CHAPTER 7 (Module 2) CHEMICAL ENERGETICS (cont)

7.3 BORN HABER CYCLE 7.3.1 Define lattice energy for simple ionic crystals in terms of the change from gaseous ions to solid lattice 7.3.2 Explain qualitatively the effects of ionic charge and ionic radius on the numerical magnitude of lattice energy values 7.3.3 Construct Born-Haber cycle for the formation of simple ionic crystals.

1. Definition of lattice energy The enthalpy of formation of 1 mole of a compound from its gaseous ions under standard conditions ((298K, 1atm )
2. Lattice enthalpy is also defined as either the: a) The enthalpy change that occurs when one mole of a solid ionic crystal is broken into its ions in the gaseous state, at standard temperature and pressure. Because all the bonds in the ionic lattice are broken, it is an endothermic process, H is positive. MX (s) M+ (g) + X- (g)

b) The enthalpy change that occurs when one mole of a solid ionic crystal is formed form its ions in the gaseous state, at standard temperature and pressure. Because all the bonds in the ionic lattice are made, it is an exothermic process, H is negative.' M+ (g) + X- (g) MX (s)

3. Remember that bond breaking is endothermic and bond making is exothermic. 4. Born-Haber Cycles (named after Fritz Haber and Max Born) are simply energy / enthalpy cycles that show how ionic compounds are formed from their constituent elements. 5. Example in calculation of lattice enthalpy of NaCl as below: a) Hf standard enthalpy of formation of sodium chloride. The enthalpy change when one mole of a NaCl is formed from its elements under standard conditions. They are exothermic because new bonds are being made between the atoms of the elements sodium and chlorine.

b) H1 standard enthalpy of atomization of chlorine. The energy required to change one mole of gaseous chlorine molecules into one mole of gaseous chlorine atoms. Endothermic because the bonds between the Cl-Cl atoms are being broken. c) H2 standard enthalpy of first electron affinity of chlorine. The energy released when one mole of gaseous chlorine atoms gains one mole of electrons to form a -1 charged ion. Exothermic because the gaseous atom needs to release energy in order to slow down sufficiently to attract and an electron.

NOTE: Non-metal elements with -2 ions have two electron affinities. For example oxygen and sulfur form -2 ions and have a first and second electron affinity. The second electron affinity is endothermic and is defined as the energy absorbed when one mole of electrons is gained by a -1 ion. Energy is absorbed because the negative ion is gaining a negative electron. Because both the ion and the electron are negatively charged they repel each other so energy needs to be absorbed in order for the process to take place.

d) H3 standard enthalpy of atomization of sodium. The energy required to change one mole of solid sodium atoms into one mole of gaseous atoms. Endothermic, energy needs to be absorbed to change the state from a solid to a gas. e) H4 first ionization energy of sodium. The enthalpy change when one mole of electrons is removed from a gaseous metal atom. Endothermic, energy needs to be absorbed to remove the electron.
The second ionisation energy is the energy absorbed when a second electron is released from a gaseous ion. Endothermic.

f) H5 lattice enthalpy of sodium chloride. The enthalpy change when one mole of ions in a solid ionic lattice is broken. Endothermic, because the ionic bonds between the sodium and chloride ions need to absorb energy in order to break them. NOTE: The enthalpies of atomization and first ionization energy are always positive (endothermic). The enthalpy of first electron affinity is negative (exothermic). g) Born-Haber Cycle for NaCl The formation of the ionic compound starts with the elements in their standard states, and ends with them as ions in a giant ionic lattice. h) Before the elements can form an ionic lattice they need to be atomized (turned into gaseous atoms) and then ionized (turned into ions). The process involved are atomization, ionization energy and electron affinity. i) A Born-Haber cycle combines all of the steps above, using the principles of Hesss Law to determine the overall lattice enthalpy

The Born Haber Cycle of NaCl (s)

6. Factors affecting the size of the lattice enthalpy Recall that lattice enthalpy is defined as the enthalpy change that occurs when one mole of a solid ionic crystal is broken into its ions in the gaseous state, at standard temperature and pressure. Its magnitude (size) depends on the size (radius) and charge on the positive and negative ions and can be represented using the following relationship.

7. As the lattice enthalpy increases the ionic lattice becomes more stable. This is because the electrostatic attraction between the positive and negative ions becomes stronger, so more energy is needed to break apart the ions.

When the charge increases the lattice enthalpy increases When the radius increases the lattice enthalpy decreases NOTE: Remember positive ions (cations) are smaller than their atoms and negative ions (anions) are larger than their atoms and ionic radius increase down a group of the periodic table and decreases across a period. 8. Therefore the lattice enthalpy will be greatest from a small sized ion with a large charge. The charge on the ion causes the lattice energy to increase more than the size of the ion (ionic radius).

9. This formula shows that increasing the charge on either ion will increase the force between them. Decreasing the size of one or both ions will decrease the distance between them and thus increase the attractive force.

Exercise 7c 1. Calculate the lattice enthalpy of calcium oxide from the following data. enthalpy of atomisation of Ca(s): 178 kJmol-1 first ionization energy of Ca(g): 590 kJmol-1 second ionization energy of Ca(g): 1150 kJmol-1 enthalpy of atomization of O2(g): 249 kJmol-1 first electron affinity of O(g): -141 kJmol-1 second electron affinity of O(g): 844 kJmol-1 enthalpy of formation of CaO(s): -635 kJmol-1 2. The standard enthalpy of formation of KCl(s) is -437 kJmol-1. In a Born-Haber cycle for the formation of KCl(s), which enthalpy change(s) are exothermic?

A. B. C. D. E.

the lattice enthalpy and the electron affinity of chlorine the electron affinity of chlorine the formation of Cl(g) from Cl2(g) the enthalpy of atomization of K(s) and the first ionization energy of K(g) lattice enthalpy

3. Calculate the lattice enthalpy of silver chloride from the following data. enthalpy of atomisation of Ag(s): 284 kJmol-1 first ionization energy of Ag(g): 731 kJmol-1 enthalpy of atomisation of Cl2(g): 122 kJmol-1 first electron affinity of Cl(g): -349 kJmol-1 enthalpy of formation of AgCl(s): -127 kJmol-1

4. Consider the reaction between Li and fluorine gas to form lithium fluoride, LiF. The reaction can take place in several steps: a) Li (s) Li (g) . atomization Hat = +107 kJ/mol + b) Li (g) Li (g) first ionization HIE = +496 kJ/mol c) F2 (g) F (g) atomization Hat = +122 kJ/mol d) F + e F- (g) .. Electron affinity HEA = -349 kJ/mol e) Li+(g) + F- (g) LiF(s) .. Lattice energy HLattice = ??? kJ/mol f) Li(s) + F2 (g) LiF (s) enthalpy formation = -411 kJ/mol Calculate the lattice enthalpy of lithium fluoride, LiF. 5. Construct a Born-Haber cycle for the formation of Na2O and use the data below to calculate the lattice energy of sodium oxide: Na(s) Na(g) H = + 108 kJ mol-1 Na(g) Na+ (g) H = + 496 kJ mol-1 Na+(g) Na2+ (g) H = + 4560 kJ mol-1 O2(g) O (g) H = + 249 kJ mol-1 O(g) + e O- (g) H = - 141 kJ mol-1 2O (g) + e O (g) H = + 798 kJ mol-1 2Na(s) + O2(g) Na2O H = -602 kJ mol-1 6. Calculate the first electron affinity of iodine from the following data. enthalpy of atomisation of Ag(s): 284 kJmol-1 first ionization energy of Ag(g): 731 kJmol-1 enthalpy of atomisation of I2(g): 107 kJmol-1 Lattice enthalpy of AgI (s): 889 kJmol-1 enthalpy of formation of AgI(s): -62 kJmol-1 7. Explain the situation below: a) Explain why the theoretical lattice energies become less exothermic from AgF to AgI. b) Explain why the values of the theoretical and experimental lattice energies are different. c) Explain why the difference between the theoretical and experimental lattice energies increases from AgF to AgI.

7.4

THE SOLUBILITY OF SOLID IN LIQUIDS 1. The enthalpy change of hydration energy Hhyd, is the enthalpy change that takes place when one mole of a gaseous ion dissolve in water to give an infinitely dilute solution. 2. The enthalpy change of hydration energy Hhyd is always negative. a) The smaller the ionic radius, the more exothermic the hydration energy. b) The higher the charge of the ion, the more exothermic the hydration energy.

3. When an ionic compound dissolves in water, two enthalpy are involved. a) b) The ions must be separated into gaseous ions. This requires lattice dissociation energy, an endothermic process. The gaseous ions interacts with water molecules. Hydration energy (exothermic) is involved.

Exercise 7b 1. Iron and chlorine react directly to form iron(III) chloride, not iron(II) chloride, so that it is not possible to directly measure the enthalpy change for the reaction Fe (s) + Cl2 (g) FeCl2 (s) The enthalpy changes for the formation of iron(III) chloride from the reaction of chlorine with iron and with iron(II) chloride are given below. Use these to calculate the enthalpy change for the reaction of iron with chlorine to form iron(II) chloride.

2. The enthalpies of combustion of ethene, ethane and hydrogen are 1390 kJ mol1, 1550 kJ mol1 and 286 kJ mol1 respectively. Use these data to calculatevthe enthalpy of hydrogenation of ethene (i.e. the reaction of ethene with hydrogen to form ethane). 3. Calculate Hf(C2H4 (g)), given: Hf(CO2(g))=395kJmol1, Hf (H2O (l)) = 287 kJ mol1 and Hcomb (C2H4 (g)) = 1416 kJ mol1. 4. Calculate the enthalpy change for the hydration of ethene, given that the enthalpy of combustion of ethene and ethanol are 1409 kJ mol-1 and 1371 kJ mol-1 respectively. 5. Given the enthalpies of atomisation of phosphorus and hydrogen (+354 kJ mol1 and +218 kJ mol1 respectively) and the phosphorus-hydrogen bond enthalpy (321 kJ mol1), calculate the approximate enthalpy of formation of a hypothetical compound PH5. 6. Use the data below, relating to the formation of barium chloride, to calculate a value of the electron affinity of the chlorine atom Enthalpy of atomisation of barium = +175 kJ mol1 Enthalpy of atomisation of chlorine = +121 kJ mol1 First ionisation energy of barium = +502 kJ mol1 Second ionisation energy of barium = +966 kJ mol1 Lattice enthalpy of barium chloride = +2018 kJ mol1 Enthalpy of formation of barium chloride = 860 kJ mol1 7. Which one of the following ionic solids would you expect to have the greatest lattice enthalpy? A. RbCl B. CaS C. BaI2 D. LiF

STPM Question 1. (a) 1.00 g of solid potassium hydroxide was dropped into 50.0 cm3 (50.0 g) of aqueous hydrogen chloride (slightly in excess) contained in a polystyrene cup. A temperature change from 30.0oC to 40.0oC was recorded with a thermometer in the solution. (The specific heat capacity of the solution is 4.0 J K-1 g-1). (i) Define the heat of neutralization. [2 mark] (ii) Write a balance equation for the above equation. [1 mark] (iii) From the experimental data provided, calculate H for the reaction. [3 marks] (iv) Give one important reason why it is preferable to use a polystyrene cup instead of a glass beaker. [1 mark] (v) Why should the solution stirred during the reaction. [1 mark] (b) Octane, C8H18 is used as fuel. (i) Define the heat of combustion with related to octane . [1 mark] (ii) Write a balance equation for the combustion of octane in excess oxygen. [1 mark] (iii) Calculate the standard enthalpy of combustion of octane by using the following information. Hf of CO2 = -394 kJ mol-1 Hf of H20 = -286 kJ mol-1 Hf of C8H18 = -250 kJ mol-1

[3 marks]

(iv) How is the knowledge of standard enthalpy of combustion useful to a chemist other than that of as fuel? [2 marks] STPM Trial 2012 2. a) On the incomplete outline below sketch the Born-Haber cycle which includes the standard enthalpy change of formation, /\H, and the lattice energy of calcium sulphide. Label all the enthalpy changes involved and the chemical species at each stage. STPM Trial 2009 Terengganu Ca2+(g) + Energy S2-(g)

Ca(s)

S(s)

CaS(s) [5 marks] b. Calculate the lattice energy of calcium sulphide The standard enthalpy changes of atomisation, H0a of calcium = 178 kJ mol-1 H0a of sulphur = 279 kJ mol-1 The sum of the first two electron affinities of sulphur = 337 kJ mol-1 The standard enthalpy change of formation, H0f of calcium sulphide = - 487 kJ mol-1 First ionisation of Calcium = +590 kJmol-1 Second ionisation of Calcium = +1150 kJmol-1 [2 marks]