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JCl CHEMISTRY2OO4
CHEMICALENERGETICS
References
l. Ciemistry,I G R Briggs.
2. A-Le\lchemistry,E.N.Ramsden
Ann& PatrickFullick
3. Chemistry,
4. A-Level
Chemistry,
HillandHolman
Bmwn,Lernay,Bursten
5. chemistry: TheCentralScience,
6. Chemistry,
Olrnsted
& williams
Content
I
Enthalpy
changes:
AH,of formation,
combustion,
hydration,
solution,
neutralisation,
atomisation,
bondenergy,latticeenergy,electronamnity.
Hess'Law,
indudingBom-Haber
cydes.
AssessmentObjectives
At the endof the lectures,shjdentsstlouldbe ableto
(a)
principally
explainthat somedlemicalreactions
are accompanied
by energychanges,
in the
(AH,negative)
formof heatenergy;theenergychanges
canbeexothermic
or endothermic.
(b)
explain
andusetheterms:
(i)
enthalpychangeof reactionand standardconditions,with particularreferenceto :
formation;
hydration;
neutralisation;
aombustion;
solution;
atomisation;
(ii)
bondenergy(AHpositive,
i.e.bondbreaking);
(iii)
latticeenergy(AHrEgative.,
i.e.gaseous
ionsto solidlaftice).
(c)
calculate
enthalpydlangesfrom appropriate
experimental
results,indudingthe use of the
relationshiD
Enthalpy
change= mc.AT
(d)
explain,in qualitative
terms,the effectof ionicdrargeand of ionicradiuson the numerical
magnitude
of a latticeenergy.
(e)
gmde energycydesandcarryoutcalculations
UseHess'Law
to conslruct
involving
suchcydes
and rele\ntenergyterm (irdudingionisation
energyand electronaffinity),with partiojlar
referenceto
(i)
determining
enthalpydanges that cannotbe foundby directexperiment,
e.9.. an
enthalpydange of formationfromenthalpyciangesof combustion.
(ia)
theforrnation
of a simpleionicsolidandof itsaqueous
solution;
(iii)
average
bondenergies.
(0
ENTHALPYCHANGES
Intrcductaon
chemicalreactions
are usuallyaccompanied
by changes
in energy,usuallyin the form
of heatenergy.Heatis a formof kineticenergywhereas
theenergyof chemical
bonds
is a form of potentialenergy.The study of the energychangesthat accompany
chemicalreactionsis calledchemicalenergeticsor thermochemistry
or chemicil
thermodynamics.
(a)
Enthalpy
: Heatcontentof a substance,
represented
bythe symbolH.
StandardEnthalpy: Heatcontentof a substance
understandardconditions
(see(d)),represented
by Ho.
Note:Standard
enthalpyof elements= O
(b)
AH = En1631Ot
changewhenreactants
reactto formDroducb.
= A H proaucs- A H reactants
= heat of reaction.
A H >0
(Endothermicreaction)
Heatabsorbedfrom the
surroundinos
AH<0
(Exothermicreaction)
Heatreleasedto the
surroundings
Enthalpy
Enthalpy
y'l.tt
Reactants : lo.r.varro$
rWL
(d)
Standardconditions
(i) a pressureof
I a+!.
tS"c'
(ii) a temperature
of
If solutions
areused,theconcentrations
mustbe
| ,'l d"-3
condibons.
aHorefersto enthalpy
changeunderstandard
In this case,when
Note: Reactions
neednot takeplaceunderstandardconditions.
pressure
quotingtheenthalpychanges,
willbe stated.
temperature
and
(e)
is the puresubstance
in a
Standard
states- Thestandardstateof a substance
specified
state(solid,liquidor gas)understandard
conditions.
Examples: chrailtttl , r.ta-solfl
It0 , cJzoA
dr, a1 ,cD7
- lr4rrA
-
0'r.
A thermochemical
equationis a balancedchemicalequauonthat includes
(i) the aH value
(ii) the physicalstateof the reactantsand products
(iii) temperature,if necessary.
Example:
1260kl of heat is evolvedwhen 4 molesof NH3reactwith 3 molesof 02 to form 2
molesof N2and 5 molesof HzOunder standardconditions.Hence,the H2Oformedis
in liquidstate. 4^)rlrl?)+ 30. I g) r
r Nr l4) + Ol'o t t)
Aq
.2b1
t! nol -r
AH = ,t$tt
StandardEnthalpyChangeof Reaction
The amountof heat absorbedor evolvedwhen molarquantitiesof reactantsas
shownin the chemicalequationreacttogetherunderstandardconditons.
Examole:
.t+B lc) * 5. 1r)
_->
) 0203(t
= - tjo I
-r\ '; n
^..-+i/"
-1"
\l
K J- -hl . r ,
J,
g, L .l- t"
1r
,"da, pt'ls
(b)
-gnlr'd
cr'6{orJ
Standard
Enthalov
Change
(AHf)
of Formation
The amountof heatabsorbedor evolvedwhenone moleof a substance
is
formedliom its oonstituent elements, all in their standad states.
Examples:
Ag (s) + trl1', (g\ a
ACct( sl
A t t!)
-t
o =
a|t1
- 7a+ k}hot
Enthalpy changes of formation are often theoretical.Such reactions may not take place
.c ls)+3 H" fg) + { ,.q) + crrlroH(t) fzrrla(c,x3ox)]
in practice.Forexample:
CzHsOH
cannotbe formedby just mixingC, H2and 02.
such
entharpy
chanses
orrormation
#'#lj,r;::ll#i;lll"i
r#'j*"'
enthalpychangesof reaction.
zHf are usually negative. Examplesof exceptionare the formation of the oxides of
nitrogen.(Endothermiccompounds)
(c)
StandardEnthalovChangeof Combustion
(aH.o)
The heat change when one mole of a substancein its standard state is
completelybumed in oxygen.The measurementsof heat being adjustedto the
standardconditionsof 29BKand 1 atmospheric
pressure.
Note : Combustionsare usuallyexothermic,i.e., AHc< O
4 H 4 (6 ) r > a L h t
frlr.lar r
(d)
.arl r.
--t co.(,1) + tl 10 fl )
rrr+talrfo ,hrr.$ pl dr'\ ur+bn 4 (i"]
StandardEnthalpvChangeof Hydration
Ls,,norr&I \
-{ 1s Lrl " ol
.
ab,.p e,.r4.r,r;c
,or.lf
llr*vni.\
Examples
:
No,' (g) + oq -+
No+lall
cL' q, -+ c", +
tl- 0,f)
- *6gu1 l-ol^a -
--
r xo.k',r ic
Standard
Enthalov
Change
of Solution
The enthalpychangeof solutionof a substance
is the heatchangewhenone
mofeof the substanceis dissolvedin a largeamountof solvent(usuallywater),
so that no fuftherheatchangeoccurson furtherdilution.Allmeasurements
are
pressure.
madeunderthe standard
conditions
of 29BKand1 atrnospheric
Exampfesi
Nact (s) * o+
uo,r tar)
, t f @I \
xa+1aq1
a H = + f . q rllt . t
(f)
^,
-,
or/
C 4C trl ri )
C r' + aot) t {t-
tai \
8 t.1
lJ
/,-!.
4rr
StandardEnthalpvChangeof Neutralisation+'r'b\-rch!- rl rrtl r ,, ".i {,c' c'r' ' .'o++v$
"
The heat changewhen an acidreactswith a baseto form a salt and one mole
of water, understandardconditionsof 298Kand 1 atmosphericpressure.
*
E x a m p fe s:N .0 H 'r I.r
,o
{ ver r +
+
srvrotl
rtrgv -.; Narjov + t{.}O
fhe neutralisationprocess
- St,tyyfuo t
loV,
,J
1
.trrt : o.J d,$.5d?itr
is afwaysexothetmic.
Thetff valueinvolving the neutralisationof a strong acid with a strong atkali is almost
the same for all strong acidsand alkalis.
This is because
(a) the strongacidsand alkalisare virhrallycompletelyionisedand
(b) the reactionbetweenthe strongacidand strongalkaliis thereforethe same :
+ OH-13q1
H+16q1
----> HzOtrt
AHo has the value of - 57.1 kJ mol-r
4ax,
ctt rJ
lt.
ewg<A
+ NaOHlay
CH3COOHlaqy
--> CH:COONalaqy
+ H2O1ry
AH = -55.2kJ mol'r
Thisis because
the ionisation
of a weakacidor baseis incomplete
andhence,some
energyis requiredto complete
process.
the ionisation
Theenergyis takenfromthe process
+ OH-1"qy
Hr1"q1
----> Hzeo
Thenet heatchange,or enthalpychangeof neubalisaUon,
is hencesmaller.
(S)
L.nt
"'' ' td)
aH"= + t1gy7f n t
.aH'. + tzrNr1,,\,l.
(h)
StandardEnthalpyChangeof Hydrogenation
The heat change when one mole of an unsaturatedgaseouscompoundis
completelyconvefted into a saturatedcompoundby reactingwith gaseous
hydrogenundera pressureof one atmosphere.
Example:
c Ar-7 6 n
1)
'i
tl r (1 ) --e
c)tcs13 (4\
AH '
- rzb Vr /not
Calorimeter
vessel(to reducethe lossor gainof heatto/fromthe
- an insulated
for
determining
the quantityof energyreleased
or absorbed
surroundings)
used
or physical
duringa chemical
change.
(b)
A simple,inexpensive
calorimeter
canbe madefromtwo nestedstyrofoam
cups
cum stirrer(coffee-cup
calorimeter).
The inner
with a coverandthermometer
cup holds the aqueousreactants,the outer cup providesextra thermal
insulation.
(c)
zo0 5
6rooI
t.s
6,r tJ
Agn
= o r r r 5.g = e .j5
NumberofmolesofAgNO:used
( = no. of molesof KCIused)
r7 -
+*-
-t t6 tt /w I
l.'
"'"rt r*
l :6 kJ
$Yt Nna,
E tlSn
= mcaT
Heatevolvedpermoleofwater=J;+
= 56.+ kT
- -50lkJ mol-r
(Molar)Enthalpy
changeof neutralisation
I
\ e*o,lh.-i,
,,
"
usinga BombCalorimeter
Change
of Combustion
Determination
of Enthalpv
of a compoundcan be found usinga bomb
The enthalpychangeof combustion
(referChemistry
by Ann& PatrickFullickp113)
calorimeter
Hess'Law of Heat Summation
reactionis constant,
and
Hess'Lawstatesthatthe overallenergychangein a chemical
not dependenton the routetakenprovidedthe initialandfinalconditionsare the same
for each route/pathway.
For example,when reactantsA and B reactto form productsC and D by route 1
(throughX),or by route2 (throughY andZ),thenaccording
to Hess'Law
the enthalpychangeof thereactionin routeI
= the enthalpychangeof reactionin route2
X
*n*
I
' auro*
AH'!
c+ D )
A +B
or* \
6ltrr
/"H',
|
I
Y -------------+
Z
e,+vleg
@t
chuq
'
alra
,L ..a1{rn
+ {H tr
:!.
+ AH ..
route2
co tnl
[srlnr]
q,y*rz,d1nfl-\/
Yrozrn\
.' \ at"
O *{b
, ) ao",
afo tr'n
@ so aoto . Ft4#4
/ v,qot
lrf
>
ir..t
SnE
r r^]arrt
aH ro
Coztsl
Esl
-21 I
AH 1o =
r aHSo
- tll
kJ mol-l
urr g,
'r.+l
2Vmrl
SLr
lic r'
rrlt|s)
M?"t
AH ro
I
;
i
COrsli
AHlo=-394
AH2o= -293
I
COz(s)
r' Wri.
Note: If the anowis goingdown,AHvalueis negative
andviceversa.
Fromthe energyleveldiagram,
10
t.d-l
Method3 : EquationMethod(LeastPrefened)
Q"l + Oasl -->
aHJ= -39akJmorr....(1)
CQts)
COley+ %O4e1->
CQtgt
----> COtgl
Qs1+ 7zO21n1
Byobservation,
Eqn(3) + Eqn(2) = Eqn(1)
or,
@ts)
= alt,t -d{;
= -3A +
-(-rfr)
I
II
= - | l l | J .r1 J
dto'5HJ-'6t'a
o rr" + (_>ttl __-9,
A,{lo.
!J.r,fi
- 1rr
fuample2 : Calculate
AH for the reaction
2F2(9) + 2H2O(l)--+
4HF(g) + O, (g)
Giventhat
Hz(9) + F2(S)-----'
zHF(q)
H = -537Umot-r
^ H = -572Umol-r
2H2(g) + Oz(g) +
2H2O0)
a
Solution
4l
--t
ztl,o (l)
t?, t \ .
\4
.Hr r.irr\
\/
4lrF lt
/,*t,
-+
o> {!)
_ ?x (_ 6]?)tsJ
2H.if'
rH:( a) a rFr'll)
3ll,
jfl..
r{ f_S!?) :
.H3
f':rrv+ )
or'1
-g11 + r,$
- So, rlralr
/t
t-1
o!{t)
7
)
'ttzt
:ane
0z ')1-A'o
Recallthat H = AHproaucr
- AHreactans
&"'r'ip"'l
ts t
'
c<w\x
rtv * L
CzH4s;+ 21/zO4s1---->
2CO21s)
+ H2O111
AHqo= -1300kJ mol-1
Calculatethe enthalpyof formationfor CzHz.
Required: 2C19+ Hu(s)--> C2H2(e)
AHf = z
l}l.o
C2H21ey
+ 21/zO4s1----> 2CO21q)+ H2O61 AH6o= -1300 kJ mol-1
o*,1
rJ
:i/o)
N.B.Theenthalpychanges
or rormaii6nof co2andH2oarethe sameasthe entharpy
changes
of combustion
of C andH2respectively.
AHf(C2H2)=
-rjoo
6artto t?.tu,t,)
- gf
-b7+
a",+".*)
- .^t,!o (t,$t)
12
>26 EJ
^ol'r//
- +
Altemativemethodof Calculation
Usingenergycyclemethod:
AHf
(s*o/+)
2Qs1+ H4ey+ 21/2O2451J+
+ 2lA0.y,sl
C2H4s1
.':'-\\
gouLgr /- ,t-
r',.
LHf
2CQsy+ H201;6nl
tc"t)
AHlo= 2169.o
o;C) + (AHco
ofH2)= 2(-3q4., + (->16) :
-roe4 rI
AHao= tr;6o o; arHz = -1300kl mol'r
AH ao =6gtoaOtto
'J
- tol { - (-reoo)
= + zr-6Ft
I
Ethyne(CzHz)
is an endothermic
compound
sinceaHrois positive.
Example2 : Calciumcarbide, CaCz, reactswifl waterto form ethyne,CzHz, and
ca(OH)2:
(s) + 2HzO(l)
(s) + CzHz(g)
CaCz
Ca(OH)2
LH =-177.28
-
(s) usingthegiven
Calculate
thestandardenthalpychangeof Bglglig! AHPof CaCz
aHroin kJ mol-r :
AHrofor HzO(l)
= -286
ca(oH),(s) = -9es
(g)
CzHz
AH;t .
= +226.7
Atlt" toAtdr -
d/.,rn
+ a( ,
$\,
Ca (s) + CC (s) +
A HE o'
-tlgL
t r:6,T
l{lo
4A q o .
:
{,
C' /
'
(71
t ^'o
{1) + o . t 3 )
4v!1o
A Hlo lo ' UL L
lo- caCz
: - 60.l kq
( - r f6 ) r z + ( - tf ,2)
nL''
BE= + 435kllmol
2H (S)
H(g)+ H(S)._--.------>
=-435kJ/mol
Hz(g)
^H
(b)The bondenergyfor the O-H bondin water is one-halfthe enthalpychangefor the
reaction:
H 2 O(g ) +
2H( s) + o( q)
nH =+9243$hd
Hence
BE(O-H)=1/zLH =1/z x924.4 = +462.2k)lmol
(c) The bond energyfor the C-H bond in methaneis one-quarterthe enthalpychange
for the reaction:
CHa(g) -=+
C (g) + aH(g)
,lH = +1665kllmol
Hence
BE(C-H) = 1/qLH = l/q x 1665 = + 416 kJ
HH
|
'
|
H- F- p-o-H
db
HH
T4
D5'F
i)
fl74t tt
rtlo4
't"+'o
c-H
N-H
o-H
ct-H
Br-H
I-H
c-c
N-N
o-o
O=O
ENERGY(k/mol)
431
410
389
460
427
364
297
343
159
142
489
BOND
ENERGY(U/mol)
c-N
c-o
c-cl
ct-cl
Br-Br
l-l
C=O in COr
C=C
N=N
301
351
33s
238
188
146
607
732
799
828
941
. Energyis absorbed
in breakingthe bondsin the reactantmorecures,
whileenergy
is evolvedin formingthe bondsin productmorecules.
Hence,the entharpy
changefor a chemical
reactioncanbe estimated
as the sumof all bondenergies
of the reactants
minusthe sumof all bondenergiesof the products
AH .eaction= I BE (bondsbroken) -
I BE (bondsformed)
.{
AH 1-ea.tion= L BE reactants-
I BE pl66rrcts
Examples
1.
Determine
the entharpychangeof combustion
of propaneusingaveragebond
energies.
CrHe(9) + 5O2(g)---------+3CO2(g)+ 4HzO(q)
Bondsbrokenin reactantmolecules:
5oz
LlnS
) c- c
: 2x t + 3t t
g.-t{
. itrro
(atc+a'rrt = tl!.lt 1 5.
Z 8e
5o=o
i 5x4 81 lJ
t'J
Bondsformedin productmolecules:
tco:.
b c= o
-- 6 xa.l4 t!
4 I't 10
I c-H
= EuGo 17
2lVt
15
3COz
4Hro
AH re"aion = X BE reaaans __a6i[
2.
I BE oroogcs
_ r. t+19
_ !063 1.T,.-f
Estimate
the enthalpychangefor the reactionusingaveEgebondenergies:
CHa(g) + Cl2(g) -------' CH:CI(g) + HCt(q)
c+
c't:
C { 3r?
3c-H
:3({ ,o)l .J
I c-c r
lacr.[s) = +r8?f lJ \
! ]'5 tt
+ . - t-t
I c t-c r
= q({ro) rJ
, lr3r5
-'. Z*
gc !
!. 4A.'6. -- fx
-
= 4)xl 1
+t0?8-
: _ lr4
| ]l -al
tqlz
!J..ol-l
,--rwc' i'
^I"t
L6
= -f E1z tJ.
I-ATTICEENERGIES
ANDBORN-HABER
CYCLES
(a)
(LatticeEnergy)
LatticeEnthalpv
Standard
KCk.l
FirstlonisationEnerqyof an Element
Theamountof energyrequired
to removeelectrons
fromonemoleof gaseous
atoms producing
onemoleof gaseousions with unitpositivecharge.
----> Na+1qy
+ e AHo= +496kl mol-r
Examples:
Na(s)
SecondlonisationEnerqvof an Element
The amountof energyrequiredto removeelectronsfrom one moleof singly
charged Fosativegaseous ions producingone moleof doubly charged
positivegaseousions
Exampfe:,o* (5\ -,
cet h) + e-
The ionisationDrocesses
are alwavsendothermic.
(c)
Examples
: Ilny+ e ----> I'(s)
Born-HaberCycle
The latticeenergiesof somecompounds
cannotbe founddirectlyfiom experiment.
Hence,suchvaluesmustbe calculated
indirectly
fromotherknownenthalpychanges
of reactionby meansof an energycycle(gom-Haber
Cycle).
Eorn-Haber
cyclefor sodiumchloride
Na(s)
Or","J
------------|
Na*Cl-(s)
I lHu*n
Na(s)
cl(s)
AHr"J
II aH"
Na-(s)
AHr
thcl2(9)
t-
Standardenthalpychange
of atomisationof Na
Standard
enthalpychangeof
atomisationof Cl.,
cl(s)
Na(s)--> Na(g)
= +109kJ mol-l
AHo
"o,''
vzct2(g)
---> Cl(S)
AHou6'. = +121 kl mol-l
Firstionisationenerg,iof lodium
Na(S)--> Na*(g)+ e
AHo1on= +494 kJ mol-t
Firstelectronaffinityof chlorine
Cl( q ) + e - - > c l- ( S )
AHoE = -364 kJ mol-t
Standardenthalpychangeof
formationof NaCl
Lafticeenergyof sodiumchloride
1B
Bytld tau
attf = allea.(Na)
(+ro4) + (+re{
( -t||r)
AHuni."o=
- 1]l tJ,/',"rr,
Example:
Constructa Bom-Habercycle for the formation of calciumchloride(s).Usingvalues
from the data booklet,calculatethe sbndard enthalpychangeof formationof calcium
chloride(s)giventhat its latdceenergyis -2218 k/mol
l9
Interpretabon
of LatticeEnergv
sincelafticeenergyis the energyevolvedon formingan ioniclatticefromconstifuent
'
gaseous
ions,it is a measure
of the strengthof the ionicbondwithinthe ionicsolid.
Hence,
(a) Ioniccompounds
withhighlatticeenergies
will havehighmehingpoints.
(b)
nl.g 11 9
t rro{orc
Thesolubility
of anioniccompound
depends
ontheretative
values
of ther"tti'lif*ifr'",e
, +,'rp.
Factors
affectingthe Magnitude
of LatticeEnergv
r The latticeenergydependson the attractiveforcesbetweenthe ions in the
crystal.Thestrongerthe aftractions,
the biggerthe latticeenergy.
o The attractiveforcesdependon the chargesof the ionq theirsizes,andthe way
theyarearranged
in a solid.
r Themagnihrde
of the lafticeenergyof an ioniclatticeis proportional
to
(chargeon cation)x (chargeon anion
' 1"*'u*
sum of ionicradii
Compound
Radiusof
cation(nm)
Radiusof
anion(nm)
t-:fu--L<\-r
s charg to silc
ratb
distance
between
LatticeEnergy
centresof ions (kJ mol-')
(nm)
NaF
0.095
0.136
0.231
-902
NaCl
0.095
0.181
0.281
-77L
NaBr
0.095
0.196
0.298
-7i3
NaI
0.095
o.216
0.323
-684
Mso
0.056
0.140
0.206
-3791
20
Solubilitv
of ioniccomoounds
Enthalpy changeof solution of an ionicsolid(X u+ Yb*) is represented
by
X a+ Yb+(s) + aq --)
Processes
involvedwhenan ionicsoliddissolves
in water:
(Usingsodiumchloride
asanexample)
(1)
Separation
of ionsin the crystallatticeto form isolatedgaseousions.
+ Cllsl
NaCllsl-------+Na+1e,
Enthalpychange= -Latticeenergy.
This processis alwaysendothermicsinceheat energyis absorbedin breaking
the electrovalent
bondsand pullingthe ionsapart.
(2)
Solvation(hydration)ofthe gaseousions.
The gaseousions formed in stage (1) form electrostaticattractions(ion-water
dipoles)with the polarwater moleculesto evolveenergy.
Na+1ey
* aQ -------+Na* (aq)
Clisl +aq
> Cl-(aq)
NaC(,1
Na+1sq1
+ Cl-1aq1
\r
\,*rr"
-.*'\
mf
\
/
Na*1ny+ Clini
2l
.."t"t a{
ql,or-
ByHess'Law,rHlo= aHzo
+ aH:o
wnere
aHro= 5n11',u1pt
changeof solution
-_ ?
aHzo= -1u61."tn..nt
= _(_77g)
kJlmol
= (Totat)Enthatpy
aH3o
change
of hydration
iof ruj'inJ CfI
= (_3e0)+ (-384)
or
Enthalpy
of Solution
= -LatticeEnergy+ Entharpy
Hydration
of cation+ Entharpy
Hydration
of anion
= -( -rqa) + [(-ao)rr-l oJ
:
+ 5 t Jr^ol,
chanoeof solutionAHo
Solubility
(mol dm-3)
Licl
Nacl
KCI
AgCl
-862
-7 7 I
-778
-883
-770
-2t
+1
+23
+75
-69s
-830
-90s
19
o
5
1.3x10-5
(insoluble)
(a)
(b)
(c)
Lo.. n,
t6au
(d)
} -ta7 qi,,rt
o. t.'t,t+i
22