Skl2213: CPLMlCAL LnClnLL8lnC 1PL8MCu?

nAMlCS
PLA1 LllLC1S
Mohammad ladll Abdul Wahab
AlmosL all chemlcal processes lnvolve heaL
Lransfer.
PeaL ls a paLh funcuon and lL ls an energy ln
Lransluon (we do noL sLore heaL, we Lransfer lL!).
1ype of heaL Lransfer eecLs.
Senslble heaL
LaLenL heaL
PeaL of reacuon
PeaL of mlxlng/soluuon
Senslble PeaL LecL
lnformauon on process,
ure subsLance
Closed sysLem
ConsLanL pressure
lnlual condluons: 1
1
and
1

llnal condluons: 1
2
and
1

no reacuon
no phase change
Liq Liq
Gas
Gas
T
1
, P
1
T
1
, P
1
T
2
, P
1
T
2
, P
1
Lnergy balance for closed sysLem.

!Q+ !W = dU + dE
K
+ dE
P

!Q+ !W = dU

!Q" PdV = dU

H = U + PV
dH = dU + PdV +VdP

dH = dU + PdV
dU = dH ! PdV

Q = !H
Also,
For constant P
Substitute and integrate
So how do we determine !H?
l = 2-1+1 = 2
!"# % & %'()*+

dH =
!H
!T
"
#
$
%
&
'
p
dT +
!H
!P
"
#
$
%
&
'
T
dP
dH = C
p
dT +
!H
!P
"
#
$
%
&
'
T
dP

dH = C
p
dT
!H = H
2
" H
1
= C
p
dT
T
1
T
2
#

For isobaric process
So this equation for !H is only valid for isobaric
process and no change of phase.
If the process is not isobaric,
the equation is also valid for ideal gas
Also applicable for liquid and solid as H is
not highly dependent on pressure
Slmllarly, leL , & ,'()-+
For isochoric process
So this equation for !U is only valid for isochoric
process and single phase.
If the process is not isochoric,
The equation is also valid for ideal gas
Also applicable for liquid and solid as U is
not highly dependent on specific volume

dU =
!U
!T
"
#
$
%
&
'
V
dT +
!U
!V
"
#
$
%
&
'
T
dV
dU = C
v
dT +
!U
!V
"
#
$
%
&
'
T
dV

dU = C
v
dT

!U = U
2
"U
1
= C
v
#
dT
Lxample
PoL oll aL (
./
ls supplled Lo a heaLer Lo heaL alr enLerlng aL
(
0/
. 1he oll exlLs aL (
.1
and Lhe alr heaLer ls LoLally
lnsulaLed.
uo Lhe energy balance ln order Lo deLermlne Lhe ouLleL alr
LemperaLure, (
01
.
Hot Oil in, o1 Hot oil out, o2
Air in, a1
Air out, a2

! m
o
C
po
l
dT
T
o
T
!
+ ! m
a
C
pa
ig
dT
T
o
T
!
= 0

! m
o
C
po
l
(T
o2
! T
o1
) + ! m
a
C
pa
ig
(T
a2
! T
a1
) = 0
! m
o
C
po
l
(T
o2
! T
o1
) = ! ! m
a
C
pa
ig
(T
a2
! T
a1
)
Solve for T
a2
Assume air is an ideal gas:
Assume constant C
P
:

!
Q+
!
W = mH
( )
!
2
" mH
( )
!
1
+ #E
K
+ #E
P
0 + 0 = mH
( )
!
2
" mH
( )
!
1
+ 0 + 0
0 = ! m
o
H
o2
+ ! m
a
H
a2
" ! m
o
H
o1
" ! m
a
H
a1
! m
o
(H
o2
" H
o1
) + ! m
a
(H
a2
" H
a1
) = 0
Steady state energy balance for open system:
PeaL CapaclLy
A funcuon of LemperaLure
A,B,C and D are constants for heat capacity and
values for ideal gas, solid and liquid are tabulated in
Table C1, C2, C3 respectively
In this textbook, the tabulated constants are for C
p
/R.
The units for C
P
depends on the unit for R.
C
p
R
= A + BT + CT
2
+ DT
!2
(4.4)
Mean PeaL CapaclLy
1o slmpllfy calculauon, leL us dene mean heaL capaclLy
as,
C
p
H
=
C
p
dT
T
o
T
!
T " T
o

! =
T
T
o
Where MCPH is a subroutine function and
C
p
H
R
= A +
B
2
T
o
(! +1) +
C
3
T
o
2
(!
2
+! +1) +
D
!T
o
2
" MCPH(T 0,T; A, B, C, D)
C
p
H
=
R (A + BT + CT
2
+ DT
!2
)dT
T
o
T
"
T ! T
o
C
p
H
=
C
p
dT
T
o
T
!
T " T
o

!H = C
p
H
T " T
0
( )

Hence,
Since
We could also wrlLe,

!H = C
p
H
T
2
" T
1
( )


C
P
mix
ig
= y
i
C
p
i
ig
!
Ideal gas mixture
C
P
mix
id
= x
i
C
p
i
!
Ideal solution
Heat capacity for ideal mixture,

!H = R A +
B
2
T
1
(" +1) +
C
3
T
1
2
("
2
+ " +1) +
D
"T
1
2
#
$
%
&
'
(
(T
2
- T
1
)

! =
T
2
T
1
Lxample 4.2
Soluuon for 2 ls sLralghL forward lf (
/
and (
1
are
known

Q= !H = R A +
B
2
T
1
(" +1) +
C
3
T
1
2
("
2
+ " +1) +
D
"T
1
2
#
$
%
&
'
(
(T
2
- T
1
)
Lxample 4.3
Soluuon for (
1
ls by lLerauon lf (
/
and 2 (or 3%)
are known

T
2
=
!H
R A +
B
2
T
1
(" +1) +
C
3
T
1
2
("
2
+ " +1) +
D
"T
1
2
#
$
%
&
'
(

+ T
1
LaLenL PeaL of vaporlzauon
lnformauon on process
ure subsLance
lnlual condluon ls saLuraLed llquld aL 1
1
(or 1
1
saL
) and
1
(or
1
saL
)

(rsL bubble appears)
llnal condluon ls saLuraLed vapor aL 1
1
and
1
(lasL drop of llquld (dew) ls Lo dlsappear))
hase change ls Laklng place
First bubble appears
Last drop of liquid is
about to disappear
Lnergy 8alance Closed SysLem

!Q+ !W = dU + dE
K
+ dE
P
!Q+ !W = dU
!Q" PdV = dU
!Q = dU + PdV = dH
Q = #H , this is delta H of vaporization at temperature T
1
note,
Q = #H
n
, this is delta H of vaporization at normal boiling point
Degree of freedom, F=2-2+1=1
Once we specified one thermodynamic properties,
other properties will depends on this.
lor example, saLuraLed P
2
C aL a specled (&/45
.
6.
a) We can use Clapeyron equauon Lo esumaLe 3%
708

P
sat
, H
v
sat
, H
l
sat
so
!H
vap
= H
v
sat
" H
l
sat
b) or from steam table we get,

!H
vap
= T!V
dP
sat
dT
(4.11)
To used eqn 4.11, we need data for P
sat
, T
sat
,V
sat liq

and V
sat vap

AL normal bolllng polnL ((
9
) we could esumaLe 3%
708
by
slmple equauon known as 8ledel equauon,

!H
vap, n
RT
n
=
1.092(ln P
c
"1.013)
0.930 " T
r
n
(4.12)

!H
n
= RT
n
1.092(ln P
c
"1.013)
0.930 "T
r
n
!H
n
= 8.314
J
mol.K
373.15K
1.092(ln 220.5 "1.013)
0.930 "
373.15
647.5
1mol
18g
!H
n
= 2328
J
g
Example, for water
Now, compare with the value from steam table
Also 1rouLons 8ule and Chens Lquauon (see
lelders 1exLbook)
lf we know 3%
708/
aL (
/
, we could esumaLe 3%
7081
aL (
1

uslng WaLson equauon,

!H
vap
!H
vap1
=
1" T
r
1" T
r1
#
$
%
&
'
(
0.38
=
T
c
" T
T
c
" T
1
#
$
%
&
'
(
0.38
(4.13)
So we could combine Riedel and Watson equations
to solve for "H
vap2
, whereby "H
vap1
is !H
n
and T
r1
is
T
rn
.
PeaL of 8eacuon
lnformauon on process
leeds (e.g. A
1
, A
2
) are reacLanLs
CuLleLs are producLs (e.g. A
3
, A
4
) of Lhe reacuon
PeaL ls released or absorbed durlng Lhe process
LxoLhermlc reacuon: 3% ls negauve
LndoLhermlc reacuon: 3% ls posluve

!
1
A
1
+ !
2
A
2
" !
3
A
3
+ !
4
A
4
Where |v
i
| is stoichiometric coefficient
e.g. CH
4
+ 2O
2
!CO
2
+ 2H
2
O
Stoichiometric reaction,
Where the value of v
i
is positive for products
and negative for reactants.
!1 CH
4
+ !2 O
2
" 1 CO
2
+ 2 H
2
O
Energy balance for steady-state open system
with stoichiometric reaction,
Q = !H
= "
3
H
3
+ "
4
H
4
# "
2
H
2
# "
1
H
1
= "
i
$
H
i
|v
1
|, |

v
2
|
|v
3
|, |

v
4
|
SLandard PeaL of 8eacuon 3%
.
(

uened as Lhe enLhalpy change from a
sLolchlomeLrlc reacuon where Lhe reacLanLs
enLerlng aL sLandard sLaLe (1=1 and =1 bar,
specled phase (:) ;) <)) and Lhe producLs are also
aL specled phases and Lhe same sLandard sLaLe.
8ewrlLe energy balance as,

Q= !H
T
o
= "
i
#
H
i
o
There are many references for tabulated data for
"H
o
298
for commonly found reactions.
|v
1
|, |

v
2
|
|v
3
|, |

v
4
|
T=25
o
C, P=1bar T=25
o
C, P=1bar
Lx. of SLandard PeaL of 8eacuon aL 1=298.13k, AP
o
298

1
2
N
2
(g) +
3
2
H
2
(g) !NH
3
(g)
"H
298
o
= #46110
J
mol NH
3
produced

!H
298
o
= "46110
J
3
2
mol H
2
reacted
!H
298
o
= "46110
J
1
2
mol N
2
reacted

N
2
(g) + 3H
2
(g) !2NH
3
(g)
"H
298
o
= #92220
J
2mol NH
3
produced

!H
298
o
= "92220
J
3mol H
2
reacted
!H
298
o
= "92220
J
mol N
2
reacted
Note: The value of standard heat of reaction
depends on stoichiometric coefficients as written
Powever, Labulauon of all posslble reacuons are
noL pracucal.
lurLhermore, noL all reacuons can Lake place aL
298k
So, how Lo calculaLe sLandard heaL of reacuon?
SLandard PeaL of lormauon 3%
.
=)>
of specles >
Here H
o
i
is calculated with reference to its elements
enthalpy (H
o
e
) to be zero at standard state
(T=298.15K)
!H
f 298,i
o
= H
i
o
" | v
e
| H
e
o
#
= H
i
o

!
1
E
1
+ !
2
E
2
" A
i
For formation of 1 mol of compound A
i
from its
elements (E),

!H
298
o
= "
i
#
!H
f 298,i
o
So we can calculate standard
heat of reaction from standard heat of
formation of the reactants and products
!H
298
o
= "
i
#
H
i
o
Lxample of formauon reacuon,

C s ( ) +
1
2
O
2
g ( ) + 2H
2
g ( ) !CH
3
OH l ( )
where
C,O
2
, H
2
are elements
Heat of formations are usually tabulated
at 298.15K, such as in Table C4.

!H
f 298
o
CO
2
(g) + H
2
(g) !CO(g) + H
2
O(g)
Example:
Calculation of std heat of rxn using std heat of formation,
!H
298
o
= "
co2
!H
f 298, co2
o
+"
H2
!H
f 298, H2
o
+"
co
!H
f 298, co
o
+"
H2O
!H
f 298, H2O
o
= #1 ( ) #393509 ( ) + #1 ( ) 0 ( ) + 1 ( ) #110525 ( ) + 1 ( ) #241818 ( )
!H
298
o
= 41166
J
mol CO
2
reacted

!H
298
o
= "
i
#
!H
f 298,i
o
!H
298
o
= "
i
#
H
i
o
noLe:
P
2
C does noL acLually exlsL as gas aL 23
o
C and 1 bar.
1hls ls hypoLheucal sLaLe of P
2
C as an ldeal gas aL 23
o
C
and 1 bar ls used for convenlence ln calculauon.
nouce also Lhe sLandard heaL of formauon of P
2
C ls
LabulaLed for llquld as well as gas aL Lhe sLandard sLaLe
(1bar, 23
o
C).
SLandard PeaL of Combusuon
1ype of heaL of reacuon LhaL ls commonly encounLered.
A reacuon beLween fuel and oxygen Lo produce waLer and
carbon dloxlde
8eacLanLs has hlgher chemlcal energy Lhan Lhe producLs,
Lherefore Lhe heaL of combusuon ls negauve.
uaLa for heaL of combusuon aL sLandard sLaLe are wldely
avallable
We could calculaLe sLandard heaL of reacuon from
sLandard heaL of combusuon as follows,

!H
298
o
= " #
i
$
!H
298,i
o
For example, for the following reaction,

4C(s) + 5H
2
(g) !C
4
H
10
(g)
"H
298
o
= # 1
( )
#2877.4
( )
+ #5
( )
#285.83
( )
+ #4
( )
#393.51
( )
$
%
&
'
"H
298
o
= #125.79
kJ
mol C
4
H
10
produced
Heat of
combustion
Note, coincidentally this is also standard heat of
formation of n-Butane.
MeasuremenL of PeaL of Combusuon
8omb CalorlmeLer for llquld and
solld fuel
8oys CalorlmeLer for gas fuel
1emperaLure uependence of ?%
.
(
MosL reacuons ln Lhe lndusLry occur aL LemperaLure
oLher Lhan sLandard sLaLe.
lor example, reacLanLs enLer a reacLor aL 200
o
C and Lhe
producLs exlL 200
o
C, so sLd heaL of reacuon ls
Slnce % ls sLaLe funcuon, we can use hypoLheucal paLh Lo
deLermlne
!H
473.15
o

!H
473.15
o
ConvenlenL paLh ls Lhrough sLandard sLaLe aL 298.13k,
Rxts(473) Prds(473)
Rxts(298) ! Prds(298)

!H
prds
!H
rxts

!H
298
o

!H
473
o
= !H
rxts
+ !H
298
o
+ !H
prds
!H
473
o
= Sensible Heat + Std Heat of Rxn at 298 + Sensible Heat

dH
473
o
= n
i
rxts473!298
"
C
p
dT + dH
298
o
+ n
i
prd 298!473
"
C
p
dT
dH
473
o
= # n
i
rxt 298!473
"
C
p
dT + dH
298
o
+ n
i
prd 298!473
"
C
p
dT
dH
473
o
= dH
298
o
+ n
i
prd 298!473
"
C
p
dT # n
i
rxt 298!473
"
C
p
dT

dH
473
o
= dH
298
o
+ v
i
prd 298!473
"
C
p
dT + v
i
rxt 298!473
"
C
p
dT
dH
473
o
= dH
298K
o
+ #
i
"
C
p
dT
dH
473
o
= dH
298K
o
+ $C
p
o
dT
For stoichiometric reaction, n
i
=|v
i
|

Where,
< !C
p
o
>
H
" Mean Heat Capacity for Reaction

and
< !C
p
o
>
H
= R !A+
!B
2
T
0
(" +1) +
!C
3
T
0
2
("
2
+" +1) +
!D
"T
0
2
#
$
%
&
'
(
(4.20)
and !M = )
i
M
i
*
, and A, B,C, D are constants for heat capacity.

In general, standard heat of reaction at temperature T,
!H
T
o
= !H
To
o
+ < !C
p
o
>
H
T " T
o
( )
(4.21)
!H
T
o
= !H
298
o
+ < !C
p
o
>
H
T " 298
( )

So,
!H
473
o
= !H
298
o
+ < !C
p
o
>
H
T " T
o
( )
!H
473
o
= !H
298
o
+ < !C
p
o
>
H
473.15" 298.15
( )
PeaL LecLs of lndusLrlal 8eacuons
MosL reacuon ln lndusLry rarely occur aL 23
o
C, 1bar and
also noL aL sLolchlomeLrlc proporuon.
8eacLanLs always conLalns excess componenL.
1he reacuon ls noL always go Lo compleuon (noL 100
converslon)
CuLleL LemperaLure ls noL Lhe same as Lhe lnleL.
resence of lnerL maLerlals
More Lhan one reacuons may Look place slmulLaneously
lor example,
WhaL ls Lhe maxlmum LemperaLure LhaL can be reached
by Lhe combusuon of 1 mol of meLhane wlLh 20 excess
alr? 8oLh Lhe meLhane and Lhe alr enLer Lhe burner aL
23
o
C.

CH
4
+ 2O
2
+ 2
79
21
!
"
#
$
%
&
N
2
'CO
2
+ 2H
2
O + 2
79
21
!
"
#
$
%
&
N
2

CH
4
+1.2 2O
2
( )
+1.2 2
79
21
!
"
#
$
%
& N
2
!
"
#
$
%
&
'CO
2
+ 2H
2
O +1.2 2
79
21
!
"
#
$
%
& N
2
!
"
#
$
%
&
+ 0.2 2 ( )O
2
With 20% excess air,
8asls of calculauon: 1 mol CP4

Inlet Outlet
1 mol CH4 1 mol CO2
2.4 mol O2 0.4 mol O2
9.03 mol N2 9.03 mol N2
2 mol H2O

Energy balance

Q+W
s
= !H + !E
K
+ !E
P
Q= !H

CH
4
+1.2 2O
2
( )
+1.2 2
79
21
!
"
#
$
%
& N
2
!
"
#
$
%
&
'CO
2
+ 2H
2
O +1.2 2
79
21
!
"
#
$
%
& N
2
!
"
#
$
%
&
+ 0.2 2 ( )O
2

!H = 0
Maximum temperature is when Q=0, so
aLh
Energy balance becomes,

!H = !H
298
o
+ !H
prd
= 0
where
!H
298
o
= "
i
#
!H
298, f
o
!H
298
o
= 1
( )
$393509
( )
+ 2
( )
$241818
( )
+ $1
( )
$74520
( )
+ $2
( )
0
( )
!H
298
o
= $802625
J
Mol
and
!H
prd
= n
i
#
C
p
T
1
T
2
%
dT = < !C
p
o
>
H
T
2
$ T
1
( )
Rxt(25
o
C) ! Prd(25
o
C)
Prd T
out
( )

!H
prd

!H
298
o

!H
prd
= n
i
"
C
p
T
1
T
2
#
dT = < !C
p
o
>
H
T
2
$ T
1
( )
!H
prd
= R !A+
!B
2
T
1
(% +1) +
!C
3
T
1
2
(%
2
+% +1) +
!D
%T
1
2
&
'
(
)
*
+
T
2
$ T
1
( )

!M = n
i
M
i
"
n
i
is mol of each component in products.

!A = 1(5.457) + 0.4(3.639) + 9.03(3.28) + 2(3.47) = 43.471
!B = [1(1.045) + 0.4(0.506) + 9.03(0.593) + 2(1.45)]x10
"3
= 9.502x10
"3
!D = [1("1.157) + 0.4("0.227) + 9.03(0.04) + 2(0.121)]x10
5
= "0.645x10
5

Outlet
1 mol CO2
0.4 mol O2
9.03 mol N2
2 mol H2O


!H
prd
= R 43.471+
9.502x10
"3
2
(298)(# +1) "
0.645x10
5
#(298)
2
$
%
&
'
(
)
T
2
" 298
( )
For T
1
=298K,
SubsuLuLe lnLo energy balance

!H = "802625
J
Mol
+ < !C
p
o
>
H
T
2
" 298
( )
= 0
"802625
J
Mol
+ 8.314
J
MolK
43.471+
9.502x10
"3
2
(298)(# +1) "
0.645x10
5
#(298)
2
$
%
&
'
(
)
T
2
" 298
( )
= 0
T
2
=
802625
8.314 43.471+
9.502x10
"3
2
(298)(# +1) "
0.645x10
5
#(298)
2
$
%
&
'
(
)
+ 298
T
2
=
96539
43.471+1.416(# +1) "
0.7263
#
$
%
&
'
(
)
+ 298

!H = !H
298
o
+ !H
prd
= 0
Solve by iteration (Use Excel or Casio fx-570)
Answer: T
2
= 2066K = 1793
o
C
What will happen to the outlet temperature (T
2
) if no
excess air is used?

T
2
=
96539
43.471+1.416(! +1) "
0.7263
!
#
$
%
&
'
(
+ 298
T
2
= 298 +
96539
43.471+1.416(
T
2
298
+1) "
0.7263
T
2
298
#
$
%
%
%
&
'
(
(
(
T
2
= 298 +
96539
44.887 + 0.00475T
2
"
216.437
T
2
#
$
%
&
'
(
8eference
SmlLh !.M., van ness P.C. , and Abbou M. M. ,
lnLroducuon Lo Chemlcal Lnglneerlng
1hermodynamlcs, 7
Lh
Ldluon, McCraw Plll,
new ?ork, 2001.