ME6170

THEORY OF FIRE PROPAGATION

(FIRE DYNAMICS)
Week 3
Prof. V. Raghavan
Department of Mechanical Engineering
Indian Institute of Technology Madras
Chennai 600017, INDIA
Email: [email protected]
Module 2: Review of thermo-chemistry,
chemical equilibrium &
Kinetics (continued)
 Heat calculations

• Heat release from a fire is an important quantity to be estimated in

fire safety engineering.
• Fire loading is a parameter that indicates the potential hazard in
case of a fire. This is calculated as the heat release flux, that is,
the heat output from a fire per unit area (J/m2).
• In general, if the calorific or heating value of the material (in J/kg)
that is burning is known and the rate at which it is burning (in kg/s)
is also known, then heat release rate is calculated as the product
of these two.
• Calorific value is the heat released when unit mass of the material
is completely burnt.
• Calorific values of materials used in several applications are
determined by using different types of calorimeters, including the
bomb calorimeter.

Dr. V. Raghavan, IIT Madras 3

 Heat calculation from I law of thermodynamics

• Theoretically, heating value is calculated using the first law of

thermodynamics.
• For this analysis, a control (constant) volume is considered with
the fire source (material that is burning) at one of its boundaries.
• Fuel gases from this fire source flow into the control volume. Air
from the ambient also flows into the control volume and products
of combustion flow out of the control volume.
• Assuming steady state and steady flow, the first law is,
𝑁 𝑀

𝑄ሶ − 𝑊𝑥ሶ = ෍ 𝑛ሶ 𝑖 ℎത 𝑖 𝑇𝑃 − ෍ 𝑛ሶ 𝑖 ℎത 𝑖 𝑇𝑅
1 1

• Here, N and M are number of product and reactant species, 𝒏ሶ is

flow rate in kmol/s and T is temperature in K. Subscripts P and R,
represent product and reactant, respectively. Usually, 𝑊𝑥ሶ = 0.
Dr. V. Raghavan, IIT Madras 4
 Heat calculation for methane oxidation

• The term 𝑄ሶ is the rate of heat transfer from or to the control

ഥ 𝒊 is called
volume, based on if it is negative or positive. The term 𝒉
standard or absolute enthalpy of ith species expressed in J/kmol.
• For example, consider single-step reaction for methane,

CH4 + 2(O2 + 3.76N2) → CO2 + 2H2O + 7.52N2

• For this reaction, the rate of heat transfer is calculated as,

ഥ 𝑪𝑶 𝑻𝑷 + 𝟐𝒉
𝑸ሶ = 𝒉 ഥ 𝑯 𝑶 𝑻𝑷 + 𝟕. 𝟓𝟐𝒉 ഥ 𝑵 𝑻𝑷
𝟐 𝟐 𝟐
ഥ 𝑪𝑯 𝑻𝑹 − 𝟐𝒉
−𝒉 ഥ 𝑶 𝑻𝑹 − 𝟕. 𝟓𝟐𝒉 ഥ 𝑵 𝑻𝑹
𝟒 𝟐 𝟐

• Standard enthalpies of the species are calculated primarily as a

function of temperature. Combustion reaction is an exothermic
oxidation reaction. Hence, 𝑄ሶ is negative.

Dr. V. Raghavan, IIT Madras 5

Standard heat of reaction and standard enthalpy

• Standard heat of reaction is defined as the heat generated when

reactants are supplied at 1 atm, 298 K (reference state) and the
products formed are also cooled to 298 K. That is, for standard
heat of reaction, the value of both TP and TR is 298 K.
• Standard enthalpy of a species i is expressed in molar basis as,
ഥ𝒊 𝑻 = 𝒉
𝒉 ഥ 𝟎𝒇,𝒊 𝑻𝒓𝒆𝒇 + ∆𝒉
ഥ𝒊 𝑻

• The first term on the right-hand side, 𝒉 ഥ 𝟎𝒇,𝒊 , is called the standard
enthalpy of formation in kJ/kmol. Overhead bar indicates that the
enthalpy is specific to number of moles. Superscript ‘0’ indicates
that the value is obtained at 1 atmosphere pressure.
• It is the increase in enthalpy, when one mole of a compound is
formed at constant pressure from its natural elements, in reference
state and after formation, it is also brought to the reference state.

Dr. V. Raghavan, IIT Madras 6

 Standard enthalpy

• For naturally occurring elements such as O2, H2, N2, C (solid), etc.,
the standard enthalpy of formation (𝒉ഥ 𝟎𝒇,𝒊 ) is assigned a value of
zero.
• For other species, its formation is considered to occur by the
reactions of the above-mentioned basic elements.
• For example, CO is considered to be formed by the reaction at
standard state between C (graphite) and O2, written as,
C (s) + 0.5 O2 → CO.
• Similarly, hydrocarbon fuel species are formed by the reaction
between C (graphite) and H2.
• ∆𝒉ഥ 𝒊 (𝑻), is the enthalpy associated with the temperature change for
that species. It is called sensible enthalpy. This is the increase in
the enthalpy due to an increase in the temperature from the
standard value (298 K) to a higher temperature, T (K).

Dr. V. Raghavan, IIT Madras 7

 Heat calculation for methane oxidation

• For methane oxidation in air, the first law is written as,

ഥ 𝑪𝑶 𝑻𝑷 + 𝟐𝒉
𝑸ሶ = 𝒉 ഥ 𝑯 𝑶 𝑻𝑷 + 𝟕. 𝟓𝟐𝒉 ഥ 𝑵 𝑻𝑷
𝟐 𝟐 𝟐
ഥ 𝑪𝑯 𝑻𝑹 − 𝟐𝒉
−𝒉 ഥ 𝑶 𝑻𝑹 − 𝟕. 𝟓𝟐𝒉 ഥ 𝑵 𝑻𝑹
𝟒 𝟐 𝟐

• For standard enthalpy for formation, neglecting superscript 0, the

standard heat of reaction is calculated as,

ഥ 𝒇,𝑪𝑶 𝑻𝒓𝒆𝒇 + 𝟐𝒉
𝑸ሶ = 𝒉 ഥ 𝒇,𝑯 𝑶 𝑻𝒓𝒆𝒇 + 𝟕. 𝟓𝟐𝒉 ഥ 𝒇,𝑵 𝑻𝒓𝒆𝒇
𝟐 𝟐 𝟐
ഥ 𝒇,𝑪𝑯 𝑻𝒓𝒆𝒇 − 𝟐𝒉
−𝒉 ഥ 𝒇,𝑶 𝑻𝒓𝒆𝒇 − 𝟕. 𝟓𝟐𝒉 ഥ 𝒇,𝑵 𝑻𝒓𝒆𝒇
𝟒 𝟐 𝟐

• Since, the enthalpies of formation for O2 and N2 are zero,

ഥ 𝒇,𝑪𝑶 𝑻𝒓𝒆𝒇 + 𝟐𝒉
𝑸ሶ = 𝒉 ഥ 𝒇,𝑯 𝑶 𝑻𝒓𝒆𝒇 − 𝒉
ഥ 𝒇,𝑪𝑯 𝑻𝒓𝒆𝒇
𝟐 𝟐 𝟒

𝑸ሶ = −𝟑𝟗𝟑. 𝟓𝟐 + 𝟐 −𝟐𝟒𝟏. 𝟖𝟑 − −𝟕𝟒. 𝟓 = −𝟖𝟎𝟐. 𝟔𝟖 𝐤 𝐉Τ𝐦 𝐨𝐥 − 𝐂𝐇𝟒

Dr. V. Raghavan, IIT Madras 8

 Standard heat of reaction & heat of combustion

• It is clear that the value of standard heat of reaction is negative,

since heat is released from the control volume to the surroundings
(exothermic reaction).
• Further, this value is obtained per mole of methane, since the
reaction between methane and air is written considering one mole
(or kmol) of methane.
• This may be converted to per kg of methane by dividing the value
by molecular mass of methane. That is, standard heat of reaction
per kg of methane is -802.68 × 1000 / 16 = -50167.5 kJ/kg-CH4 or
-50.2 MJ/kg-CH4.
• Standard heat of combustion or the heating value or the
calorific value is just the negative of the standard heat of
reaction. Thus, the heating value of methane is 50.2 MJ/kg-CH4.
This is the heat received by the surroundings, which is positive.

Dr. V. Raghavan, IIT Madras 9

 Higher and lower calorific values

• In the above calculation, water in the product is taken to be in

vapor state (the enthalpy of formation of water vapor has been
used). Thus, there is some amount of energy available in the
product gas equal to latent heat of vaporization of water vapor that
can be extracted. Therefore, the heating value, thus obtained, is
called the lower heating value.
• On the other hand, if the water in the products is considered to be
in liquid state, using the enthalpy of formation of liquid water equal
to -283.83 kJ/mol, the latent heat of water vapor has already been
extracted. In this case, higher heating value is obtained.
• In reality, some water in the products can condense on walls and
surfaces and some remain in vapor state. Therefore, practically,
the heat of combustion will be in between the higher and lower
heating values.

Dr. V. Raghavan, IIT Madras 10

 Standard heat of combustion per kg of oxygen

• The heat of reaction can be calculated per mole and per kg of

oxygen consumed during the combustion.
• For instance, the standard heat of reaction of methane is
calculated per mol of oxygen, as, -802.68 / 2 = -401.34 kJ/mol-O2,
since for one mole of methane burnt, 2 moles of oxygen are burnt.
• The heat of reaction on oxygen mass basis is: -401.34 × 1000 / 32
= -12542 kJ/kg-O2 or heat of combustion per kg of oxygen
consumed is 12.54 MJ/kg-O2.
• If the same calculations are carried out for methanol, the values of
heat of combustion are obtained as 19.9 MJ/kg-methanol and 13.3
MJ/kg-O2.
• Thus, it can be shown that the heat of combustion per kg-oxygen,
for several fire sources (fuels) lies within 13.1 ± 0.7 MJ/kg-O2. This
concept is used in oxygen calorimetry.

Dr. V. Raghavan, IIT Madras 11

 Standard heat of combustion per kg of CO2

• Similarly, the standard heat of combustion per kg-CO2 produced

is: 802.68 × 1000 / 44 = 18243 kJ/kg-CO2. In fact, this is an
extreme value obtained for methane combustion.
• For pentane to dodecane, this value lies in a smaller range, given
as: 14.7 MJ/kg-CO2 to 14.2 MJ/kg-CO2.
• The average value of heat of combustion per kg-CO2, for several
fuels is 13.3 ± 1.5 MJ/kg-CO2.
• This concept is used in carbon-dioxide calorimetry.

Dr. V. Raghavan, IIT Madras 12

 Standard heat of combustion of liquid fuel

• The stoichiometric combustion of n-heptane (C7H16), a commonly

used liquid fuel, is given as,
C7H16 + 11(O2 + 3.76N2) → 7CO2 + 8H2O + 41.36N2
• Standard enthalpy of formation of gaseous (or vapor) n-heptane is
-189.3 kJ/mol and that of liquid n-heptane is -225.9 kJ/mol. Based
on the state of the fuel, liquid or vapor, appropriate value of
enthalpy of formation is to be used.
• On mass basis, the heat of reaction of vapor heptane can be
calculated as -45000 kJ/kg-fuel. Here, water is in vapor state.
Thus, the lower calorific value of n-heptane is 45 MJ/kg-heptane.
The lower heating value of n-heptane, if it is in liquid state initially,
can be shown to be 44.6 MJ/kg.

Dr. V. Raghavan, IIT Madras 13

 Heat of combustion

• Standard heat of combustion is obtained when reactant enter and

products leave at standard conditions of 1 atm and 298 K. If the
products exit the control volume at a higher temperature, the heat
of combustion will be lower than the standard value.
• For example, consider n-heptane burning with 125%
stoichiometric air, written as,

C7H16 + 13.75(O2 + 3.76N2) → 7CO2 + 8H2O + 2.75O2 + 51.7N2

• If the reactants enter at 298 K and the products leave at 1200 K,

the heat of reaction is calculated as follows:

𝑄ሶ = 7 −393.52 + ∆ℎത 𝐶𝑂2 1200 + 8 −241.83 + ∆ℎത 𝐻2𝑂 1200

+2.75∆ℎത 𝑂2 1200 + 51.7∆ℎത 𝑁2 1200 − −189.3

Dr. V. Raghavan, IIT Madras 14

 Sensible enthalpy

• Sensible enthalpies are obtained from tabulated data or from

specific heat data that is usually available as a piece-wise
polynomial of temperature (NIST database) as shown below:

1200
∆ℎത 𝑖 1200 = න 𝐶𝑝,𝑖 𝑇 𝑑𝑇
298
1200
= 1000 න 𝐴 + 𝐵𝑇 ∗ + 𝐶𝑇 ∗2 + 𝐷𝑇 ∗3 + 𝐸𝑇 ∗−2 𝑑𝑇 ∗
298

• Here, T* = (T/1000). For instance, considering i = CO2, A =

24.99735, B = 55.18696, C = -33.69137, D = 7.948387, E = -
0.136638 (NIST database). Using such expressions, 𝑄ሶ is got as:

𝑄ሶ = 7 −393.52 + 44.47 + 8 −241.83 + 34.51 + 2.75 29.7

+51.7 28.11 − −189.3 = −2377.65 kJ/mol − C7 H16

Dr. V. Raghavan, IIT Madras 15

 Heat calculation for multicomponent fuel

• Consider LPG that typically contains 0.03% CH4, 0.96% C2H6,

13.31% C3H8, 10.22% C3H6, 30.23% i-C4H10, 25.32% n-C4H10,
3.98% C4H8, 5.03% i-C4H8, 4.99% trans-2-C4H8, 3.64% cis-2-
C4H8, 1.96% i-C5H12 and 0.33% n-C5H12, by volume.
• Volume fractions translate to mole fractions. For example, mole
fraction of propane, Xpropane, in LPG is 0.1331.
• Molecular weight of LPG is obtained by a chain mixing rule called
Kay’s rule, given as, MWLPG = ∑ (Xi × MWi). Here, Xi is the mole
fraction of the ith species and MWi is its molecular mass. Molecular
mass of LPG is obtained as 54.2 kg/kmol.
• Standard enthalpy of formation of LPG is obtained using similar
chain rule, given as,

ഥ 𝟎𝒇,𝑳𝑷𝑮 = ෍ 𝑿𝒊 × 𝒉
𝒉 ഥ 𝒐𝒇,𝒊 𝒌𝑱/𝒎𝒐𝒍

Dr. V. Raghavan, IIT Madras 16

 Heat calculation for multicomponent fuel

• It should be noted that if mass fractions of the constituents of LPG

have been given, then, the values of enthalpies of formation of
individual species used in the calculations should be specific to
mass (kJ/kg).
• These are obtained by dividing the molar enthalpy of formation
(kJ/kmol) of a component by its molecular mass (kg/kmol).
• Mixture enthalpy of formation (for LPG) may be concerted back to
molar form by using the molecular mass of the mixture, MWLPG.
• Global single step reaction of LPG and air, as shown earlier, is
written as,

C3.77H8.98 + 6.015(O2 + 3.76N2) → 3.77CO2 + 4.49H2O + 22.6N2

• Standard heat of reaction of LPG and air is calculated as,

ഥ 𝒇,𝑪𝑶 𝟐𝟗𝟖 + 𝟒. 𝟒𝟗𝒉
𝑸ሶ = 𝟑. 𝟕𝟕𝒉 ഥ 𝒇,𝑯 𝑶 𝟐𝟗𝟖 − 𝒉
ഥ 𝒇,𝑳𝑷𝑮 𝟐𝟗𝟖
𝟐 𝟐

Dr. V. Raghavan, IIT Madras 17

 Standard heat of reaction of LPG

• Substituting the values of heat of formation, the standard heat of

reaction for LPG-air reaction is:

𝑄ሶ = 3.77 −393.52 + 4.49 −241.83 − −90.3 = −2479.1 k JΤm ol − LPG

• Here, standard heat of formation of LPG calculated using mixing

rule, based on the composition considered is -90.3 kJ/mol.
• Lower heating value is: 2479.1×1000/54.2 = 45740 kJ/kg-LPG.
• Heat of reaction per mol of O2: -2479.1/6.015= -412.15 kJ/mol-O2.
• Heating value per kg of O2: 412.15x1000/32= 12880 kJ/kg-O2, or
12.88 MJ/kg-O2.

Dr. V. Raghavan, IIT Madras 18

 Enthalpy of formation of solid fuel

• Percentages of volatiles and fixed carbon (flammable

components) and elemental composition of C, H, O, N and S can
be determined.
• A consolidated fuel in terms of CxHyOzNp can be formulated and
the values of x, y, z and p can be evaluated using the data from
proximate and ultimate analyses.
• For calculating heat of reaction, enthalpy of formation of the
consolidated fuel is required. For this, composition of volatiles in
terms of species such as CH4, C2H2, C2H4, CO, H2, O2 and N2, are
required. These can be determined by heating the solid fuel in an
inert environment and determining the proportions of these gases
using gas chromatography.
• If the heating value of the solid fuel is determined by calorimetry,
then it can be used to calculate its enthalpy of formation.

Dr. V. Raghavan, IIT Madras 19

 Flame temperature

• Flame temperature is an important parameter that affects the fire

propagation, ignition of neighbouring commodities and their mass
loss rates.
• Flame temperature is affected by the heat loss to surroundings.
• Maximum temperature in a given space is attained if the heat loss
is zero. That is,
𝑁 𝑀

𝑄ሶ = 0 = ෍ 𝑛ሶ 𝑖 ℎത 𝑖 𝑇𝑃 − ෍ 𝑛ሶ 𝑖 ℎത 𝑖 𝑇𝑅
1 1
• Therefore, the enthalpy of the reactant mixture, calculated at
TR, is equal to the enthalpy of the product mixture, calculated
at TP, when there is no heat transfer to the surroundings.
• TP will be the maximum temperature attainable for the given
conditions and is called the adiabatic flame temperature.

Dr. V. Raghavan, IIT Madras 20

 Adiabatic flame temperature

• Calculation of enthalpy of reactant mixture is straight forward, as

seen in the heat calculations.
• To calculate the maximum product temperature, the exact
proportions of the species constituting the products should be
known.
• If complete combustion is assumed, then for a stoichiometric
reactant mixture, CO2, H2O and N2, in some proportions, would
contribute to the product mixture.
• Adiabatic flame temperature calculated by balancing the
enthalpies of the reactant and product mixtures for this case
(theoretical case without dissociation) is generally found to be
much higher than the measured value.
• This is because dissociation of the major product species has not
been considered in the above procedure.

Dr. V. Raghavan, IIT Madras 21

 Equilibrium flame temperature

• Only when the exact proportions of the species in the product

mixture are taken in to account considering dissociation of species
such as CO2, H2O and so on, a realistic value of adiabatic flame
temperature can be obtained.
• In order to evaluate the exact product species, the concept of
chemical equilibrium is used.
• The flame temperature calculated using equilibrium approach is
found to be closer to the measured values.
• Equilibrium codes such as NASA CEA can be used to obtain
equilibrium flame temperature.

Dr. V. Raghavan, IIT Madras 22

 Example calculation – no dissociation

• Consider char (solid carbon) initially at 298 K burns in air in a

furnace.
• Air flow is measured to be 150% theoretical air. Since this is a
case with excess air, the resultant temperature is expected to be
low and the chance of dissociation is also small.
• Therefore, neglecting the dissociation of CO2 formed, the adiabatic
flame temperature is calculated as illustrated below. Combustion
reaction is written in the form:

C(s) + 1.5(O2 + 3.76N2) → CO2 + 0.5O2 + 5.64N2

• Enthalpy of reactant is zero (naturally occurring elements at 298

K). Enthalpy of product is calculated using the expression:

𝐻𝑃 = ℎത𝑓,𝐶𝑂2 298 + ∆ℎത 𝐶𝑂2 𝑇𝑝 + 0.5∆ℎത 𝑂2 𝑇𝑃 + 5.64∆ℎത 𝑁2 𝑇𝑃 .

Dr. V. Raghavan, IIT Madras 23

 Example calculation – no dissociation

• Here, ℎത𝑓,𝐶𝑂2 (298) is standard heat of formation of CO2.

• ∆ℎത 𝑖 (i = CO2, O2, N2) represents the sensible heat.
• Since the enthalpy of reactant is zero, the value of TP should be
such that the value of HP is zero.
• For this, a value of TP is assumed.
• In NIST database, the values of standard enthalpies of several
species are listed as a polynomial of temperature. Using the
polynomial, plugging the assumed value of TP, HP is evaluated.
• If (HP – 0) is < 10-5 (a very small number), then that value of TP is
the adiabatic flame temperature.
• For char combustion, when TP is assumed as 1800 K, the value of
HP is -12.011 kJ. When TP is assumed as 1900 K, the value of HP
is 15.9 kJ. Thus, by linear interpolation, the correct value of TP is
estimated as 1843 K. This is a realistic value for the given case.

Dr. V. Raghavan, IIT Madras 24

 Example calculation – considering dissociation

• Consider an adiabatic flow reactor in which vaporized benzene

(C6H6) and stoichiometric air flow steadily at 1 atm, 298 K, and the
products of combustion leaves the reactor.

C6H6 + 7.5(O2 + 3.76N2) → 6CO2 + 3H2O + 28.2N2

• If dissociation of CO2 and H2O are neglected, the adiabatic flame

temperature is obtained, by a similar calculation illustrated above,
as 2529 K.
• If dissociation of CO2 & H2O is considered, using chemical
equilibrium approach, adiabatic flame temperature is evaluated as
2341 K. This calculation is done using NASA CEA.
• Mole fractions of CO, CO2, H2 and H2O, in the product mixture, at
the equilibrium temperature are evaluated as 0.0215, 0.1374,
0.002 and 0.075, respectively.

Dr. V. Raghavan, IIT Madras 25

 Simplified approach for flame temperature

• A thermodynamic approach can be used to evaluate the flame

temperature using the specific heat of the product mixture,
calculated at an average temperature.
• There are several thumb rules available in literature, illustrating
the value of the average temperature used to obtain the properties
such as specific heat.
• Consider the stoichiometric reaction of benzene vapor and air:
C6H6 + 7.5(O2 + 3.76N2) → 6CO2 + 3H2O + 28.2N2
• Enthalpies of reactant and product, expressing the sensible
enthalpy in terms of specific heat at constant pressure of the
mixture, are written as,
𝐻𝑅 = ℎത𝑓,𝐵𝑒𝑛𝑧𝑒𝑛𝑒 𝐻𝑃 = 6 −393.52 + 6 −241.83 + 𝑛𝑃 𝑐𝑝,𝑚𝑖𝑥
ҧ (𝑇𝑃 − 298)

Dr. V. Raghavan, IIT Madras 26

 Flame temperature using mixture specific heat

• Here, nP is the total number of product moles, equal to 37.2 as per

single step chemical reaction.
• Molar specific heat at constant pressure of the product mixture is
evaluated using the mole fractions of individual species and Kay’s
rule as:

𝑐𝑝,𝑚𝑖𝑥
ҧ = ෍(𝑋𝑖 𝑐𝑝,𝑖
ҧ ൯ k JΤm ol. K

• Mole fraction of CO2 is 0.161, H2O is 0.081 and N2 is 0.758.

• Values of molar specific heats of individual species are evaluated
at an average temperature (Tavg).

Dr. V. Raghavan, IIT Madras 27

 Choice of average temperature

• It can be recognized that to calculate the adiabatic flame

temperature, HR = HP. Therefore, the problem of estimating TP,
simplifies to solving the following equation.

𝑻𝑷 − 𝟐𝟗𝟖 = (𝑯𝑹 −[𝟔 −𝟑𝟗𝟑. 𝟓𝟐 + 𝟑 −𝟐𝟒𝟏. 𝟖𝟑 ])/(𝒏𝑷 × 𝒄ത 𝒑,𝒎𝒊𝒙 )

𝟖𝟐. 𝟗𝟑 − 𝟔 −𝟑𝟗𝟑. 𝟓𝟐 + 𝟑 −𝟐𝟒𝟏. 𝟖𝟑

⇒ 𝑻𝑷 = 𝟐𝟗𝟖 +
𝒏𝑷 × 𝒄ത 𝒑,𝒎𝒊𝒙

• Let cp,mix be evaluated at 298 K. Values of cp in kJ/kg-K for CO2,

H2O and N2, at 298 K are 0.844, 1.93 and 1.04, respectively.
• Mixture specific heat is calculated as,

𝑐𝑝,𝑚𝑖𝑥
ҧ = 0.161 × 0.844 × 44 + 0.081 × 1.93 × 18 + 0.758 × 1.04 × 28 Τ1000 k JΤm ol. K

• With this value, TP is evaluated as 3058 K, which is unrealistic.

Dr. V. Raghavan, IIT Madras 28
 Choice of average temperature

• Let specific heats at constant pressure be calculated at 1200 K,

which is typically an average temperature in a reactive flow field.
• Values of cp in kJ/kg-K, at 1200 K, for CO2, H2O and N2, are 1.28,
2.43 and 1.2, respectively.

𝑐𝑝,𝑚𝑖𝑥
ҧ = 0.0381 k JΤm ol. K

• With this value of mixture specific heat, TP is evaluated as 2534 K.

This is a better estimation.
• The procedure can still be simplified. Since nitrogen is the primary
constituent in the products of combustion using air, the specific
heat of the mixture is approximated as specific heat of nitrogen.
• Based on the application and necessity of the accuracy of the
data, a proper approach with necessary details is adopted.

Dr. V. Raghavan, IIT Madras 29

 Analysis of systems

• Till this point, a flow reactor (control volume) has been considered
in the analysis of heat and temperature calculations.
• A system is considered to understand a device or closed
compartment, where the mass remains constant during the
analysis and volume may vary.
• As the first example, a piston-cylinder arrangement is considered,
where combustion of a fuel with an oxidizer takes place in the
volume in the cylinder, enclosed by the piston.
• The first law of thermodynamics for the system, in the absence of
changes in potential and kinetic energies, is written as,
Q – W = E2 – E1 = U2 – U1
• Here, Q is the heat interaction, W is the displacement work
originating due to movement of the piston causing a volume
change and (U2 – U1) is the change in the internal energy.

Dr. V. Raghavan, IIT Madras 30

 Reaction at constant pressure

• When a combustion reaction takes place inside the cylinder, the

piston rises up to maintain the pressure constant at the value of
the initial reactant pressure. The displacement work for a volume
change of (V2 – V1), is calculated as p × (V2 – V1). The first law is
now written as,
Q – p(V2 – V1) = U2 – U1
Q = p(V2 – V1) + U2 – U1 = H2 – H1 = ∆HR.

• Enthalpy of reactant (H1) and product (H2) are calculated using

similar way using enthalpy of formation and sensible enthalpy.
• For exothermic reactions, ΔHR is negative and heat is transferred
from system to the surroundings.
• If the system is adiabatic, the products will reach the maximum
temperature, the adiabatic flame temperature.

Dr. V. Raghavan, IIT Madras 31

 Reaction at constant volume

• If the system is a rigid such that its volume remains constant,

similar to a closed compartment, where a fire is initiated, noting
that displacement work will be zero as ΔV = 0, the first law is
written as,
Q = U2 – U1 = UP – UR
• The heat of reaction in this case is the difference between the
internal energies of the product mixture and the reactant mixture.
• Internal energy is obtained using the values of enthalpy:
UP = HP - pP × V and UR = HR – pR × V
• Gas mixture inside the system is treated as an ideal gas mixture,
obeying: pV = nRuT. Here, n is the number of moles of the mixture
and Ru is the universal gas constant. Using this,
UP = HP – nPRuTP and UR = HR – nRRuTR

Dr. V. Raghavan, IIT Madras 32

 Constant volume combustor – pressure rise

• Let a closed rigid container contain propene, C3H6, and 150%

theoretical air at 100 kPa and 298 K.
• Let the mixture be ignited and complete combustion takes place.
Let heat be transferred so that the temperature of the products is
maintained at 1200 K.
• The chemical reaction is written as:
C3H6 + 6.75(O2 + 3.76N2) → 3CO2 + 3H2O + 2.25O2 + 25.38N2
• Final pressure is estimated using the equation of state, noting that
the volume remains constant.
• State 1 is that of reactant and state 2 is that of products.
• Number of moles of reactants and products being n1 = 33.13 and
n2 = 33.63, respectively, the final pressure is estimated using,
p2/p1 = n2T2/(n1T1)
=> p2 = 100(33.63×1200)/(33.13×298) = 408.76 kPa

Dr. V. Raghavan, IIT Madras 33

 Constant volume combustor – heat of reaction

• Applying first law to the system:

Q = U2 – U1 = (H2 – n2RuT2) - (H1 – n1RuT1)
• The values of enthalpies are calculated by the usual procedure.
𝐻1 = 1 × ℎത𝑓,𝑝𝑟𝑜𝑝𝑒𝑛𝑒 = 20.41 𝑘𝐽

𝐻2 = 3 −393.52 + ∆ℎത 𝐶𝑂2 1200

+3 −241.83 + ∆ℎത 𝐻2𝑂 1200
+2.25∆ℎത 𝑂 1200 + 25.38∆ℎത 𝑁 1200
2 2

• Substituting the values from NIST database, H2 = -887.84 kJ.

• The heat of interaction is calculated as,
Q = -887.84 – 33.63×8.31415×10-3×1200 – (20.41 –
33.13×8.31415×10-3×298)
⇒ Q = -1161.69 kJ/mol-C3H6.

Dr. V. Raghavan, IIT Madras 34

 Chemical kinetics - global reaction

• Chemical kinetics is used to evaluate the rate at which a reaction

takes place.

• Rate of a reaction primarily depends upon the temperature and

the concentrations of the reactants.

• When a reaction represents the overall reactants and major

products, it is generally called a global reaction. An example:

CH4 + 2(O2 + 3.76 N2) → CO2 + 2 H2O + 7.52 N2.

• A global reaction cannot occur in a single step as shown above

nor it is reversible. The numbers in front of the species represent
the number of moles; here, 1 kmol of CO2, 2 kmol H2O, etc.

Dr. V. Raghavan, IIT Madras 35

 Elementary reaction

• A global reaction usually occurs in several steps. These steps are

part of a chain reaction having four stages.
• First stage, as a result of which, reactants are disintegrated (their
bonds are broken), is called chain initiation. This also forms some
species called radicals, which are highly reactive.
• Second stage is called chain propagation. Here, meta stable
species and radicals are formed.
• Third stage is called chain branching. This stage accelerates the
overall reaction by producing multiple highly reactive radicals.
• Final stage is called chain termination. Here, major products such
as CO2 and H2O are formed by the reactions involving radicals.
These four stages occur simultaneously.
• All these chain reactions are ELEMENTARY reactions. They are
molecular level reactions and are reversible.

Dr. V. Raghavan, IIT Madras 36

 Elementary reactions

Examples for ELEMENTARY reactions: consider methane + oxygen

as reactants. Here, M is third body (other species or even wall).
O2 (+M) ↔ 2O (+M) (initiation)
O2 + CH4 ↔ HO2 + CH3 (initiation)
CH4 (+M) ↔ CH3 + H (+M) (initiation)
O + H ↔ OH (branching)
H + O2 ↔ O + OH (branching)
CH3 + OH ↔ CH3O + H (propagation)
H + CH3O ↔ H2 + CH2O (propagation)
CH2O (+M) ↔ H2 + CO (+M) (propagation)
H + CH2O ↔ HCO + H2 (propagation)
OH + H2 ↔ H + H2O (propagation)
CO + OH ↔ CO2 + H (propagation)
H + OH (+M) ↔ H2O (+M); CO + O (+M) ↔ CO2 (+M) (termination)

Dr. V. Raghavan, IIT Madras 37