Lattice Energy & Enthalpy Change of Atomisation « Enthalpy change (AH) refers to the amount of heat energy transferred during a chemical reaction, at aconstant pressure Enthalpy change of atomisation * The standard enthalpy change of atomisation (AH,,°)is the enthalpy change when 1 mole of gaseous atoms is formed from its element under standard conditions © Standard conditions in this syllabus are a temperature of 298 K and a pressure of 101 kPa The AH, /*is always endothermic as energy is always required to break any bonds between the atoms in the element, to break the element into its gaseous atoms © Since thisis always an endothermic process, the enthalpy change will always have a positive value Equations can be written to show the standard enthalpy change of atomisation (AH,;°) for elements For example, sodium in its elemental formis a solid The standard enthalpy change of atomisation for sodium is the energy required to form 1 mole of gaseous sodium atoms: Na(s) — Na(g) AH,(° = +107 kJ mol”Worked example: Writing equations for the standard enthalpy change of atomisation Write down the equations for the standard enthalpy change of atomisation, (AHS) for: Question 1: Potassium Question 2: Mercury Answer Answer 1: Potassiumin its elemental formis a solid, therefore the standard enthalpy change of atomisationis the energy required to form | mole of K(g) from K(s) K(s) > K(g) Answer 2: Mercury in its elemental formis a liquid, so the standard enthalpy change of atomisation of mercury is the energy required to form mole of Hg(g) from Hal!) Hg(l) + Hg(g)Lattice energy * The lattice energy (AH/,:;*)is the enthalpy change when 1 mole of anionic compounds formed from its gaseous ions (under standard conditions) * The AHar®is always exothermic, as when ions are combined to form anionic solid lattice there is an extremely large release of energy © Since thisis always an exothermic process, the enthalpy change will always have a negative value © Because of the huge release in energy when the gaseous ions combine, the value will be avery large negative value * Thelarge negative value of AHjsx#@ suggests that the ionic compound is much more stable thanits gaseousions © Thisis due to the strong electrostatic forces of attraction between the oppositely chargedions inthe solid lattice © Since there are no electrostatic forces of attraction between the ions in the gas phase, the gaseous ions are less stable than the ionsin the onic lattice © Themore exothermic the value is, the stronger the ionic bonds within the lattice are + The AHar? of an ionic compound cannot be determined directly by one single experiment ‘* Multiple experimental values and an energy cycle are used to find the Hsp of ionic compounds © The lattice energy (AHjan*) of an ionic compound canbe written as an equation © Forexample, magnesium chloride is an ionic compound formed from magnesium (Mg”*) and chloride (Cr)ions © Since the lattice energy is the enthalpy change when 1 mole of magnesium chlorides formed from gaseous magnesium and chloride ions, the equation for this processis: Mg?*(g) + 2CI-(g) > MgCla(s)Worked Example: Writing equations for lattice energy Y Write down the equations which represent the lattice energy of: Question 1: Magnesium oxide Question 2: Lithium chloride Answer Answer 1: Mg**(g) + O7-(g) > MgO(s) Answer 2: Li*(g) + CI-(g) > LiCl(s)Electron Affinity Electron affinity * The first electron affinity (EA) is the enthaloy change when 1 mole of electrons is added to Imole of gaseous atoms, to form mole of gaseous ions each witha single negative charge under stancard X(g) +e" > X-(g) + EA;is usually exothermic, as energy is released © Since this is generally an exothermic process, then the value for EA;will usually be a negative number « Anelement can also accept more than one electron, in which case successive electron affinities are used © For example, the second electron afhnity (EA2) and third electron affinity (EA3) of anelement represent the formation of mole of gaseous ions with 2- and 3- charges respectively * The second and third electron affinities are endothermic, as energy is absorbed © This is because the incoming electronis added to an already negative ion © Energyis required to overcome the repulsive forces between the incoming electronand negative ion © Since these are endothermic processes, the values will be positiveSecond & third electron affinity table Electron Endothermic/ ON al hs a Equation Toh aa TallFactors affecting electron affinity + The value of the electron affinity depends on how strongly the incoming electronis attracted to the nucleus © The greater the attractive forces between the electron and nucleus, the more enerayis released and therefore the more exothermic (more negative) the EA, value willbe + The factors affecting the electron affinity of an element are the same as those that affect the ionisation energy (the formation of positive ions via the loss of electrons) * These are: © Nuclear charge: the greater the nuclear charge, the stronger the attractive forcesbetweenan incoming electron and the nucleus © Distance: the greater the distance between the nucleus and the outermost shell/orbital where the electron is added, the weaker the force of attraction © Shielding: the greater the number of shells, the greater the shielding effect and the weaker the force of attractionTrends in electron affinity of Group 16 & Group 17 elements * Electron affinities of non-metals become more exothermic across a period, with amaximum at Group 17 * There is generally a downwards trend in the size of the electron affinities of the elements in Group 16 and17 © Theelectronaffnities generally become less exothermic for each successive element going down both Groups, apart from the first member of each Group (oxygen and fluorine respectively)Electron affinity table Castel w: Gadi inant 1 a) Group 16 Group 17 O=-141 F =-328 Se = -195 Br = -325+ Anatom of chlorine has agreater nuclear charge than an atom of sulfur * Chlorine will therefore have a greater attractive force between its nucleus and its outer electrons © More energy is released upon adding an electron to chlorine, so the EA)of Clis more exothermic than forS. * Going down Group 16 and 17: The outermost electrons are held|ess tightly to thenucleus as they are further away The number of electron shells increases causing an increased shielding of the outermost electrons It gets more difficult to add an electron to the outer shell Less energy is released upon adding an electron to the outershell So generally, the EA;becomes less exothermic ° * Fluorine isan exception and has a lower EA;than chlorine © Fluorine has a very small atomic radius © This means that the electron density of fluorine is high © Thereis more repulsion between the incoming electron and the electrons that are already present in fluorine © These repulsive forces reduce the attractive forces between the incoming electron and nucleus © Asaresult, the E4;of fluorine isless exothermic than expectedConstructing Born-Haber Cycles To calculate the lattice energy (AMt®) of anionic compound, a Born-Haber cycle is used, whichis a special type of energy cycle To find the AHjg12@ of anionic compound, the following values must be known’ © Enthalpy change of formation (AH?) © The various enthalpy changes involved when going from elements in their standard states to their gaseous ions (the sum of all of these canbe referred to as AH#*) The various enthalpy changes involved when going from elements in their standard states to their gaseousions include: Enthalpy change of atomisation of each element First ionisation energy of the metal Successive ionisation energies of the metalif applicable First electron affinity of the non-metal Successive electron affinities of the non-metalif applicable ° ° ° ° ° The order that these are written in the Born-Haber cycleis important - they must be done in the order written above © Firstionisation energy cannot take place before atomisation, because frst ionisation energy is the process of turning gaseous atoms into gaseous ions © Electron affinity cannot take place before first ionisation energy, since the electrons must be lost from the metal first during ionisation, to be present in order for the non-metal to gain themHess's law states that ‘the enthalpy change ina chemical reactionis the same regardless of the route taken, as long as the final and initial conditions and states of reactants and products are the same for each route’ Although a Born-Haber cycle is usually constructed and used to calculate the lattice energy of an ionic compound, the cycle could be used to calculate any stage in the cycle, since an energy change is the same regardless of the route taken For example, the energy cycle shows that there are two routes to go from the elements in their standard states to the ionic compound: © Eachroute begins at the same stage of the cycle and ends at the same stage of the cycle According toHess’s law, the enthalpy change for both routesis the same, so the cycle canbe used to calculate an unknown value within the cycleHYDRATION ENTHALPIES (aHhyd) IONS IN GASEOUS HYDRATED STATE |ONS STANDARD ENTHALPY OF SOLUTION (aH5o)) LATTICE ENERGY (aHate) IONIC SOLID The green arrow shows the Indirect route, which Is equal in energy to the direct route of the element in the standard states changing into the ionic compound (blue arrow)Worked example: Constructing a Born-Haber cycle for KCI 2 Construct a Born-Haber cycle which can be used to calculate the lattice energy of potassium chloride. Enthalpy i Thar) Change Convert K(s) atoms K(s) —> K(g) into K(g) atoms K(g) —> K*(g) + = Convert K(g) atoms into K"(g) ions Convert Cl) 4C1slo) —> Clig) Aho, molecules into Clg) atoms Convert Cliighatoms | Clig)+e- —>Ct(g) | EA, into Cl (g) ions Add up all values to ay get AHF Apply Hess’s Law to find Hou.THE DIRECT AND INDIRECT ROUTE START AT THE SAME POINT ON THE CYCLE, AND END AT THE SAME POINT ON THE CYCLE K*(g) + CLG) |= _| K*(g) + Clg) + e- Le] | K(g) + Cig) [areecu | Kig) + SCl,f9) AHSLK) I Kis) + $C1,(g) KCUs)» Construct a Born-Haber cycle which can be used to calculate the lattice ° energy of magnesium oxide. alt 4 = [eh are) Change Convert Mg(s) atoms into Mg(g) atoms Mg(s) —> Mata) Convert Mg(g) atoms into Mg*(g) ions Mg(g) —> Mg*(g) + e- Convert Mg*(g) ions into Mg*(g) ions Mg*(g) —> Mg?*(g) + e- Convert On(g) molecules into O(g) atoms $0,(g) —> Olg) Convert O(g) atoms into O-(g) ions Olg) + e~ —> O(g) Convert O7(g) ions O(g) + e- —> 07 (g) into O7"(g) ions Add up all values to get AHS Apply Hess’s Law to are: find AHeeeMg?*(g) + O(g) + 2e~ Mg?*(g) + O7°(g) iE, | Mg*(g) + O(g) + e- IE li Ma(a) + Ofg) AHS (0) | Ma(g) + 40,(9) aes AHge(Mg) I Mg(s) + 40,(9) He | MgO(s)i) Exam Tip When constructing Born-Haber cycles, be sure to use ionisation energies (IE)for metals (as metals lose electrons) and electron affinities (EA) fornon-metals (as non-metals gain electrons). Remember that the order that the steps go in is important!Lattice Energy: lonic Charge & Radius The two key factors which affect lattice energy, AHiz.2, are the charge and radius of the ions that make up the erystalline lattice radius * Thelattice energy becomes less exothermic as the ionic radius of the ions increases © This is because the charge on the ions is more spread out over the ion when the ions are larger * Theions are also further apart from each other in the lattice © Theattraction between ions is between the centres of the ions involved, so the bigger the ions the bigger the distance between the centre of the ions * Therefore, the electrostatic forces of attraction between the oppositely chargedions in the lattice are weaker * Forexample, the lattice energy of caesium fluoride (CsF) is less exothermic than the lattice energy of potassium fluoride (KF) © Since both compounds contain a fluoride (F’) ion, the difference in lattice energy must be due to the caesium (Cs*)ion in CsF and potassium (k*) ion in KF Potassiumis a Group 1and Period 4 element Caesiumis a Group land Period 6 element This means that the Cs* ionis larger than the K*ion There are weaker electrostatic forces of attraction between the Cs* and F- ions compared to K* and F-ions © Asaresult, the lattice energy of CsF is less exothermic than that of KF~1400 <= -1000 -900 @ -800 5 -700 -600 LATTICE ENTHALPY (kJ mol”) © The lattice energies get less exothermic as the ionic radius of the ions increases >lonic charge * Thelattice energy gets more exothermic as the ionic charge of the ionsincreases * The greater the ionic charge, the higher the charge density * This results in stronger electrostatic attraction between the oppositely charged ionsin the lattice * Asaresult, the lattice energy is more exothermic * For example, the lattice energy of calcium oxide (CaO)is more exothermic than the lattice energy of potassium chloride (KC) ° ° Calcium oxide is anionic compound which consists of calcium (Ca2*) and oxide (O*-) ions Potassium chloride is formed from potassium (K*) and chloride (CI-) ions Theions in calcium oxide have a greater ionic charge than the ions in potassium chloride This means that the electrostatic forces of attraction are stronger between the Ca** and 02> compared to the forces between K* and Cr Therefore, the lattice energy of calcium oxide is more exothermic, as more energy is released upon its formation from its gaseous ions Ca?* and O?- are also smallerions than K* and CI’, so this also adds to the value for the lattice energy being more exothermicEnthalpy Change of Hydration & Solution Enthalpy change of solution * The standard enthalpy change of solution (AH.9/*) is the enthalpy change when 1 mole of anionic substance dissolves in sufficient water to form avery dilute solution * The symbol (aq) is used to show that the solid is dissolvedin sufficient water © For example, the enthalpy changes of solution for potassium chloride are described by the following equations: KCl(s) +aq— KCl(aq) OR KCI(s) + aq — K*(aq) + Cl-(aq) * AHco canbe exothermic (negative) or endothermic (positive)Enthalpy change of hydration « The lattice energy (AMjar,®) of KClis -711kJ mol"? © Thismeans that 711 ki mol"Tis released when the KClionic lattice is formed © Therefore, to break the attractive forces between the K* and CI ions, +711kJ mol"lisneeded * However, the AHsof’ of KClis +26 ki mol"? * Thismeans that another +685 k) mol"1(711 - 26) is required to break the KCllattice * Thisis compensated for by the standard enthalpy change of hydration (AHhyd?) * The standard enthalpy change of hydration (AHpyc?) is the enthalpy change when I mole of a specified gaseous ion dissolves in sutficient water to forma very dilute solution © For example, the enthalpy change of hydration for magnesium ions is described by the following equation: Mg?*(g) + aq—> Mg?*(aq) © Hydration enthalpies are the measure of the energy thats released when there is an attraction formed between the ions and water molecules © Hydration enthalpies are exothermic ‘* When anionic solid dissolves in water, positive and negative ions are formed © Wateris a polar molecule with a 6- oxygen (O) atom and 6+ hydrogen (H) atoms which will form ion- dipole attractions with the ions present in the solution * The oxygen atomin water will be attracted to the positive ions and the hydrogen atoms will be attracted to the negative ions * Since the AMjyd? of KClis -685 kJ mol", 685 kJ mo!tis released in forming these ion-dipole attractions when KC! dissolves in water © This compensates for the remaining +685 kJ mol"! which was needed to break down the KC latticeION-DIPOLE BONDS WATER MOLECULES AND THE ION FORM BETWEEN THE THE ELECTROSTATIC ATTRACTION BETWEEN THE K* AND THE Cl” IONS WEAKEN The polar water molecules will form ion-dipole bonds with the ions in solution (a) causing the ions to become hydrated (b)Energy Cycle Using Enthalpy Changes & Lattice Energy * The standard enthalpy change of hydration (AHy¢*) can be calculated by constructing energy cycles and applying Hess'slaw Se @ Fal GASEOUS IONS io IONIC LATTICE MOLECULE HYDRATED IONS Energy cycle involving enthalpy change of solution, lattice energy, and enthalpy change of hydrationThe energy cycle shows that there are two routes to go from the ionic lattice to the hydratedionsin an aqueous solution: © Route 1: going fromionic solid ions in aqueous solution (thisis the direct route) AH; oP = Enthalpy of solution Route 2: going fromionic lattice > gaseousions — ions in aqueous solution (thisis the indirect route) —AHjar:® + AHnyd? = reverse lattice enthalpy + hydration enthalpies Lattice enthalpy usually means Lattice formationenthalpy, in other words bond forming, If we are breaking the lattice then thisis reversing the enthalpy change so a negative signis addedin front of the term (alternatively tis called lattice dissociationenthalpy) According to Hess’s law, the enthalpy change for both routes is the same, such that Hof = ~AHiat®° + DHhyeP DMP = Aso? + Mat? Each ionwill have its own enthalpy change of hydration, AHjy¢®, which will need to be taken into account during calculations © The total AMjyc*is found by adding the AHj,<® values of both anions and cations togetherWorked example: Constructing an energy cycle and energy level diagram of KCI » Construct an energy cycle and energy level diagram to calculate the e ae ° AHyy Of the chloride ion in KCI. Answer Energy cycle: EACH ION HAS AN INDIVIDUAL (OU HYDRATE K* 1ON SEPARATELY o aHiya = OHpyg(KT] + aHpyg CO] aH bya K*(g) + CI (g)aHbys = SHfee [KCL] + aHgot (KCLI AH gfK*] + aHpyglCl] = aie fKCL] + aHgo (KCL aHpyglCU] = aHieeelKCL] + aHfo [KCL — aHpyg (K*I Energy level diagram Hyd = SHbyg (KTD + aHpyg (COI K*(g) + Cg) ° aioe KCLs) ae ate K*(aq) + CE (aq)K*(g) + Clg) K*(aq) + CI(g) Hie KCU K*(aq) + C0aq) = ron) + [arc]Worked example: Constructing an energy cycle and energy level diagram of MgCl » Construct an energy cycle and energy level diagram to calculate the e ae : ‘ ° AH ya Of magnesium ions in magnesium chloride. Answer Energy cycle ES ie \o 2+ oe aH byd = SH pyg (Mo"*] + ic =) eee EES 2aHiyd (cl SINCE THERE ARE 2 MOLES OF Cl, THE HYDRATION ENTHALPY (aHiya) WILL BE DOUBLE Mg?*(g) + 2CI(g) | MgCl.(s) Mg**(aq) +(2C1taq)Hb = aHfoelMaCls] + Hoi [MaCl 2] Hyg Mo?" + 2aHyyglCl] = atiyeelMgCl,] + aHfo{MaCl2] * aH yglMo2*] = atigelMgClz] + aHgo[MgCl] — 2aHpygiCl J Energy level diagram: Mg?*(g) + 2Cl(g) | aH yyalMg?*1 Hraee MgCl] Mg?*(aq) + 2CI (g) MgCl,(s) aHyalCl] He. [MgCl] Mg?*(aq) + 2CL (aq) aH = Hig (MCL) + aH®(MoCl,] AHP yIMg?1 + 2a? [CL] = aHRy{MaCL] + aH2,{MeCL.] aH fyalMg?1 = aHigge MgCl] + aH®,(MgCl} — 2aHy,4C01Energy Cycle Calculations The energy cycle involving the enthalpy change of solution (AH,o°). lattice energy (AHis1®). and enthalpy change of hydration (AMpyc®) can be used to calculate the different enthalpy values According to Hess's law, the enthalpy change of the direct and of the indirect route will be the same, such that: DH nyc? = DHjaee? + DH go? This equation can be rearranged depending on which enthalpy value needs to be calculated For example, AH: can be calculated using Dbjate? = DH pyc? ~ DHso? Remember: the total AHiy.#is found by adding the AMiy<® values of both anions and cations together Remember: take into account the number of each ion when completing calculations © Forexample, MgCl, has two chloride ions, so when completing calculations this willneedto be accounted for © Inthis case, you would need to double the value of the hydration enthalpy, since you are hydrating 2 moles of chloride ions instead of 1Worked example: Calculating the enthalpy change of hydration of chloride g» Calculate the AH;,, of the chloride ion in potassium chloride using the following data: AH®, [KCl] = -711 kJ mol AH®, [KCl] = +26 kJ mol AHR,IK+] = -322 kJ mol"Answer Step 1: Draw the energy cycle of KCI vs aH = SHpygIK7] + Hp glCl] (EACH ION HAS AN INDIVIDUAL ali, VALUE — YOU HYDRATE K* ION AND Cl ION SEPARATELY a K*(g) + CI"(g) *(aq) + CI(aq) KCLs)Hiya = SHfee (KCL + aHso [KCL aHpyg(KT] + atpyglCU] = aHiee (KCL + aHso [KCL “ aHpyglCO] = atta lKCL + algo [KCL — aHfyg(K*] * Step 2: Apply Hess's law to find AH hyc? [Cl'] DH py? = (AHiar@TKCI]) + (AHsoP [KCI]) (DApyPIK*]) + (AH py? LCI ]) = (AAjatPLKCI]) + (Aco [KCI]) (AH pyP ICM) = (AH jae [KCI]) + (AHsoP [KCI]) - (AM nyc? LK*]) ‘* Step 3: Substitute the values to find AH pyc? [Cl] AHnyd? [Cl] = (-711) + (+26) - (-322) = -363 kJ molWorked example: Calculating the enthalpy change of hydration of magnesium 2 Calculate the DHia of the magnesium ion in magnesium chloride using the following data: AHisu [MgCl,] = -2592 kJ mol AHS, [MgCl,] = -55 kJ mol* AH, a[Cl'] = -363 kJ molAnswer * Step 1: Draw the energy cycle of MgCl, oH yg = SHpyg (MoT + 2aHpyg (Cl SINCE THERE ARE 2 MOLES OF 2Cl", THE HYDRATION ENTHALPY (aHfyg) WILL BE DOUBLE | Mg?*(g) + 2CI(g), Mg**(aq) +@Cl (aq)Hp = 2HtaeelMgClz] + Heo [MgCl] aHyyglMo"*] + 2aHhyglCl] = aHigelM@Cl,] + aHsoilMgCla] * aHhyglMa*] = aHieeelMaCl] + aHsoulMgCla] — 2aHpyglCU * Step 2: Apply Hess's law to find AMpy.° [Mg?*] DM hyd? = (AA iate°LMgCl2]) + (AH so? IMgCl2]) (AM pycPIMg?*]) + (20pye? [CI]) = (AHieee® MgCl2]) + (AHs0 IMgClz]) (DM pyPIMg?*1) = (AHjzee°IMgClz]) + (AHsoPIMgCl2}) ~ (20H pyP ICI“]) * Step 3: Substitute the values to find AH jy? IMg”4] DHpycPIMg?*] = (-2592) + (55) - (2x -363) = -1921k) mol”Group 2: Thermal Decomposition of Nitrates & Carbonates Thermal decomposition is the breakdown of a compound into two or more different substances using heat Thermal decomposition of carbonates * The Group 2 carbonates break down (decompose) when they are heated to form the metal oxide and give off carbon dioxide gas * The general equation for the decomposition of Group 2 carbonates is: XCO3(s) “* x0 (s) + CO, (g) X= Group 2 element * Going down the group, more heat is needed to break down the carbonates HEAT MgCOs(s)— MgO (s) + CO2(s)Thermal decomposition of nitrates * Group 2 nitrates also undergo thermal decomposition * Group 2 nitrates decompose to form the metal oxide, nitrogen dioxide gas and oxygen gas * The general equation for the decomposition of Group 2 nitrates is X(NO3)2(s) =~ XO(s) + 2NO2(g) + %2O2(g) OR HEAT 2X(NO3)2(s) “+ 2X0 (s) + 4NO2(g) + O2(g) X = Group 2element * Nitrogen dioxide gas is observed as brown fumes andis toxic * Anexample of this reactionis: HEAT 2Ca(NOz)2(s) ——> 2CaO (s) + 4NO2(g) + O2(g)Trend in thermal stabilities * Going down Group 2, more heat is needed to break down the carbonate and nitrate ions * The thermal stability of the Group 2 carbonates and nitrates therefore increases down the group © The smaller positive ions at the top of the groups will polarise the anions more than the larger ions at the bottom of the group = The small positive ion attracts the delocalised electrons in the carbonate ion towards itself = The higher the charge and the smaller the ion the higher the polarising power © The more polarised they are, the more likely they are to thermally decompose as the bonds in ‘the carbonate and nitrate ions become weakerGroup 2 sulfates * The solubility of the Group 2 sulfates decreasing going down the group MgSQy CaSO, SrSOy BaSO, Going down the group, the solubility of the sulfates decreases