Equilibrium Charts

Equilibrium Charts
The composition of the working fluid changes during the
engine operating cycle
Process
SI Engines
CI Engines_________
Intake
Air, Fuel, Recycled
Air, Recycled exhaust,
exhaust, Residual gas Residual gas
Compression Air, Fuel vapour,
Air, Recycled exhaust,
Recycled exhaust,
Residual gas
Residual gas
Expansion
Combustion products Combustion products
(mixture of N2, H2O,
(mixture of N2, H2O,
CO2, CO, H2, O2, NO, CO2, CO, H2, O2, NO,
OH, O, H, ...)
OH, O, H, ...)

Equilibrium Charts
Process
Exhaust

SI Engines
CI Engines_________
Combustion products Combustion products
[mainly N2, CO2, H2O [mainly N2, CO2, H2O,
and either O2 ( < 1) and O2]
or CO and H2 ( > 1)]
The composition of the unburned mixture does not
change significantly during intake and compression the
composition is thus assumed frozen
The combustion products or burned mixture gases,
during the combustion process and much of the
expansion process, are close to thermodynamic
equilibrium

Equilibrium Charts
Towards the end of the expansion process, the gas
composition departs from the equilibrium composition;
recombination can no longer occur fast enough to maintain
the reacting mixture in equilibrium

During the exhaust process, reactions are sufficiently

slow so that for calculating thermodynamic properties
the composition can be regarded as frozen
The equilibrium compositions of the products of
combustion have been compiled in the form of tables,
charts, and algebraic relationships
Two types of charts are required for each fuel: unburned
mixture charts for the properties of the fluid before
combustion, and burned mixture charts for the chemical
equilibrium properties of the fluid after combustion

Equilibrium Charts
Charts for the following pure fuels are available:
isooctane (2-2-4 trimethylpentane), nitroethane,
nitromethane, methanol, ethanol, benzene, methane,
and hydrogen
The properties of fluid depend directly upon the relative
amounts of fuel, air, and residual in the mixture
Since neither the fuel-air ratio nor the amount of residual
are constant for all conditions of operations, an infinite
number of charts would, theoretically, be required

However, to cover the range of mixtures ordinarily

encountered in SI engines, three charts are used one
for the chemically correct charge ( = 1), one for lean
charge ( = 0.8), and one for rich charge ( = 1.2)

Unburned Mixture Composition

Two other charts for the value of equals 0.4 and 0.6 are
also available

The mass of charge trapped in the cylinder (mc) is the

inducted mass per cycle (mi), plus the residual mass (mr)
left over from the previous cycle
The residual fraction (xr) is the ratio of the residual mass
to the mass of charge trapped in the cylinder
Typical residual fractions in spark-ignition engines range
from 20 percent at light load to 7 percent at full load
In diesels, the residual fraction is smaller (a few percent)
due to the higher compression ratio, and in naturally
aspirated engines is approximately constant since the
intake is unthrottled

Unburned Mixture Composition

If the inducted mixture is fuel and air (or air only), then
the burned gas fraction (xb) in the unburned mixture
during compression equals the residual fraction
In some engines, a fraction of the engine exhaust gases
is recycled to the intake to dilute the fresh mixture for
control of NOx emissions
If the percent of exhaust gas recycled (%EGR) is defined
as the percent of the total intake mixture which is
recycled exhaust
EGR (%) = (mEGR/mi) x 100
where mEGR is the mass of exhaust gas recycled, then
the burned gas fraction in the fresh mixture is

Unburned Mixture Composition

mEGR mr EGR
xb

(1 xr ) xr

mc
100
Up to about 30% of the exhaust can be recycled; the
burned gas fraction during compression, can, therefore,
approach 30 to 40%
The composition of burned gas fraction in the unburned
mixture can thus be calculated using combustion
equation for a hydrocarbon fuel (discussed in previous
topics)
Charts can also be used for engine cycle calculations
which provide an easy and accurate method

Unburned Mixture Charts

The thermodynamic properties of each unburned fuel-air
mixture are represented by two charts
The first chart is designed to relate the mixture
temperature, pressure, and volume at the beginning and
at the end of the compression process; the second gives
the mixture internal energy and enthalpy as functions of
temperature

The following assumptions are made:

The compression process is reversible and adiabatic
The fuel is in the vapor phase
The mixture composition is homogeneous and frozen (no
reactions between the fuel and air)
Each species in the mixture can be modeled as an ideal gas
The burned gas fraction is zero

Unburned Mixture Charts

Zero internal energy or enthalpy to the unburned
mixture at a datum of 298.15 K and internal energy and
enthalpies relative to this datum are called sensible
internal energy us or sensible enthalpy hs i.e., resulting
from temperature alone

Unburned mixture composition for charts (for xb = 0)

Unburned Mixture Charts

Sensible enthalpy and internal energy of unburned isooctane-air

mixtures as function of temperature

Unburned Mixture Charts

Isentropic compression functions, and , as function of temperature

for unburned isooctane-air mixtures

Burned Mixture Charts

The primary burned mixture charts are for the products
of combustion at high temperatures, i.e., for the working
fluid during the expansion process
The following assumptions are made:
Each species in the mixture can be modeled as an ideal
gas
The mixture is in thermodynamic equilibrium at
temperatures above 1700 K; the mixture composition is
frozen below 1700 K
Datum. At the datum state of 298.15 K (25C or 77F) and
1 atm the chemical elements in their naturally occurring
form (N2, O2, H2 as diatomic gases and C as solid graphite)
are assigned zero enthalpy and entropy

Burned Mixture Charts

The charts were prepared with the NASA equilibrium
program
The C/H/O/N ratio of the mixture is specified for each
chart
The extensive properties (internal energy, enthalpy,
entropy, and specific volume) are all expressed per unit
mass of air in the original mixture; i.e., they correspond
to the combustion of 1 kg of air with the appropriate
mass of fuel
The mass basis for the unburned and burned mixture
charts are the same

Burned Mixture Charts

As the burned gases in an engine cylinder cool during
the expansion process, the composition eventually
"freezes" - becomes fixed in composition - because the
chemical reactions become extremely slow - usually
assumed to occur at about 1700K
The equilibrium assumption is then no longer valid
For lean and stoichiometric mixtures this distinction is
not important because the mole fractions of dissociated
species below this temperature are small
For rich mixtures, a frozen composition must be selected
and used because [he mole fractions of CO2, CO, H2O,
and H2 would continue to change if equilibrium is
assumed as the temperature decreases

Burned Mixture Charts

Internal energy versus entropy chart for equilibrium burned gas mixture,
isooctane fuel; equivalence ratio 0.4

Burned Mixture Charts

Internal energy versus entropy chart for equilibrium burned gas mixture,
isooctane fuel; equivalence ratio 0.6

Burned Mixture Charts

Internal energy versus entropy chart for equilibrium burned gas mixture,
isooctane fuel; equivalence ratio 0.8

Burned Mixture Charts

Internal energy versus entropy chart for equilibrium burned gas mixture,
isooctane fuel; equivalence ratio 1.0

Burned Mixture Charts

Internal energy versus entropy chart for equilibrium burned gas mixture,
isooctane fuel; equivalence ratio 1.2

Burned Mixture Charts

Sensible enthalpy and internal energy of low-temperature burned gases as

function of temperature, isooctane fuel

Burned Mixture Charts

Relation Between Unburned and Burned Mixture Charts

The datum for internal energy and enthalpy for the
unburned mixture is different from the datum for internal
energy and enthalpy for the burned mixture
For the unburned mixture, zero internal energy and
enthalpy for the mixture is assumed at 298.15 K while for
the burned mixture, zero enthalpy for the gaseous species
O2, N2, and H2, and C (solid graphite) is assumed at
298.15 K

These data can be related through the enthalpies of

formation, from O2, N2, H2, and C, of each species in the
unburned mixture

Relation Between Unburned and Burned Mixture Charts

~o

If hf,i is the enthalpy of formation of species i at 298.15 K, per

~o

kilomole, and hf,u is the enthalpy of formation of the unburned

mixture at 298.15 K, per kg of air in the original mixture, then
~o

~o

hf,u = ni h f,i
i

where ni is the number of kilomoles of species i per kg of air

The unburned mixture enthalpy h, with the same datum as the
burned mixture enthalpy, is therefore given by the sum of the
~o

sensible enthalpy hs, u and h f,u :

~o

hu = hs, u + hf,u

Relation Between Unburned and Burned Mixture Charts

Similarly, the internal energy uu is given by

uu = us, u + uof,u
uof,u can be obtained from
~o

uof,u = ni uf,i
i

Alternately,
u

o
f,u

= h

o
f,u

- (nP nR )R T

Relation Between Unburned and Burned Mixture Charts

Expressions for hof, u and uof, u in kJ/kg of air can be obtained

for various values of :

Relation Between Unburned and Burned Mixture Charts

Relation Between Unburned and Burned Mixture Charts

The combustion process links the unburned and burned
mixture properties as follows:
For an adiabatic constant-volume combustion process,

ub uu us,u uof,u

and v b v u
Thus, given us,u, and vu, the state of the burned mixture
can be determined from the appropriate burned mixture
chart
For an adiabatic constant-pressure combustion process,

hb hu hs,u hof,u
since ub hb pv b

Relation Between Unburned and Burned Mixture Charts

Given hs, u and p, ub and vb must be found by trial and
error along the specified constant-pressure line on the
appropriate burned gas mixture chart