Lattice energy · Lablypedia

Lattice energy and lattice enthalpy

The concept of lattice energy was originally applied to the formation of compounds with structures like rocksalt (NaCl) and sphalerite (ZnS) where the ions occupy high-symmetry crystal lattice sites. In the case of NaCl, lattice energy is the energy change of the reaction:

${Na}^{+} (g) + {Cl}^{-} (g) ⟶ NaCl (s)$

which amounts to −786 kJ/mol.

Some chemistry textbooks as well as the widely used CRC Handbook of Chemistry and Physics define lattice energy with the opposite sign, i.e. as the energy required to convert the crystal into infinitely separated gaseous ions in vacuum, an endothermic process. Following this convention, the lattice energy of NaCl would be +786 kJ/mol. Both sign conventions are widely used.

The relationship between the lattice energy $Δ U_{l}$ and the lattice enthalpy $Δ H_{l}$ at pressure $P$ is given by the following equation:

Δ U_{l} = Δ H_{l} - P Δ V_{m}

where $Δ U_{l}$ is the lattice energy (i.e., the molar internal energy change), $Δ H_{l}$ is the lattice enthalpy, and $Δ V_{m}$ the change of molar volume due to the formation of the lattice. Since the molar volume of the solid is much smaller than that of the gases, $Δ V_{m} < 0$ . The formation of a crystal lattice from ions in vacuum must lower the internal energy due to the net attractive forces involved, and so $Δ U_{l} < 0$ . The $- P Δ V_{m}$ term is positive but is relatively small at low pressures, and so the value of the lattice enthalpy is also negative (and exothermic). Both, lattice energy and lattice enthalpy are identical at 0 K and the difference may be disregarded in practice at normal temperatures.

2 more chapters are free with a Lably account.

Theoretical treatments

Lattice energy of ionic compounds

The lattice energy of an ionic compound depends strongly upon the charges of the ions that comprise the solid, which must attract or repel one another via Coulomb's law. More subtly, the relative and absolute sizes of the ions influence $Δ H_{l}$ . London dispersion forces also exist between ions and contribute to the lattice energy via polarization effects. For ionic compounds made up of molecular cations and/or anions, there may also be ion-dipole and dipole-dipole interactions if either molecule has a molecular dipole moment. The theoretical treatments described below are focused on compounds made of atomic cations and anions, and neglect contributions to the internal energy of the lattice from thermalized lattice vibrations.

Born–Landé equation

In 1918 Max Born and Alfred Landé proposed that the lattice energy could be derived from the electric potential of the ionic lattice and a repulsive potential energy term. This equation estimates the lattice energy based on electrostatic interactions and a repulsive term characterized by a power-law dependence (using a Born exponent, $n$ ). It was published building on earlier work by Born on ionic lattices.

Δ U_{l} = - \frac{N_{A} M z^{+} z^{-} e^{2}}{4 π ε_{0} r_{0}} (1 - \frac{1}{n})

where $N_{A}$ is the Avogadro constant, $M$ is the Madelung constant, $z^{+}$ / $z^{-}$ are the charge numbers of the cations and anions, $e$ is the elementary charge (1.6022×10⁻¹⁹ C), $ε_{0}$ is the permittivity of free space ( $4 π ε_{0}$ = 1.112×10⁻¹⁰ C²/(J·m)), $r_{0}$ is the distance to the closest ion (nearest neighbour) and $n$ is the Born exponent (a number between 5 and 12, determined experimentally by measuring the compressibility of the solid, or derived theoretically).

The Born–Landé equation above shows that the lattice energy of a compound depends principally on two factors:

as the charges on the ions increase, the lattice energy increases (becomes more negative)
when the ions are closer together, the lattice energy increases (becomes more negative)

Barium oxide (BaO), for instance, which has the NaCl structure and therefore the same Madelung constant, has a bond radius of 275 picometers and a lattice energy of −3054 kJ/mol, while sodium chloride (NaCl) has a bond radius of 283 picometers and a lattice energy of −786 kJ/mol. The bond radii are similar but the charge numbers are not, with BaO having charge numbers of (+2,−2) and NaCl having (+1,−1); the Born–Landé equation predicts that the difference in charge numbers is the principal reason for the large difference in lattice energies.

Born–Mayer equation

In 1932, Born and Joseph E. Mayer refined the Born–Landé equation by replacing the power-law repulsive term with an exponential term $e^{- r_{0} / ρ}$ which better accounts for the quantum mechanical repulsion effect between the ions. This equation improved the accuracy for the description of many ionic compounds:

$Δ U_{l} = - \frac{N_{A} M z^{+} z^{-} e^{2}}{4 π ε_{0} r_{0}} (1 - \frac{ρ}{r_{0}})$

where $N_{A}$ is the Avogadro constant, $M$ is the Madelung constant, $z^{+}$ / $z^{-}$ are the charge numbers of the cations and anions, $e$ is the elementary charge (1.6022×10⁻¹⁹ C), $ε_{0}$ is the permittivity of free space (8.854×10⁻¹² C² J⁻¹ m⁻¹), $r_{0}$ is the distance to the closest ion and $ρ$ is a constant that depends on the compressibility of the crystal (30 - 34.5 pm works well for alkali halides), used to represent the repulsion between ions at short range. Same as before, it can be seen that large values of $r_{0}$ results in low lattice energies, whereas high ionic charges result in high lattice energies.

Kapustinskii equation

Developed in 1956 by Anatolii Kapustinskii, this is a generalized empirical equation useful for a wide range of ionic compounds, including those with complex ions. It builds upon the previous equations and provides a simplified way to estimate the lattice energy of ionic compounds based on the charges and radii of the ions. It is an approximation that facilitates calculations compared to the Born–Landé and Born–Mayer equations, easier for quick estimates where high precision is not required.

$Δ U_{l} = - \frac{κ Z | z^{+} z^{-} |}{r_{0}} (1 - \frac{ρ}{r_{0}})$

where $κ$ is the Kapustinskii constant (1.202·10⁵ (kJ·Å)/mol), $Z$ is the number of ions per formula unit, $z^{+}$ / $z^{-}$ are the charge numbers of the cations and anions, $r_{0}$ is the distance to the closest ion and $ρ$ is a constant that depends on the compressibility of the crystal (30 - 34.5 pm works well for alkali halides), used to represent the repulsion between ions at short range.

Polarization effects

For certain ionic compounds, the calculation of the lattice energy requires the explicit inclusion of polarization effects. In these cases the polarization energy E_pol associated with ions on polar lattice sites may be included in the Born–Haber cycle. As an example, one may consider the case of iron-pyrite FeS₂. It has been shown that neglect of polarization led to a 15% difference between theory and experiment in the case of FeS₂, whereas including it reduced the error to 2%.

Representative lattice energies

The following table presents a list of lattice energies for some common compounds as well as their structure type.