Born-Haber cycle ionic

Born-Haber cycle A thermodynamic cycle derived by application of Hess s law. Commonly used to calculate lattice energies of ionic solids and average bond energies of covalent compounds. E.g. NaCl ... 

In a Born-Haber cycle, we imagine that we break apart the bulk elements into atoms, ionize the atoms, combine the gaseous ions to form the ionic solid, then form the elements again from the ionic solid (Fig. 6.32). Only the lattice enthalpy, the enthalpy of the step in which the ionic solid is formed from the gaseous ions, is unknown. The sum of the enthalpy changes for a complete Born-Haber cycle is zero, because the enthalpy of the system must be the same at the start and finish. 

The ligand field stabilization is expressed in the lattice energies of the halides MX2. The values obtained by the Born-Haber cycle from experimental data are plotted v.v. the d electron configuration in Fig. 9.5. The ligand field stabilization energy contribution is no more than 200 kJ mol-1, which is less than 8% of the total lattice energy. The ionic radii also show a similar dependence (Fig. 9.6 Table 6.4, p. 50). 

Fig. 1. Born-Haber cycle for the formation of solvated ions from an ionic crystal [M+X ]w. U lattice energy, Affsoiv. enthalpy of ion solvation...

It is quite remarkable that electrostatic calculations based on a simple model of integral point charges at the nuclear positions of ionic crystals have produced good agreement with values of the cohesive energy as determined experimentally with use of the Born-Haber cycle. The point-charge model is a purely electrostatic model, which expresses the energy of a crystal relative to the assembly of isolated ions in terms of the Coulombic interactions between the ions. 

A Born-Haber cycle is the application of Hess s Law to the enthalpy of formation of an ionic solid at 298 K. Hess s law states that the enthalpy of a reaction is the same whether the reaction takes place in one step or in several. A Born-Haber cycle for a metal chloride (MCI) is depicted in Figure 1.56 the metal chloride is formed from the constituent elements in their standard state in the equation at the bottom, and by the clockwise series of steps above. From Hess s law, the sum of the enthalpy changes for each step around the cycle can be equated with the standard enthalpy of formation, and we get that ... 

In principle, we can use the Born-Haber cycle to predict whether a particular ionic compound should be thermodynamically stable, on the basis of calculated values of U, and so proceed to explain all of the chemistry of ionic solids. The relevant quantity is actually the free energy of formation, AGf, and this is calculable if an entropy cycle is set up to complement the Born-Haber enthalpy cycle. However, in practice AHf dominates the energetics of formation of ionic compounds. 

Born-Haber cycle A closed series of reactions used to express the enthalpy of formation of an ionic solid in terms of contributions that include the lattice enthalpy. 

An important property of an ionic crystal is the energy required to break the crystal apart into individual ions, this is the crystal lattice energy. It can be measured by a thermodynamic cycle, called the Born-Haber cycle. 

In cases where the lattice energy is known from the Born-Haber cycle, the Kapustinskii equation can be used to derive the ionic radii of complex anions such as S042- and P043-. The values determined in this way are known as thermochemical radii some values are shown in Table 4.2.6. 

The Born-haber cycle It is used to estimate the lattice energy of ionic solids. It makes use of Hess s law... 

The enthalpy of formation of an ionic compound can be calculated with an accuracy of a few percent by means of the Born-Land equation (Eq. 4.13) and the Born-Haber cycle. Consider NaCI. for example. Wc have seen that by using the predicted internuclear distance of 283 pm (or the experimental value of 281.4 pm), the Madelung constant of 1.748, the Born exponent, n, and various constants, a value of —755kJmor could be calculated for the lattice energy. The heat capacity correction is 2.1 kJ mol", which yields = —757 kJ moP. The Bom-Haber summation is then... 

In the sulphides, selenides, tellurides and arsenides, all types of bond, ionic, covalent and metallic occur. The compounds of the alkali metals with sulphur, selenium and tellurium form an ionic lattice with an anti-fluorite structure and the sulphides of the alkaline earth metals form ionic lattices with a sodium chloride structure. If in MgS, GaS, SrS and BaS, the bond is assumed to be entirely ionic, the lattice energies may be calculated from equation 13.18 and from these values the affinity of sulphur for two electrons obtained by the Born-Haber cycle. The values obtained vary from —- 71 to — 80 kcals and if van der Waal s forces are considered, from 83 to -- 102 kcals. 

Formation of ionic compounds from the elements appears to be one of the simpler overall reactions, but can also be written as a series of steps adding up to the overall reaction. The Born-Haber cycle is the process of considering the series of component reactions that can be imagined as the individual steps in compound formation. For the example of lithium fluoride, the first five reactions added together result in the sixth overall reaction. 

Quite apart from its theoretical calculation, by the use of one of the expressions developed above, it is possible to relate the lattice energy of an ionic crystal to various measurable thermodynamic quantities by means of a simple Hess s law cycle. This cycle was first proposed and used by Bom 15) and represented in its familiar graphical form by Haber (45). It is now usually referred to as the Born-Haber cycle. The cycle is given below for a uni-univalent salt in terms of enthalpies. 

Sherman (114) and other workers have compared crystal energies obtained by the Born-Haber cycle from experimental thermochemical data with theoretical values calculated assuming strict ionic character. The differences obtained have been used to indicate deviations from strict heteropolarity. Sherman 114) in his review gives results for 50 crystals, the computations being made with the Born-Lande equation. 

The energy drop when an extra electron is taken up by an atom is its electron affinity. This is generally estimated indirectly by applying the Born-Haber cycle to ionic compounds (p. 92). 

Ionic lattice energies are measured experimentally by means of a thermodynamic cycle developed by Max Born and Fritz Haber. The Born-Haber cycle is an application of Hess s law (the first law of thermodynamics). It is illustrated by a determination of the lattice energy of sodium chloride, which is A for the reaction... 

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