16 May 2016

Heat Effects of Industrial Reactions

 Heats of Reaction

Standard heats of reaction are specified for a reference

temperature T0 = 298.15 K.
Standard values are determined from summing up heats of formation,
also specified at T0 = 298.15 K
Hr,298.15 i f ,298.15

i
H

If reaction proceeds at a temperature not equal to T0, we use a

computational path to determine the new value of the heat of
reaction at T.
 Computational Path

Always keep in mind: standard heats of reaction are always

specified at a reference temperature (T0)
Bring down the reactants from T to T0 (sensible heating)
Allow the reaction to proceed at T0
Bring up the products from T0 to T (sensible heating)
The standard heat of reaction at T is the sum of all the enthalpy
changes from the computational path
Computational Path

aA bB cC dD
Products at T

Reactants at T T

T0
H C dT
i p

H C dT
i p
T0

Reactants at T0 Products at T0

Hr,T0 H
i

f ,T0
 Example

Calculate the standard heat of the methanol synthesis reaction at

800C.
CO( g ) 2H 2( g ) CH 3OH( g )

Heat Capacity: CPig / R A BT CT 2 DT 2 (T in K)

CO: A = 3.376, B = 0.557x10-3, C = 0, D = -0.031x105
H2: A = 3.249, B = 0.422x10-3, C = 0, D = 0.083x105
CH3OH: A = 2.211, B = 12.216x10-3, C = -3.450x10-6, D = 0

Heats of formation:
CH3OH: -200,660 J/mol
CO: -110,525 J/mol
 Solution

Bring down all reactants from T = 800C to T = 25C:

298.15
H i C p dT CPig 8.314 molJK A BT CT 2 DT 2
1073.15

CO : C p dT 24,151.083 mol
J

H 2 : C p dT 22,965.936 mol
J

H1 24,151.083 2 22,965.936
H1 70082.955 molJK
 Solution

Allow the reaction to proceed at T = 25C:

H
r ,298.15 H
i

f ,298.15

Hr,298.15 200,660 (110,525) 90,135 mol

J
 Solution

Bring up the products from T = 25C to T = 800C:

1073.15
H i C p dT CPig 8.314 molJK A BT CT 2 DT 2
298.15

CH 3OH : C p dT 56,652.000 mol

J

H 2 56,652.00 mol
J
 Solution

Summing up all enthalpy changes, the standard heat of reaction

at T = 800C is:

Hr,1073.15 H1 Hr,298.15 H 2
Hr,1073.15 70,082.955 90135 56,652.00

H r ,1073.15 103,565.955 mol
J
 Heat Effects of Industrial Reactions

Using the same principle of computational paths, the total heat

required for an industrial process may be computed:
Perform material balances first to determine all amounts
Bring down the inlet stream from T to T0 (sensible heating)
Allow the reaction to proceed at T0
Bring up the outlet stream from T0 to T (sensible heating)
Sum up all enthalpy changes in the computational path
Computational Path

Products at T

Reactants at T T

T0
H n C dT
i p

H n C dT
i p
T0

Reactants at T0 Products at T0

Hr ,T0 ni Hr,T0
where ni mol extent
 Example

One method for the manufacture of synthesis gas is the catalytic

reforming of CH4 with steam at high temperature and atmospheric
pressure:
CH 4 g H 2O g CO g 3H 2 g

The only other reaction to be considered is the water-gas-shift

reaction:
CO g H 2O g CO2 g H 2 g

If the reactants are supplied in the ratio 2 mol steam to 1 mol

methane, and if heat is supplied to the reactor so that the products
reach a temperature of 1300 K, the CH4 is completely converted and
the product stream contains 17.4 mol% CO. Assuming the reactants
to be preheated to 600 K, calculate the heat requirement for the
reactor.
 Example

Heat Capacity:

CPig / R A BT CT 2 DT 2 (T in K)

Component A B C D
CH4 1.702 9.081x10-3 -2.164x10-6 0
H 2O 3.470 1.450x10-3 0 0.121x105
CO 3.376 0.557x10-3 0 -0.031x105
H2 3.249 0.422x10-3 0 0.083x105
CO2 5.457 1.045x10-3 0 -1.157x105
 Example

Heats of formation (J/mol) at T = 298.15 K:

CH4 = -74,520
H2O = -241,818
CO = -110,525
H2 = 0
CO2 = -393,509
 Solution

The system can be represented by the following block diagram:

w mol CO
1 mol CH4 x mol CO2
REACTOR
2 mol H2O y mol H2
z mol H2O

C balance:
1 11 w 11 x 11 w x 1
H balance:
1 14 2 12 y 12 z 12 2y 2z 8
 Solution

The system can be represented by the following block diagram:

w mol CO
1 mol CH4 x mol CO2
REACTOR
2 mol H2O y mol H2
z mol H2O

O balance:
2 11 w 11 x 12 z 11 w 2x z 2

Additional: w
0.174
w x y z
 Solution

Solving simultaneously:
w x 1
y z 4
w 2x z 2
w
0.174
w x y z

w 0.87 mol CO y 3.13 mol H2

x 0.13 mol CO2 z 0.87 mol H2O
 Solution

Bringing down the reactants from T = 600 K to T = 298.15 K:

298.15
H ni C p dT CPig 8.314 molJK A BT CT 2 DT 2
600

CH 4 : C p dT 13,369.062 mol
J

H 2O : C p dT 10,512.128 mol
J

H1 1 13,369.062 2 10,512.128
H1 34,393.318J
 Solution

Allowing the reactions to proceed at T = 298.15 K:

All heats of reaction refer to a per mol extent of reaction (mol reactant
consumed, or mol product formed)

CH 4 g H 2O g CO g 3H 2 g

Hr1,298.15 1 110,525 1 74,520 1 241,818 205,813 mol

J

CO g H 2O g CO2 g H 2 g

Hr2,298.15 1 393,509 1 110,525 1 241,818 41,166 mol

J
 Solution

Allowing the reactions to proceed at T = 298.15 K:

All heats of reaction refer to a per mol extent of reaction (mol reactant
consumed, or mol product formed)

Hr ,T0 ni Hr,T0 Hr1,298.15 205,813 mol

J

where ni mol extent Hr2,298.15 41,166 mol

J

Hr ,298.15 1 205,813 0.13 41,166 200,461.42J

 Solution

Bringing up the product stream from T = 298.15 K to T =

1300 K:
1300
H ni C p dT CPig 8.314 molJK A BT CT 2 DT 2
298.15

CO : C p dT 31,760.652 mol
J
H 2 : C p dT 30,049.272 mol
J

CO2 : C p dT 49,922.360 mol

J
H 2O : C p dT 38,813.890 mol
J

H 2 0.87 31,760.652 0.13 49,922.360

3.13 30,049.272 0.87 38,813.890
H 2 161,943.980J
 Solution

Calculating for the heat requirement of the reactor:

Assume: negligible KE and PE changes in reactor, no shaft work

Q nH
Q H1 Hr ,298.15 H 2

Q 34,393.318 200,461.42 161,943.980

Q 328,012.082J