Enthalpies of solution and hydration

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Enthalpy change of solution: The enthalpy change of solution,𝛥𝐻𝑠𝑜𝑙 is the energy absorbed or

released when 1 mole of an ionic solid dissolves in sufficient water to form a very dilute solution.

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Example: MgCl2(s) + aq MgCl2 (aq) 𝛥𝐻𝑠𝑜𝑙 = –55 kJmol–1

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Or MgCl2(s) + aq Mg2+ (aq) + 2Cl–(aq) 𝛥𝐻𝑠𝑜𝑙 = –55 kJmol–1

Note that:

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the symbol for enthalpy change of solution is 𝛥𝐻𝑠𝑜𝑙

 the symbol ‘aq’ represents the very large amount of water used

 enthalpy changes of solution can be positive (endothermic) or negative (exothermic)

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a compound is likely to be soluble in water only if 𝛥𝐻𝑠𝑜𝑙 is negative or has a small positive

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value; substances with large positive values of 𝛥𝐻𝑠𝑜𝑙 are relatively insoluble.
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Enthalpy change of hydration: The enthalpy change of hydration,𝛥𝐻ℎ𝑦𝑑 , is the enthalpy change

when 1 mole of a specified gaseous ion dissolves in sufficient water to form a very dilute solution.

Example:

Note that:

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the symbol for enthalpy change of hydration is ΔHhyd
 the enthalpy change of hydration is always exothermic
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Factors affecting the value of 𝚫𝐇𝐡𝐲𝐝
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Following two factors affect the value of 𝛥𝐻ℎ𝑦𝑑

 ionic radius
 ionic charge
Ionic radius:
For the ions with same charge

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The 𝛥𝐻ℎ𝑦𝑑 for smaller ion is more exothermic.
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For example: For Li+ & Na+ lithium ion has more exothermic 𝛥𝐻ℎ𝑦𝑑 because Li+ size is smaller
than Na+.
Ionic charge:
For the ions with same size

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The 𝛥𝐻ℎ𝑦𝑑 for ion having larger charge is more exothermic.
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For example: Mg+2 and Li+ both have same size but 𝛥𝐻ℎ𝑦𝑑 for Mg+2 is more exothermic
because of larger size.
Calculating enthalpy changes in solution

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By using following enthalpy cycle we can calculate 𝛥𝐻ℎ𝑦𝑑 and𝛥𝐻𝑠𝑜𝑙 .

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Following equation can be used to calculate 𝛥𝐻ℎ𝑦𝑑 ∅
and𝛥𝐻𝑠𝑜𝑙 .

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𝛥𝐻ℎ𝑦𝑑 ∅
Values for both anions and cations are added together to get the total value of𝛥𝐻ℎ𝑦𝑑 .

For Example:

Determine the enthalpy change of solution of sodium fluoride using the following data:

■■ Lattice energy = –902kJmol–1

■■ Enthalpy change of hydration of sodium ions = –406kJmol–1

■■ Enthalpy change of hydration of fluoride ions = –506kJmol–1

Step 1: draw the enthalpy cycle

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Step 2: rearrange the equation and substitute the figures to find 𝛥𝐻𝑠𝑜𝑙 .

So

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𝛥𝐻𝑠𝑜𝑙 = (–406) + (–506) – (–902)

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𝛥𝐻𝑠𝑜𝑙 [𝑁𝑎𝐹] = −10 kJ mol–1