Heat of Reaction

∆𝐻𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = ෍(𝑛𝑖 ℎ෨ 𝑖 ) − ෍(𝑛𝑗 ℎ෨𝑗 )

𝑖,𝑝 𝑗,𝑟
Enthalpy of formation
Sensible enthalpy change
of products at T=298 K
relative to T=298 K

Δ𝐻 = ෍ 𝑛𝑖 𝐻𝑇∘2 − 𝐻𝑇∘0 + Δ𝐻𝑓∘

𝑇0
𝑖,𝑝𝑟𝑜𝑑 𝑖
− ෍ 𝑛𝑗 𝐻𝑇∘1 − 𝐻𝑇∘0 + Δ𝐻𝑓∘ = −𝑄𝑝
𝑇0
𝑖,𝑟𝑒𝑎𝑐𝑡 𝑗

Sensible enthalpy change Enthalpy of formation

relative to T=298 K of products at T=298 K
This term is zero if reactants
enter the system at T=298 K
• Note on sign of Q is negative. This is consistent with the 1st Law, but you must recall that Qp the is heat
evolved, or the heat given off by the system, or the heat of combustion or heat of reaction. 1
 Enthalpy of formation ∆𝒉𝒐𝒇
Enthalpy of formation is the enthalpy change associated
with the reaction to form one mole from its initial
elements at standard state ( 1 atm, 25 C =298.15 K).
Note that ∆𝒉𝒐𝒇 = 𝟎 for O2, N2 ,C, S and H2
Consider two reactions:
H2+½O2 → H2O
• Heat of formation (gas): -241.83 kJ/mol

More Endothermic
• Reaction is exothermic

More Exothermic
½O2 → O
• Heat of formation (gas): 249.17 kJ/mol
• Reaction is endothermic

H2O → H2+½O2
• Reaction 1 going backwards
• Reaction is endothermic
2
 Example:
ADDED, BUT HIGHLY IMPORTANT, COMPLEXITY
• Enthalpy often approximated as
h(T)=CpT

• In combustion chemistry, enthalpy

must consider variable specific heats,
h(T)=Cp(T)*T

• If Cp(T) can be fit with quadratic,

solution for flame temperature for
certain classes of problems f < 1 and
T < 1,250 K leads to closed form
solutions

• For higher order fits or f > 1 and/or T

> 1,250 K, iterative closure schemes
are required for solution of flame
temperature

3
 ෪𝒊
Absolute (standardized) enthalpy 𝒉

ℎ෨ 𝑖 𝑇 = ∆ℎ෨𝑓,𝑖
𝑜
+ ∆ℎ෨ 𝑖𝑜
Enthalpy of formation at Sensible enthalpy
Absolute enthalpy Change going from
standard reference state
At temperature T T0 to T
(1 atm, To)

Where,
𝑇
𝑘𝐽
∆ℎ෨ 𝑖𝑜 = ℎ෨ 𝑖𝑜 𝑇 − ∆ℎ෨ 𝑖𝑜 𝑇𝑜 = න 𝐶ሚ𝑝,𝑖 𝑇 𝑑𝑇 ( )
𝑘𝑚𝑜𝑙𝑒
−298.15𝐾

𝐶ሚ𝑝,𝑖 is the molar specific heat at constant pressure of species i

Enthalpy of C, CO,
CO 2, H 2, H 2O,
N 2, O 2
 GRAPHICAL EXAMPLE

• Physical interpretation of
enthalpy of formation: net
change in enthalpy
associated with breaking
the chemical bonds of the
standard state elements
and forming news bonds to
create the compound of
interest

Graphical interpretation of absolutely enthalpy, heat of formation and sensible enthalpy

6
ENTHALPY OF COMBUSTION AND HEATING VALUES
• The heat of combustion, also known as heating value or heat of reaction, is numerically equal to enthalpy
of reaction, but with opposite sign

• Heat of combustion (or heat of reaction) = - enthalpy of combustion (or = - enthalpy of reaction)
• If enthalpy of combustion (or enthalpy of reaction) is positive → Endothermic
• If enthalpy of combustion (or enthalpy of reaction) is negative → Exothermic
Heating Value
• The heating value HV or calorific value of a fuel is the magnitude of the heat of reaction at constant pressure
or at constant volume at a standard temperature [usually 25°C ] for the complete combustion of unit mass
(or volume) of fuel.

• The upper or higher heating value, HHV, is the heat of combustion calculated assuming that all of water in
products has condensed to liquid.
• The lower heat value, LHV, corresponds to case where none of water is assumed to condense

7
∆𝐻𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = σ𝑖,𝑝(𝑛𝑖 ℎ෨ 𝑖 ) − σ𝑗,𝑟(𝑛𝑗 ℎ෨𝑗 )

• If you consider water in gaseous state, the value of heat based

on LHV
• If you consider water in condensed (liquid) state, the value of
heat based on HHV
As you know Latent Heat of Vaporization (also called enthalpy of
valorization), hfg: Heat required in a constant P process to
completely vaporize a unit mass of liquid at a given T
hfg(T,P) ≡ hvapor(T,P)-hliquid(T,P)

𝑚𝐻2𝑂 𝑘𝐽
𝐻𝐻𝑉 = 𝐿𝐻𝑉 + ℎ𝑓𝑔 𝑎𝑡 25𝐶 [ ] T, v diagram for heat process
𝑚𝑓𝑢𝑒𝑙 𝑘𝑔 of water at P=1 atm

𝑛𝐻2𝑂 ∗ 18 𝑘𝐽
𝐻𝐻𝑉 = 𝐿𝐻𝑉 + ∗ 2442 [ ]
𝑀𝑊𝑓𝑢𝑒𝑙 𝑘𝑔
8
SELECTED PROPERTIES OF HYDROCARBON FUELS

9
 ADIABATIC FLAME TEMPERATURE
• For an adiabatic combustion process, with no change in KE or PE, temperature of products
is called Adiabatic Flame Temperature
• Maximum temperature that can be achieved for given concentrations of reactants
• Incomplete combustion or heat transfer from reactants act to lower temperature

• Adiabatic flame temperature is generally a good estimate of actual temperature achieved

in a flame, since chemical time scales are often shorter than those associated with transfer
of heat and work

• Most common is constant-pressure adiabatic flame temperature

𝐻𝑟𝑒𝑎𝑐 𝑇𝑖 , 𝑃 = 𝐻𝑝𝑟𝑜𝑑 𝑇𝑎𝑑 , 𝑃

෍ 𝑛𝑖 𝐻𝑇∘ 𝑎𝑑 − 𝐻𝑇∘0 + Δ𝐻𝑓∘ = ෍ 𝑛𝑗 𝐻𝑇∘1 − 𝐻𝑇∘0 + Δ𝐻𝑓∘
𝑇0 𝑇0
𝑖,𝑝𝑟𝑜𝑑 𝑖 𝑖,𝑟𝑒𝑎𝑐𝑡 𝑗

• Conceptually simple, but in practice difficult to evaluate because requires detailed

knowledge of product composition, which is function of temperature
10
ADIABATIC COMBUSTION EQUILIBRIUM
• Solution Scheme
1. Guess a T=Tguess
2. Do equilibrium calculation to solve for species concentrations at Tguess
3. Plug into 1st Law

𝐹 𝑇𝑔𝑢𝑒𝑠𝑠 = ෍ 𝑛𝑖 𝐻𝑇∘ 𝑎𝑑 − 𝐻𝑇∘0 + Δ𝐻𝑓∘ − ෍ 𝑛𝑗 𝐻𝑇∘1 − 𝐻𝑇∘0 + Δ𝐻𝑓∘ =0

𝑇0 𝑇0
𝑖,𝑝𝑟𝑜𝑑 𝑖 𝑖,𝑟𝑒𝑎𝑐𝑡 𝑗

• We want F(Tguess)=0
• If F(Tguess) > 0, then initial guess was too high
• If F(Tguess) < 0, then initial guess was too low
4. Increment Tguess

11
Adiabatic Flame temperature
 Combustion Efficiency of an Internal Combustion Engine
The maximum amount of fuel energy supplied to the control volume
around the engine that can be released by combustion is mf Q HV. Hence, the
combustion efficiency—the fraction of the fuel energy supplied that is
released in the combustion process—is given by

Fig. Control volume surrounding engine. Δ WU is

the useful work produced by the engine; Δ Q is the
heat lost from the cylinder charge to the walls.

• For spark-ignition engines, for lean equivalence ratios, the

combustion efficiency is usually in the range of 95 to 98%.
For mixtures richer than stoichiometric, lack of oxygen
prevents complete combustion of the fuel carbon and
hydrogen, and the combustion efficiency steadily decreases
as the mixture becomes richer.
• For diesel engines, which always operate lean, the
combustion efficiency is slightly higher—about 98%.