Tutorial on Chemical Energetics

Lattice enthalpies
1 The table contains values of some standard enthalpy changes in kJ mol1. Use the data to calculate: a the lattice enthalpy of sodium sulfide (Na2S) b the lattice enthalpy of iron(II) sulfide (FeS) c the enthalpy of formation of zinc chloride (ZnCl2) Enthalpy change Hof Hoat (metal) Hoat (non-metal) Hoi1 (metal) Hoi2 (metal) Hoea1 (non-metal) Hoea2 (non-metal) Holatt 2 The table contains some standard lattice enthalpy values. Substance CaF2 MgO CaO NaCl CaS RbI a b c d e f Holatt/ kJ mol1 2602 3889 3513 771 2966 609 [1] [1] [1] [1] [2] Substance KBr SrCl2 LiF SrO MgCl2 Holatt/ kJ mol1 670 2112 1022 3310 2492 Na2S 375 +109 +223 +494 n/a 200 +532 FeS 95 +418 +223 +762 +1560 200 +532 +130 +121 +908 +1730 362 n/a 2698 ZnCl2

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Rank the compounds in order of lattice enthalpy, starting with the most negative (MgO). What do the first four in your list have in common? What do the next three in your list have in common? What do the last four in your list have in common? Use your answers to parts b, c and d to suggest a general rule for one factor that affects how negative the lattice enthalpy is. The last four compounds in your list should be made up of elements from Groups 1 and 7 of the Periodic Table. By considering whereabouts the elements appear in these two groups, suggest another general rule for a second factor that affects how negative the lattice enthalpy is. Score:

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COAS Chemistry 2 Teacher Resources

Original material Cambridge University Press 2005, 2007, 2009

Tutorial on Chemical Energetics

Enthalpies of hydration
1 The enthalpies of hydration of various ions are shown in the table below. Ion Li+ Na+ K+ Rb+ Cs+ Mg2+ Ca2+ Sr2+ Ba2+ Al3+ Ionic radius/nm 0.068 0.098 0.133 0.148 0.167 0.065 0.094 0.110 0.134 0.045 Enthalpy of hydration /kJ mol1 519 406 322 301 276 1920 1650 1480 1360 4690 [4] [2] [3]

a Explain the trend in enthalpy of hydration as a group is descended. b The ions Na+, Mg2+ and Al3+ are isoelectronic. i Explain the term isoelectronic. ii Explain the trend in enthalpy of hydration as the charges on the ions increase. 2 The table below gives the values for various molar enthalpy changes for potassium chloride. Enthalpy lattice enthalpy enthalpy of solution enthalpy of hydration of K+(aq) a Value /kJ mol1 701 +17.2 322

Draw a Hesss law cycle that can be formed using the lattice enthalpy, the enthalpy of solution and the enthalpy of hydration of KCl. [5] b Give equations that represent the changes taking place for the three enthalpy changes shown in the table above. [6] c Calculate the enthalpy of hydration of the Cl ion. [4] Score: %

COAS Chemistry 2 Teacher Resources

Original material Cambridge University Press 2005, 2007, 2009

In each part, deduct one mark per error. BornHaber cycles are not essential for a correct answer. a

Lattice enthalpy for Na2S = Hof(Na2S) 2Hoat(Na) 2Hoi1(Na) Hoat(S) Hoea1(S) Hoea2(S) = 375 2 (+109) 2 (+494) (+223) (200) (+532) = 2136 kJ mol1 b [4]

Lattice enthalpy for FeS = Hof (FeS) Hoat(Fe) Hoi1(Fe) Hoi2(Fe) Hoat(S) Hoea1(S) Hoea2(S) = 95 (+418) (+762) (+1560) (+223) (200) (+532) = 3390 kJ mol1 [4]

COAS Chemistry 2 Teacher Resources

Original material Cambridge University Press 2005, 2007, 2009

Enthalpy of formation for ZnCl2 = Hoat(Zn) + Hoi1(Zn) + Hoi2(Zn) + 2Hoat(Cl) + 2Hoea1(Cl) + Holatt(ZnCl2) = +130 + (+908) + (+1730) + 2 (+121) + 2 (362) + (2698) = 412 kJ mol1 2 a b c d e f 1 a MgOCaOSrOCaSCaF2MgCl2SrCl2LiFNaClKBrRbI 2+ ions combined with 2 ions 2+ ions combined with 1 ions 1+ ions combined with 1 ions Ions with higher charges cause a more negative value of Holatt. Ions with smaller radii cause a more negative value of Holatt. [4] [1] [1] [1] [1] [1] [1] [1] [1] [1] [1] [1] [1] [1] [1] [1] [1] [1]

As a group is descended, ions increase in size so the charge density on ions decreases; therefore the (electrostatic) attraction between ions and dipoles on water molecules gets weaker, and so the enthalpy of hydration decreases, as the group is descended. b i same number of electrons ii Charge density on ions increases; stronger (electrostatic) attraction between ions and dipoles on water molecules. a

arrows in correct directions correct labels on each of the three arrows correct substances in boxes b Lattice enthalpy: K+(g) + Cl(g) KCl(s)

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COAS Chemistry 2 Teacher Resources

Original material Cambridge University Press 2005, 2007, 2009

reactants products Enthalpy of hydration: K+(g) + Cl(g) + (aq) K+(aq) + Cl(aq) reactants products Enthalpy of solution: KCl(s) + (aq) K+(aq) + Cl(aq) reactants products +17.2 = 701 322 + Hhyd(Cl) Hhyd(Cl) = 17.2 701 + 322 = 362 kJ mol1

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COAS Chemistry 2 Teacher Resources

Original material Cambridge University Press 2005, 2007, 2009