158 CHAPTER 4.

Heat Effects

The simplest procedure here is to sum the mean-heat-capacity equations for the
products, each multiplied by its appropriate mole number. Because C = 0 for each
product gas (Table C.1), Eq. (4.9) yields:

[i T T0 ]
∑ i n i Bi ∑ i n i Di
⟨CP°⟩H = ∑ n i ⟨CP°i⟩H = R ∑ n i Ai + _ (T − T0) + _
i 2
Data from Table C.1 are combined as follows:

A = ∑ ni Ai = (1)(5.457) + (2)(3.470) + (0.4)(3.639) + (9.03)(3.280) = 43.471

i

Similarly, B = ∑ ni Bi = 9.502 × 10 −3 and D = ∑ n i Di = − 0.645 × 10 5.

i i

For the product stream ⟨CP°⟩H / R is therefore represented by:

MCPH( . , T; . , . × − , . ,− . × )
Equations (A) and (B) are combined and solved for T:
ΔH298 °
T = 298.15 − ___________
⟨CP°⟩H

Because the mean heat capacities depend on T, one first evaluates ⟨C P°⟩H for an
assumed value of T > 298.15, then substitutes the result in the preceding equation.
This yields a new value of T for which ⟨CP°⟩H is reevaluated. The procedure con-
tinues to convergence on the final value,

T = 2066 K or 1793° C

Again, solution can be easily automated with the Goal Seek or Solver function
in a spreadsheet or similar solve routines in other software packages.

Example .
One method for the manufacture of “synthesis gas” (a mixture of CO and H ) is the
catalytic reforming of CH with steam at high temperature and atmospheric pressure:
CH (g) + H O(g) → CO(g) + H (g)

The only other reaction considered here is the water-gas-shift reaction:

CO(g) + H O(g) → CO (g) + H (g)

Reactants are supplied in the ratio mol steam to mol CH , and heat is added to the
reactor to bring the products to a temperature of K. The CH is completely con-
verted, and the product stream contains . mol-% CO. Assuming the reactants to be
preheated to K, calculate the heat requirement for the reactor.
4.7. Heat Effects of Industrial Reactions 159

Solution .
The standard heats of reaction at 25°C for the two reactions are calculated from
the data of Table C.4:
CH 4(g) + H 2O(g) → CO(g) + 3H 2(g) ° = 205,813 J
ΔH298

CO(g) + H 2O(g) → CO 2(g) + H 2(g) ° = −41,166 J

ΔH 298

These two reactions may be added to give a third reaction:

CH 4(g) + 2H 2O(g) → CO 2(g) + 4H 2(g) ° = 164,647 J
ΔH 298

Any pair of the three reactions constitutes an independent set. The third reaction is
not independent; it is obtained by combination of the other two. The reactions
most convenient to work with here are the first and third:
CH 4(g) + H 2O(g) → CO(g) + 3H 2(g) ° = 205,813 J
ΔH298 (A)

CH 4(g) + 2H 2O(g) → CO 2(g) + 4H 2(g) ° = 164,647 J

H 298 (B)
First one must determine the fraction of CH4 converted by each of these reactions.
As a basis for calculations, let 1 mol CH4 and 2 mol steam be fed to the reactor. If
x mol CH4 reacts by Eq. (A), then 1 − x mol reacts by Eq. (B). On this basis the
products of the reaction are:

CO: x
H2: 3x + 4(1 − x) = 4 − x
CO2: 1−x
H2O: 2 − x − 2(1 − x) = x
Total: 5 mol products

The mole fraction of CO in the product stream is x/5 = 0.174; whence x = 0.870.
Thus, on the basis chosen, 0.870 mol CH4 reacts by Eq. (A) and 0.130 mol reacts
by Eq. (B). Furthermore, the amounts of the species in the product stream are:

Moles CO = x = 0.87
Moles H 2 = 4 − x = 3.13
Moles CO 2 = 1 − x = 0.13
Moles H 2O = x = 0.87

We now devise a path, for purposes of calculation, to proceed from reactants at

600 K to products at 1300 K. Because data are available for the standard heats of
reaction at 25°C, the most convenient path is the one that includes the reactions at
25°C (298.15 K). This is shown schematically in the accompanying diagram. The
dashed line represents the actual path for which the enthalpy change is ΔH.
Because this enthalpy change is independent of path,

ΔH = ΔH R° + ΔH298
° + ΔHP°
160 CHAPTER 4. Heat Effects

Products at 1 bar
and 1300 K
. mol CO
. mol H
∆H . mol CO
. mol H O
∆H Po

Reactants at 1 bar
and 600 K ∆H Ro
mol CH
mol H O
o
∆H 298

° , reactions (A) and (B) must both be taken into

For the calculation of ΔH 298
account. Because 0.87 mol CH4 reacts by (A) and 0.13 mol reacts by (B),
° = (0.87)(205,813) + (0.13)(164,647) = 200,460 J
ΔH 298

The enthalpy change of the reactants when they are cooled from 600 K to 298.15 K is:

ΔH R° = (∑ n i ⟨CP°i⟩H) (298.15 − 600)

i
where subscript i denotes reactants. The values of ⟨C P°i⟩H / R are:
CH 4 : MCPH( . , ; . , . × − ,− . × − , . )= .
H 2O : MCPH( . , ; . , . × − , . , . × )= .
and
ΔHR° = (8.314)[(1)(5.3272)+(2)(4.1888)](298.15 − 600) = − 34,390 J

The enthalpy change of the products as they are heated from 298.15 to 1300 K is
calculated similarly:

ΔH P° = ( ∑ n i ⟨CP°i⟩H) (1300 − 298.15)

i

where subscript i here denotes products. The ⟨CP°i⟩H / R values are:

CO: MCPH( . , ; . , . × − , . ,− . × ) = 3.8131

H 2: MCPH( . , ; . , . × − , . ,− . × ) = 3.6076
CO 2: MCPH( . , ; . , . × − , . ,− . × ) = 5.9935
H 2O: MCPH( . , ; . , . × − , . , . × ) = 4.6599

Whence,
ΔHP° = (8.314)[(0.87)(3.8131) + (3.13)(3.6076)
+ (0.13)(5.9935) + (0.87)(4.6599)] × (1300 − 298.15)
= 161, 940 J
4.7. Heat Effects of Industrial Reactions 161

Therefore,
ΔH = −34,390 + 200,460 + 161,940 = 328,010 J

The process is one of steady flow for which Ws, Δz, and Δu2/2 are presumed
negligible. Thus,
Q = ΔH = 328, 010 J
This result is on the basis of 1 mol CH4 fed to the reactor.

Example .
Solar-grade silicon can be manufactured by thermal decomposition of silane at moder-
ate pressure in a fluidized-bed reactor, in which the overall reaction is:

SiH (g) → Si(s) + H (g)

When pure silane is preheated to °C, and heat is added to the reactor to promote
a reasonable reaction rate, % of the silane is converted to silicon and the products
leave the reactor at °C. How much heat must be added to the reactor for each
kilogram of silicon produced?

Solution .
For a continuous-flow process with no shaft work and negligible changes in kinetic
and potential energy, the energy balance is simply Q = ΔH, and the heat added is
the enthalpy change from reactant at 300°C to products at 750°C. A convenient
path for calculation of the enthalpy change is to (1) cool the reactant to 298.15 K,
(2) carry out the reaction at 298.15 K, and (3) heat the products to 750°C.
On the basis of 1 mol SiH4, the products consist of 0.2 mol SiH4, 0.8 mol Si,
and 1.6 mol H2. Thus, for the three steps we have:

298.15K

∫573.15K
ΔH1 = C P°(SiH 4) dT

°
ΔH2 = 0.8 × ΔH298
1023.15K

∫298.15K [
ΔH3 = 0.2 × CP°(SiH 4) + 0.8 × CP°(Si) + 1.6 × CP°(H 2)]dT

Data needed for this example are not included in App. C, but are readily
obtained from the NIST Chemistry WebBook (http://webbook.nist.gov). The
reaction here is the reverse of the formation reaction for silane, and its standard
° = − 34,310 J. Thus, the reaction is mildly
heat of reaction at 298.15 K is ΔH 298
exothermic.