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

ropy C&an'es

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. 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. #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. %t is defined slightly differently for elements and compounds. The atomisation enthalpy of an element is the energy required to produce one mole of free gaseous atoms of that element. 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. Eg *H+(g) *(g) , +H(g) %n gas phase reactions- the bonds which are broken and formed are co!alent bonds. 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). . B(g) .(g) , B(g) Bond *H #H ** *=* *=# H6 H *l *l *l Br Br #=# H (k/mol ' ,+'0 ,+1+ ,0+2 ,1') ,345 ,513 ,+0) ,)+0 ,'70 ,+73

These bond enthalpies are mean !alues8 the e9act strength of a bond depends on its en!ironment. 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- gi!en bond dissociation enthalpies and atomisation enthalpies" Eg *alculate the appro9imate energy change for the reaction" *H+(g) , )#)(g) *#)(g) , )H)#(g) Bonds broken" + 9 * H- ) 9 4=4 Energy required = +(+'0) , )(+73) = )1+3 k/mol ' Bonds formed" ) 9 *=#- + 9 # H Energy released = )(340)- +(+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. *alculations based on Hess; <aw do not rely on such appro9imations and so are more reliable

()*+ATI)N )( I)NIC C)+P)UN,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 = (bonds broken) (bonds formed) =eactions in!ol!ing ionic compounds- howe!er- in!ol!e a more comple9 sequence of processes and must be treated by a different method. =eactions in!ol!ing the formation of ionic compounds from their elements can be broken down into three stages" - formation of free gaseous atoms from the elements in their standard states. - addition or remo!al of electrons to form ions. - attraction of the ions to form the ionic compound. *onsider the reaction &a(s) , '()*l)(g) &a*l(s) a) 6ormation of free gaseous atoms from the elements in their standard states. The enthalpy changes required to form free gaseous atoms can be obtained from the atomisation enthalpies or the bond dissociation enthalpies. 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. Eg &a(g) &a,(g) , 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) , e *l (g) %n cases where the ions ha!e a charge of ,) or )- 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,(g) >g),(g) , 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. Eg # (g) , e #) (g) c) .ttraction of the ions to form an ionic compound

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. Eg &a,(g) , *l (g) &a*l(s) The formation of sodium chloride from sodium and chlorine thus consists of the following fi!e processes" ?rocess .tomisation enthalpy of sodium .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,(g) , e *l(g) , e *l (g) &a,(g) , *l (g) &a*l(s) Enthalpy change( k/mol ' ,'42 ,')) ,+71 0+3 234

.tomisation enthalpies and ionisation enthalpies are always positi!e (ie endothermic). 6irst electron affinities (usually) and lattice enthalpies are negati!e (ie e9othermic). 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"

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) = ,'42 , ')) , +71 , ( 0+3) , ( 234) = +40 k/mol '. 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- since these are difficult processes to measure directly.

,ISS)L.ING I)NIC C)+P)UN,S %ons are strongly attracted to water- 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,(g) >9,(aq) &ot all ionic compounds are soluble- howe!er- since the ions in the solid state are also attracted to each other (cf lattice energy). The energy required to break up an ionic lattice is known as the lattice dissociation enthalpy. The enthalpy change when one mole of an ionic compound dissol!es in e9cess water is known as the enthalpy of solution. The more e9othermic the enthalpy of solution- the more likely the compound is to dissol!e. 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- the larger the hydration energy. %on Hydration energy(k/mol ' &a, +41 B, 0)) >g), '7)4 *a), '154 *l 01+ Br 002

.Colubility of ionic compounds in water thus !aries widely- and depends on the balance between the hydration energy of the ions and the lattice energy of the compound. >ost ionic compounds are at least partially soluble in water.

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)), 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+ = ,'4 k/mol ' The greater the lattice energy- the harder it is to separate the ions and the lower the solubility. The greater the hydration energy- the greater the energy released when the ions dissol!e in water and the greater the solubility.

SP)NTANE)US *EACTI)NS %t is often cited that reactions take place in order that the substances can become more stable (i.e. lower their potential energy). This is what happens during e9othermic reactions. 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) , *#)(g) at temperatures abo!e '444o* %t follows that there must be other factors- other than the enthalpy change- which determine whether or not a reaction will proceed spontaneously8 the enthalpy change is important but not the only factor. ENT*)PY The other factor which determines whether or not a reaction will take place is the change in entropy. Ent!opy is a measure of the degree of disorder of a system. . high degree of disorder makes a substance more stable. 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 .luminium Hater *arbon mono9ide *arbon dio9ide .rgon Entropy( /mol 'B ' ).+ 5.2 )3.0 17.7 '72.1 )'0.1 '5+.2

%t is possible to calculate the entropy change for a reaction by applying the formula" C = Cproducts Creactants eg *alculate the entropy change for the reaction *(s) , *#)(g) )*#(g) DC = )('72.1) : )'0.1 : 5.2 = '25.7 /mol 'B '

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