CAcT HomePage
Enthalpy of Hydration
Discussion Questions
What is the energy of hydration? How is hydration energy related to lattice energy? What is enthalpy of solvation?
Hydration
The formation of a solution involves the interaction of solute with solvent molecules. Many different liquids can be used as solvents for liquid solutions, and water is the most commonly used solvent. When water is used as the solvent, the dissolving process is called hydration. The interaction between water molecules and sodium ion is illustrated as one of the diagram below. This is a typical ion-dipole interaction. At the molecular level, the ions interact with water molecules from all directions in a 3-dimensional space. This diagram depicts the concept of interaction only.
The above diagram also display hydrogen-bonding, dipole-dipole, ion-induced dipole, and dipole-induced dipole interactions. In the absence of these interactions, solvation takes place due to dispersion. Definitions of these terms are obvious from the diagrams. The meaning of the words used in the term also hints the nature of the interactions.
What is the energy of hydration?
Enthalpy of hydration, Hhyd, of an ion is the amount of energy released when a mole of the ion dissolves in a large amount of water forming an infinite dilute solution in the process, Mz+(g) + mH2O Mz+(aq) where Mz+(aq) represents ions surrounded by water molecules and dispersed in the solution. The approximate hydration energies of some typical ions are listed here. The table illustrates the point that as the atomic numbers increases, so do the ionic size, leading to a decrease in absolute values of enthalpy of hydration. Enthalpy of Hydration (Hhyd kJ/mol) of Some Typical Ions Ion Hhyd Ion Hhyd Ion Hhyd
H+ -1130 -Li+ -520 Na+ -406 K+ -322 Rb+ -297 Cs+ -276 -Cr2+ -1904 Co2+ -1996 Zn2+ -2046
Al3+ -4665 Be2+ -2494 Mg2+ -1921 Ca2+ -1577 Sr2+ -1443 Ba2+ -1305 Mn2+ -1841 Ni2+ -2105 Cd2+ -1807
Fe3+ -4430 F-505 Cl -363 Br -336 I-295 ClO4 -238 Fe2+ -1946 Cu2+ -2100 Hg2+ -1824
From the above table, an estimate can be made for the hydration energy of sodium chloride. This amount is very close to the energy of crystallization, Ecryst. The hydration energy of an ionic compound consists of two inseparable parts. The first part is the energy released when the solvent forms a coordination compound with the ions. This energy released is called the energy of ligation, Hlig. The processes related to these energies are shown below: Mz+ + nL = MLnz+, Hlig MLnz+ + solvent = MLnz+ (solution), Hdisp The second part is to disperse the ions or hydrated ions into the solvent medium, which has a dielectric constant different from vacume. This amount of energy is called energy of dispersion, Hdisp. Therefore, Hhyd = Hdisp + Hlig. This idea is brought up just to point out that the formation of aqua complex ions is part of the hydration process, even though the two energies are not separable. When stronger coordination is made between the ions and other ligands, they replace the coordinated water molecules if they are present. In the presence of NH3 molecules, they replace the water of Cu(H2O)62+: Cu(H2O)62+ + 6NH3 Cu(NH3)62+ + 6H2O
How is hydration energy related to enthalpy of crystallization?
In the discussion of lattice energy, we consider the ions separated into a gas form whereas in the disolution process, the ions are also separated, but this time into ions dispersed in a medium with solvent molecules between ions. The medium or solvent has a dielectric constant. The molar enthalpy of solvation, Hsolv, is the energy released when one mole solid is dissolved in a solvent. This quantity, the enthalpy of crystallization, and energy of hydration forms a cycle. Taking the salt NaCl as an example, the following relationship is obvious,
Hhyd = Hcrystallization + Hsolv from the following diagram.
-------Na+(g)+Cl-(g)-------| | | | | |Hcryst |Hhyd | | | ----NaCl(s)--| | | |Hsolv -------Na+(aq)+Cl-(aq)--------
The term enthalpy of crystallization is used in this diagram instead of lattice energy so that all the arrows point downward. Note that enthalpy of crystallization Hcryst, and energy of crystallization, Ecryst referr to the same quantity, and they are used interchangably. The energies of solvation for some salts can be positive values, in these cases the temperatures of the solution decrease as the substances dissolve. The solvation is an endothermic reaction. The energy levels of solids and solutions reverse in order of hight. The cycle is shown below.
-------Na+(g)+Cl-(g)------| | | | | |Hcryst |Hhyd | | | | ---Na+(aq)+Cl-(aq )---| | Hsolv | | | ---------NaCl(s)--------
In these cases, the enthalpies of hydration are less negative than the enthalpies of crystallization.
What is enthalpy of solvation?
The molar enthalpy of solvation, Hsolv, is the energy released when one mole solid is dissolved in a solvent. Note that Hsolv is also called molar heat of solution or molar energy of solution in some literature. Sometimes the enthalpy of hydration is also (mis)understood as Hsolv. When apply these values, make sure you understand the process involved. The following enthalpies of solvation are given in Chemistry by Radel and Navidi, West Publishing Co.
Enthalpy of Solvation (Hsolv kJ/mol) of Some Common Electrolytes Substanc Hsolv Substance Hsolv AlCl3(s) -373.63 H2SO4(l) -95.28 LiNO3(s) -2.51 LiCl(s) -37.03 NaNO3(s) 20.50 NaCl(s) 3.88 KNO3(s) 34.89 KCl(s) -17.22 NaOH(s) -44.51 NH4Cl(s) 14.77 These values indicates that when aluminum chloride and sulfuric acid are dissolved in water, much heat is released. Due to the very small value of enthalpies of solvation, the temperature changes are hardly noticed when LiNO3 and NaCl are dissolving. Example 1 The lattice energy of NaCl calculated from a physics view point using the Madlung constant of the NaCl structure type is 788 kJ/mol. The estimated enthalpy of hydration for sodium and chloride ions are 406 and 363 kJ/mol respectively. Estimate the enthalpy of solvation for NaCl. Solution Using the cycle shown above and the formula, we have Hhyd = Hcrystallization + Hsolv Hsolv = -769 - (-788) kJ = 19 kJ/mol. Discussion A positive value indicates an endothermic reaction. However, the value is small, and depending on the source of data, the estimated value may change. This value of 19 kJ/mol is too high compared to the value given earlier for NaCl of 3.88 kJ/mol, due to a high value of lattice energy used. Example 2 The enthalpy of crystallization for KCl is -715 kJ/mol. The enthalpies of hydration for potassium and chloride are -322 and -363 kJ/mol respectively. From these values, estimate the enthalpy of solvation for KCl. Solution The enthalpy of hydration for KCl is estimated to be Hhyd= -322 + (-363) = -685 kJ/mol Thus, the enthalpy of solvation is Hsolv= -685 - (-715) = 30 kJ/mol
Discussion The enthalpy of solvation given above is -17.22. The two values here indicates that the solvation is an endothermic reaction or change. Should temperature decrease or increase when KCl dissolves?
Confidence Building Questions
What types of interaction are present when CaCl2 dissolves in ethanlol? Skill Identify the type of interactions in the solvation process.
What is the major type of interaction when toluene dissolves in benzene? Discussion Toluene and benzene form ideal solution in that total vapor pressure of the solution is the sum of the partial pressures of benzene and toluene. These two compounds are so much a like that their molecules disperse into each other. The major driving force for solution is entropy.
Which ion has a larger absolute value of enthalpy of hydration, Na+ or Ca2+? Skill The ion-dipole interaction is stronger between Ca2+ and water molecules than between Na+ and water molecules.
Which ion is larger, Na+ or Cl-? Discussion What are their electronic configuration? The sodium ion has the same electronic configuration as Ne, but the chloride ion has the same electronic configuration as Ar, which is larger than Ne. Which one release more energy when hydrated?
When KNO3 is dissolving in water, will the temperature decrease or increase? Discussion Among the substances listed in the table above, KNO3 absorbed the most energy per mole when dissolved.
Skill [email protected]
