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Thermodynamics

Question
CBSEENCH11006230

How can the lattice enthalpy of an ionic NaCl be determined by using Born-Haber cycle?

Solution

Formation of NaCl may be done by two different methods:
(a) Indirect method
(b) Direct method.
(a) Indirect method: Various terms involved are:
left parenthesis straight i right parenthesis thin space increment straight H subscript 1 superscript 0 space equals Enthalpy space Change space for space the space sublimation space of space
space Na left parenthesis straight s right parenthesis space rightwards arrow space Na left parenthesis straight g right parenthesis
  Since enthalpy is required for the process (endothermic), therefore increment straight H subscript 1 superscript 0 is taken as a positive quantity.
(ii) space space increment straight H subscript 2 superscript 0 space equals space Enthalpy space change space for space the space dissociation space of
space 1 half Cl subscript 2 left parenthesis straight g right parenthesis space space rightwards arrow space Cl left parenthesis straight g right parenthesis
The process is endothermic, therefore increment straight H subscript 2 superscript 0 is taken as a positive quantity. 
left parenthesis iii right parenthesis space increment straight H subscript 3 superscript 0 space equals space Enthalpy space change space for space ionization space of
space space Na left parenthesis straight g right parenthesis space space rightwards arrow Na to the power of plus left parenthesis straight g right parenthesis space plus straight e to the power of minus
Since the process is endothermic, therefore, ionisation enthalpy is taken as a positive quantity.
left parenthesis iv right parenthesis space increment straight H subscript 4 superscript 0 space equals space Enthalpy space change space for space electron space gain space by space
space Cl left parenthesis straight g right parenthesis space plus straight e to the power of minus space space rightwards arrow space space Cl to the power of minus left parenthesis straight g right parenthesis
Since the process is exothermic, therefore electron gain enthalpy is taken as a negative quantity. 
left parenthesis straight v right parenthesis space increment straight H subscript 5 superscript 0 space equals space Enthalpy space change space for space lattice space formation.
space space space space space space space Na to the power of plus left parenthesis straight g right parenthesis space plus space Cl to the power of minus left parenthesis straight g right parenthesis space space rightwards arrow space space space NaCl left parenthesis straight s right parenthesis
Enthalpy is released in this process i.e. process is exothermic, therefore increment straight H subscript 5 superscript 0 is always taken as a negative quantity. 
(b) Direct method:  Let increment subscript straight f straight H to the power of 0 be the enthalpy of formation of 1 mol of NaCl(s) from its constituent species. 
               Na left parenthesis straight s right parenthesis space plus space 1 half Cl subscript 2 left parenthesis straight g right parenthesis space rightwards arrow space space space NaCl left parenthesis straight s right parenthesis
According to Hess's law, the enthalpy of formation of one mole of sodium chloride should be the same irrespective of the fact whether it takes place directly in one step.
(Direct method) or through a number of steps (Indirect method).
therefore space space space increment subscript straight f straight H to the power of 0 space equals space increment straight H subscript 1 superscript 0 space plus space increment straight H subscript 2 superscript 0 space plus space increment straight H subscript 3 superscript 0 space plus space increment straight H subscript 4 superscript 0 space plus space increment straight H subscript 5 superscript 0
or space space space space increment straight H subscript 5 superscript 0 space equals space increment subscript straight f straight H to the power of 0 space space minus space increment straight H subscript 1 superscript 0 space minus space increment straight H subscript 2 superscript 0 space minus space increment straight H subscript 3 superscript 0 space minus space increment straight H subscript 4 superscript 0
where increment straight H subscript 5 superscript 0 is the enthalpy change for lattice formation from
  Na to the power of plus left parenthesis straight g right parenthesis space plus space Cl to the power of minus left parenthesis straight g right parenthesis space space space rightwards arrow space space NaCl space left parenthesis straight s right parenthesis
The reverse of the above equation i.e.
  NaCl left parenthesis straight s right parenthesis space space rightwards arrow space space Na to the power of plus left parenthesis straight g right parenthesis space plus space Cl to the power of minus left parenthesis straight g right parenthesis
defines the lattice enthalpy of NaCl.
Thus by using the Born- Haber cycle,  one can determine the lattice enthalpy of an ionic compound.