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Heat Effects: Skf2213: Chemical Engineering Thermodynamics
Heat Effects: Skf2213: Chemical Engineering Thermodynamics
HEAT EFFECTS
• Heat
is
a
path
funcKon
and
it
is
an
energy
in
transiKon
(we
do
not
store
heat,
we
transfer
it!).
• Also, H = U + PV
dH = dU + PdV + VdP
dH = Cp dT
• For isobaric process
T2
ΔH = H2 − H1 = ∫ Cp dT
T1
• Do
the
energy
balance
in
order
to
determine
the
outlet
air
temperature,
Ta2.
( ) − ∑ ( mH ) + ΔE
Q + W = ∑ mH 2 1 K
+ ΔE P
0 + 0 = ∑ ( mH ) − ∑ ( mH ) + 0 + 0
2 1
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
Assume air is an ideal gas:
T T
m o ∫ C po
l
dT + m a ∫ C pa
ig
dT = 0
To To
Cp
= A + BT + CT 2 + DT −2 (4.4)
R
∫C p dT
=
To
Cp
H T − To
R ∫ (A + BT + CT 2 + DT −2 )dT
=
To
Cp
H T − To
Cp B C D
H
= A+ To (τ + 1) + To2 (τ 2 + τ + 1) + 2 ≡ MCPH (T 0,T ; A, B,C, D)
R 2 3 τ To
∫C p dT
=
To
Cp
H T − To
Hence,
ΔH = C p
H
(T − T ) 0
• We
could
also
write,
ΔH = C p
H
(T
2
− T1 ) τ=
T2
T1
⎡ B C 2 2 D ⎤
ΔH = R ⎢ A + T1 (τ + 1) + T1 (τ + τ + 1) + 2 ⎥ (T2 - T1 )
⎣ 2 3 τT1 ⎦
C ig
Pmix = ∑ y iC ig
pi Ideal gas mixture
CPidmix = ∑ x iC p i Ideal solution
• Example
4.2
SoluKon
for
Q
is
straight
forward
if
T1
and
T2
are
known
⎡ B C 2 2 D ⎤
Q = ΔH = R ⎢ A + T1 (τ + 1) + T1 (τ + τ + 1) + 2 ⎥ (T2 - T1 )
⎣ 2 3 τT1 ⎦
• Example
4.3
SoluKon
for
T2
is
by
iteraKon
if
T1
and
Q
(or
∆H)
are
known
ΔH
T 2= + T1
⎡ B C 2 2 D ⎤
R ⎢ A + T1 (τ + 1) + T1 (τ + τ + 1) + 2 ⎥
⎣ 2 3 τT1 ⎦
Latent
Heat
of
VaporizaKon
• InformaKon
on
process
– Pure
substance
– IniKal
condiKon
is
saturated
liquid
at
T1
(or
T1sat)
and
P1
(or
P1sat)
(first
bubble
appears)
∂Q + ∂W = dU + dEK + dEP
∂Q + ∂W = dU
∂Q − PdV = dU
∂Q = dU + PdV = dH
Q = ΔH , this is delta H of vaporization at temperature T1
note,
Q = ΔHn , this is delta H of vaporization at normal boiling point
dP sat
ΔH vap = T ΔV (4.11)
dT
To used eqn 4.11, we need data for Psat, Tsat ,Vsat liq
and Vsat vap
1.092(ln Pc −1.013)
ΔH n = RTn
0.930 − Trn
J 1.092(ln 220.5 −1.013) 1mol
ΔH n = 8.314 373.15K
mol.K 373.15 18g
0.930 −
647.5
J
ΔH n = 2328
g
Now, compare with the value from steam table
• Also
Trouton’s
Rule
and
Chen’s
EquaKon
(see
Felder’s
Textbook)
• If
we
know
∆Hvap1
at
T1,
we
could
esKmate
∆Hvap2
at
T2
using
Watson
equaKon,
0.38 0.38
ΔH vap ⎛ 1− Tr ⎞ ⎛ Tc − T ⎞
=⎜ ⎟ =⎜ ⎟ (4.13)
ΔH vap1 ⎝ 1− Tr1 ⎠
T −
⎝ c 1⎠ T
ν1 A1 + ν 2 A2 → ν 3 A3 + ν 4 A4
−1 CH 4 + −2 O2 → 1 CO2 + 2 H 2O
|v1|, | v2| |v3|, | v4|
Q = ΔH
= ν 3 H 3 + ν 4 H 4 − ν 2 H 2 − ν1 H 1
= ∑νi H i
Standard
Heat
of
ReacKon
∆HoT
• Defined
as
the
enthalpy
change
from
a
stoichiometric
reacKon
where
the
reactants
entering
at
standard
state
(T=T
and
P=1
bar,
specified
phase
(g,
l,
s))
and
the
products
are
also
at
specified
phases
and
the
same
standard
state.
Q = ΔH T = ∑ ν i H
o o
i
• There are many references for tabulated data for
∆Ho298 for commonly found reactions.
1
2
N2 (g) + 32 H2 (g) → NH3 (g)
J J
ΔH298
o
= −46110
ΔH298
o
= −46110 3
mol H2 reacted
mol NH3 produced 2
J
ΔH298
o
= −46110 1
2
mol N2 reacted
ν1 E1 + ν 2 E 2 → Ai
ΔH o
f 298,i = H − ∑ | ve | H = H
i
o o
e i
o
ΔH o
298 = ∑νi H i
o
ΔH 298
o
= ∑ i f 298,i
ν ΔH o
• Example
of
formaKon
reacKon,
C ( s) + 12 O2 ( g) + 2H 2 ( g) → CH 3OH ( l)
where
C,O2 ,H 2 are elements
ΔH o
298 = ∑νi H i
o
ΔH 298
o
= ∑ i f 298,i
ν ΔH o
ΔH 298
o
= ν co2 ΔH of 298,co2 + ν H 2 ΔH of 298, H 2 + ν co ΔH of 298,co + ν H 2O ΔH of 298, H 2O
= ( −1) ( −393509 ) + ( −1) ( 0 ) + (1) ( −110525 ) + (1) ( −241818 )
ΔH 298
o
= 41166 mol CO2J reacted
• Note:
H2O does not actually exist as gas at 25oC and 1 bar.
This
is
hypotheKcal
state
of
H2O
as
an
ideal
gas
at
25oC
and
1
bar
is
used
for
convenience
in
calculaKon.
NoKce
also
the
standard
heat
of
formaKon
of
H2O
is
tabulated
for
liquid
as
well
as
gas
at
the
standard
state
(1bar,
25oC).
Standard
Heat
of
CombusKon
• Type
of
heat
of
reacKon
that
is
commonly
encountered.
• Data
for
heat
of
combusKon
at
standard
state
are
widely
available
• We
could
calculate
standard
heat
of
reacKon
from
standard
heat
of
combusKon
as
follows,
Heat of
ΔH 298
o
∑
= − ν i ΔH 298,i o
combustion
• Since
H
is
state
funcKon,
we
can
use
hypotheKcal
path
to
determine
ΔH 473.15
o
Convenient
path
is
through
standard
state
at
298.15K,
Rxts(473) Prds(473)
ΔH rxts
ΔH prds
Rxts(298) → Prds(298)
ΔH o
298
ΔH 473
o
= ΔH rxts + ΔH 298
o
+ ΔH prds
ΔH 473
o
= Sensible Heat + Std Heat of Rxn at 298 + Sensible Heat
o
dH 473 = ∑ niC p dT + dH 298
o
+ ∑ niC p dT
rxts473→298 prd 298→473
o
dH 473 =− ∑ niC p dT + dH 298
o
+ ∑ niC p dT
rxt 298→473 prd 298→473
o
dH 473 = dH 298
o
+ ∑ niC p dT − ∑ niC p dT
prd 298→473 rxt 298→473
For stoichiometric reaction, ni =|vi|
o
dH 473 = dH 298
o
+ ∑ viC p dT + ∑ viC p dT
prd 298→473 rxt 298→473
o
dH 473 = dH 298
o
K
+ ∑ ν iC p dT
o
dH 473 = dH 298
o
K
+ ΔC o
p
dT
Where,
< ΔC po > H ≡ Mean Heat Capacity for Reaction
and
⎛ ΔB ΔC 2 2 ΔD ⎞
< ΔC > H = R ⎜ ΔA +
o
T0 (τ + 1) + T0 (τ + τ + 1) + 2 ⎟ (4.20)
p
⎝ 2 3 τ T0 ⎠
and ΔM = ∑ ν i M i , and A, B,C, D are constants for heat capacity.
So,
ΔH 473
o
= ΔH 298
o
(
+ < ΔC po > H T − To )
ΔH 473
o
= ΔH 298
o
(
+ < ΔC po > H 473.15 − 298.15 )
(
ΔHTo = ΔHToo + < ΔC po > H T − To ) (4.21)
ΔHTo = ΔH 298
o
(
+ < ΔC po > H T − 298 )
Heat
Effects
of
Industrial
ReacKons
• Most
reacKon
in
industry
rarely
occur
at
25oC,
1bar
and
also
not
at
stoichiometric
proporKon.
• The
reacKon
is
not
always
go
to
compleKon
(not
100%
conversion)
⎛ ⎛ 79⎞ ⎞ ⎛ ⎛ 79⎞ ⎞
CH 4 + 1.2( 2O2 ) + 1.2⎜ 2⎜ ⎟ N 2 ⎟ → CO2 + 2H 2O + 1.2⎜ 2⎜ ⎟ N 2 ⎟ + 0.2( 2)O2
⎝ ⎝ 21⎠ ⎠ ⎝ ⎝ 21⎠ ⎠
⎛ ⎛ 79⎞ ⎞ ⎛ ⎛ 79⎞ ⎞
CH 4 + 1.2( 2O2 ) + 1.2⎜ 2⎜ ⎟ N 2 ⎟ → CO2 + 2H 2O + 1.2⎜ 2⎜ ⎟ N 2 ⎟ + 0.2( 2)O2
⎝ ⎝ 21⎠ ⎠ ⎝ ⎝ 21⎠ ⎠
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 = ΔH + ΔE K + ΔE P
Q = ΔH
• Maximum temperature is when Q=0, so
ΔH = 0
Prd (Tout )
• Path
ΔH prd
ΔH 298
o
Rxt(25 o C) → Prd(25 o C)
ΔH 298
o
( )( ) ( )( ) ( )(
= 1 −393509 + 2 −241818 + −1 −74520 + −2 0 ) ( )( )
J
ΔH 298
o
= −802625
Mol
and
T2
(
ΔH prd = ∑ ni ∫ C p dT = < ΔC po > H T2 − T1 )
T1
T2
(
ΔH prd = ∑ ni ∫ C p dT = < ΔC po > H T2 − T1 )
T1
⎛ ΔB ΔC 2 2 ΔD ⎞
ΔH prd = R ⎜ ΔA +
⎝ 2
T1 (τ + 1) +
3 τ T1 ⎠
(
T1 (τ + τ + 1) + 2 ⎟ T2 − T1 )
ΔM = ∑ ni M i
Outlet
n i is mol of each component in products. 1 mol CO2
0.4 mol O2
9.03 mol N2
ΔA = 1(5.457) + 0.4(3.639) + 9.03(3.28) + 2(3.47) = 43.471 2 mol H2O
For T1=298K,
⎛ 9.502x10−3 0.645x105 ⎞
ΔH prd = R ⎜ 43.471 +
⎝ 2
(298)(τ + 1) − 2 ⎟
τ (298) ⎠
(
T2 − 298 )
SubsKtute
into
energy
balance
ΔH = ΔH 298
o
+ ΔH prd = 0
J
ΔH = −802625
Mol
(
+ < ΔC po > H T2 − 298 = 0 )
J J ⎛ 9.502x10−3 0.645x105 ⎞
−802625
Mol
+ 8.314
MolK ⎜⎝
43.471 +
2
(298)(τ + 1) − 2 ⎟
τ (298) ⎠
( )
T2 − 298 = 0
802625
T2 = + 298
⎛ 9.502x10 −3
0.645x10 ⎞
5
8.314 ⎜ 43.471 + (298)(τ + 1) −
⎝ 2 τ (298)2 ⎟⎠
96539
T2 = + 298
⎛ 0.7263 ⎞
⎜⎝ 43.471 + 1.416(τ + 1) −
τ ⎟⎠
96539
T2 = + 298
⎛ 0.7263 ⎞
⎜⎝ 43.471 + 1.416(τ + 1) − τ ⎟⎠
96539
T2 = 298 +
⎛ ⎞
⎜ T2 0.7263 ⎟
⎜ 43.471 + 1.416( + 1) − ⎟
⎜ 298 T2 ⎟
⎝ 298 ⎠
96539
T2 = 298 +
⎛ 216.437 ⎞
⎜ 44.887 + 0.00475T2 − T ⎟
⎝ 2 ⎠