# Topic 5.1 THERMODYNAMICS Born-Haber Cycles Sol bili!y o" Ionic Co#po n\$s in %a!er En!

ropy C&an'es

By considering the relationship ∆H = Ea(forward) Ea(re!erse) The enthalpy change for a chemical reaction can be calculated from the following equation" ∆H = Energy required to break bonds in reactants Energy required to break bonds in products.'70 .345 . Eg *H+(g)  *(g) . %t is defined slightly differently for elements and compounds.+'0 .CALCULATING ENTHALPY CHANGES a) atomisation enthalpy and bond dissociation enthalpy The enthalpy change for a chemical reaction can be deduced from consideration of the energy required to break bonds in the reactants and the energy released when the bonds in the products are formed.1') . +H(g) %n gas phase reactions.0+2 . The atomisation enthalpy of an element is the energy required to produce one mole of free gaseous atoms of that element.+0) .)+0 . B(g) Bond *H #H ** *=* *=# H6 H *l *l *l Br Br #=# ∆H (k/mol ' .(g) . B(g)  .+73 . #r ∆H = \$∆Hb(bonds broken) \$∆Hb(bonds formed) The energy required to separate all the bonds in an element or a compound is known as the atomisation enthalpy. .513 .the bonds which are broken and formed are co!alent bonds.+1+ . The energy required to separate completely the atoms in one mole of co!alent bonds is known as the bond dissociation enthalpy of that bond (∆Hb). Eg &a(s)  &a(g) or '()*l)(g)  *l(g) The atomisation enthalpy of a compound is the energy required to con!ert one mole of a compound into its free gaseous atoms.

)#)(g)  *#)(g) .gi!en bond dissociation enthalpies and atomisation enthalpies" Eg *alculate the appro9imate energy change for the reaction" *H+(g) . *alculations based on Hess. )(+73) = )1+3 k/mol ' Bonds formed" ) 9 *=#. Thus bond enthalpies calculated from different reactions may !ary slightly. b) Calculatin app!o"imate ene! y chan es The appro9imate ∆H of any reaction can be calculated.These bond enthalpies are mean !alues8 the e9act strength of a bond depends on its en!ironment.) 9 4=4 Energy required = +(+'0) .+ 9 # H Energy released = )(340). )H)#(g) Bonds broken" + 9 * H. <aw do not rely on such appro9imations and so are more reliable .+(+1+) = 0+1) k/mol ' Energy change = )1+3 : 0+1) = 3'5 k/mol ' N#\$ \$ecause the %alues used a!e mean bond ene! ies& these calculations a!e only app!o"imate# The %alue of the bond st!en ths in the substances in%ol%ed in the !eaction 'ill be diffe!ent f!om the mean %alues.

(g) .in!ol!e a more comple9 sequence of processes and must be treated by a different method. e The fi!st elect!on affinity of an atom is the energy change when one electron is added to each of a mole of free gaseous atoms of that element. Eg *l(g) .S The enthalpy changes during reactions in!ol!ing co!alent compounds can be e9plained in terms of simple bond breaking and bond making" ∆H = Σ(bonds broken) Σ(bonds formed) =eactions in!ol!ing ionic compounds. . . e  #) (g) c) . e The second electron affinity of an atom is the energy change when one electron is added to each of a mole of free gaseous uninegati!e ions of that element.ttraction of the ions to form an ionic compound .howe!er. Eg # (g) .(g) . Eg &a(g)  &a.formation of free gaseous atoms from the elements in their standard states.other electrons must be transferred" The second ionisation energy of an element is the energy required to remo!e one electron from each of a mole of free gaseous unipositi!e ions of that element" Eg >g. e  *l (g) %n cases where the ions ha!e a charge of .()*+ATI)N )( I)NIC C)+P)UN.attraction of the ions to form the ionic compound. =eactions in!ol!ing the formation of ionic compounds from their elements can be broken down into three stages" .(g)  >g). '()*l)(g)  &a*l(s) a) 6ormation of free gaseous atoms from the elements in their standard states. b) 6ormation of the ions from free gaseous atoms The fi!st ionisation ene! y of an atom is the energy required to remo!e one electron from each of a mole of free gaseous atoms of that element.addition or remo!al of electrons to form ions. The enthalpy changes required to form free gaseous atoms can be obtained from the atomisation enthalpies or the bond dissociation enthalpies. *onsider the reaction &a(s) .) or ).

(g) .(g) . *l (g)  &a*l(s) Enthalpy change( k/mol ' .'42 .tomisation enthalpy of sodium . e  *l (g) &a.tomisation enthalpy of chlorine 6irst ionisation energy of sodium 6irst electron affinity of chlorine <attice energy of sodium chloride Equation &a(s)  &a(g) '()*l)(g)  *l(g) &a(g)  &a. 6irst electron affinities (usually) and lattice enthalpies are negati!e (ie e9othermic).The lattice enthalpy of an ionic compound is the energy released when one mole of the compound is formed from its free gaseous ions under standard conditions.+71 0+3 234 . *l (g)  &a*l(s) The formation of sodium chloride from sodium and chlorine thus consists of the following fi!e processes" ?rocess . e *l(g) . The sequence of processes making up the formation of an ionic compound can be shown as an energetic cycle known as a \$o!n-Habe! cycle" . Eg &a.tomisation enthalpies and ionisation enthalpies are always positi!e (ie endothermic).')) .(g) .

( 0+3) . . ')) .'42 . Born Haber cycles can be used to calculate any of the abo!e processes if all the others are known. %n practice it is usually used to calculate the electron affinity or the lattice enthalpy.Na+(g) + e + Cl(g) -348 +496 Na+(g) + Cl-(g) Na(g) + Cl(g) +107 Na(s) + Cl(g) +122 Na(s) + 1/2Cl2(g) -780 NaCl(s) The enthalpy of formation of &a*l can be calculated from Hess@ <aw" ∆Hf(&a*l) = .since these are difficult processes to measure directly. ( 234) = +40 k/mol '. +71 .

'154 *l 01+ Br 002 .the larger the hydration energy. >ost ionic compounds are at least partially soluble in water. +41 B.(aq) &ot all ionic compounds are soluble.Colubility of ionic compounds in water thus !aries widely. .since water is a polar molecule and so cations are attracted to the # atoms in water and anions are attracted to H atoms" The energy released when a gaseous ion is dissol!ed in water is known as the hyd!ation enthalpy of the ion" >9. Eg &a*l(s)  &a*l(aq) Na+(g) + Cl-(g) Na+(aq) + Cl-(aq) NaCl(s) The hydration energy depends on the charge and the siAe of the ions" the larger the charge and the smaller the siAe.ISS)L.the more likely the compound is to dissol!e.S %ons are strongly attracted to water.and depends on the balance between the hydration energy of the ions and the lattice energy of the compound. The enthalpy change when one mole of an ionic compound dissol!es in e9cess water is known as the enthalpy of solution.(g)  >9.since the ions in the solid state are also attracted to each other (cf lattice energy). '7)4 *a). 0)) >g)..howe!er. The more e9othermic the enthalpy of solution. The energy required to break up an ionic lattice is known as the lattice dissociation enthalpy. %on Hydration energy(k/mol ' &a.ING I)NIC C)+P)UN.

The solubility of ionic compounds can be calculated using the lattice energy of the compound and the hydration energy of the ions according to the following Hess@ <aw cycle" DH(solution) = \$(DH(hydration)) DH(lattice formation) or DH(solution) = \$(DH(hydration)).the harder it is to separate the ions and the lower the solubility. . DH(lattice dissociation) eg for sodium chloride" lattice dissociation enthalpy of &a*l" .234 k/mol ' hydration enthalpy of sodium ion" +41 k/mol ' hydration enthalpy of chloride ion" 01+ k/mol ' enthalpy of solution of &a*l = 234 : +41 : 01+ = .the greater the energy released when the ions dissol!e in water and the greater the solubility. The greater the hydration energy.'4 k/mol ' The greater the lattice energy.

2 = '25.2 %t is possible to calculate the entropy change for a reaction by applying the formula" ∆C = ΣCproducts ΣCreactants eg *alculate the entropy change for the reaction *(s) .2 )3. This is what happens during e9othermic reactions.1 '5+.1 : 5. Ent!opy is a measure of the degree of disorder of a system.luminium Hater *arbon mono9ide *arbon dio9ide .+ 5. *#)(g) at temperatures abo!e '444o* %t follows that there must be other factors. *#)(g)  )*#(g) DC = )('72. Howe!er this cannot be reconciled with the fact that many endothermic reactions proceed readily under normal conditions. Two common endothermic reactions are" &H+*l(s) &H+*l(aq) at room temperature *a*#0(s)  *a#(s) . Eg entropy increases solids E liquids E gases Fenerally metals ha!e a higher entropy than non metallic solids Typical entropy !alues are" Cubstance Giamond Fraphite .which determine whether or not a reaction will proceed spontaneously8 the enthalpy change is important but not the only factor.rgon Entropy( /mol 'B ' ). lower their potential energy).7 /mol 'B ' .e.7 '72. high degree of disorder makes a substance more stable.SP)NTANE)US *EACTI)NS %t is often cited that reactions take place in order that the substances can become more stable (i.1) : )'0.other than the enthalpy change. ENT*)PY The other factor which determines whether or not a reaction will take place is the change in entropy. .0 17.1 )'0.

%f DC is . *hemical reactions are fa!oured if they are accompanied by an increase in entropy. T = DH(DC .so DH = TDC.the effect of entropy becomes more important at higher temperatures.the reaction will be spontaneous only below a certain temperature. %f DF = . %f DC is :!e then a reaction is unlikely. These two quantities combine to gi!e a single term.known as free energy.the reaction will be spontaneous at all temperatures.!e. %f DH and DC are both :!e.but they cannot be used to predict whether or not a reaction will take place. (*EE ENE*GY Hhether or not a reaction will proceed thus depends on a balance between entropy and enthalpy. Co enthalpy changes in chemical reactions are useful.e!en if DH = !e.the reaction will not proceed. >any endothermic reactions proceed spontaneously under normal conditions because there is an increase in entropy. %f DH is :!e and DC is positi!e.the reaction will not be spontaneous at any temperature. Howe!er if DH and DC are both . Come e9othermic reactions do not proceed spontaneously because there is a decrease in entropy.the reaction will be spontaneous only abo!e a certain temperature.!e.!e then a reaction is likely. The change in free energy of a reaction is the ultimate test of whether it will proceed. The critical temperature is the temperature at which DF = 4. C*ITICAL TE+PE*ATU*E Because the free energy change DF depends on TDC. DF = DH TDC DF = change in free energy DH = change in enthalpy DC = change in entropy %f DF = !e.!e (though it may be !ery slow if the reactants ha!e kinetic stability). %f DH is .the reaction will proceed.e!en if DH = .!e and DC is negati!e.