead as uncoordinated water of crystallization outside it.

In more detail

This is a form of structural isomerism closely related to ionization isomerism: as water molecules swap places with an anion (commonly chloride) between the coordination sphere and the outer sphere, the number of ions the complex releases in solution changes. Because free ions and coordinated ions behave differently, hydrate isomers can be distinguished by molar conductivity measurements or by treatment with excess silver nitrate, which precipitates only the uncoordinated (free) chloride ions as AgCl. Hydrate isomers often display distinct colors, since replacing a water ligand with a chloride ligand in the coordination sphere changes the ligand field around the metal.

Key facts

Formula (classic example)CrCl3·6H2O
Isomerism classStructural isomerism, related to ionization isomerism
Distinguishing testAgNO3 precipitation / molar conductivity
FieldInorganic Chemistry
Example

Chromium(III) chloride hexahydrate, CrCl3·6H2O, exists as three hydrate isomers: violet [Cr(H2O)6]Cl3 (all six waters coordinated, three free Cl-), blue-green [CrCl(H2O)5]Cl2·H2O (one Cl- and five waters coordinated, one water of crystallization, two free Cl-), and dark green [CrCl2(H2O)4]Cl·2H2O (two Cl- and four waters coordinated, two waters of crystallization, one free Cl-).

Frequently asked questions

How are hydrate isomers told apart in the lab?

By measuring the molar conductivity of a solution (more free ions give higher conductivity) or by adding excess AgNO3, which instantly precipitates only the uncoordinated chloride ions as AgCl, allowing the free versus coordinated chloride to be quantified.

Is hydrate isomerism the same as ionization isomerism?

They are closely related: hydrate isomerism is the specific case where water molecules exchange places with a coordinated anion, so both isomers have the same formula but release different numbers of ions in solution.

Related terms