Advanced Thermodynamics

Note 3
Heat Effects

Lecturer: 郭修伯
 Heat
• The manufacture of ethylene glycol:
– The catalytic oxidation reaction is most effective when
carried out at temperatures near 250°C.
– The reactants, ethylene and air are heated to this
temperature before they enter the reactor.
– Heat is removed from the reactor to maintain the
reaction temperature at 250 °C and to minimize the
production of CO2.
• Heat effects are important.
 Sensible heat effects
• Heat transfer to a system in which there are no
phase transition, no chemical reactions, and no
changes in composition cause the temperature of
the system to change.
• Relation:
– Quantity of heat transferred
– The resulting temperature change
• Two intensive properties establishes its state: U =
U (T,V)
  U   U 
U  U (T ,V ) dU    dT    dV
 T V  V T

 U 
dU  CV dT    dV
 V T
constant-volume

dU  CV dT
mechanically reversible constant-volume process
T2
Q  U   CV dT
T1

.OR.
  H   H 
H  H (T , P) dH    dT    dP
 T  P  P T

 H 
dH  C P dT    dP
 P T
constant-pressure

dH  C P dT
mechanically reversible constant-pressure process
T2
Q  H   C P dT
T1
 T T2
• Since Q   Cor  Cneed
Q , we C = f (T).
2

V dT P dT
T1 T1
• From empirical equation:
CP
 A  BT  CT 2  DT  2
R
• For gases, it is the ideal-gas heat capacity, rather than the actual heat capacity,
that is used in the evaluation of such thermodynamic properties as the
enthalpy.
– Calculate values for a ideal-gas state wherein ideal-gas heat capacities are used
– Correction to real-gas value
• Ideal-gas heat capacities:

• The two ideal-gas heat capacities:

C Pig in the ideal-gas2 state:  2

• The molar heat capacity of the mixture
 A  BT  CT  DT
R
CVig C Pig
 1
R R

C Pigmixture  y AC PA
ig
 y B C PB
ig
 yC C PC
ig
 T CP  B C 2 2 D 
 T  T0 
T
• With   T0 R dT   A  T0 (  1)  T0 (    1)  2
T0  2 3 T0 

T CP T C
T0 R dT  ICPH (T 0, T ; A, B , C , D ) H  R T0 R dT  CP
P
H
(T  T0 )

The function name is ICPH

Mean heat capacity; subscript
“H” denotes a mean value
specific to enthalpy calculations.

CP H
 MCPH (T 0, T ; A, B, C , D) H
R T  T0
CP H
The function name is MCPH
It can be used to evaluate C P H
Calculate the heat required to raise the temperature of 1 mol of methane from 260
to 600°C in a steady-flow process at a pressure sufficiently low that methane may
be considered an ideal gas.

T 600  273.15
   1.6377
T0 260  273.15
ig
CP
T 873.15 C
Q  H  R  dT   P
dT
T0 R 533.15 R

 9.08110 3 2 2 2.164  10 6 3 3 
 8.3141.702T0 (  1)  T0 (  1)  T0 (  1)
 2 3 
 8.314  ICPH (533.15,873.15;1.702,9.081E  3,2.164 E  6,0.0)
 8.314  MCPH (533.15,873.15;1.702,9.081E  3,2.164 E  6,0.0) 873.15  533.15
 19778 J
What is the final temperature when heat in the amount of 0.4 x 10 6 Btu is added to
25 (lb mol) of ammonia initially at 500 °F in a steady-flow process at 1 (atm)?

Q 0.4 106 Btu J

H    16000  37218
n 25 lb mol mol

T0  500 F  533.15 K

H
T  T0
CP H

CP H
 MCPH (533.15, T ;3.578,3.020E  3,0.0,0.186E  5)
R

Start with a value T ≧ T0, T converges no the final value T = 1250K

 Latent heats of pure substances
• A pure substance is liquefied from the solid state of vapori
zed from the liquid at constant pressure, no change in temp
erature
– The latent heat of fusion
– the latent heat of vaporization
• the coexistance of two phases
– According to the phase rule, its intensive state is determined by jus
t one intensive property.
dP sat
H  TV
dT

Latent heat Vapor pressure

• Rough estimates of latent heats of vaporization for pure liquids at their normal po
ints (Trouton‘s rule):

H n
~ 10
RTn
• Riedel (1954):
Absolute temperature of the normal boiling point
Critical temperature (bar)
H 1.092(ln PC  1.013)

– Accurate! Error rarely exceedn5%
– Water: RTn 0.930  Trn
Reduced temperature at Tn
• latent heat of vaporization of a pure liquid at any temperature, (Watson, 1943):

H n 1.092(ln 220.55  1.013) H n  13.56  8.314  373.15

  13.56
RTn 0.930  0.577

0.38
H 2  1  Tr 2 
  
H1  1  Tr1 
Given that the latent heat of vaporization of water at 100°C is 2257 J/g, estimate
the latent heat at 300 °C.
0.38
H 2  1  Tr 2 
  
H1  1  Tr1 

H1 (100 C )  2257

H 2 (300 C )  ?
Tr1  373.15 / 647.1  0.577
Tr 2  573.15 / 647.1  0.886

J
H 2 (300 C )  1371
g
 Standard heat of reaction
• A standard state is a particular state of species at
temperature T and at specified conditions of pressure,
composition, and physical condition as e.g., gas, liquid, or
solid.
– Gases: the pure substance in the ideal-gas state at 1 bar. C P  C Pig
– Liquids and solids: the real pure liquid or solid at 1 bar. C 
P
– All conditions for a standard state are fixed except temperature.
Standard-state properties are therefore functions of temperature
only.
• Heat of reaction: 1 3
N 2  H 2  NH 3 H 298

 46100 J
2 2

N 2  3H 2  2 NH 3 H 298

 92220 J
 Standard heat of formation
• A formation reaction is defined as a reaction which forms a
single compound from its constituent elements, e.g.,:
1
C  O2  2 H 2  CH 3OH
2
• The heat of formation is based on 1 mol of the compound
formed.
• The standard heat of formation : 298.15 K  H 
f 298

• The standard heat at 25°C for the reaction:

4 HCl( g )  2 H 2 ( g )  2Cl2 ( g ) H 298

 (4)(92307)

2 H 2( g )  O2 ( g )  2 H 2O( g ) H 298

 (2)(241818)

4 HCl( g )  O2( g )  2 H 2O( g )  2Cl2 ( g ) H 298


 114408
 Standard heat of combustion
• A combustion reaction is defined as a reaction
between an element or compound and oxygen to
form specific combustion products.
– Many standard heats of formation com from standard
heats of combustion, measured calorimetrically.
– Data are based on 1 mol of the substance burned.
4C( s )  4O2( g )  4CO2 ( g ) H 298

 (4)(393509)
1
5 H 2 ( g )  2 O2( g )  5 H 2O(l ) H 298

 (5)(285830)
2
1
4CO2( g )  5H 2O(l )  C4 H10 ( g )  6 O2 ( g ) H 298

 2877396
2
4C( s )  5H 2 ( g )  C4 H10( g ) H 298

 125790
Temperature dependence of ΔH°
• A general chemical reaction:
v1 A1  v2 A2  ...  v3 A3  v4 A4  ...
– standard heat of reaction:
H    vi H i
i
– if the standard-state enthalpies of all elements are
arbitrary set equal to zero as the basis of calculation:
H    vi H i   vi H fi
i i
– For standard reactions, products and reactants are
always at the standard-state pressure of 1 bar:
dH i  C Pi dT
dH  C dT
i
 
Pi
 v dH   v C
i
i i


i
i

Pi dT

 i i  i i  i Pi dT
i
d ( v H 
)  d ( v H 

i
)  v C 

H    (vi H i ) C P   vi C Pi
i i

dH   C P dT

C P T
H   H 0  C P (T  T0 )
H  H  R 
 
0 dT H
T0 R

H   H 0  R  IDCPH (T0 , T ; DA, DB, DC , DD)

H   H 0  R  MDCPH (T0 , T ; DA, DB, DC , DD)  (T  T0 )

Calculate the standard heat of the methanol-synthesis reaction at 800 °C.
CO( g )  2 H 2( g )  CH 3OH ( g )

H 0  H 298

K  200660  ( 110525)  90135

C P
T
H  H  R 
 
0 dT
T0 R

H   H 0  R  ( MDCPH (298.15,1073.15;7.663,10.815 E  3,3.450 E  6,0.135 E  5)(T  T0 )

 90135  8.314  (1615.5)  (1073.15  298.15)
 103566
What is the maximum temperature that can be reached by the combustion of
methane with 20% excess air? Both the methane and the air enter the burner at
25°C. CH  2O  CO  2 H O
4( g ) 2( g ) 2( g ) 2 (g)

H 0  H 298

K  393509  ( 2)(241818)  ( 74520)  802625

Maximum attainable temperature → adiabatic, Q = 0 → ΔH = 0

H 298

 H P  H  0
Products at 1 bar and T K
H 298

1 mol CO2
T  298.15  
CP 2 mol H2O
H

Start with T > 298.15 K 0.4 mol O2

and converge on a final ΔH = 0 9.03 mol N2
value of T = 2066K H P
  ni C Pi
H
 T  298.15
Reactants at 1 bar and 25°C i

1 mol CH4  C P
H
 T  298.15
2.4 mol O2
H 298

K
9.03 mol N2
Catalytic reforming of CH4: CH 4( g )  H 2O( g )  CO( g )  3H 2 ( g )
The only other reaction occurs: CO( g )  H 2O( g )  CO2( g )  H 2 ( g )
Calculate the heat requirement.
CH 4( g )  H 2O( g )  CO( g )  3H 2 ( g ) H 298

 205813
CO( g )  H 2O( g )  CO2 ( g )  H 2 ( g ) H 298

 41166 Not independent, choose
(1) and (3) reactions
CH 4( g )  2 H 2O( g )  CO2 ( g )  4 H 2 ( g ) H 298

 164647

ΔH = 0 Products at 1 bar and 1300 K

0.87 mol CO
3.13 mol H2
Reactants at 1 bar and 600K 0.13 mol CO2
1 mol CH4 0.87 mol H2O
2 mol H2O H P
  ni C Pi
H
 T  298.15
H 
R
i

 C P
H
 T  298.15
H 298

K
H  H R  H 298

 H P

CH 4 ( g )  H 2O( g )  CO( g )  3H 2 ( g ) H 298


 205813

CH 4 ( g )  2 H 2O( g )  CO2( g )  4 H 2 ( g ) H 298


 164647

0.87 mol CH4 by (1) and 0.13 mol CH4 by (3)

H 298

K  (0.87)( 205813)  (0.13)(164647)  200460

H R
  ni C Pi
H
 298.15  600
i

 (1)(MCPH (600,298.15;1.702,9.081E  3,2.164E  6,0.0)  

 8.314    298.15  600
 (2)(MCPH (600,298.15;3.470,1.450E  3,0.0,0.121E  5) 
 34390
H P
  ni C Pi
H
1300  298.15  161940
i

H  H R  H 298

 H P  328010 Q  H  328010
Steady flow, no shaft work, kinetic and
potential energy changes are negligible