COMBUSTION AND THERMOCHEMISTRY

O VERVIEW

❑ Definition & mathematical determination of chemical equilibrium

❑ Definition/determination of adiabatic flame temperature
❑ Prediction of composition and temperature of combusted gases as a
function of initial temperature
❑ Prediction of amounts of fuel & oxidizer
❑ Thermochemical changes during expansion process in nozzle

❑ Performance Parameters:
𝛾+1 𝛾−1
2𝛾 2 2 𝛾−1 𝑝𝑒 𝛾 𝑝𝑒 − 𝑝𝑎
𝐶𝐹 = 1− + 𝜀
𝛾−1 𝛾+1 𝑝𝑜 𝑝𝑜

𝛾+1
𝑅𝑇𝑜 𝛾 + 1 𝛾−1 Performance depends on:
𝑐∗ = T, MW, p0 , pe , pa , γ
𝛾 2
 O VERVIEW

❑ Important Concepts & Elements of Analysis

▪ Conversion of Chemical Energy to Heat

▪ Simple Treatment of Properties of Gases

▪ Balancing Chemical Reactions - Stoichiometry

▪ Adiabatic Flame Temperature

▪ Chemical Equilibrium and Gibbs Free Energy

▪ Nozzle Expansion Effects

▪ Thermochemical Calculations
THERMODYNAMICS OF GAS MIXTURES
 P ERFECT G AS

❑ Perfect Gas Law relates pressure, temperature and density for a perfect
gas/ mixture of gases :
𝑝𝑉 = 𝑛𝑇 = 𝑚𝑅𝑇 <=> 𝑝𝑣 = 𝑅𝑇

▪ Universal Gas Constant:  = 8.314 J/mol-K


▪ Gas Constant: 𝑅=
ഥ
𝑀

▪ Calorically Perfect Gas:

➢ Internal Energy du = cv dT u2 − u1 = cv (T2 − T1 )
➢ Enthalpy dh = cp dT h2 − h1 = cp (T2 − T1 )

𝑐𝑝
▪ Specific Heat Relationships: cp − cv = R 𝛾=
𝑐𝑣

❑ Definition of “Mole”:
A mole represents the amount of gas, which contains Avogadro’s number of gas
molecules: 6.02·1023 molecules/mol.
 G IBBS -DALTON LAW

❑ Properties of a mixture is determined by the properties of

constituents according to Gibbs–Dalton Law:
Vcontainer
▪ The pressure of a mixture of gases is equal to the sum of the pressure of TContainer
each constituent when each occupies alone the volume of the mixture at the PContainer
temperature of the mixture.
▪ The internal energy and the entropy of a mixture are equal, respectively, to
the sums of the internal energies and the entropies of its constituents when
each occupies alone the volume of the mixture at the temperature of the
mixture.
➢ Temperature Tmix = T1 = T2 = … = TN
𝑁

➢ Pressure pmix = p1 + p2 + p3 … + pN = ෍ 𝑃𝑖
𝑖=1

➢ Volume V mix = mmixvmix = m1v1 = m2 v2 = … = mN vN

“Bar” denotes Property
𝑁
with respect to
➢ Energy Emix = mmixemix = m1e1 + m2 e2 +… + mN eN = ෍ 𝑚𝑖 𝑒𝑖 Molar Quantity

𝑖=1

➢ Entropy Smix = mmix smix = m1 s1 + m2 s2 + … + mN sN 𝑠𝑚𝑖𝑥

ҧ = 𝑆𝑚𝑖𝑥 Τ𝑛𝑚𝑖𝑥

➢ Enthalpy H mix = mmix hmix = m1 h1 + m2 h2 + … + mN hN ℎത 𝑚𝑖𝑥 = 𝐻𝑚𝑖𝑥 Τ𝑛𝑚𝑖𝑥

 MIXTURE OF G ASES

❑ Composition of a gas mixture is expressed by either the constituent

mass fractions or mole fractions.
𝑁
𝑚𝑖 𝑚𝑖
❑ Definition of Mass Fraction: 𝑦𝑖 = = 𝑁 ⇒ ෍ 𝑦𝑖 = 1
𝑚𝑚𝑖𝑥 σ𝑖=1 𝑚𝑖
𝑖=1

VContainer
1 𝑚𝑚𝑖𝑥
▪ Equivalent Molecular Weight: 𝑀
ഥ𝑚𝑖𝑥,𝑒𝑞𝑢𝑖𝑣 = 𝑦𝑖 = TContainer
σ𝑁 𝑛𝑚𝑖𝑥
ഥ𝑖
𝑖=1 𝑀 pContainer

▪ Perfect Gas Law pi V = mi R i T = ni T

𝑁

▪ Pressure (Gibbs-Dalton Law) 𝑝 = ෍ 𝑃𝑖

𝑖=1

▪ Enthalpy ℎ𝑚𝑖𝑥 = ෍ 𝑦𝑖 ℎ𝑖
𝑖

▪ Entropy
𝑠𝑚𝑖𝑥 𝑇, 𝑝 = ෍ 𝑦𝑖 𝑠𝑖 𝑇, 𝑝
𝑖
𝑝𝑖
➢ where species entropy is 𝑠𝑖 𝑇, 𝑝𝑖 = 𝑠𝑖 𝑇, 𝑝𝑟𝑒𝑓 − 𝑅𝑙𝑛
𝑝𝑟𝑒𝑓
 MIXTURE OF G ASES
n n N
❑ Definition of Mole Fraction: xi = i = N i
nmix
 x =1 i

n i i=1

1
N
mmix
▪ Equivalent Molecular Weight: ഥ = x𝑀
𝑀 ഥ =
mix i i
equiv i=1 nmix

VContainer
𝑝𝑉𝑖 = 𝑚𝑖 𝑅𝑖 𝑇= 𝑛𝑖 𝑇 TContainer
▪ Perfect Gas Law
𝑁 pContainer

▪ Volume 𝑉 = ෍ 𝑉𝑖
𝑖=1

▪ Partial Volume: 𝑉𝑖 = 𝑥𝑖 𝑉

▪ Enthalpy ℎത 𝑚𝑖𝑥 = ෍ 𝑥𝑖 ℎത 𝑖
𝑖

▪ Entropy 𝑠𝑚𝑖𝑥
ҧ 𝑇, 𝑝 = ෍ 𝑥𝑖 𝑠𝑖ҧ 𝑇, 𝑝
𝑖
➢ where species entropy is 𝑝𝑖
𝑠𝑖ҧ 𝑇, 𝑝𝑖 = 𝑠𝑖ҧ 𝑇, 𝑝𝑟𝑒𝑓 − 𝑙𝑛
𝑝𝑟𝑒𝑓
 MIXTURE OF G ASES

❑ Definitions:
𝑉𝑖 𝑝𝑖 ഥ𝑚𝑖𝑥
𝑀
▪ Relationship = = 𝑥𝑖 = 𝑦𝑖
𝑉 𝑝 ഥ𝑖
𝑀

▪ Specific Heat 𝑐𝑝,𝑚𝑖𝑥 = ෍ 𝑐𝑝,𝑖 𝑦𝑖

𝑖=1

𝑐𝑝,𝑚𝑖𝑥 𝑐𝑝,𝑚𝑖𝑥
▪ Ratio of Specific Heat 𝛾𝑚𝑖𝑥 = =
𝑐𝑣,𝑚𝑖𝑥 𝑐𝑝,𝑚𝑖𝑥 − 𝑅𝑚𝑖𝑥
 MIXTURE OF G ASES (S UMMARY )

❑ Definitions by Mass Based Molar Based

▪ PG Law 𝑝𝑖 𝑉 = 𝑚𝑖 𝑅𝑖 𝑇= 𝑛𝑖 𝑇 𝑝𝑉𝑖 = 𝑚𝑖 𝑅𝑖 𝑇= 𝑛𝑖 𝑇
𝑁 𝑁

▪ Pressure 𝑝 = ෍ 𝑃𝑖 𝑉 = ෍ 𝑉𝑖
𝑖=1 𝑖=1
𝑁 𝑁
𝑚𝑖 ഥ𝑖
𝑀 𝑛𝑖 ഥ𝑚𝑖𝑥
𝑀
▪ Fraction of Species 𝑦𝑖 =
𝑚𝑚𝑖𝑥
= 𝑥𝑖
ഥ𝑚𝑖𝑥
𝑀
෍ 𝑦𝑖 = 1 𝑥𝑖 =
𝑛𝑚𝑖𝑥
= 𝑦𝑖
ഥ𝑖
𝑀
෍ 𝑥𝑖 = 1
𝑖=1 𝑖=1

▪ Enthalpy ℎ𝑚𝑖𝑥 = ෍ 𝑦𝑖 ℎ𝑖 ℎത 𝑚𝑖𝑥 = ෍ 𝑥𝑖 ℎത 𝑖

𝑖 𝑖

▪ Entropy 𝑠𝑚𝑖𝑥 𝑇, 𝑝 = ෍ 𝑦𝑖 𝑠𝑖 𝑇, 𝑝 𝑠𝑚𝑖𝑥

ҧ 𝑇, 𝑝 = ෍ 𝑥𝑖 𝑠𝑖ҧ 𝑇, 𝑝
𝑖 𝑖

𝑝𝑖 𝑝𝑖
𝑠𝑖 𝑇, 𝑝𝑖 = 𝑠𝑖 𝑇, 𝑝𝑟𝑒𝑓 − 𝑅𝑙𝑛 𝑠𝑖ҧ 𝑇, 𝑝𝑖 = 𝑠𝑖ҧ 𝑇, 𝑝𝑟𝑒𝑓 − 𝑙𝑛
𝑝𝑟𝑒𝑓 𝑝𝑟𝑒𝑓

▪ Equivalent Molecular Weight

𝑁
ഥ𝑚𝑖𝑥,𝑒𝑞𝑢𝑖𝑣
𝑚 𝑚 1 𝑚 σ𝑁 ഥ
𝑖=1 𝑛𝑖 𝑀𝑖
𝑀 = = = ഥ𝑚𝑖𝑥,𝑒𝑞𝑢𝑖𝑣
𝑀 = = = ෍ 𝑥𝑖 𝑀𝑖
𝑛 σ𝑁 𝑚𝑖 σ𝑁 𝑦𝑖 𝑛 𝑛
ഥ𝑖
𝑖=1 𝑀 ഥ𝑖
𝑖=1 𝑀 𝑖=1
1 ST LAW OF THERMODYNAMICS
 1 ST LTD - F IXED MASS
❑ First law of thermodynamics embodies the fundamental principle
of conservation of energy.
▪ Q and W are path functions and occur only at the system boundary.
▪ E is a state variable (property), ∆E is path independent.
System Boundary enclosing Fixed Mass

m, E
W

Q − W = E1→2
Heat added to Work done by system Change in total system
system in going on surrounding in energy in going
from state 1→2 going from state 1 → 2 from state 1 → 2

Q − W = dE / dt
q − w = de / dt

1
𝐸 = 𝑚 𝑢 + 𝑣 2 + 𝑔𝑧
2
 1 ST LTD - C ONTROL VOLUME

❑ Conservation of energy for a steady-state, steady-flow system.

Control Surface (CS) enclosing Control Volume (CV)

𝑑𝑚𝐶𝑉 𝑑𝐸𝐶𝑉 𝑚ሶ 𝑒 + 𝑝𝑣
𝑚ሶ 𝑒 + 𝑝𝑣 𝑖𝑛𝑙𝑒𝑡 =0 =0 𝑜𝑢𝑡𝑙𝑒𝑡
𝑑𝑡 𝑑𝑡

QCV WCV
𝑸ሶ 𝑪𝑽 − 𝑾ሶ 𝑪𝑽 = ሶ 𝒐𝒖𝒕𝒍𝒆𝒕
𝒎𝒆 − ሶ 𝒊𝒏𝒍𝒆𝒕
𝒎𝒆 + 𝒎ሶ 𝒑𝟎 𝒗𝟎 − 𝒑𝒊 𝒗𝒊
Rate of heat Rate of all work Rate of energy Rate of energy Net rate of work
transferred across done by CV, flowing out flowing into associated with pressure
the CS, from the including shaft work of CV. CV. forces where fluid
surrounding to the CV. but excluding flow work. crosses CS, flow work.

1 2
𝑄ሶ 𝐶𝑉 − 𝑊ሶ 𝐶𝑉 = 𝑚ሶ ℎ0 − ℎ𝑖 + 𝑣0 − 𝑣𝑖2 + 𝑔 𝑧0 − 𝑧𝑖
2
❑ Assumptions:
▪ Control Volume is fixed relative to the coordinate system.
➢ Eliminates any work interactions associated with a moving boundary,
➢ Eliminates consideration of changes in kinetic and potential energies of CV itself.
▪ Properties of fluid at each point within CV, or on CS, do not vary with time.
▪ Fluid properties are uniform over inlet and outlet flow areas.
▪ There is only one inlet and one exit stream.
 THERMODYNAMIC PROCESSES

❑ Energy Equation (1st Law of TD)

E = U + Epotential + Ekinetic = Q − W shaft − W flow
❑ Energy Change due to a process going from State 1 to State 2:
U = U 2 − U 1 = Q − W flow = Q − p V

❑ Constant–Volume (Isochoric) Process:

U = Q

❑ Constant–Pressure (Isobaric) Process:

U = Q − p V

U + p V = Q

H = Q
REACTANT AND PRODUCT MIXTURES
 STOICHIOMETRY

❑ The stoichiometric quantity of oxidizer (substance A) is just that amount

needed to completely burn a quantity of fuel (substance B):
▪ An oxidizer-fuel mixture is LEAN, when there is more than a stoichiometric
quantity of oxidizer in the mixture.
▪ An oxidizer-fuel mixture is RICH, when there is less than a stoichiometric quantity
of oxidizer in the mixture.

❑ Stoichiometric Chemical Reaction:

▪ Examples:
CH 4 + 2O2 → CO2 + 2H 2O
➢ One mole of methane and 2 moles of oxygen form one mole
of carbon dioxide and 2 mole of water.
1
𝐻2 + 𝑂2 → 𝐻2 𝑂
2
➢ One mole of H2 and a half mole of O2 form one mole of H2O.
 STOICHIOMETRY
Note: 1 kmol O2 + 3.76 kmol N2 = 4.76 kmol air
❑ Stoichiometric Oxidizer-Fuel Ratio:
𝑂 𝑚𝑜𝑥𝑖𝑑𝑖𝑧𝑒𝑟 𝐴 𝑚𝑎𝑖𝑟 𝑛𝑎𝑖𝑟 𝑀 ഥ𝑎𝑖𝑟 4.76 ∙ 𝑎 𝑀 ഥ𝑎𝑖𝑟
= = = ∙ = ∙
𝐹 𝑚𝑓𝑢𝑒𝑙 𝐹 𝑚𝑓𝑢𝑒𝑙 𝑛𝑓𝑢𝑒𝑙 𝑀ഥ𝑓𝑢𝑒𝑙 1 ഥ𝑓𝑢𝑒𝑙
𝑀
𝑠𝑡𝑜𝑖𝑐 𝑠𝑡𝑜𝑖𝑐 𝑠𝑡𝑜𝑖𝑐 𝑠𝑡𝑜𝑖𝑐

❑ Equivalence Ratio Φ :
𝑂 Τ𝐹 𝑠𝑡𝑜𝑖𝑐 𝐹 Τ𝑂 𝑂 𝑛𝑜𝑥𝑦𝑔𝑒𝑛 𝑀ഥ𝑜𝑥𝑦𝑔𝑒𝑛
Φ = 𝑂 Τ𝐹 = 𝐹 Τ𝑂 𝑤ℎ𝑒𝑟𝑒
𝐹
=
𝑛𝑓𝑢𝑒𝑙
∙
ഥ𝑓𝑢𝑒𝑙
𝑀
𝑠𝑡𝑜𝑖𝑐

▪ This ratio is a quantitative indicator whether a fuel-oxidizer mixture is

➢ Lean: Φ 1
➢ Rich: Φ 1
➢ Stoichiometric: Φ =1

❑ Other Parameters:
100%
▪ Percent Stoichiometric Oxidizer: % 𝑠𝑡𝑜𝑖𝑐ℎ𝑖𝑜𝑚𝑒𝑡𝑟𝑖𝑐 𝑜𝑥𝑖𝑑𝑖𝑧𝑒𝑟 =
Φ
1−Φ
▪ Percent Excess Oxidizer: % 𝑒𝑥𝑐𝑒𝑠𝑠 𝑜𝑥𝑖𝑑𝑖𝑧𝑒𝑟 = 100%
Φ
 AIR (O2)/FUEL COMBUSTION

❑ Stoichiometric Combustion of Air and Fuel (Hydrocarbon)

𝑦
𝐶𝑥 𝐻𝑦 + 𝑎 ∙ 𝑂2 + 3.76𝑁2 → 𝑥 ∙ 𝐶𝑂2 + ∙ 𝐻 𝑂 + 3.76𝑎 ∙ 𝑁2
2 2
x & y define the 𝑦
hydrocarbon fuel!
⇒𝑎=𝑥+
4
❑ Lean Combustion of Air and Fuel
𝐶𝑥 𝐻𝑦 + 𝑎 ∙ 𝑂2 + 3.76𝑁2 → 𝑏 ∙ 𝐶𝑂2 + 𝑐 ∙ 𝐻2 𝑂 + 𝑑 ∙ 𝑂2 + 3.76𝑎 ∙ 𝑁2
▪ Balancing Chemical Reaction: C: x=b b=x
H : y = 2c c = (1/2)y
O : 2a = 2b + c + 2d a = x + (1/4)y + d

❑ Rich Combustion of Air and Fuel

𝐶𝑥 𝐻𝑦 + 𝑎 ∙ 𝑂2 + 3.76𝑁2 → 𝑏 ∙ 𝐶𝑂2 + 𝑐 ∙ 𝐻2 𝑂 + 𝑑 ∙ 𝐶𝑥 𝐻𝑦 + 3.76𝑎 ∙ 𝑁2

▪ Balancing Chemical Reaction: C : x = b + xd b = x (1 − d)

H : y = 2c + yd c = (1/2) y (1 − d)
O : 2a = 2b + c a = [ x + (1/4)y ]∙(1 − d)
 EXAMPLES

Consider a gas mixture that consists of 3 kg of O2, 5 kg of N2, and 12 kg of CH4.

(a) The mass fraction of each component

(b) The mole fraction of each component
(c) The average molar mass and gas constant of the mixture
 EXAMPLES

A small, low-emission, stationary gas-turbine engine operates at full load at an

equivalence ratio of 0.286 with an air flowrate of 15.9 kg/s. The equivalent
composition of the fuel (natural gas) is C1.16H4.32. Determine the fuel mass flow rate
and the operating air-fuel ratio for the engine.
 E NERGIES IN C HEMICAL REACTIONS

❑ Absolute (Standardized) Enthalpy and Enthalpy of Formation

▪ Any species (by itself or in a mixture) has a certain enthalpy depending on its
state (T, p, V, etc.)
▪ The process of formation for any species is expressed by absolute
(standardized) enthalpy.
▪ The Absolute Enthalpy is the sum of:
➢ Enthalpy of Formation: energy associated with chemical bonds (or lack thereof),
➢ Sensible Enthalpy Change: energy associated only with temperature.
0
ℎ(𝑇) = ℎ𝑓𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛 (𝑇𝑟𝑒𝑓 ) + ∆ℎ𝑠𝑒𝑛𝑠𝑖𝑏𝑙𝑒 (𝑇)
Absolute Enthalpy Enthalpy of Formation Sensible Enthalpy Change
at temperature T. at standard reference in going from
state (Tref, pref). Tref →T.

0
▪ Sensible Enthalpy is defined as: ∆ℎ𝑠 = ℎ 𝑇 − ℎ𝑓,𝑟𝑒𝑓

▪ Standard Reference State: Tref = 298.15K = 25C pref = 1atm = 101, 325 Pa

▪ Enthalpy of Formation is zero for elements, when their naturally occurring state is at
the reference state temperature and pressure. ℎ0 =0
𝑓,𝑂2 298
 E NERGIES IN C HEMICAL REACTIONS (C ONTD .)

▪ Sensible enthalpy is absolute enthalpy minus enthalpy of formation:

0
∆ℎ𝑠𝑒𝑛𝑠𝑖𝑏𝑙𝑒 (𝑇) = ℎ(𝑇) − ℎ𝑓𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛 (𝑇𝑟𝑒𝑓 )

▪ The sensible enthalpy of any compound is zero under standard conditions. It

then rises as the temperature increases according to
𝑇
∆ℎ𝑠𝑒𝑛𝑠𝑖𝑏𝑙𝑒 𝑇 = න 𝐶𝑝 𝑇 𝑑𝑇
𝑇𝑟𝑒𝑓

For this reason, sensible enthalpy is also known as thermal enthalpy.

 G RAPHICAL ILLUSTRATION

❑ Physical Interpretation:
▪ Enthalpy of Formation is the net change in enthalpy associated with breaking
chemical bonds of standard state elements and forming new bonds to create
the compound of interest.
Sensible Enthalpy Change
in going from
Tref → T.

Absolute Enthalpy
at temperature T.

Figure 2.6, page 25

Turns

Enthalpy of Formation
at standard reference
state (Tref, pref).

To form oxygen atoms at (standard conditions) requires energy. The dissociation energy to
break the bond for O2 at 298 K is 498,390 kJ/kmol. The enthalpy of formation for atomic
oxygen is
ℎത𝑓,𝑂
0
= 249,195 𝑘𝐽/𝑘𝑚𝑜𝑙
298
 E XAMPLE
❑ Example:
▪ A gas stream at 1 atm contains a mixture of CO, CO2, and N2 in which the CO
mole fraction is 0.10 and the CO2 mole fraction is 0.20. The gas stream
temperature is 1,200 °K. Determine the absolute enthalpy of the mixture on both
a mole (kJ/kmol) and mass (kJ/kg) basis. Also determine the mass fractions of the
three-component gas.