ME301A Energy Systems I

Combustion
Internal Combustion Engines

Pranav Joshi
Dept. of Mech. Engg., IIT Kanpur

Sept-Dec 2020
Combustion & IC engines

Combustion

https://en.wikipedia.org/wiki/Candle

https://flamingoappliance.com/oven-repair/what-to-
do-when-your-gas-cooktop-has-weak-flames/

https://en.wikipedia.org/wiki/Coal-fired_power_station

https://ec.europa.eu/jrc/en/news/more-countries-ever-hit-forest-fires-2018
https://www.somagnews.com/happens-aircraft-engine-fails-flight/

Internal Combustion (IC) engines https://video.nationalgeographic.com/video/science/101-videos/0000016b-dd68-d9ed-a5fb-ddfc68550000

https://en.wikipedia.org/wiki/Marine_LNG_Engine

http://www.crankshift.com/internal-combustion-engine/

https://www.indiamart.com/proddetail/cummins-diesel-generator-set-
20294183597.html

https://24coaches.com/indian-railways-wdm-series/
https://www.carhelpcanada.com/volkswagen-settlement-reached/
 Standardized enthalpy
&
Enthalpy of reaction

Adiabatic Flame Temperature (AFT)

Combustion

Chemical equilibrium

Chemical kinetics
Review: Ideal gas mixtures
Definitions 𝑛𝑛𝑖𝑖 ≡ number of moles of species 𝑖𝑖
𝑚𝑚𝑖𝑖 ≡ mass of species 𝑖𝑖
Species 𝑖𝑖 = 1: 𝑁𝑁

𝑛𝑛𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 = ∑ 𝑛𝑛𝑖𝑖 ≡ total number of moles in the gas-mixture

𝑚𝑚𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 = ∑ 𝑚𝑚𝑖𝑖 ≡ total mass of the gas-mixture
𝑛𝑛𝑖𝑖 𝑛𝑛𝑖𝑖
Mole fraction of species 𝑖𝑖: 𝑥𝑥𝑖𝑖 = = Note: � 𝑥𝑥𝑖𝑖 = 1
∑ 𝑛𝑛𝑖𝑖 𝑛𝑛𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡

� 𝑦𝑦𝑖𝑖 = 1
𝑚𝑚𝑖𝑖 𝑚𝑚𝑖𝑖
Mass fraction of species 𝑖𝑖: 𝑦𝑦𝑖𝑖 = =
∑ 𝑚𝑚𝑖𝑖 𝑚𝑚𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡

Note:
Molecular weight of the mixture:
Molecular weight of the mixture is the
𝑚𝑚𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡
𝑀𝑀𝑀𝑀𝑚𝑚𝑚𝑚𝑚𝑚 = weighted average of the molecular
𝑛𝑛𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 weights of all the species in the
mixture.
∑ 𝑛𝑛𝑖𝑖 𝑀𝑀𝑀𝑀𝑖𝑖
= = ∑ 𝑥𝑥𝑖𝑖 𝑀𝑀𝑀𝑀𝑖𝑖
𝑛𝑛𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡
Review: Ideal gas mixtures

Relation between mole fraction and mass fraction of a particular species:

𝑚𝑚𝑖𝑖
𝑦𝑦𝑖𝑖 =
𝑚𝑚𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡

𝑛𝑛𝑖𝑖 𝑀𝑀𝑀𝑀𝑖𝑖 𝑥𝑥𝑖𝑖 𝑛𝑛𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 𝑀𝑀𝑀𝑀𝑖𝑖 𝑛𝑛𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 1

= = = 𝑥𝑥𝑖𝑖 𝑀𝑀𝑀𝑀𝑖𝑖 = 𝑥𝑥𝑖𝑖 𝑀𝑀𝑀𝑀𝑖𝑖
𝑚𝑚𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 𝑚𝑚𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 𝑚𝑚𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 𝑀𝑀𝑀𝑀𝑚𝑚𝑚𝑚𝑚𝑚

𝑀𝑀𝑀𝑀𝑖𝑖
𝑦𝑦𝑖𝑖 = 𝑥𝑥𝑖𝑖
𝑀𝑀𝑀𝑀𝑚𝑚𝑚𝑚𝑚𝑚

Similarly, one can show that

𝑅𝑅𝑢𝑢 𝑅𝑅𝑢𝑢
𝑅𝑅𝑚𝑚𝑚𝑚𝑚𝑚 = , just as 𝑅𝑅 = for a single gas.
𝑀𝑀𝑀𝑀𝑚𝑚𝑚𝑚𝑚𝑚 𝑀𝑀𝑊𝑊
Review: Ideal gas mixtures
Partial pressure Note:
Each species occupies the same volume and
Partial pressure (𝑝𝑝𝑖𝑖 ): is assumed to be at the same temperature in
The pressure of the species 𝑖𝑖 if it alone occupies the same a gas mixture.
volume as that of the mixture at the same temperature.
Species 𝑖𝑖 = 1: 𝑁𝑁
Pressure 𝑝𝑝𝑖𝑖
Dalton’s Law of Partial pressure (law of additive pressures): Temperature 𝑇𝑇

Mixture pressure 𝑝𝑝: 𝑝𝑝 = � 𝑝𝑝𝑖𝑖

Note:
Since 𝑝𝑝𝑝𝑝 = 𝑛𝑛𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 𝑅𝑅𝑢𝑢 𝑇𝑇 The law holds exactly only for ideal gases,
and is only approximately true for real gases.
and 𝑝𝑝𝑖𝑖 𝑉𝑉 = 𝑛𝑛𝑖𝑖 𝑅𝑅𝑢𝑢 𝑇𝑇
𝑝𝑝 𝑝𝑝𝑖𝑖
Dalton’s Law  = i.e., 𝑝𝑝𝑖𝑖 = 𝑥𝑥𝑖𝑖 𝑝𝑝
𝑛𝑛𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 𝑛𝑛𝑖𝑖
 Review: Ideal gas mixtures
Mixture properties
Molar-specific mixture enthalpy ℎ� 𝑚𝑚𝑚𝑚𝑚𝑚 = � 𝑥𝑥𝑖𝑖 ℎ� 𝑖𝑖 (𝑇𝑇)
Mass-specific mixture enthalpy
and similarly for internal energies:
Molar-specific mixture internal energy 𝑢𝑢� 𝑚𝑚𝑚𝑚𝑚𝑚 = � 𝑥𝑥𝑖𝑖 𝑢𝑢� 𝑖𝑖 (𝑇𝑇)
Mass-specific mixture internal energy
and for entropies:
Molar-specific mixture entropy
Mass-specific mixture entropy
ℎ𝑚𝑚𝑚𝑚𝑚𝑚 = � 𝑦𝑦𝑖𝑖 ℎ𝑖𝑖 (𝑇𝑇)
𝑢𝑢𝑚𝑚𝑚𝑚𝑚𝑚 = � 𝑦𝑦𝑖𝑖 𝑢𝑢𝑖𝑖 (𝑇𝑇)
𝑠𝑠𝑚𝑚𝑚𝑚𝑚𝑚
̅ = � 𝑥𝑥𝑖𝑖 𝑠𝑠𝑖𝑖 (𝑇𝑇, 𝑝𝑝𝑖𝑖 )
𝑠𝑠𝑚𝑚𝑚𝑚𝑚𝑚 = � 𝑦𝑦𝑖𝑖 𝑠𝑠𝑖𝑖 (𝑇𝑇, 𝑝𝑝𝑖𝑖 )
We will use the overbar ( � ) to indicate
molar-specific quantities, and variables
without the overbar to indicate mass-
specific quantities.
Note:
1. For ideal gases ℎ and 𝑢𝑢 are functions of 𝑇𝑇
alone.
2. Since the components in the gaseous
mixture are assumed to be at the same
temperature, all the enthalpies and internal
energies are evaluated at the mixture
temperature 𝑇𝑇.
Note:
1. For ideal gases 𝑠𝑠 is a function of 𝑇𝑇 and 𝑝𝑝.
2. The entropy of the gas i depends on its
temperature (which is the same as the
mixture temperature, 𝑇𝑇) and its partial
pressure 𝑝𝑝𝑖𝑖 .
 Review: First Law of Thermodynamics
A) For a system (fixed mass)
𝑄𝑄 = ∆𝐸𝐸 + 𝑊𝑊 In going from state 1 to state 2.

Heat added to the system Work done by the system

Change in
system energy on the surrounding
For a system with mass 𝑚𝑚,
1 2 specific internal energy 𝑢𝑢, speed
Here, the energy 𝐸𝐸 = 𝑚𝑚(𝑢𝑢 + 𝑐𝑐 + 𝑔𝑔𝑔𝑔) 𝑐𝑐 and elevation 𝑧𝑧 above a
2
datum. 𝑔𝑔 is acceleration due to
gravity.
B) For a control volume
Assumptions:
1. Control volume is fixed w.r.t. the coordinate system.
2. Steady-state steady-flow process

𝑄𝑄̇ + 𝑚𝑚𝑒𝑒 ̇ 𝑖𝑖𝑖𝑖 𝑣𝑣𝑖𝑖𝑖𝑖 = 𝑊𝑊̇ + 𝑚𝑚𝑒𝑒

̇ 𝑖𝑖𝑖𝑖 + 𝑚𝑚𝑝𝑝 ̇ 𝑜𝑜𝑜𝑜𝑜𝑜 + 𝑚𝑚𝑝𝑝
̇ 𝑜𝑜𝑜𝑜𝑜𝑜 𝑣𝑣𝑜𝑜𝑜𝑜𝑜𝑜
1 2
i.e., ̇ ̇
𝑄𝑄 − 𝑊𝑊 = 𝑚𝑚̇ (ℎ𝑜𝑜𝑜𝑜𝑜𝑜 − ℎ𝑖𝑖𝑖𝑖 ) + 𝑐𝑐𝑜𝑜𝑜𝑜𝑜𝑜 − 𝑐𝑐𝑖𝑖𝑖𝑖2
+ 𝑔𝑔(𝑧𝑧𝑜𝑜𝑜𝑜𝑜𝑜 − 𝑧𝑧𝑖𝑖𝑖𝑖 )
2
Stoichiometry
 Stoichiometry

Stoichiometry describes the mass balance in a chemical reaction

For a hydrocarbon fuel CxHy, the oxidation reaction

can be represented as air
Note:
CxHy + 𝑎 (O2 + 3.76 N2) → xCO2 + (y/2)H2O + 3.76𝑎 N2 Air contains 21% O2 and 79% N2 by volume.
Since
Equating the number of oxygen atoms on both sides, 𝑝𝑉𝑂2 = 𝑛𝑂2 𝑅𝑢 𝑇 and 𝑝𝑉𝑁2 = 𝑛𝑁2 𝑅𝑢 𝑇
𝑦 𝑦
2𝑎 = 2𝑥 + i.e., 𝑎=𝑥+ We have, 𝑉𝑂2 𝑛𝑂2 21
2 4 = =
𝑉𝑁2 𝑛𝑁2 79
Thus, the complete oxidation of 1 mole of the fuel requires
𝑎 moles of O2 + 3.76𝑎 moles of N2 i.e., 𝑛𝑁2 =3.76 𝑛𝑂2
Thus for each mole of O2, air contains
3.76 moles of N2.
e.g., in case of burning of methane (CH4), 𝑎 = 1 + 1 = 2.
CH4 + 2 (O2 + 3.76 N2) → CO2 + 2H2O + (3.76 × 2) N2
Thus, the complete oxidation of 1 mole of methane requires
2 moles of O2 & 3.76 × 2 = 7.52 moles of N2
 Stoichiometry

Define:
Stoichiometric quantity of oxidizer: minimum amount
needed to completely burn a given quantity of fuel.
➢ In most cases, atmospheric air is the oxidizer.

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

The complete oxidation of 1 mole (16 gm) of methane requires:

2 moles (64 gm) of O2 + 7.52 moles (210.56 gm) of N2

Quantity of CH4 Stoichiometric quantity of air

1 mole (16 gm) 64 gm of O2 + 210.56 gm of N2
=274.56 gm of air
2 moles (32 gm) 274.56 x 2 = 549.12 gm of air
 Stoichiometry

Stoichiometric air-fuel ratio: the stoichiometric

quantity of air per unit mass of the fuel is called the Note: The term Stoichiometric
Stoichiometric air-fuel ratio: 𝑚𝑎𝑖𝑟 fuel-air ratio, (𝐹/𝐴)𝑠𝑡𝑜𝑖𝑐 , is
(𝐴/𝐹)𝑠𝑡𝑜𝑖𝑐 = also widely used.
𝑚𝑓𝑢𝑒𝑙
𝑠𝑡𝑜𝑖𝑐

𝑛𝑎𝑖𝑟 𝑀𝑊𝑎𝑖𝑟
=
𝑛𝑓𝑢𝑒𝑙 𝑀𝑊𝑓𝑢𝑒𝑙
𝑠𝑡𝑜𝑖𝑐

𝑎 + 3.76𝑎 𝑀𝑊𝑎𝑖𝑟 Molecular weight of the air

= (neglecting gases other than O2 and
1 𝑀𝑊𝑓𝑢𝑒𝑙
N2) is
𝑀𝑊𝑎𝑖𝑟 = 𝑥𝑂2 𝑀𝑊𝑂2 + 𝑥𝑁2 𝑀𝑊𝑁2
2 + 3.76(2) 28.84 1 3.76
e.g., for methane (CH4), 𝑎 = 2. So (𝐴/𝐹)𝑠𝑡𝑜𝑖𝑐 = × = 17.16 = 𝑀𝑊𝑂2 + 𝑀𝑊𝑁2
1 16 4.76 4.76

i.e., 17.16 g (or kg) of air is required to completely burn 1 g (or kg) of methane. = 28.84

Thus, (𝐴/𝐹)𝑠𝑡𝑜𝑖𝑐 for methane is 17.16.

Stoichiometry

𝐴/𝐹 𝑠𝑡𝑜𝑖𝑐
Equivalence ratio Φ=
(𝐴/𝐹)
For combustion of
methane
Rich mixture
Φ>1 Less than stoichiometric quantity of oxidizer (𝐴/𝐹) < 17.16
(Fuel-rich mixture)
Φ<1 Lean mixture
Greater than stoichiometric quantity of oxidizer (𝐴/𝐹) > 17.16
(Oxidizer-rich mixture)

Φ=1 Stoichiometric
Stoichiometric quantity of oxidizer (𝐴/𝐹) = 17.16
mixture
 Example

A gas mixture consists of 2 kg of O2, 5 kg of N2, and 7 kg of CO2.

Determine (a) the mass fraction of each component, (b) the mole fraction of each
component, and (c) the average molar mass and gas constant of the mixture.

Answer:
(a) 𝑦𝑂2 = 0.143
𝑦𝑁2 = 0.357
𝑦𝐶𝑂2 = 0.5

(b) 𝑥𝑂2 = 0.1562

𝑥𝑁2 = 0.4463
𝑥𝐶𝑂2 = 0.3976

(c) 𝑀𝑊𝑚𝑖𝑥 = 34.99 kg/kmol

𝑅𝑚𝑖𝑥 = 0.237 kJ/kgK

ME301A Energy Systems I

Pranav Joshi
Dept. of Mech. Engg., IIT Kanpur

Sept-Dec 2020
 Combustion

Lecture 2: Standardized enthalpy and enthalpy of reaction

Standardized enthalpy

Standardized enthalpy
Take into account the chemical energy changes in reactions
Enthalpy of reaction

Chemical energy (𝒖𝒄𝒉𝒆𝒎 ): energy associated with the chemical bonds of a

substance.

Why do we need to consider chemical energy?

Breaking chemical bonds needs energy

E
e.g., dissociation of oxygen: O2 2O

Energy
Interatomic distance
Conversely, formation of new bonds releases energy
 Standardized enthalpy

Why do we need to consider chemical energy in reactions?

A chemical reaction involves both breaking and formation of bonds

e.g., burning of carbon: C + O2 → CO2

Breaking of O − O bond Formation of C − O bonds

Energy associated with all the bonds (𝒖𝒄𝒉𝒆𝒎 ) is different →

energy will be absorbed/released in chemical reactions

This chemical energy (𝒖𝒄𝒉𝒆𝒎 ) needs to be accounted for when analysing reacting systems

Non-reacting systems: 𝑄 − 𝑊 = 𝑢 + 𝐾𝐸 + 𝑃𝐸 + 𝑝𝑉 𝑜𝑢𝑡 − 𝑢 + 𝐾𝐸 + 𝑃𝐸 + 𝑝𝑉 𝑖𝑛 (First Law for SSSF system)

But in reacting systems, 𝑄 − 𝑊 = 𝑢 + 𝐾𝐸 + 𝑃𝐸 + 𝒖𝒄𝒉𝒆𝒎 + 𝑝𝑉 𝑜𝑢𝑡 − 𝑢 + 𝐾𝐸 + 𝑃𝐸 + 𝒖𝒄𝒉𝒆𝒎 + 𝑝𝑉 𝑖𝑛

Standardized enthalpy

𝑄 − 𝑊 = 𝑢 + 𝐾𝐸 + 𝑃𝐸 + 𝒖𝒄𝒉𝒆𝒎 + 𝑝𝑉 𝑜𝑢𝑡 − 𝑢 + 𝐾𝐸 + 𝑃𝐸 + 𝒖𝒄𝒉𝒆𝒎 + 𝑝𝑉 𝑖𝑛

Neglecting changes in KE and PE,

𝑄 − 𝑊 = 𝑢 + 𝒖𝒄𝒉𝒆𝒎 + 𝑝𝑉 𝑜𝑢𝑡 − 𝑢 + 𝒖𝒄𝒉𝒆𝒎 + 𝑝𝑉 𝑖𝑛

𝑄 − 𝑊 = ℎ𝑜𝑢𝑡 − ℎ𝑖𝑛

where ℎ = 𝑢 + 𝒖𝒄𝒉𝒆𝒎 + 𝑝𝑉 Standardized enthalpy

How to evaluate h? 𝑇,𝑝

ℎ 𝑇, 𝑝 = ℎ 𝑇𝑟𝑒𝑓 , 𝑝𝑟𝑒𝑓 + ∆ℎ 𝑇𝑟𝑒𝑓 ,𝑝𝑟𝑒𝑓

ℎ due to chemical composition (bond energy) Sensible enthalpy change

Enthalpy of formation: ℎ𝑓
Standardized enthalpy
𝑇,𝑝
ℎ 𝑇, 𝑝 = ℎ 𝑇𝑟𝑒𝑓 , 𝑝𝑟𝑒𝑓 + ∆ℎ 𝑇𝑟𝑒𝑓 ,𝑝𝑟𝑒𝑓

ℎ due to chemical composition (bond energy) Sensible enthalpy change

Enthalpy of formation: ℎ𝑓

ഥ 𝒇 ):
Enthalpy of formation (𝒉
∆ℎ associated with the breaking of chemical bonds of elements at the
standard state and forming new bonds to create the compound of
interest at the standard state.
e.g. C + O2 → CO2
Standard reference state: 𝑇 = 25 oC,
𝑝 =1 atm (1.01325×105 Pa)
 Standardized enthalpy
ഥ𝒇?
How to calculate 𝒉
Convention:
ഥ 𝒇 for elements in their naturally occurring state
𝒉
(chemically stable form) at reference 𝑇 and 𝑝 is zero, i.e., ഥ𝑓0 𝑇𝑟𝑒𝑓 = 0
𝒉

ഥ𝑓0 𝑇𝑟𝑒𝑓 = 0
𝒉 for N2
but ഥ𝑓0 𝑇𝑟𝑒𝑓 ≠ 0
𝒉 for N

Energy required to break N—N bond:

Bond dissociation energy for N2 at 298K is 945258 kJ/kmol of N2
Both N2 and N at
945258
Thus, ഥ𝑓,𝑁
𝒉 0
𝑇 = 298 K = = 472629 kJ/kmol of N at 298 K reference conditions !
2
Standardized enthalpy

ഥ𝑓0 > 0
𝒉 Heat is absorbed during the formation of the substance
ഥ𝑓0 < 0 Heat is released from its stable-state elements
𝒉
Q
N2 → N+N ഥ𝑓,𝑁
𝒉 0
>0

Note: In principle, ℎ𝑓 can also be defined at non-reference conditions.

But the conditions for both reactants and products must be the same !

Note: If more than one stable states exist for an element, choose one of
them to have 𝒉 ഥ𝑓0 𝑇𝑟𝑒𝑓 = 0

e.g.: ഥ𝑓0 𝑇𝑟𝑒𝑓 = 0

𝒉 for graphite
but ഥ𝑓0 𝑇𝑟𝑒𝑓 ≠ 0
𝒉 for diamond
 Standardized enthalpy

Standardized enthalpy: ℎ 𝑇 = ℎത𝑓0 𝑇𝑟𝑒𝑓 + ∆ℎ𝑠 (𝑇)

Enthalpy of formation at reference state Sensible enthalpy change

(No chemical energy changes)

N2 → N+N

472629 kJ/kmol
Standardized enthalpy tables
Standardized enthalpy tables
Standardized enthalpy tables
 Standardized enthalpy

For a steady-state steady flow (SSSF) process/reaction,

𝑄𝑄 = ℎ𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 − ℎ𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟

𝑄𝑄 = (ℎ𝑓𝑓0 + ∆ℎ)𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 −(ℎ𝑓𝑓0 + ∆ℎ)𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟

If both reactants and products are at the reference state,

then
∆ℎ𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 = 0 and ∆ℎ𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = 0

Thus (ℎ𝑓𝑓0 )𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 = 𝑄𝑄 + (ℎ𝑓𝑓0 )𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟

So we can calculate (ℎ𝑓𝑓0 )𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 if we measure 𝑄𝑄 and we know (ℎ𝑓𝑓0 )𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟

C + O2  CO2
 Standardized enthalpy

Example: calculating enthalpy of gas mixtures

Standardized enthalpy

ℎ� 𝑚𝑚𝑚𝑚𝑚𝑚
ℎ𝑚𝑚𝑚𝑚𝑚𝑚 =
𝑀𝑀𝑀𝑀𝑚𝑚𝑚𝑚𝑚𝑚

ℎ𝑚𝑚𝑚𝑚𝑚𝑚 = −3,813 kJ/kg of

mixture
 Enthalpy of reaction

Consider a SSSF reaction, e.g.: C

CO2
298 K, 1 atm
298 K, 1 atm
O2
𝑊𝑊 = 0
𝑞𝑞 = ℎ𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 − ℎ𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟

Define enthalpy of reaction: ∆ℎ𝑅𝑅 = 𝑞𝑞 = ℎ𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 − ℎ𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟

assuming  The reaction is complete

 Reactants and products are at the same state (𝑇𝑇 and 𝑝𝑝)
*Not necessarily at the reference 𝑇𝑇 and 𝑝𝑝.

Note: ∆ℎ𝑅𝑅 will be different at different 𝑇𝑇 𝑎𝑎𝑎𝑎𝑎𝑎 𝑝𝑝 !

∆ℎ𝑅𝑅 = ℎ𝐶𝐶𝐶𝐶2 − (ℎ𝐶𝐶 + ℎ𝑂𝑂2 )

 Enthalpy of reaction

∆ℎ𝑅𝑅 = ℎ𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 − ℎ𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟

If both reactants and products are at the reference 𝑇𝑇 and 𝑝𝑝,

=0 =0
∆ℎ𝑅𝑅 = (ℎ𝑓𝑓0 + ∆ℎ𝑠𝑠 )𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 −(ℎ𝑓𝑓0 + ∆ℎ𝑠𝑠 )𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟

∆ℎ𝑅𝑅 = (ℎ𝑓𝑓0 )𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 −(ℎ𝑓𝑓0 )𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟

0 0 0
e.g., ∆ℎ𝑅𝑅 = ℎ𝑓𝑓,𝐶𝐶𝐶𝐶2 − (ℎ𝑓𝑓,𝐶𝐶 + ℎ𝑓𝑓,𝑂𝑂𝑂 )

For combustion reaction, Enthalpy of combustion = ∆ℎ𝑅𝑅

∆ℎ𝑅𝑅 < 0 For an exothermic reaction (combustion)

∆ℎ𝑅𝑅 > 0 For an endothermic reaction

Enthalpy of reaction

∆ℎ𝑅𝑅 = ℎ𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 − ℎ𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟

Hess’s Law
If two or more chemical equations (reactions) are added to give another chemical equation (reaction),
the corresponding reaction enthalpies, ∆ℎ𝑅𝑅 , must also be added to get the ∆ℎ𝑅𝑅 for the resulting overall
reaction.

 Enthalpy is a state function, and is independent of the path taken to get to that state.

e.g., C + O2  CO2

1
C+ O  CO ∆ℎ𝑅𝑅 = −110,541 kJ/kmol
2 2
All at 298 K, 1 atm
+ CO +
1
O
2 2
 CO2 ∆ℎ𝑅𝑅 = −283,005 kJ/kmol

C + O2  CO2 ∆ℎ𝑅𝑅 = −393,546 kJ/kmol

To find ∆ℎ𝑅𝑅 : 1) ∆ℎ𝑅𝑅 = (ℎ𝑓𝑓 )𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 −(ℎ𝑓𝑓 )𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟

2) Use Hess’s law
Heat of combustion
Define heat of combustion OR heating value as ∆ℎ𝐶𝐶 = −∆ℎ𝑅𝑅

assuming  The reaction (combustion) is complete

 Reactants and products are at the same state

C + O2  CO2
∆ℎ𝐶𝐶 = 393,546 kJ/kmol
∆ℎ𝑅𝑅 = −393,546 kJ/kmol

Higher and Lower heating values

Higher heating value (HHV): When H2O in products is in the liquid state

When H2O in products is in the vapour state

Lower heating value (LHV):

HHV = LHV + (𝑁𝑁ℎ�𝑓𝑓𝑓𝑓 )𝐻𝐻2𝑂𝑂

𝑁𝑁 = Number of moles
ℎ�𝑓𝑓𝑓𝑓 = Molar enthalpy of vaporization at the specified state
Heating values of fuel

Example:
Determine the HHV and LHV of gaseous octane (C8H18) at 298 K and 1 atm.
Solution
Combustion equation (stoichiometric)

C8H18(g) +12.5(O2 +3.76 N2)  8CO2 +9H2O (l or g) +12.5(3.76)N2

HV = −∆ℎ𝑅𝑅
= −(ℎ𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑡𝑡𝑡𝑡 − ℎ𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 )

= ℎ�𝑓𝑓0 + ∆ℎ� 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 + 12.5 ℎ�𝑓𝑓0 + ∆ℎ� 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 +12.5 × 3.76 ℎ�𝑓𝑓0 + ∆ℎ� 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠
𝐶𝐶𝐶𝐶𝐶𝐶𝐶 𝑂𝑂𝑂 𝑁𝑁2

−8 ℎ�𝑓𝑓0 + ∆ℎ� 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 − 9 ℎ�𝑓𝑓0 + ∆ℎ� 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 −12.5 × 3.76 ℎ�𝑓𝑓0 + ∆ℎ� 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠
𝐶𝐶𝐶𝐶𝐶 𝐻𝐻𝐻𝐻𝐻 𝑁𝑁2

Note: ∆ℎ� 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 = 0, (ℎ�𝑓𝑓0 )𝑂𝑂𝑂 = 0, (ℎ�𝑓𝑓0 )𝑁𝑁2 = 0

LHV = ℎ�𝑓𝑓0 − 8 ℎ�𝑓𝑓0 − 9 ℎ�𝑓𝑓0

𝐶𝐶𝐶𝐶𝐶𝐶𝐶 𝐶𝐶𝐶𝐶𝐶 𝐻𝐻𝐻𝐻𝐻,(𝑔𝑔)
 Heating values of fuel

LHV = ℎ�𝑓𝑓0 − 8 ℎ�𝑓𝑓0 − 9 ℎ�𝑓𝑓0

𝐶𝐶𝐶𝐶𝐶𝐶𝐶 𝐶𝐶𝐶𝐶𝐶 𝐻𝐻𝐻𝐻𝐻,(𝑔𝑔)

LHV = −208,447 − 8(−393,546) − 9(−241,845)

Table B.1 Table A.2 Table A.6 Stephen Turns, Intro to Combustion

LHV = 5,116,526 kJ/kmol of C8H18

For HHV use ℎ�𝑓𝑓0 = ℎ�𝑓𝑓0 − ℎ�𝑓𝑓𝑓𝑓

𝐻𝐻𝐻𝐻𝐻, 𝑙𝑙 𝐻𝐻𝐻𝐻𝐻,(𝑔𝑔) 𝐻𝐻𝐻𝐻𝐻,298K)

HHV = LHV + 9 ℎ�𝑓𝑓𝑓𝑓

𝐻𝐻𝐻𝐻𝐻,298K)

= LHV + 9 44,010 = 5,512,616 kJ/kmol of C8H18

ME301A Energy Systems I

Pranav Joshi
Dept. of Mech. Engg., IIT Kanpur

Sept-Dec 2020
 Combustion

Lecture 3: Adiabatic flame temperature

First-law analysis of combustion system

Steady state steady flow (SSSF) system:

𝑄𝑄̇ − 𝑊𝑊̇ = 𝑚𝑚(ℎ
̇ 𝑜𝑜𝑜𝑜𝑜𝑜 − ℎ𝑖𝑖𝑖𝑖 ) ℎ is the standardized enthalpy

In terms of the number of moles, say per mole of the fuel:

𝑄𝑄 − 𝑊𝑊 = � 𝑛𝑛𝑝𝑝 ℎ� 𝑝𝑝 − � 𝑛𝑛𝑟𝑟 ℎ� 𝑟𝑟
𝑝𝑝 𝑟𝑟

𝑄𝑄 − 𝑊𝑊 = � 𝑛𝑛𝑝𝑝 (ℎ�𝑓𝑓0 + ∆ℎ� 𝑠𝑠 )𝑝𝑝 − � 𝑛𝑛𝑟𝑟 (ℎ�𝑓𝑓0 + ∆ℎ� 𝑠𝑠 )𝑟𝑟

𝑝𝑝 𝑟𝑟

𝑄𝑄 − 𝑊𝑊 = � 𝑛𝑛𝑝𝑝 (ℎ�𝑓𝑓0 )𝑝𝑝 − � 𝑛𝑛𝑟𝑟 (ℎ�𝑓𝑓0 )𝑟𝑟 + � 𝑛𝑛𝑝𝑝 ( ∆ℎ� 𝑠𝑠 )𝑝𝑝 − � 𝑛𝑛𝑟𝑟 ( ∆ℎ� 𝑠𝑠 )𝑟𝑟
𝑝𝑝 𝑟𝑟 𝑝𝑝 𝑟𝑟

Enthalpy of reaction
𝑄𝑄 − 𝑊𝑊 = ∆ℎ𝑅𝑅 + � 𝑛𝑛𝑝𝑝 ( ∆ℎ� 𝑠𝑠 )𝑝𝑝 − � 𝑛𝑛𝑟𝑟 ( ∆ℎ� 𝑠𝑠 )𝑟𝑟
𝑝𝑝 𝑟𝑟
First-law analysis of combustion system
Closed system (fixed mass):
𝑄𝑄 − 𝑊𝑊 = 𝐸𝐸𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 − 𝐸𝐸𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 𝐸𝐸 is the energy, 𝑈𝑈 is the
internal energy
𝑄𝑄 − 𝑊𝑊 = 𝑈𝑈𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 − 𝑈𝑈𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 ---neglecting KE and PE

Similar to ℎ�𝑓𝑓0 , we can define the internal energy of formation, say 𝑢𝑢�𝑓𝑓0 : 𝑢𝑢� = 𝑢𝑢�𝑓𝑓0 + ∆𝑢𝑢� 𝑠𝑠

But we note that 𝑢𝑢� = ℎ� − 𝑝𝑝𝑣𝑣̅

Thus, 𝑄𝑄 − 𝑊𝑊 = � 𝑛𝑛𝑝𝑝 𝑢𝑢� 𝑝𝑝 − � 𝑛𝑛𝑟𝑟 𝑢𝑢� 𝑟𝑟

𝑝𝑝 𝑟𝑟

can be written as 𝑄𝑄 − 𝑊𝑊 = � 𝑛𝑛𝑝𝑝 ℎ� − 𝑝𝑝𝑣𝑣̅ 𝑝𝑝

− � 𝑛𝑛𝑟𝑟 ℎ� − 𝑝𝑝𝑣𝑣̅ 𝑟𝑟
𝑝𝑝 𝑟𝑟

𝑄𝑄 − 𝑊𝑊 = � 𝑛𝑛𝑝𝑝 ℎ�𝑓𝑓0 + ∆ℎ� 𝑠𝑠 − 𝑝𝑝𝑣𝑣̅ − � 𝑛𝑛𝑟𝑟 ℎ�𝑓𝑓0 + ∆ℎ� 𝑠𝑠 − 𝑝𝑝𝑣𝑣̅

𝑝𝑝 𝑟𝑟
𝑝𝑝 𝑟𝑟
First-law analysis of combustion system
Closed system example
 Adiabatic Flame Temperature (AFT)
AFT important from metallurgical considerations −𝑄𝑄
C
CO2
298 K, 1 atm
𝑊𝑊 = 0 600 K, 1 atm
O2

𝑄𝑄𝑖𝑖𝑖𝑖 = −𝑄𝑄𝑜𝑜𝑜𝑜𝑜𝑜 = 𝑚𝑚(ℎ

̇ 𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 − ℎ𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 )
𝑄𝑄𝑜𝑜𝑜𝑜𝑜𝑜
ℎ𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑐𝑐𝑡𝑡𝑡𝑡 = ℎ𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 −
𝑚𝑚̇

ℎ𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑐𝑐𝑡𝑡𝑡𝑡 highest when 𝑄𝑄𝑜𝑜𝑜𝑜𝑜𝑜 = 0 (adiabatic system)

Assuming the (generally) gaseous products to be ideal gases with ℎ = ℎ(𝑇𝑇)

𝑇𝑇𝑝𝑝𝑝𝑝𝑝𝑝𝑑𝑑𝑑𝑑𝑑𝑑𝑡𝑡𝑡𝑡 highest when 𝑄𝑄𝑜𝑜𝑜𝑜𝑜𝑜 = 0 Adiabatic Flame Temperature (AFT)

Adiabatic Flame Temperature (AFT): max temperature the combustion

products will reach when the combustion process is adiabatic.
 Adiabatic Flame Temperature (AFT)

AFT

constant-pressure AFT constant-volume AFT 𝑝𝑝

For a steady-flow combustion process For a fixed mass of reactants undergoing

at constant pressure, e.g. gas-turbine combustion at constant volume, e.g., in
combustors, furnaces etc. an ideal IC engine Otto cycle 𝑣𝑣

Find AFT using Find AFT using

ℎ𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 = ℎ𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 𝑢𝑢𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 = 𝑢𝑢𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟

� 𝑛𝑛𝑝𝑝 ℎ�𝑓𝑓0 + ∆ℎ� 𝑠𝑠 = � 𝑛𝑛𝑟𝑟 ℎ�𝑓𝑓0 + ∆ℎ� 𝑠𝑠 � 𝑛𝑛𝑝𝑝 ℎ�𝑓𝑓0 + ∆ℎ� 𝑠𝑠 − 𝑝𝑝𝑣𝑣̅ − � 𝑛𝑛𝑟𝑟 ℎ�𝑓𝑓0 + ∆ℎ� 𝑠𝑠 − 𝑝𝑝𝑣𝑣̅
𝑝𝑝 𝑟𝑟 𝑝𝑝 𝑟𝑟
𝑝𝑝 𝑟𝑟 𝑝𝑝 𝑟𝑟

𝑝𝑝𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑉𝑉 = fixed 𝑝𝑝𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖

𝑝𝑝𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑣𝑣̅ = 𝑅𝑅𝑢𝑢 (𝑨𝑨𝑨𝑨𝑨𝑨) 𝑉𝑉 = fixed

𝑝𝑝𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 𝑣𝑣̅ = 𝑅𝑅𝑢𝑢 𝑇𝑇𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖
Adiabatic Flame Temperature (AFT)

Graphical representation

Constant pressure AFT Constant volume AFT

Adiabatic Flame Temperature (AFT)

AFT example
Adiabatic Flame Temperature (AFT)

If product composition is known,

a) 𝑐𝑝ҧ = 𝑓 𝑇
𝑇𝑎𝑑
∆ℎത 𝑠 = න 𝑐𝑝ҧ 𝑑𝑇 = 𝑔(𝑇𝑎𝑑 )
298𝐾

b) 𝑐𝑝,𝑎𝑣𝑒𝑟𝑎𝑔𝑒
ҧ

c) Trial and error

• Assume 𝑇𝑎𝑑

• ത 𝑎𝑑 ) for all species

Look up charts for ℎ(𝑇

• Check if 𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 = 𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 is satisfied.

• If not, choose a different 𝑇𝑎𝑑 .

Adiabatic Flame Temperature (AFT)

Points to note

If equations for sensible enthalpy changes are not available, determination of AFT requires an
iterative process in general.

• Assume 𝑇𝑎𝑑
ത 𝑎𝑑 ) for all species
• Look up charts for ℎ(𝑇
• Check if 𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 = 𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 is satisfied.

Maximum temperature attained in a combustion reaction is less than the AFT due to:
− Incomplete combustion
− Heat loss to the surroundings
− Dissociation of combustion products at high temperature

Maximum temperature attained can be adjusted by controlling the amount of excess air which
acts as a coolant.
Adiabatic Flame Temperature (AFT)

AFT depends on

− The state of the reactants

− Degree of completion of the reaction

− AFT depends on composition of the products (e.g. different 𝑐𝑝ҧ ),
1 “For a specified fuel
CO + O2 → CO2
2 @specified state burned with
Reaction complete → only CO2 in product air @specified state,
Reaction incomplete → CO, O2 and CO2 in product AFT is max when complete
combustion occurs with Φ =
− Composition of products in turn depends on AFT (e.g. dissociation) 1.”
• So guess AFT → determine product composition → check AFT

− Amount of excess air

− System pressure – higher pressure tends to suppress dissociation
Adiabatic Flame Temperature (AFT)
Dependence of AFT on excess air (or 𝜱):
Composition → 𝑄 released
𝑄 decreases, but 𝑐𝑝 of products decreases faster

Methane-air system: Φ~1.05

𝑇𝑖𝑛𝑖𝑡𝑖𝑎𝑙 = 600 K
~2350 K

~2200 K 𝑇𝑖𝑛𝑖𝑡𝑖𝑎𝑙 = 300 K

𝑇𝑎𝑑 (K)

≠ 600 − 300 K
Due to dissociation
Excess air Incomplete combustion
𝐴/𝐹 𝑠𝑡𝑜𝑖𝑐
Φ= Φ = 1.0
(𝐴/𝐹) Lean Φ Rich
Adiabatic Flame Temperature (AFT)
Dependence of AFT on pressure:
AFT increases with pressure due to a reduction in the dissociation of species – Le Chatelier principle

Methane-air system, 𝚽 = 𝟏

2300 K

𝑇𝑎𝑑 (K)
2200 K

3 bar
𝑝
ME301A Energy Systems I

Pranav Joshi
Dept. of Mech. Engg., IIT Kanpur

Sept-Dec 2020
 Combustion

Lecture 4: Chemical equilibrium and Gibb’s free energy

Chemical composition of a reaction mixture

Assume AFT Products composition Re-calculate AFT

ℎ𝑝𝑟𝑜𝑑𝑐𝑢𝑡𝑠 = ℎ𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 These relations will

Given conditions of 𝑇 and 𝑃, calculate give AFT only if
the mixture composition, i.e. mole or product composition
fractions of all the product species 𝑢𝑝𝑟𝑜𝑑𝑐𝑢𝑡𝑠 = 𝑢𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 is known

EQUILIBRIUM COMPOSITION

For a given 𝑇 and 𝑃, assume that the product species are in chemical equilibrium.

To develop criterion for chemical equilibrium:

Consider a reacting system at a fixed 𝑇 and 𝑝.
Chemical equilibrium

Consider:
− Simple compressible system at a fixed 𝑇 and 𝑃
𝑇, 𝑃
− Fixed mass
− Quasi-equilibrium work allowed

First Law: 𝑑𝑈 + 𝑃𝑑𝑉 = 𝛿𝑄

𝛿𝑄
Second Law: ≤ 𝑑𝑆
𝑇

𝑑𝑈 + 𝑃𝑑𝑉 ≤ 𝑇𝑑𝑆

𝑑𝑈 + 𝑃𝑑𝑉 − 𝑇𝑑𝑆 ≤ 0 (1)

Chemical equilibrium
𝑑𝑈 + 𝑃𝑑𝑉 − 𝑇𝑑𝑆 ≤ 0 (1)

Gibb’s Free Energy: 𝐺 = 𝐻 − 𝑇𝑆

At constant 𝑇 and 𝑃, (𝑑𝐺) 𝑇,𝑃 = (𝑑𝐻) 𝑇,𝑃 −𝑇(𝑑𝑆) 𝑇,𝑃

(𝑑𝐺) 𝑇,𝑃 = (𝑑 𝑈 + 𝑃𝑉 ) 𝑇,𝑃 −𝑇(𝑑𝑆) 𝑇,𝑃

(𝑑𝐺) 𝑇,𝑃 = 𝑑𝑈 + 𝑃𝑑𝑉 − 𝑇𝑑𝑆 (2)

Combining (1) and (2) (𝑑𝐺) 𝑇,𝑃 ≤ 0

Thus, Second Law states that, at a specified 𝑇 and 𝑃, a chemical

reaction will proceed in the direction of decreasing G.

& For chemical equilibrium: (𝑑𝐺) 𝑇,𝑃 = 0

Chemical equilibrium
Isolated system
Thus, Second Law states that, at a specified 𝑇 and 𝑃, a chemical
reaction will proceed in a direction such that (𝑑𝐺) 𝑇,𝑃 ≤ 0.
𝑑𝑆 ≥ 0
For chemical equilibrium: (𝑑𝐺) 𝑇,𝑃 = 0
For equilibrium: 𝑑𝑆 = 0

Violation of the 2nd Law

𝐺 𝑑𝐺 > 0 𝑑𝐺 > 0 At specified 𝑇 and 𝑃

𝑑𝐺 < 0 𝑑𝐺 < 0

Equilibrium composition 100 %

100 %
(reactants & products) products
reactants

If 𝑇 and/or 𝑃 change, equilibrium composition changes

∆𝑮 and spontaneity of reactions

𝐺 = 𝐻 − 𝑇𝑆
∆𝐺 ∆𝐻
=− − + ∆𝑆
∆𝐺 = ∆𝐻 − ∆(𝑇𝑆) 𝑇 𝑇

Change in
Constant T and P ∆𝐺 = ∆𝐻 − 𝑇∆𝑆 −(Total Δ𝑆) entropy of
system
Change in
Change in entropy entropy of
surrounding
Exothermic/endothermic
Change in entropy
of the universe
Sign of ∆𝐺 Spontaneity of reaction

Ice → water at room temp ∆𝐺 < 0

 Criterion for chemical equilibrium

Consider a reaction: A+𝐵 → C+D

Exist in chemical equilibrium

Let 𝑛𝐴 , 𝑛𝐵 , 𝑛𝐶 , 𝑛𝐷 = Number of moles of A, B, C ,D
at the specified 𝑇 and 𝑃

Small change in mixture composition: 𝑑𝑛𝐴 moles of A 𝑑𝑛𝐶 moles of C

with 𝑇 and 𝑃
+ +
held constant!
𝑑𝑛𝐵 moles of B 𝑑𝑛𝐷 moles of D

For the mixture,

𝐺(𝑇, 𝑃) = ෍ 𝑛𝑖 𝑔ҧ𝑖 (𝑇, 𝑃𝑖 ) 𝑔ҧ𝑖 = molar Gibbs function of species 𝑖

=0 (check later)
Thus, for equilibrium to exist, (𝑑𝐺) 𝑇,𝑃 = ෍ 𝑛𝑖 𝑑 𝑔ҧ𝑖 + ෍ 𝑑𝑛𝑖 𝑔ҧ𝑖 = 0

(𝑑𝐺) 𝑇,𝑃 = 𝑔ҧ𝐴 𝑑𝑛𝐴 + 𝑔ҧ𝐵 𝑑𝑛𝐵 + 𝑔ҧ𝐶 𝑑𝑛𝐶 + 𝑔ҧ𝐷 𝑑𝑛𝐷 = 0
Criterion for chemical equilibrium
Relation between 𝒅𝒏𝑨 , 𝒅𝒏𝑩 , 𝒅𝒏𝑪 , 𝒅𝒏𝑫
The theoretical stoichiometric reaction can be expressed as
𝜈𝐴 A + 𝜈𝐵 𝐵 ⇌ 𝜈𝐶 C + 𝜈𝐷 D

where 𝜈𝐴 , 𝜈𝐵 , 𝜈𝐶 , 𝜈𝐷 are the stoichiometric coefficients

Suppose the reaction proceeds by a small extent in the forward direction. Then,
𝑑𝑛𝐴 = −𝜀𝜈𝐴 , 𝑑𝑛𝐵 = −𝜀𝜈𝐵 Decrease in A and B 𝜀 → 0 represents
the small extent of
𝑑𝑛𝐶 = 𝜀𝜈𝑐 , 𝑑𝑛𝐷 = 𝜀𝜈𝐷 Increase in C and D the reaction

Thus, the condition 𝑔ҧ𝐴 𝑑𝑛𝐴 + 𝑔ҧ𝐵 𝑑𝑛𝐵 + 𝑔ҧ𝐶 𝑑𝑛𝐶 + 𝑔ҧ𝐷 𝑑𝑛𝐷 = 0
becomes
−𝜈𝐴 𝑔ҧ𝐴 + −𝜈𝐵 𝑔ҧ𝐵 + 𝜈𝐶 𝑔ҧ𝐶 + 𝜈𝐷 𝑔ҧ𝐷 = 0

i.e.,
𝜈𝐶 𝑔ҧ𝐶 + 𝜈𝐷 𝑔ҧ𝐷 −𝜈𝐴 𝑔ҧ𝐴 −𝜈𝐵 𝑔ҧ𝐵 = 0 Criterion for chemical equilibrium
Criterion for chemical equilibrium

𝜈𝐶 𝑔ҧ𝐶 + 𝜈𝐷 𝑔ҧ𝐷 −𝜈𝐴 𝑔ҧ𝐴 −𝜈𝐵 𝑔ҧ𝐵 = 0

CO + (1/2)𝑂2 → CO2
A 𝐵 C
𝜈𝐴 =1 𝜈𝐵 = 0.5 𝜈𝐶 = 1 𝜈𝐷 = 0

𝜈𝐶𝑂2 𝑔ҧ𝐶𝑂2 −𝜈𝐶𝑂 𝑔ҧ𝐶𝑂 −𝜈𝑂2 𝑔ҧ𝑂2 = 0 (1)𝑔ҧ𝐶𝑂2 −(1)𝑔ҧ𝐶𝑂 −0.5𝑔ҧ𝑂2 = 0

Note that 𝑔ҧ𝑖 = 𝑔ҧ𝑖 (𝑇, 𝑃𝑖 )

Thus for given 𝑇 and 𝑃,
we have to find values of 𝑃𝑖 (and hence 𝑛𝑖 , i.e. composition)

such that ෍ 𝑃𝑖 = 𝑃 & (1)𝑔ҧ𝐶𝑂2 −(1)𝑔ҧ𝐶𝑂 −0.5𝑔ҧ𝑂2 = 0

Note

=0
(𝑑𝐺) 𝑇,𝑃 = ෍ 𝑛𝑖 𝑑 𝑔ҧ𝑖 + ෍ 𝑑𝑛𝑖 𝑔ҧ𝑖 = 0

𝑔ҧ 𝑇, 𝑃 = 𝑔ҧ 𝑇, 𝑃0 + (∆𝑔)ҧ 𝑇, 𝑃0→𝑃

𝑃
ത ҧ
(∆𝑔)ҧ 𝑇,𝑃0→𝑃 = ∆ℎ − 𝑇∆𝑆 = −𝑇 −𝑅𝑢 ln( )
𝑃0
𝑃𝑖
Thus, 𝑔ҧ𝑖 𝑇, 𝑃𝑖 = 𝑔ҧ 𝑇, 𝑃0 + 𝑅𝑢 𝑇 ln
𝑃0

𝑑𝑃𝑖
෍ 𝑛𝑖 𝑑 𝑔ҧ𝑖 = ෍ 𝑛𝑖 𝑅𝑢 𝑇 𝑛𝑖 𝑃𝑖
𝑃𝑖 =
σ 𝑛𝑖 σ 𝑃𝑖
σ 𝑛𝑖 𝑛
= 𝑅𝑢 𝑇 ෍ 𝑑𝑃 = 𝑅𝑢 𝑇 ෍ 𝑑𝑃𝑖 = 0
σ 𝑃𝑖 𝑖 𝑃
 Equilibrium composition
Find partial pressures such that they satisfy the criterion
𝜈𝐶 𝑔ҧ𝐶 + 𝜈𝐷 𝑔ҧ𝐷 −𝜈𝐴 𝑔ҧ𝐴 −𝜈𝐵 𝑔ҧ𝐵 = 0 (A)

To find 𝑔(𝑇,
ҧ 𝑃), 𝑔ҧ 𝑇, 𝑃 = 𝑔ҧ 𝑇, 𝑃0 + (∆𝑔)ҧ 𝑇, 𝑃0→𝑃

𝑃
At constant 𝑇, ത ҧ
(∆𝑔)ҧ 𝑇, 𝑃0→𝑃 = ∆ℎ − 𝑇∆𝑆 = −𝑇 −𝑅𝑢 ln( ) Only for ideal gases !
𝑃0
𝑃𝑖
Thus, 𝑔ҧ𝑖 𝑇, 𝑃𝑖 = 𝑔ҧ 𝑇, 𝑃0 + 𝑅𝑢 𝑇 ln
𝑃0

𝑃𝐶 𝑃𝐷
Criterion (A) becomes 𝜈𝐶 𝑔ҧ𝐶0 𝑇 + 𝑅𝑢 𝑇𝑙𝑛 + 𝜈𝐷 𝑔ҧ𝐷0 𝑇 + 𝑅𝑢 𝑇𝑙𝑛
𝑃0 𝑃0

𝑃𝐴 𝑃𝐵
− 𝜈𝐴 𝑔ҧ𝐴0 𝑇 + 𝑅𝑢 𝑇𝑙𝑛 − 𝜈𝐵 𝑔ҧ𝐵0 𝑇 + 𝑅𝑢 𝑇𝑙𝑛 =0
𝑃0 𝑃0
 Equilibrium composition
𝑃𝐶 𝑃𝐷
𝜈𝐶 𝑔ҧ𝐶0 𝑇 + 𝑅𝑢 𝑇𝑙𝑛 + 𝜈𝐷 𝑔ҧ𝐷0 𝑇 + 𝑅𝑢 𝑇𝑙𝑛
𝑃0 𝑃0

𝑃𝐴 𝑃𝐵
− 𝜈𝐴 𝑔ҧ𝐴0 𝑇 + 𝑅𝑢 𝑇𝑙𝑛 − 𝜈𝐵 𝑔ҧ𝐵0 𝑇 + 𝑅𝑢 𝑇𝑙𝑛 =0
𝑃0 𝑃0
i.e.
𝑃𝐶 𝑃𝐷 𝑃𝐴 𝑃𝐵
𝜈𝐶 𝑔ҧ𝐶0 𝑇 + 𝜈𝐷 𝑔ҧ𝐷0 𝑇 − 𝜈𝐴 𝑔ҧ𝐴0 𝑇 − 𝜈𝐵 𝑔ҧ𝐵0 𝑇 + 𝑅𝑢 𝑇 𝜈𝐶 𝑙𝑛 + 𝜈𝐷 𝑙𝑛 − 𝜈𝐴 𝑙𝑛 − 𝜈𝐴 𝑙𝑛 =0
𝑃0 𝑃0 𝑃0 𝑃0

∆𝐺 0 𝑇 = [𝜈𝐶 𝑔ҧ𝐶0 + 𝜈𝐷 𝑔ҧ𝐷0 − 𝜈𝐴 𝑔ҧ𝐴0 − 𝜈𝐵 𝑔ҧ𝐵0 ] 𝑇 Thus the equilibrium criterion

has been expressed in terms of
“Standard-state Gibbs function change” for the reaction
𝑃𝑖 . This is one of the relations
that the partial pressures have to
𝑃𝐶 𝜈𝐶 𝑃𝐷 𝜈𝐷 satisfy.
Thus, ( ) ( )
0 𝑃0 𝑃0 Other relations use balance of
∆𝐺 𝑇 = −𝑅𝑢 𝑇𝑙𝑛
𝑃𝐴 𝜈𝐴 𝑃𝐵 𝜈𝐴 atoms of each species on the
( ) ( )
𝑃0 𝑃0 reactants and products side.
 Gibbs function of formation
∆𝐺 0 𝑇 = [𝜈𝐶 𝑔ҧ𝐶0 + 𝜈𝐷 𝑔ҧ𝐷0 − 𝜈𝐴 𝑔ҧ𝐴0 − 𝜈𝐵 𝑔ҧ𝐵0 ] 𝑇
Gibbs function of formation defined as
𝑔ҧ𝑓0 𝑇 ≡ 𝑔ҧ 0 𝑇 − ෍ 𝜈′𝑖 𝑔ҧ𝑖0 𝑇
where
𝑖
𝑡ℎ
𝜈′𝑖 ≡ stoichiometric coefficient of the 𝑖 element required to form 1 mole of the compound of interest
e.g., C + 𝑂2 → CO2
for which 𝜈′𝐶 = 1 𝜈′𝑂2 = 1
0 0
𝑔ҧ𝑓,𝐶𝑂2 𝑇 ≡ 𝑔ҧ𝐶𝑂2 𝑇 − 1 𝑔ҧ𝐶0 𝑇 + (1)𝑔ҧ𝑂2
0
𝑇

Note: 𝑔ҧ𝑓0 𝑇 ≡ 0 for naturally occurring elements

𝑔ҧ𝑓0 for a compound is a measure of its stability relative to its elements

Thus, ∆𝐺 0 𝑇 = 𝜈𝐶 𝑔ҧ𝐶0 (𝑇) + 𝜈𝐷 𝑔ҧ𝐷0 (𝑇) − 𝜈𝐴 𝑔ҧ𝐴0 (𝑇) − 𝜈𝐵 𝑔ҧ𝐵0 (𝑇)

0 0 0 0
∆𝐺 0 𝑇 = 𝜈𝐶 𝑔ҧ𝑓,𝐶 (𝑇) + 𝜈𝐷 𝑔ҧ𝑓,𝐷 (𝑇) − 𝜈𝐴 𝑔ҧ𝑓,𝐴 (𝑇) − 𝜈𝐵 𝑔ҧ𝑓,𝐵 (𝑇)
Gibbs free energy tables

Stephen Turns, ‘An Introduction to Combustion’

Gibbs free energy tables

Stephen Turns, ‘An Introduction to Combustion’

Gibbs free energy tables

Stephen Turns, ‘An Introduction to Combustion’

Gibbs free energy tables

𝑔ҧ𝑓0 for H decreases with increasing 𝑇 and becomes negative at 𝑇~3800 K

Stephen Turns, ‘An Introduction to Combustion’

ME301A Energy Systems I

Pranav Joshi
Dept. of Mech. Engg., IIT Kanpur

Sept-Dec 2020
 Combustion

Lecture 5: Equilibrium constant and Le Chatelier’s principle

 Equilibrium constant
𝑃𝐶 𝜈𝐶 𝑃𝐷 𝜈𝐷
(
) ( )
𝑃 𝑃0
𝜈𝐶 𝑔ҧ𝐶 + 𝜈𝐷 𝑔ҧ𝐷 −𝜈𝐴 𝑔ҧ𝐴 −𝜈𝐵 𝑔ҧ𝐵 = 0 ∆𝐺 0 𝑇 = −𝑅𝑢 𝑇 ln 0
𝑃 𝑃
( 𝐴 )𝜈𝐴 ( 𝐵 )𝜈𝐴
𝑃0 𝑃0
0 0 0 0
where ∆𝐺 0 𝑇 = 𝜈𝐶 𝑔ҧ𝑓,𝐶 (𝑇) + 𝜈𝐷 𝑔ҧ𝑓,𝐷 (𝑇) − 𝜈𝐴 𝑔ҧ𝑓,𝐴 (𝑇) − 𝜈𝐵 𝑔ҧ𝑓,𝐵 (𝑇) “Standard-state Gibbs function
change” for the reaction
Define “equilibrium constant” 𝐾𝑝 for the chemical equilibrium of ideal gas mixtures
𝑃𝐶 𝜈𝐶 𝑃𝐷 𝜈𝐷
( ) ( )
𝑃 𝑃0
𝐾𝑝 = 0 (B)
𝑃 𝑃
( 𝐴 )𝜈𝐴 ( 𝐵 )𝜈𝐴
𝑃0 𝑃0 𝐾𝑝 in terms of partial pressures

All partial pressures @ equilibrium !!

Thus, ∆𝐺 0 𝑇 = −𝑅𝑢 𝑇 ln𝐾𝑝

−∆𝐺 0 𝑇 𝐾𝑝 for a particular reaction is a

𝐾𝑝 = exp
𝑅𝑢 𝑇 function of 𝑇 only
 Equilibrium constant

𝑃𝐶 𝜈𝐶 𝑃𝐷 𝜈𝐷 𝐾𝑝 indicates mixture
( ) ( )
𝑃0 𝑃0 composition at equilibrium –
𝐾𝑝 = (B)
𝑃 𝑃 whether the partial pressures of
( 𝐴 )𝜈𝐴 ( 𝐵 )𝜈𝐴
𝑃0 𝑃0 the products will be high or low
w.r.t. reactants at equilibrium

𝜈𝐶 +𝜈𝐷 −𝜈𝐴 −𝜈𝐵

𝑛𝑖 𝑛𝐶 𝜈𝐶 𝑛𝐷 𝜈𝐷 𝑃
Use 𝑃𝑖 = 𝑃 in (B) to get 𝐾𝑝 = 𝜈 𝐾𝑝 in terms of # moles of species
𝑛 𝑛𝐴 𝐴 𝑛𝐵 𝜈𝐵 𝑛𝑃0

𝑛𝑖 𝜈𝐶 +𝜈𝐷 −𝜈𝐴 −𝜈𝐵

And since 𝑥𝑖 = , 𝑥𝐶 𝜈𝐶 𝑥𝐷 𝜈𝐷 𝑃 𝐾𝑝 in terms of mole fractions of
𝑛 𝐾𝑝 = 𝜈 species
𝑥𝐴 𝐴 𝑥𝐵 𝜈𝐵 𝑃0

These relations can be extended to

any number of reactants and products
Equilibrium constant: different forms

𝑃𝐶 𝜈𝐶 𝑃𝐷 𝜈𝐷 𝑁 𝑁
( ) ( ) ς 𝜈𝑖′′
𝑃0 𝑃0 (𝑃 /𝑃
𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 𝑖 0 )
𝐾𝑝 = = ෍ 𝜈𝑖′ 𝑋𝑖 ෍ 𝜈𝑖′′ 𝑋𝑖
𝑃𝐴 𝜈𝐴 𝑃𝐵 𝜈𝐵 ς 𝜈 ′
𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠(𝑃𝑖 /𝑃0 )
𝑖
( ) ( ) 𝑖=1 𝑖=1
𝑃0 𝑃0

Other forms of equilibrium constant:

Based on mole fractions:
σ 𝜈𝑖′′ −σ 𝜈𝑖′
𝜈𝑖′′ 𝑃
𝑥𝐶 𝜈𝐶 𝑥𝐷 𝜈𝐷 ς𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠(𝑥𝑖 ) 𝐾𝑝 = 𝐾𝑥
𝐾𝑥 = 𝜈 𝜈 = ′ & 𝑃0
𝑥𝐴 𝑥𝐵
𝐴 𝐵
ς𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠(𝑥𝑖 )𝜈𝑖

Based on molar concentrations:

𝜈𝑖′′ σ 𝜈𝑖′′ −σ 𝜈𝑖′
[𝐶]𝜈𝐶 [𝐷]𝜈𝐷 ς𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠[𝑋]𝑖 𝑅𝑢 𝑇
𝐾𝐶 = =
𝜈𝑖′
& 𝐾𝑝 = 𝐾𝐶
[𝐴]𝜈𝐴 [𝐵]𝜈𝐵 ς𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠[𝑋]𝑖 𝑃0
Equilibrium composition example

Example: CO2 ⇌ CO + (1/2)O2

Find the composition of the mixture when originally pure CO2 is subjected to 𝑇 = 2000 K
and 𝑃 = 10 atm.
Solution:
Equilibrium composition example

𝐾𝑝 can also be read from tables, if available.

But be careful!
CO2 ⇌ CO + (1/2)O2
2CO2 ⇌ 2CO + O2

If there are more than one reactions

occurring, then equations similar to
(1) can be written down for each of
those reactions.
Equilibrium composition example
Equilibrium composition example
Equilibrium composition example
Equilibrium composition example: Dissociation of CO2

Stephen Turns, ‘An Introduction to Combustion’

Equilibrium constant and direction of reaction
=0
(𝑑𝐺) 𝑇,𝑃 = ෍ 𝑛𝑖 𝑑 𝑔ҧ𝑖 + ෍ 𝑑𝑛𝑖 𝑔ҧ𝑖

𝑑𝐺 = 𝑔ҧ𝐴 𝑑𝑛𝐴 + 𝑔ҧ𝐵 𝑑𝑛𝐵 + 𝑔ҧ𝐶 𝑑𝑛𝐶 + 𝑔ҧ𝐷 𝑑𝑛𝐷

Define Δ𝐺 = −𝑔ҧ𝐴 𝜈𝐴 − 𝑔ҧ𝐵 𝜈𝐵 + 𝑔ҧ𝐶 𝜈𝐶 + 𝑔ҧ𝐷 𝜈𝐷

𝑃 𝑃
( 𝐶 )𝜈𝐶 ( 𝐷 )𝜈𝐷
0 𝑃0 𝑃0
∆𝐺 = ∆𝐺 𝑇 + 𝑅𝑢 𝑇 ln
𝑃 𝑃
( 𝐴 )𝜈𝐴 ( 𝐵 )𝜈𝐴
𝑃0 𝑃0
𝑃 𝑃
( 𝐶 )𝜈𝐶 ( 𝐷 )𝜈𝐷
𝑃 𝑃0
∆𝐺 = ∆𝐺0 + 𝑅𝑢 𝑇 ln𝑄 where 𝑄= 0 𝑄 ≡ Reaction quotient.
𝑃 𝑃
( 𝐴 )𝜈𝐴 ( 𝐵 )𝜈𝐴 Actual partial pressures: need
𝑃0 𝑃0
Note that 0 = ∆𝐺0 + 𝑅𝑢 𝑇 ln𝐾𝑝 not be under equilibrium !!
∆𝐺 = −𝑅𝑢 𝑇 ln𝐾𝑝 + 𝑅𝑢 𝑇 ln𝑄 𝐾𝑝 = 𝑄|𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚
𝑄
i.e., ∆𝐺 = 𝑅𝑢 𝑇 ln
𝐾𝑝
𝑄, when compared to 𝐾𝑝 , tells us in which
∆𝐺 < 0 → forward reaction will occur
direction the reaction will proceed.
∆𝐺 > 0 → reverse reaction will occur
Equilibrium constant

Example: CO2 ⇋ CO + (1/2)O2

From the previous problem, at 𝑇 = 2000 K, 𝐾𝑝 = 0.0013.

If 𝑃𝐶𝑂2 = 2 atm, 𝑃𝐶𝑂 = 0.01 atm, 𝑃𝑂2 =0.04 atm,

In which direction will the reaction proceed?

𝑃𝐶𝑂 𝑃𝑂2 0.5

( )( ) 0.01 × 0.040.5 −0.5
𝑃0 𝑃0
𝑄= = 𝑃0 = 0.001
𝑃𝐶𝑂2 2
( )
𝑃0

𝑄 < 𝐾𝑝 ∆𝐺 < 0 → forward reaction will occur

𝑄
∆𝐺 = 𝑅𝑢 𝑇 ln
𝐾𝑝
Notes on 𝐾𝑝

− 𝐾𝑝 of a reaction depends only on 𝑇 𝑃𝐶 𝜈𝐶 𝑃𝐷 𝜈𝐷

−∆𝐺 0 𝑇 ( ) ( )
𝑃0 𝑃0
− Independent of pressure of the mixture 𝐾𝑝 = exp =
𝑅𝑢 𝑇 𝑃 𝑃
− Unaffected by the presence of inert gases ( 𝐴 )𝜈𝐴 ( 𝐵 )𝜈𝐴
𝑃0 𝑃0
− 𝐾𝑝 of the reverse reaction is 1/𝐾𝑝

− Larger the 𝐾𝑝 , the more complete the reaction is

− 𝐾𝑝 > 1000 → ~complete [∆𝐺 0 ≪ 0 → spontaneous reaction]
− 𝐾𝑝 < 0.001 → ~reaction does not occur [∆𝐺 0 ≫ 0 → spontaneous reverse reaction]

− 𝐾𝑝 says noting about the rate of the reaction, but only about the extent to which the reaction
will proceed.
− Mixture pressure does not affect 𝐾𝑝 , but affects equilibrium composition
− Presence of inert gases does not affect 𝐾𝑝 , but affects equilibrium composition
𝜈𝐶 +𝜈𝐷 −𝜈𝐴 −𝜈𝐵
𝑛𝐶 𝜈𝐶 𝑛𝐷 𝜈𝐷 𝑃
𝐾𝑝 = 𝜈
𝑛𝐴 𝐴 𝑛𝐵 𝜈𝐵 𝑛𝑃0
 Le Chatelier’s principle
Any system initially in a state of equilibrium when subjected to a change (e.g. changing 𝑃𝑃
or 𝑇𝑇 or composition) will shift in composition in such a way as to minimize the change.
Principle of Le Chatelier indicates qualitatively how the system will respond, i.e. in which direction the
equilibrium will shift, if the conditions are changed.

Change in pressure CO2 ⇋ CO + (1/2)O2

(For gas-phase systems) 𝑛𝑛𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 =1 𝑛𝑛𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 = 1.5

Increase in 𝑃𝑃  equilibrium shifts so as to decrease # moles

endo
Change in temperature CO2 ⇌ CO + (1/2)O2
exo
Increase in 𝑇𝑇  equilibrium shifts so as to decrease 𝑇𝑇  Endothermic reaction favoured

Change in composition

Increase in CO2 equilibrium shifts so as to decrease CO2

Le Chatelier’s principle

Change in pressure
CO2 ⇋ CO + (1/2)O2
𝑛𝑛𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = 1 𝑛𝑛𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 = 1.5

Increase in 𝑃𝑃  equilibrium shifts so as to decrease # moles  reverse reaction favoured

𝑃𝑃𝐶𝐶𝑂𝑂,𝑒𝑒𝑒𝑒.1 𝑃𝑃𝑂𝑂𝑂,𝑒𝑒𝑒𝑒.1/2
𝑄𝑄𝑒𝑒𝑒𝑒. = 𝐾𝐾𝑝𝑝 =
𝑃𝑃𝐶𝐶𝐶𝐶𝐶,𝑒𝑒𝑒𝑒.1

If total pressure is doubled, partial pressures of all species will double momentarily

reverse
(2𝑃𝑃𝐶𝐶𝑂𝑂,𝑒𝑒𝑒𝑒. )1 (2𝑃𝑃𝑂𝑂𝑂,𝑒𝑒𝑒𝑒. )1/2 𝑄𝑄
𝑄𝑄𝑛𝑛𝑛𝑛𝑛𝑛 = = 2𝐾𝐾𝑝𝑝 ∆𝐺𝐺𝑛𝑛𝑛𝑛𝑛𝑛 = 𝑅𝑅𝑢𝑢 𝑇𝑇 ln >0 reaction
(2𝑃𝑃𝐶𝐶𝐶𝐶𝐶,𝑒𝑒𝑒𝑒. )1 𝐾𝐾𝑝𝑝
favoured

Changes in 𝑃𝑃 do not affect equimolar reactions

Le Chatelier’s principle

Change in composition

CO2 ⇋ CO + (1/2)O2

(𝑃𝑃𝐶𝐶𝑂𝑂 )1 (𝑃𝑃𝑂𝑂𝑂 )1/2

Increase in [CO2] 𝑄𝑄𝑛𝑛𝑛𝑛𝑛𝑛 = 1
< 𝐾𝐾𝑝𝑝
(𝑃𝑃𝐶𝐶𝐶𝐶𝐶,𝑛𝑛𝑛𝑛𝑛𝑛 )

𝑄𝑄𝑛𝑛𝑛𝑛𝑛𝑛 𝑄𝑄
<1 ∆𝐺𝐺𝑛𝑛𝑛𝑛𝑛𝑛 = 𝑅𝑅𝑢𝑢 𝑇𝑇 ln <0
𝐾𝐾𝑝𝑝 𝐾𝐾𝑝𝑝

Equilibrium shifts toward right (products)

If an inert gas is added to increase 𝑃𝑃 at constant 𝑇𝑇  no change in equilibrium

Le Chatelier’s principle

Change in temperature
 Dependence of 𝐾𝐾𝑝𝑝 on temperature
−∆𝐺𝐺 0 𝑇𝑇
𝐾𝐾𝑝𝑝 = exp
𝑅𝑅𝑢𝑢 𝑇𝑇

1 1
ln𝐾𝐾𝑝𝑝,1 = ∆𝐺𝐺10 & ln𝐾𝐾𝑝𝑝,2 = ∆𝐺𝐺20
−𝑅𝑅𝑢𝑢 𝑇𝑇1 −𝑅𝑅𝑢𝑢 𝑇𝑇2

1 ∆𝐺𝐺20 ∆𝐺𝐺10 1 ∆𝐻𝐻20 − 𝑇𝑇2 ∆𝑆𝑆20 ∆𝐻𝐻10 − 𝑇𝑇1 ∆𝑆𝑆10

ln𝐾𝐾𝑝𝑝,2 − ln𝐾𝐾𝑝𝑝,1 = − = −
−𝑅𝑅𝑢𝑢 𝑇𝑇2 𝑇𝑇1 −𝑅𝑅𝑢𝑢 𝑇𝑇2 𝑇𝑇1

𝐾𝐾𝑝𝑝,2 ∆𝐻𝐻 1 1
ln ≈ − Van’t Hoff equation
𝐾𝐾𝑝𝑝,1 𝑅𝑅𝑢𝑢 𝑇𝑇1 𝑇𝑇2

∆𝐻𝐻 < 0 (exothermic) : 𝑇𝑇1 < 𝑇𝑇2 𝐾𝐾𝑝𝑝,1 >𝐾𝐾𝑝𝑝,2

ME301A Energy Systems I

Pranav Joshi
Dept. of Mech. Engg., IIT Kanpur

Sept-Dec 2020
 Combustion

Lecture 6: Chemical kinetics

Reactions: Rate expressions, Rate laws, Order of a reaction

aA + bB → cC + dD

𝑑A 𝑑B 𝑑C 𝑑D
Rate expressions: , , , 2H2 + O2 → 2H2O
𝑑𝑡 𝑑𝑡 𝑑𝑡 𝑑𝑡
1𝑑 A 1𝑑 B 1𝑑 C 1𝑑 D 𝑑 H2 O 𝑑 O2
Unique Rate: = = = = −2
𝑎 𝑑𝑡 𝑏 𝑑𝑡 𝑐 𝑑𝑡 𝑑 𝑑𝑡 𝑑𝑡 𝑑𝑡

𝑚 𝑛…
Rate laws 𝑟𝑎𝑡𝑒 = 𝑘 A B
− 𝑘 is a constant, 𝑘 = 𝑘(𝑇), units vary
− Reaction is of order 𝑚 in A and of order 𝑛 in B
− Overall order of the reaction: 𝑚 + 𝑛
− 𝑚 and 𝑛 need not be integers, need not be positive

In general, we cannot predict the rate law from the stoichiometry of the reaction

𝑚 𝑛 𝑝
𝑟𝑎𝑡𝑒 = 𝑘 A B C → rate law can also have products in the equation (but not usually)
Global/Elementary reactions

Chemical kinetics: Study of reactions and their rates

Chemical reactions

Global reactions Elementary reactions

Burning of hydrogen: 2H2 + O2 → 2H2O Global reaction

(‘black-box approach’)
The actual process occurs in multiple steps involving reactions such as:
H2 + O2 → HO2 + H
More than 20 such H + O2 → OH + O
reactions for Elementary reactions
OH + H2 → H2O + H
2H2 + O2 → 2H2O
Global/Elementary reactions

Global reactions Elementary reactions

2H2 + O2 → 2H2O H2 + O2 → HO2 + H

Can have more than two reactant Only two reactant molecules
molecules
Minimal number of bonds broken
and new bonds formed
Bonds broken: 2 Not likely
2OH
Bonds formed: 2
H2 + O 2

HO2 + H Bonds broken: 1 More likely

Bonds formed: 1

Reaction Mechanism: The collection of elementary reactions necessary

to describe an overall reaction
Types of elementary reactions
Unimolecular, bimolecular, termolecular reactions (molecularity of reactions)
Unimolecular reactions – involves one reactant molecule
A → B ……………….isomerization
A → B+C ……………….decomposition
e.g. O2 → 2O
CO2 → CO + O 𝑑A
= −𝑘𝑢𝑛𝑖 A
O3 → O2 + O 𝑑𝑡

Bimolecular reactions – two reactant molecules collide and react

A+B → C
A+B → C+D
e.g. 𝑑A
CO + O → CO2 = −𝑘𝑏𝑖𝑚𝑜𝑙 A B
𝑑𝑡
H2 + O2 → HO2 + H
Types of elementary reactions
Unimolecular, bimolecular, termolecular reactions

Termolecular reactions – involves three reactant molecules

A+B+M → C+M
M: ‘third body’
e.g. H + H + M → H2 + M
In radical-radical reactions
H + OH + M → H2O + M
M needed to carry away energy
𝑑A
= −𝑘𝑡𝑒𝑟 A B M
𝑑𝑡
Elementary reaction rates

Reaction rate of an elementary bimolecular reaction:

A+B → C+D

Rate at which reaction proceeds: 𝑑A or 𝑑B or 𝑑C or 𝑑D

𝑑𝑡 𝑑𝑡 𝑑𝑡 𝑑𝑡
A ≡ concentration of species A in kmol/m3

𝑑A
Reaction rate: = −𝑘𝑏𝑖𝑚𝑜𝑙 A B
𝑑𝑡

𝑘𝑏𝑖𝑚𝑜𝑙 ≡ rate coefficient

𝑘𝑏𝑖𝑚𝑜𝑙 = 𝑘𝑏𝑖𝑚𝑜𝑙 (𝑇), independent of A and B

For example, CO + O → CO2

𝑑 CO 𝑑O 𝑑 CO2
= = −𝑘 CO O = −
𝑑𝑡 𝑑𝑡 𝑑𝑡
 Bimolecular reaction rate

Bimolecular reaction rate based on Molecular Collision Theory:

− Reactions can occur between molecules

only when they collide

− But, a collision need not result in a reaction! -- Molecule A

-- Molecule B

𝑑A # collisions between A and B kmol of A

− = × 𝑷(collision leads to reaction) ×
𝑑𝑡 volume × time # molecules of A
 Bimolecular reaction rate

𝑑A # collisions between A and B kmol of A

− = × 𝑷(collision leads to reaction) ×
𝑑𝑡 volume × time # molecules of A

1
−𝐸𝐴
𝑷 = 𝑝 exp 𝑁𝐴𝑣
𝑅𝑢 𝑇
 Bimolecular reaction rate

𝑑A # collisions between A and B kmol of A

− = × 𝑷(collision leads to reaction) ×
𝑑𝑡 volume × time # molecules of A

1
−𝐸𝐴
𝑷 = 𝑝 exp 𝑁𝐴𝑣
𝑅𝑢 𝑇

𝑇𝑙𝑜𝑤 Energy factor (EF)

EF: Fraction of collisions that
𝑇ℎ𝑖𝑔ℎ occur with an energy above 𝐸𝐴
Fraction of
𝑝′
molecules 𝐸𝐴 = Activation energy: Min energy
(per kmol) necessary for reaction to
occur

KE 𝐸𝑚𝑖𝑛
 Bimolecular reaction rate

𝑑A # collisions between A and B kmol of A

− = × 𝑷(collision leads to reaction) ×
𝑑𝑡 volume × time # molecules of A

1
Steric factor −𝐸𝐴
𝑷 = 𝑝 exp 𝑁𝐴𝑣
~ geometry of collisions between A and B 𝑅𝑢 𝑇
OH + H → H2O
(O—H ) (H—O—H )
𝑇𝑙𝑜𝑤 Energy factor (EF)
H H
EF: Fraction of collisions that
O—H 𝑇ℎ𝑖𝑔ℎ occur with an energy above 𝐸𝐴
Fraction of
𝑝′
molecules 𝐸𝐴 = Activation energy: Min energy
(per kmol) necessary for reaction to
occur

KE 𝐸𝑚𝑖𝑛
 Activation energy 𝑬𝑨
“Activated complex”
Exothermic or Endothermic
transition state
𝐸𝐴,𝑓 𝐸𝐴,𝑟
𝐸𝐴,𝑓
reactants products
PE 𝐸𝐴,𝑟 PE
∆𝐻𝑅 < 0 ∆𝐻𝑅 > 0

products reactants

Extent of reaction Extent of reaction

Activation energy 𝐸𝐴 is always positive

 Bimolecular reaction rate

𝑑A # collisions between A and B kmol of A

− = × 𝑷(collision leads to reaction) ×
𝑑𝑡 volume × time # molecules of A

From Kinetic theory of gases, assuming:

1/2 − Elastic collisions between molecules
𝑛𝐴 𝑛𝐵 2 8𝑘𝐵 𝑇
𝜋𝜎𝐴𝐵 − Molecules approximated as spheres
𝑉 𝑉 𝜋𝜇
− Only two species A and B present
𝑛𝐴 = # molecules of species A
𝑛𝐵 = # molecules of species B
𝑉 = volume
𝜎𝐴 + 𝜎𝐵 𝜎 , 𝜎 are diameters of molecules A and B in m
𝜎𝐴𝐵 = , 𝐴 𝐵
2
𝑘𝐵 = Boltzmann constant = 1.381𝑥10−23 J/K
𝑚𝐴 𝑚𝐵
𝜇= = reduced mass, 𝑚𝐴 , 𝑚𝐵 are masses of molecules A and B in kg
𝑚𝐴 + 𝑚𝐵
 Bimolecular reaction rate
1/2
𝑑A 𝑛𝐴 𝑛𝐵 2 8𝑘𝐵 𝑇 −𝐸𝐴 1
− = 𝜋𝜎𝐴𝐵 × 𝑝 exp ×
𝑑𝑡 𝑉 𝑉 𝜋𝜇 𝑅𝑢 𝑇 𝑁𝐴𝑣

𝑛𝐴 𝑛𝐵
Note: = A 𝑁𝐴𝑣 , = B 𝑁𝐴𝑣
𝑉 𝑉
1/2
𝑑A 2
8𝜋𝑘𝐵 𝑇 −𝐸𝐴
Thus − = A B 𝑁𝐴𝑣 × 𝜎𝐴𝐵 × 𝑝 exp
𝑑𝑡 𝜇 𝑅𝑢 𝑇

1/2
𝑑A 2
8𝜋𝑘𝐵 𝑇 −𝐸𝐴
− = 𝑝𝑁𝐴𝑣 𝜎𝐴𝐵 exp A B
𝑑𝑡 𝜇 𝑅𝑢 𝑇

1/2
𝑑A 2
8𝜋𝑘𝐵 𝑇 −𝐸𝐴
Comparing with − = 𝑘𝑏𝑖𝑚𝑜𝑙 A B 𝑘𝑏𝑖𝑚𝑜𝑙 = 𝑝𝑁𝐴𝑣 𝜎𝐴𝐵 exp
𝑑𝑡 𝜇 𝑅𝑢 𝑇
Also, 𝑘𝑏𝑖𝑚𝑜𝑙 = 𝑘𝑏𝑖𝑚𝑜𝑙 (𝑇)
 Reaction rate constant 𝑘

1/2
2
8𝜋𝑘𝐵 𝑇 −𝐸𝐴
𝑘= 𝑝𝑁𝐴𝑣 𝜎𝐴𝐵 exp
𝜇 𝑅𝑢 𝑇
……gives the dependence of 𝑘 on 𝑇, but does not let us calculate 𝑘

Three-parameter functional form for 𝑘𝑏𝑖𝑚𝑜𝑙𝑒𝑐

−𝐸𝐴
𝑘(𝑇) = 𝐴𝑇 𝑏 exp 𝐴, 𝑏, 𝐸𝐴 are empirical parameters
𝑅𝑢 𝑇

For modest temperature ranges, Arrhenius form for 𝑘𝑏𝑖𝑚𝑜𝑙𝑒𝑐

−𝐸𝐴
𝑘 𝑇 = 𝐴 exp
𝑅𝑢 𝑇
Reaction rate constant 𝑘

Arrhenius form
−𝐸𝐴
𝑘 𝑇 = 𝐴 exp
𝑅𝑢 𝑇
𝐴 and 𝐸𝐴 are independent of 𝑇, but depend on the reaction.

High 𝐸𝐴

ln 𝑘 Slope −𝐸𝐴 /𝑅𝑢

Low 𝐸𝐴

1/𝑇
Large 𝐸𝐴 → reaction rate is very sensitive to ∆𝑇
Relation between rate coefficient and equilibrium constant
Consider a bimolecular reaction: 𝑘𝑓
A+B 𝐶+D
𝑘𝑏

𝑑A
= −𝑘𝑓 A B + 𝑘𝑏 C D
𝑑𝑡
@ equilibrium, 𝑑A
=0
𝑑𝑡
𝑘𝑓 C 𝑒𝑞 D 𝑒𝑞
= = 𝐾𝑐
𝑘𝑏 A 𝑒𝑞 B 𝑒𝑞

𝑘𝑓 (𝑇)
= 𝐾𝑐 (𝑇)
𝑘𝑏 (𝑇)

Kinetic parameters Thermodynamic equilibrium parameter

(difficult to measure) (easier to measure)
 Temperature dependence of 𝐾

Exothermic “Activated complex”

𝐸𝐴,𝑓

reactants
PE 𝐸𝐴,𝑟 High 𝐸𝐴
∆𝐻𝑅 < 0 Slope −𝐸𝐴 /𝑅𝑢
ln 𝑘 Low 𝐸𝐴

products
1/𝑇
Extent of reaction
𝑘𝑓 (𝑇)
𝐾𝑐 𝑇 =
𝑘𝑏 (𝑇)
Reaction rates for multistep mechanisms
Consider the H2 − O2 mechanism: 𝑘𝑓,1
H2 + O 2 HO2 + H
𝑘𝑏,1 Incomplete set of elementary
reactions for the global
𝑘𝑓,2 reaction:
H + O2 OH + O
𝑘𝑏,2 H2 + O 2 2H2O
𝑘𝑓,3
OH + H2 H2 O + H 𝑑 H2 O
𝑘𝑏,3 = 𝑘[H2]𝛼 [O2]𝛽
𝑑𝑡
𝑑 O2
= −𝑘𝑓,1 H2 O2 + 𝑘𝑏,1 HO2 H − 𝑘𝑓,2 H O2 + 𝑘𝑏,2 OH O
𝑑𝑡
…and similar equations for other species

Solve: 𝑑 𝑋𝑖 (𝑡)
= 𝑓 𝑋1 𝑡 , 𝑋2 𝑡 , … , 𝑋𝑛 𝑡
𝑑𝑡
with 𝑋𝑖 𝑡 = 0 = 𝑋𝑖 0
Chain reactions
Chain reactions: involve production of a radical species that subsequently reacts to produce
another radical.
Overall reaction: H2 + Br2 → 2HBr

Mechanism: Heat or light can initiate the reaction by decomposing Br2

Br2 ⇌ Br + Br Chain initiating step

Br + H2 ⇌ HBr + H Chain-carrying or chain-propagating step

Usually fast → Radicals seldom build up

H + Br2 ⇌ HBr + Br
in high concentrations

Br + Br → Br2 Chain-terminating step

Example of Chain-branching step: O + H2O → OH + OH

 Steady state approximation (SSA)
Generally applies to radical intermediates
𝑘1
i) A2 A+A Slow
𝑘2
ii) A + B2 AB + B Fast

𝑑 AB 𝑑A
= 𝑘2 A B2 = 2𝑘1 A2 − 𝑘2 A B2
𝑑𝑡 𝑑𝑡
ii) i)
𝑑A i)
𝑑𝑡
A Approximation: 𝑑 A = 0
𝑑𝑡
2𝑘1 A2 = 𝑘2 A B2
2𝑘1 A2
A =
ii) 𝑘2 B2
Algebraic eqn as opposed
to differential eqn
 Steady state approximation (SSA)
Zeldovich mechanism for O2+ N2 → 2NO

𝑘1
i) O + N2 NO + N
Reverse reactions are very
𝑘2 slow and are neglected
ii) N + O2 NO + O

𝑑N
= 𝑘1 O N2 − 𝑘2 N O2
𝑑𝑡
i) ii)
Slow Fast

Steady state approximation 𝑑N 𝑘1 O N2

=0 N =
𝑑𝑡 𝑘2 O2
Partial equilibrium approximation (PEA)
When a fast (both forward and reverse) and a slow reaction co-exist
i) AB + A2 A2 B + A Fast (forward and reverse)
𝑘2
ii) A + AB A2B Slow
Assume: Reaction i) has equilibrated
Amount of species A consumed in reaction ii) is small
and does not affect the equilibrium in reaction i)
σ 𝜈𝑖′′ −σ 𝜈𝑖′
𝑅𝑢 𝑇 A2B A
𝐾𝑝 = 𝐾𝐶 =
𝑃0 AB A2

𝐾𝑝 AB A2 Algebraic eqn for [A] instead

A =
A2B of a differential eqn

Assuming equilibrium for reaction i)

– Partial equilibrium approximation
 Illustration of SSA and PEA
Zeldovich (thermal) mechanism for formation of NO from N2

Overall reaction: O 2+ N2 2NO

with 𝑑 NO 𝑚 𝑛
= 𝑘𝐺 N2 O2
𝑑𝑡
O2 dissociates first and O atoms attack N2 molecules
Attains equilibrium quickly, reactions
i) O2 O+O
much faster than ii) and iii)
𝑘1
ii) N2 + O NO + N
Reverse reactions
negligible iii) much faster than ii)
𝑘2
iii) N + O2 NO + O
 Illustration of SSA and PEA

i) O2 O+O

𝑘1
ii) N2 + O NO + N

𝑘2
iii) N + O2 NO + O
 Illustration of SSA and PEA

i) O2 O+O

𝑘1
ii) N2 + O NO + N

𝑘2
iii) N + O2 NO + O
Illustration of SSA and PEA

O 2+ N2 2NO