Chapter 5

Two-Step Exothermic Chemical Reaction

for Heat Transfer Investigation
in a Convective Cylinder

R. S. Lebelo and O. D. Makinde

Abstract In this article, the investigation of transient heat in a stockpile whose

materials react spontaneously with the oxygen trapped within it is carried out. A
reactive material in this context refers to any substances that contain carbon or hydro-
carbons and readily react with oxygen in contact. The process whereby a carbon
containing material reacts automatically with oxygen is called exothermic chemical
reaction. The study is modelled in a domain that is cylindrical and loses heat by
convection to the surrounding environment. The combustion process for the heat
transfer study is very complicated and nonlinear in nature, and therefore, the partial
differential equation governing the problem cannot be solved exactly, but numeri-
cally. For this purpose, the Finite Difference Method (FDM) was employed to solve
the problem. The heat transfer investigation is performed by observing effects of
selected embedded thermo-physical parameters like the reaction rate on the temper-
ature of the system. The thermo-physical parameters may either increase or reduce
the temperature of the system during combustion of reactive materials. The results
obtained indicate that the rate of reaction and some parameters increase the tempera-
ture profiles during combustion, whereas the heat loss parameter lowers the levels of
the temperature. The results are presented graphically and discussed appropriately.

Keywords Two-step exothermic chemical reaction · Heat transfer investigation ·

Convective cylinder · Finite difference method

5.1 Introduction

Heat transfer investigation of in stockpiles of combustible materials attracted the

attention of many researchers in the past years. This is because of applications of heat

R. S. Lebelo (B)
Vaal University of Technology, Vanderbijlpark 1911, South Africa
e-mail: sollyl@vut.ac.za
O. D. Makinde
Stellenbosch University, Saldanha 7395, South Africa

© The Author(s), under exclusive license to Springer Nature Switzerland AG 2021 49

J. Xu and K. M. Pandey (eds.), Mechanical Engineering and Materials,
Mechanisms and Machine Science 100,
https://doi.org/10.1007/978-3-030-68303-0_5
50 R. S. Lebelo and O. D. Makinde

transfer in engineering and industrial products manufacturing [1, 2]. Examples of heat
transfer applications include, among others, heavy oil recovery, storage of cellulose
materials, solids combustion, biomass and coal pyrolysis, waste incineration, and
coal gasification [3]. Furthermore, ignorance of heat transfer and thermal stability
applications during the manufacturing of industrial products using reactive materials
may lead to bending or deformation and decolorization those products [4].
Combustible materials are those that react spontaneously with oxygen because
of exothermic chemical reaction [5]. This study considers a two-step exothermic
chemical reaction like the one occurring in methane combustion. Heat transfer is
considered in a stockpile whose materials are reactive. An example can be a stock-
pile of wood or hay, and the study is modelled in a cylindrical pipe, such as the
one carried out in [6]. The investigation of heat transfer in stockpiles was conducted
experimentally in [7, 8], where physical properties like the material’s coarseness,
surface area thereof, its humidity and the surrounding temperature were studied. In
this study, a theoretical approach is conducted where the thermo-physical parame-
ters including the reaction rate and activation energy, which are embedded on the
governing differential equation, are analyzed. The analysis is carried out by varying
selected parameters to see how they affect temperature profiles during combustion.
Transient heat analysis for exothermic chemical reaction in two-step was studied
in [9], where the combustion process was modelled in a rectangular slab and coupled
convective and radiative boundary conditions were applied. The analysis considered
a temperature dependent thermal conductivity, and the reactant diffusion was also
included, but in this case, a constant thermal conductivity is observed. In [10] the
analysis was conducted in a spherical domain of reactive materials, where heat loss by
convection was considered. The mathematical modelling of a two-step exothermic
chemical reaction was given by Makinde et al. [11], and their investigation was
conducted with or without reactant consumption, with no extensive consideration of
the reactant consumption. The objective of this study is to investigate the transfer of
heat in a combusting stockpile of reactive materials which loses heat to the immediate
environment by convection in an exothermic chemical reaction undergoing two steps.
From the literature above, this investigation was not intensely carried out.

5.2 Mathematical Modelling

An example of a two-step exothermic chemical reaction taking place within a stock-

pile of combustible materials modelled in a cylindrical domain is given as Eqs. (5.1)
and (5.2):

2CH4 + 0.22N2 + 3(O2 + 3.76N2 ) → 2CO + 4H2 O + 11.50N2 (Step 1) (5.1)

2CO + O2 + 3.76N2 → 2CO2 + 3.76N2 (Step 2) (5.2)

5 Two-Step Exothermic Chemical Reaction for Heat Transfer Investigation … 51

Fig. 5.1 The geometry of the problem

Above equations represent a two-step combustion of the methane gas in air, where
the second step helps to eliminate the toxic gas carbon monoxide. Heat loss to the
environment is assumed to be convective and follows Newton’s law of cooling with
the expression − hk [T − Tw ], where h is the heat transfer coefficient, k is the thermal
conductivity of the material, T is the absolute temperature of the cylinder, and Tw
is the ambient temperature. The geometry of the problem is illustrated in Fig. 5.1
below.
Equation (5.3) below represents the transient heat energy equation for chemical
reaction [10, 12–15],
   
∂T k ∂ ∂T − K T m −E1 /RT
pc p − = − − r + Q 1 A1 C 1 e
∂t r ∂r ∂r vl
 
K T m −E2 /RT h
+ Q 2 A2 C 2 e − (T − Tw ) (5.3)
vl k

The respective initial and boundary conditions are given in Eq. (5.4):
−     
∂T − −
T r , 0 = T0 ; − 0, t = 0; T a, t = Tw (5.4)
∂r
In this case, T0 is the cylinder initial temperature, Q 1 is the first step heat of
reaction,A1 is the first step rate constant and C1 the first step reactant’s concentration.
It follows that Q 2 ,A2 and C2 , are respectively, the second step’s heat of reaction, rate
constant, and reactant’s concentration. E 1 and E 2 are the activation energies for the
first and second steps, respectively. m is for the type of kinetics, where m = −2 is for
light induced kinetics, the Arrhenius kinetics is represented by m = 0 and m = 0.5
presents bimolecular type.
The following dimensionless variables were introduced as Eq. (5.5):

E 1 (T − Tb ) E 1 (T0 − Tb ) r̄ RTb E2 k t¯ a2 h
θ= 2
, θ0 = 2
,r = ,ε = ,ε = ,t = 2
,ϕ = ,
RTb RTb a E1 E1 pc p a k
 m
Q 2 A2 E 2 (E 1 −E2 )/RT K Tb Q 1 A1 E 1 a 2 C1 −E1 /RT
ω= e ,α = e . (5.5)
Q 1 A1 E 1 vl k RTb2
52 R. S. Lebelo and O. D. Makinde

Equations (5.3) and (5.4) now have the following forms (Eq. (5.6)):

∂θ ∂ 2θ 1 ∂θ
= 2 + + α(1 + εθ )m e[θ/(1+εθ)] + αω(1 + εθ )m e[θ/(1+εθ)] − ϕθ.
∂t ∂r r ∂r
(5.6)

The initial and boundary conditions are shown in Eq. (5.7):

∂θ
θ (r, 0) = θ0 ; (0, t) = 0; θ (1, t) = 0. (5.7)
∂r
Here θ and θ0 are the respective dimensionless temperature and initial temperature.
The dimensionless parameters α, ε, r and  are Frank-Kamenetskii (reaction rate),
activation energy, radial distance, and activation energy ratio, respectively. Lastly,
the dimensionless parameters for two-step reaction and heat loss are represented by
ω and ϕ.

5.2.1 Numerical Approach

The numerical solution for the governing equation using the semi-implicit FDM
followed the following route.

θ N +1 − θ N ∂2 1 ∂ N  N
= 2 θ N +τ + θ + α (1 + εθ )m e[θ/(1+εθ)]
t ∂r r ∂r
 [εθ/(1+εθ)]  N
+ αω e − ϕθ N (5.8)

The τ is an arbitrary number such that 0 ≤ τ ≤ 1 and τ = 1 for the convenience

of using larger time steps. Rearranging Eq. (5.8), multiplying through by t and
t N +τ
taking γ = r 2 yielded the expression for θ as follows:

N +1 
−τ γ θ j+1 + (1 + 2τ γ )θ jN +1 − τ γ θ j−1
N +1
= −γ (1 − τ )θ j+1
N
+ 1 − 2γ (1 − τ ) − ϕ θ jN
1  N 
− γ (1 − τ )θ j−1
N
+ γ θ j+1 − θ j−1
N
2r
N
+ αt (1 + εθ )m e[θ/(1+εθ)] + ωe[θ/(1+εθ)]
(5.9)

A tri-diagonal matrix system was derived from Eq. (5.9) and Maple software was
used to solve the system.
5 Two-Step Exothermic Chemical Reaction for Heat Transfer Investigation … 53

Fig. 5.2 α effects

Fig. 5.3 m effects

5.3 Results and Discussion

Effects of selected kinetic parameters on the temperature behavior are presented in

this section. Arbitrary parameter values chosen were:

m = 0.5, ω = 0.1,  = 0.1, α = 0.1, ϕ = 1, ε = 0.1, t = 1.

54 R. S. Lebelo and O. D. Makinde

Fig. 5.4 ε effects

Fig. 5.5 ω effects

Fig. 5.6 ϕ effects

5 Two-Step Exothermic Chemical Reaction for Heat Transfer Investigation … 55

5.3.1 Effects of Thermo-physical Parameters on Temperature

(Unsteady State)

Figures 5.2, 5.3, 5.4, 5.5 and 5.6 show the effects of α, m, ε, ω and ϕ on the tempera-
ture behavior during combustion. From Figs. 5.2, 5.3, 5.4 and 5.5, it can be observed
that an increase in α (reaction rate parameter), m (chemical kinetics type), ε (activa-
tion energy) and ω (two-step exothermic chemical reaction) shows that the profiles
of temperature increase correspondingly. Therefore, a combusting stockpile will
increase its heat release rate under the effects of these parameters and fire may ulti-
mately ignite if no control measures are done. In other words, these parameters
enhance spontaneous reaction of oxygen trapped within the stockpile with its carbon
or hydrocarbon substances to sustain the combustion process, which results with heat
release. A high temperature profile increase in Fig. 5.2 shows that α’s effect on the
exothermic chemical reaction is so intense to fast-track the combustion process for
emission of more heat within the stockpile. Figure 5.3 indicates that the chemical
reaction that is exothermic is very quick in the kinetic type of bimolecular and that it
slows down in the light induced one. In Fig. 5.6 a different scene is illustrated which
shows that an increase in ϕ (heat loss parameter) reduces the levels of temperature.
The parameter in the latter figure enhances the loss of more heat from the cylinder’s
surface to reduce the accumulation of heat inside the stockpile, which is the reason
for the decline in the levels of temperature.

5.3.2 Steady State Heat Transfer Analysis

The temperature independent state is represented by the following ordinary differ-

ential equation (Eq. (5.10)):

∂ 2θ 1 ∂θ
+ + α(1 + εθ )m e[θ/(1+εθ)] + αω(1 + εθ )m e[θ/(1+εθ)] − ϕθ = 0,
∂r 2 r ∂r
(5.10)

with the boundary conditions as shown in Eq. (5.11)

∂θ
(0) = 0; θ (1) = 0. (5.11)
∂r
The numerical solution in this case is obtained by using the Runge–Kutta Fehlberg
(RKF45) method coupled with Shooting technique. Equation (5.10) is reduced to 1st

order ordinary differential equation by letting θ = s1 , θ = s2 . We express Eqs.
(5.10)–(5.11) as Eqs. (5.12), (5.13) and (5.14):

s1 = s2 (5.12)
56 R. S. Lebelo and O. D. Makinde

1 ∂s1
s2 = − − α(1 + εs1 )m e[s1 /(1+εs1 )] − αω(1 + εs1 )m e[εs1 /(1+εs1 )] + ϕs1 ,
r ∂r
(5.13)

s2 (0) = 0, s1 (1) = 0. (5.14)

The solutions are illustrated in Figs. 5.7 and 5.8 showing the steady state situation
as t → ∞. It is noted that high values of the temperature are experienced at the
center of the cylinder and that the values decrease towards the surface thereof, due
to convective heat loss. Figure 5.7 demonstrates temperature distribution in a two-
dimensional domain, whereas Fig. 5.8 shows a three-dimensional one.

Fig. 5.7 Steady state 2-D

t →∞

Fig. 5.8 Steady state 3-D

t →∞
5 Two-Step Exothermic Chemical Reaction for Heat Transfer Investigation … 57

5.4 Conclusion

The work in this article investigated the heat in transit of a chemical reaction under-
going a two-step mechanism occurring in a stockpile whose materials react sponta-
neously with the trapped oxygen. The study was modelled in a cylindrical domain.
A theoretical analysis using mathematical application was conducted to understand
the heat transfer process by observation of effects selected thermo-physical param-
eters have on the temperature during combustion. The study considered both the
temperature dependent and independent scenarios to demonstrate the heat transfer
process clearly. It was observed that parameters which increase the temperature
during combustion are α (reaction rate parameter), m (chemical kinetics type), ε (acti-
vation energy) and ω (two-step exothermic chemical reaction). The raise in temper-
ature of the system is not good for environmental purposes, because global warming
and depletion of the ozone layer are the results. Global warming has contributed so
much to climate change. The parameter that lowers the system’s temperature was
identified as ϕ (heat loss parameter). In general, the results obtained agree with the
literature in [2, 3, 6, 8]. A future study can consider material’s thermal conductivity
that is temperature dependent.

References

1. Hamza, B.H., Massawe, E.S., Makinde, O.D.: Analysis of transient heating due to exothermic
reaction in a stockpile of combustible material. Int. J. Phys. Sci. 6(18), 4337–4341 (2011)
2. Lebelo, R.S., Okosun, K.O., Mtunzi, F., Muthuvalu, M.S., Mahlobo, R.K.: Thermal stability
and reactant consumption analysis in a reactive cylinder of variable thermal conductivity. Int.
Rev. Mech. Eng. 11, 787–796 (2017)
3. Lebelo, R.S.: Thermal stability investigation in a reactive sphere of combustible material. Adv.
Math. Phys. 1, 1–6 (2016)
4. Bebernes, J., Eberly, D.: Mathematical Problems from Combustion Theory. Springer, New
York (1989)
5. Frank-Kamenetskii, D.A.: Diffusion and Heat Transfer in Chemical Kinetics. Plenum Press,
New York (1969)
6. Lebelo, R.S., Makinde, O.D., Chinyoka, T.: Thermal decomposition analysis in a sphere of
combustible materials. Adv. Mech. Eng. 9(2), 1–14 (2017)
7. Lohrer, C., Krause, U., Steinbach, J.: Self-ignition of combustible bulk materials under various
ambient conditions. Process Saf. Environ. Prot. 83(2), 145–150 (2005)
8. Hensel, W., Krause, U., Loffler, U.: Self-ignition of materials (including dust). In: Hartwig, M.,
Steen, H. (eds.) Handbook of explosion prevention and protection. Wiley-VCH 2.7, Weinheim,
pp. 227–270 (2004)
9. Makinde, O.D., Tshehla, M.S.: Analysis of thermal stability in a convecting and radiating
two-step reactive slab. Adv. Mech. Eng. 1, 1–9 (2013)
10. Lebelo, R.S., Moloi, K.C., Okosun, K.O., Mukamuri, M., Adesanya, S.O., Muthuvalu, M.S.:
Two-step low-temperature oxidation for thermal stability analysis of a combustible sphere.
Alexandria Eng. J. 57(4), 2829–2835 (2018)
11. Makinde, O.S., Adegbie, K.S., Fasoranbaku, O.A.: Mathematical modelling of two-step
exothermic reactions with and without reactants consumption. FUTA J. Res. Sci. 1, 44–53
(2013)
58 R. S. Lebelo and O. D. Makinde

12. Gajjela, N., Matta, A., Kaladhar, K.: The effects of Soret and Dufour, chemical reaction, Hall
and ion currents on magnetized micropolar flow through co-rotating cylinders. AIP Adv. 7(11),
1–16 (2017)
13. Nagaraju, G., Garvandha, M.: Magnetohydrodynamic viscous fluid flow and heat transfer in a
circular pipe under an externally applied constant suction. Heliyon 5(2), 1–25 (2019)
14. Ramana Murthy, J.V., Nagaraju, G., Sai, K.S.: Numerical solution for MHD flow of Micro
polar fluid between two concentric rotating cylinders with porous lining. Int. J. Nonlinear Sci.
13(2), 183–193 (2012)
15. Govardha, K., Nagaraju, G., Kaladhar, K., Balasiddulu, M.: MHD and radiation effects on
mixed convection unsteady flow of micropolar fluid over a stretching sheet. Procedia Comput.
Sci. 57, 65–76 (2015)