ENCH427 Chemical Engg ENCH427ChemicalEngg

Thermodynamics
Dr.Maen Husein
Dep Chem & Petr Engg Dep.Chem.&Petr.Engg
L3:HeatEffects
Ch 4 Textbook Ch4Textbook
HeatEffects
Sensible Heat: SensibleHeat:
Puresubsor
mixture{Ch.4}
H t f RXN
HeatofMixing:
Mixture{Ch12}
{ }
HeatofRXN:
Mixture{Ch.4}
2
4 1 S ibl H t Eff t 4.1SensibleHeatEffects
3
Heat effects of chemical rxn phase change Heateffectsofchemicalrxn,phasechange,
formation/separationofsolutions(Ch12)
constant temp constanttemp
Forpuresubs(orhomogeneoussysof
constant composition): U=U(TV) constantcomposition):U=U(T,V)
4
ForV=constprocess(regardlessofsubs); p ( g );
ForU=f(V)(regardlessofprocess):Truefor
ideal gas; real gas low pressures; idealgas;realgaslowpressures;
incompressibleliq &solids
5
Also,forsinglephasepuresubs(or
homogeneous sys of constant composition): homogeneoussysofconstantcomposition):
H=H(T,P)
For P=const process (regardless of subs); ForP constprocess(regardlessofsubs);
ForH=f(P)(regardlessofprocess):Truefor
ideal gas; real gas low pressures & solids* idealgas;realgaslowpressures&solids
6
C
p
&C
V
=f(T)foragivensubs*,oridealgas,
p V
empirical:
A,B,C,etc=f(gas/subs) (g )
7
C
P
ig
=f(T,gas)important1
st
calcthermoprop
P
( ,g ) p p p
foridealgas;2
nd
correctforrealgas
Determined experimentally+knowledge of Determinedexperimentally+knowledge of
molecularstructure(statisticalmechanics)
No available experimentsestimate methods Noavailableexperimentsestimatemethods
{beyondourscope}
Parameters:TableC.1
8
C
p
ig
=f(T,gas):
Increasesmoothlytoupper
limit(modesofmolecular
motion(?)fullyexcited)
C
P
ig
isgasdependent,since
d id l di i evenunderidealconditions,
molecularstructurereflectson
properties
9
C
p
idealgasmixture,liq &solids
Const.compositiongasmixturespuresubs
C
p
ig
mixtureidealgases:
C liquids+solidsexperiments; Eq
n
similar to Cliquids+solidsexperiments;Eq similarto
(4.4)(TablesC.2&C.3)ORcorrelation(Perrys
Handbook) Handbook)
10
Evaluationsensibleheatintegral
where
OR
where(C
P
)
H
isanaverageC
p
calcfromtheintegral
IfTunknown,iterationmakesusof: If T unknown, iteration makes us of:
11
e.g.useC
P
ig
12
Suggestedprob.:4.2;4.3;4.6;4.8
4.2LatentHeatofPureSubs
h i l h
WARNING: P133,2
ND
PARA:ITISNOTTHEINTENSIVESTATE
physicalchanges
OFTHESYSTEMWHICHISDETERMINED,BUTRATHERTHE
INTENSIVESTATEOFEACHPHASEINEQUILIBRIUM.
13
Any phase change at P=const (pure subs AnyphasechangeatP const(puresubs
T=const);ClausiusClapeyron Eq
n
(derivedCh6):
P d H P d
sat sat
A
(4.11) ) (
T d
P d
V T H
V T
H
T d
P d
A = A
A
A
=
P d
sat
slopefromPT
diagramsforthegivenT
) (
T d
P d
sat
g g
Evaporation:
14
f v
vap
H H H = A
f v
vap
V V V = A
Hphasechangeestimatedfrom:1)Clausius
Clapeyron Eq
n
;2)measuredcalorimeter;3)
correlationH=(T;material)
H@Tofinterestmightnotbeavailable
(UNIVAP providesalternative{notcovered}) ( p { })
Ofinterest:1)H
vap
@T
n
(1atm)
1 1) Rough estimate Troutons rule*
10
vap
n
H A
1.1)Roughestimate:Troutons rule*:
1.2)Moreaccurate:Riedelseq
n
*:
10 ~
n
n
RT
(4.12)
930 . 0
) 013 . 1 (ln 092 . 1
r
C
n
vap
n
T
P
RT
H

=
A
P
c
criticalP[=]bar;reducedTatn.b.p.(?)
15
n
r n
n
r
T
e.g.Ridiel eq
n
SuggestedProb:4.10;4.12;4.14
16
contdofinterest:2)EstimateH
vap
@T
2
*
2
whenH
vap
@T
1
*isknown(fairlyaccurate)
1
38 . 0
| |
vap
T
(4.13)
1
1
1
2
1
2
|
|
.
|

\
|

=
A
A
r
r
vap
vap
T
T
H
H
17
e.g.EstimateH
vap
@T
2
whenH
vap
@T
1
known
18
4.3StandardHeatofRXN
h i l h chemicalchanges
19
Energycontentreactant>energycontent
productHeatreleasedH
rxn
(viseversa)
CollectionH
rxn
ofallrxns impossiblecalcH
rxn
fromrxn carriedinstandardwaymindata
F i H f(T t t & d t ) Foragivenrxn,H
rxn
=f(Treactants&products)
Standardize:sameTforreactants&products
20
Standardheatofrxn H
rxn
o
enthalpychangewhen
rxn
amolesofAreactwithbmolesofBintheir
STDstateatagivenT toproducemolesofL
and m moles of M in their STD state at the same andmmolesofMintheirSTDstateatthesame
T
aA + bB L + mM aA +bB L +mM
STDstateofspeciesatagivenT=f(P,composition,
state g,L,s) state g,L,s )
P
STD
1atm;morerecent 1bar
Composition Pure substance Composition Puresubstance
State:1) gas idealgasgasesseldomdeviatefrom
ideality @ 1 bar; 2) liq&solid real ideality@1bar ;2) liq&solid real
STDstate=f(T)
21
4 4 St d d H t f F ti 4.4StandardHeatofFormation
22
H
o
rxn
=Ev
i
(H
o
f
)
i
v
i
stoichiometric coefficient(+ve product;ve
reactant){usebalancedeq
n
only}
H
o
f
formationrxn ofcompound:rxn forms1
moleofcompoundstartingfromits
tit t l t constituentelements
H
o
f298
tabulated(TableC.4).Ifrxn @different
T ibl h t f t t & d t i T,sensibleheatforreactants&products,is
used
1
st
l & f t th t H i t t f ti H 1
st
law&factthatH isstatefunctionHesss
lawapplies:rxns &H
o
rxn
canbeadded
23
H
o
f
element 0 convenience*since:
f
1)ifreactants&productsarecompounds
samemolesofanelementwillappearon
bothsideswhileusingHessslaweliminate
2)ifareactantoraproductisanelement
energyrelativetotheelementisaccounted
forinoftheH
o
f
compound
/ Stateofelement/compoundindicatedinthe
rxn equation
DifferencebetweenisH
o
f,H2O(l)
&H
o
f,H2O(g)
~
H
vap
298K
24
e.g.H
o
rxn
calc.
25
4.5StandardHeatof
C b ti Combustion
26
Combustionrxns easilycarriedincalorimeter
d t i i H
o
d servedeterminingH
o
f
compounds
e.g.P139
27
e.g.H
o
rxn
fromheatofcombustion
28
Suggestedprob.:4.19;4.20;4.24;4.26
4.6TemperatureDependenceof
H
o
H
o
rxn
29
H
o
rxn
=f(T)onlydependenceofH
o
rxn
onTcan
be calc : becalc.:
A
A c
A
o
o
rxn
o
dT C dT
H
H d ) (
}
A =
c
= A
T
o o o
P P
rxn
T rxn
d
dT C dT
T
H d
,
) (

}
A
A + A = A
o o
o
P
o o
T rxn
C C where
dT C H H
298
298 ,
v

= A
i P i P
C C where
,
v
Theaboveanalysisimpliesthatanychangesof
H
o
rxn
fromreferenceTarecapturedbysensible
heat calc of reactants & products heatcalc.ofreactants&products
30
Integralevaluatedasbelow
ORusingmeanC
P
:
) 298 (
298 ,
A + A = A T C H H
o
P
o o
T rxn
31
4.7HeatEffectsofIndustrial
RXN RXNs
32
e.g.IndustrialRXNs
Suggested prob.: 4.29; 4.31; 4.38; 4.39
33
Suggestedprob.:4.29;4.31;4.38;4.39