THERMODYNAMICS OF

INDUSTRIAL REACTIONS
CH126P
arcaparanga / cbmes / mapua
Thermodynamics of Industrial Reactions
• Industrial reactions are rarely carried out under standard conditions.
• In reality:
• Reactants may not be present in stoichiometric proportions.
• Reaction may not go to completion.
• Final temperature may differ from initial temperature.
• Inert species my be present.
• Simultaneous reaction may occur.

arcaparanga / mapua / cbmes 2

Heat Effects
• SENSIBLE HEAT
• heat change that is due to change in temperature
• LATENT HEAT
• heat change that is due to phase change (condensation, evaporation, melting,
etc.)
• HEAT OF REACTION
• heat change that is associated with chemical reaction (formation,
decomposition, combustion, etc.)

arcaparanga / mapua / cbmes 3

SENSIBLE HEAT EFFECTS
U  U T ,V  • For any closed-system constant-
volume process.
 U   U  • Whenever internal energy is
dU    dT    dV
 T V  V T independent of volume, as for the
ideal-gas state and the
 U  incompressible fluid.
dU  CV dT    dV
 V T dU  CV dT

• For simple heating (a mechanically

reversible constant-volume
process):
T2
Q  U   CV dT
T1
arcaparanga / mapua / cbmes 4
H  H T , P  • For any constant-pressure process.
• Whenever enthalpy is independent of pressure,
 H   H 
dH    dT    dP regardless of process. This is exactly true for
 T  P  P T the ideal-gas state and approximately for real
gases at low P and high T.
 H 
dH  C P dT    dP dH  C P dT
 P T

• For mechanically reversible, constant-pressure,

closed-system processes and for heat transfer
in steady flow, with negligible kinetic energy,
potential energy, and shaft work.
T2
Q  H   C P dT
T1
arcaparanga / mapua / cbmes 5
Temperature-dependence of Heat Capacity

CP
   T  T 2
R
CP
 a  bT  cT 2 Table C.1
Heat capacities of gases in the ideal-gas state
R
in combined form : Table C.2
Heat capacities of solids
CP 2
 A  BT  CT  DT
2
Table C.3
R Heat capacities of liquids

arcaparanga / mapua / cbmes

Heat Capacity in the Ideal-gas State
Statistical mechanics provides a basic  H 
CP   
equation for the temperature
dependence of the ideal-gas-state
 T  P
internal energy.  f T  
CP  2 R  
5

U  32 RT  f T   T  P

For the ideal-gas state: accounts for all

represents rotational and
H  U  PV translational vibrational kinetic
kinetic energy of energies associated
H  U  RT the molecules with the molecule
Combining:
C P  52 R monatomic gases
H  52 RT  f T  C P  72 R diatomic gases
arcaparanga / mapua / cbmes 7
Heat Capacity in the Ideal-gas State

C P  CV  R

FOR IDEAL
GAS ONLY!!!!!!

arcaparanga / mapua / cbmes 8

Heat Capacity in the Ideal-gas State
Heat capacity of gas mixtures (with N components) in the ideal-gas state:

C P ,mix  y1C P ,1  y2C P ,2  y3C P ,3  ...  y N C P ,N

i N
C P ,mix   yi C P ,i
i 1

yi mole fraction of component i

arcaparanga / mapua / cbmes 9

LATENT HEAT OF PURE SUBSTANCES
CLAPEYRON EQUATION TROUTON’S RULE
• for a pure species at T • rough estimate of latent heat of
vaporization for pure liquids at
dP sat their normal boiling point (Hn)
H  TV
dT H n
 10
H latent heat (enthalpy change RTn
due to phase change)
V volume change due to phase Tn normal boiling point (absolute
change temperature)
Psat saturation pressure (pressure
at which phase change occurs;
function of T)
arcaparanga / mapua / cbmes 10
LATENT HEAT OF PURE SUBSTANCES
RIEDEL EQUATION WATSON’S METHOD
• for liquid at normal boiling point • estimation of H of vaporization of
a pure liquid at any temperature
H n 1.092ln Pc  1.013 from the known value at a single

RTn 0.930  Trn temperature.

0.38
H 2  1  Tr 2 
Pc critical pressure (bar)   
Trn reduced temperature (Tn/Tc) H1  1  Tr1 

arcaparanga / mapua / cbmes 11

STANDARD HEAT OF REACTION
Ea activation energy
Reaction coordinates for exothermic and endothermic reactions: H heat of reaction

EXOTHERMIC REACTION ENDOTHERMIC REACTION

arcaparanga / mapua / cbmes 12

STANDARD STATE Standard states apply at any temperature.
• There is no specification of
For a given temperature, a STANDARD temperature for any standard state.
STATE is defined as the state of a • Reference temperatures, also in use
substance at specified pressure, with heats of reaction, are entirely
composition, and physical condition (e.g., independent of standard states.
gas, liquid, or solid).

Standard states: All conditions for standard state are fixed

except temperature, which is always the
Gases: pure substance in ideal-gas state temperature of the system. Standard-state
at 1 bar. properties are therefore functions of
Liquids/solids: temperature only.
real pure liquid or solid at 1 bar

arcaparanga / mapua / cbmes 13

STANDARD HEAT OF FORMATION
• Table C.4

C s   O2  g   CO2  g  ΔH f ,298  393,509 J

1
2
H 2  g   12 Cl2  g   HCl  g  ΔH f ,298  92,307 J
H 2  g   Cl2  g   2 HCl  g  ΔH f ,298  184,307 J

• Standard heat of formation data are always based on 1 mol of

product formed.

arcaparanga / mapua / cbmes 14

STANDARD HEAT OF COMBUSTION
Standard heat of combustion data are always based on 1 mol of
substance burned.

C s   O2  g   CO2  g  ΔH 298  393,509 J

H 2  g   12 O2  g   H 2Ol  ΔH 298  285,830 J
H 2  g   12 O2  g   H 2O g  ΔH 298  241,818 J
C4 H10  g   132 O2  g   4CO2  g   5 H 2Ol  ΔH 298  2,877 ,396 J
C4 H10  g   132 O2  g   4CO2  g   5 H 2O g  ΔH 298  2,657 ,336 J
arcaparanga / mapua / cbmes 15
Higher heat of combustion, where water formed is in liquid phase, H2O(l)
Lower heat of combustion, where water formed is in gas phase, H2O(g)

H 2  g   12 O2  g   H 2Ol  ΔH 298  285,830 J

H 2  g   12 O2  g   H 2O g  ΔH 298  241,818 J
C4 H10  g   13
2
O2g   4CO2 g   5H 2Ol  
ΔH 298  2,877 ,396 J
C4 H10  g   132 O2  g   4CO2  g   5 H 2O g  
ΔH 298  2,657 ,336 J

H 2O g   H 2O( l ) ΔH 298  44 ,012 J

arcaparanga / mapua / cbmes 16
TEMPERATURE DEPENDENCE OF H
T

H  H 0   C P dT
T0

Reactants at T Products at T

T

 P dT
C Path representing the
T0
procedure for calculating a
standard heat of reaction at
temperature T from the value
at reference temperature T0.
Reactants at T0 Products at T0

H 0

arcaparanga / mapua / cbmes 17

Example 1
Calculate the standard heat of reaction at 800 C of the following
reaction:
COg   2 H 2 g   CH 3OH ( g )

arcaparanga / mapua / cbmes 18

Solution:
COg   2 H 2 g   CH 3OH ( g )
H 0  H 298

  200,660   110,525  0  90,135 J Table C.4

C P
T T

 

H  H 0 C P dT
 H 0
R dT
T T
R
C P
  
D    1 

T 0 0
B 2 2 C 3 3
dT  AT0   1 
T

T0
R 2
T0   1 
3
T0   1 
T

0  


where  
T0

Alternately:

H   H 0  C P
H
T  T0 
C P
R
H
 
 A 
B

2

T0   1  
C 2 2
 D
T0     1  2
3 T0
arcaparanga / mapua / cbmes 19
Solution (con’t) COg   2 H 2 g   CH 3OH ( g )

i vi A B C D
CH3OH 1 2.211 12.216x10-3 -3.450x10-6 0
CO -1 3.376 0.557x10-3 0 -0.031x105
H2 -2 3.249 0.422x10-3 0 0.083x105

A  (1)(2.211)  (1)(3.376)  (2)(3.249)  7.663

B  [(1)(12.216)  (1)(0.557)  (2)(0.422)]  10 3  0.010815
C  [(1)(3.450)  (1)(0)  (2)(0)]  10 6  3.45  10 6
D  [(1)(0)  (1)(0.031)  (2)(0.083)]  105  0.135  10 6
 D 
C P  R A  
B
T0   1  
C 2 2

T0     1  2 
T0 

1073
 3.60
 2 3 298
H

arcaparanga / mapua / cbmes 20

C P

 8.314  - 7.663 
0.010815
2983.60  1  
- 3.45  10 -6    
(298) 3.60  3.60  1 
- 0.135  105
  
2 2

 2 3 3.60 2982
C P  17.343

H   H 0  C P
H
T  T0 
H   90.135  (17.343)1073  298

H   103,576 J

arcaparanga / mapua / cbmes 21

HEAT EFFECTS OF INDUSTRIAL REACTIONS
• Example 2
What is the maximum temperature that can be reached by the
combustion of methane with 20% excess air? Both methane and air
enter the burner at 25°C?

CH 4 g   2O2 g   CO2 ( g )  2 H 2O( g )

arcaparanga / mapua / cbmes 22

 CH 4 g   2O2 g   CO2 ( g )  2 H 2O( g )

O2,theo  1(2)  2
CO2, H2O, O2,supp  2(1.2)  2.4
CH4 O2, N2
Basis: 1 mol N 2,supp  2.4 79
21
  9.03
Air

i Initial Reaction final (product)

CH4 1 -1 0
O2 2.4 -2 0.4
N2 9.03 - 9.03
CO2 - +1 1
H2O - +2 2

arcaparanga / mapua / cbmes 23

 1 bar, T = ? H  0  H 298

 H P
CO2 – 1 mol
H 298

 [393,509  2(241,818)]  [74520  2(0)]  802,635 J
H2O – 2 mol
O2 – 0.4 mol H P  C P
H
T  298
N2 – 9.03 mol
H  0  802,625  C P
H
T  298
 802,625
T  298.15 
C P
H

H P C P
H
 n
i
i

C Pi
H
?

H 298


1 bar, 298 K
CH4 – 1 mol
O2 – 2.4 mol
N2 – 9.03 mol

arcaparanga / mapua / cbmes 24

 i ni A B C D
CO2 1 5.457 1.045x10-3 0 -1.157x105
H2O (g) 2 3.470 1.450x10-3 0 0.121x105
O2 0.4 3.639 0.506x10-3 0 -0.227x105
N2 9.03 3.280 0.593x10-3 0 0.040x105

A  (1)(5.457)  (2)(3.470)  (0.40)(3.369)  (9.03)(3.280)  43.471

B  [(1)(1.045)  (2)(1.450)  (0.40)(0.506)  (9.03)(0.593)]  10 3  0.009502
C0
D  [(1)(1.157)  (2)(0.121)  (0.40)(0.227)  (9.03)(0.040)]  105  0.645  105

 D 
C P  R A  

B
T0   1 
C 2 2
 
T0     1  2 
T0 

T
 2 3 298
H

arcaparanga / mapua / cbmes 25

  802,625
T  298.15  (1)
C P
H
 D 
C P 
B C 2 2

 R A  T0   1  T0     1  2 
T0 
 
T

T
(2)
 2 3 T0 298
H

ITERATION PROCEDURE:
a. Assume a value of T > 298.
b. Substitute this assumed T into equation 2 to solve for mean heat capacity.
c. Substitute this mean heat capacity into equation 1 to solve for T. If this value of T is not equal to the
assumed value in (a), you can use this value as your new assumption.
d. Go back to (a) and use this new value of T as assumption.
e. Repeat (a) to (d) until your previously assumed value is the same as the value obtained from
equation 1.

Applying this procedure, we get

T  2066 K 1793C

arcaparanga / mapua / cbmes 26