Case Study 1

Based on the paper:

Technical note: Thermodynamic analysis and

generalised computer program for
hydrocarbon (CmHn)air mixtures
By: M. Nagamori and P.J. Mackey

Prepared by:
Sarbari Ganguly
143110007

CONTENT

Theory:
3-7
Inspiration
Thermodynamic analysis
4-6
Application of N-R Method
6-7

Results
8
References
9

THEORY

Inspiration:
Combustion products of non-stoichiometric fuel-air mixtures are
used in many metallurgical processes to carry out high
temperature reactions. Most common examples would be
deoxidisation of copper, and the reduction or fuming of
metallurgical slags for the recovery of metal values. In these
operations, the fuel mixture is injected beneath the melt surface
where complete combustion occurs at the melt temperature,
accompanied by reduction reactions within the bath. Other
examples of utilisation of combustion products in metallurgical
processing are the smelting and partial reduction of iron and
nickel ores, atmosphere control for steel heat treatment and kiln
reduction of oxidised nickel ores.
In all these processes it can be assumed that the fuel mixture
attains equilibrium on combustion and the gas compositions may
be determined by solving the simultaneous equilibrium for the
particular system. These gas compositions associated with the

defined system, are useful in understanding and controlling the

process.
The work in this paper developed out of the need to have
information on combustion product compositions for problems in
metallurgical processing. A thermodynamic study of hydrocarbonair mixtures over a range of temperatures and pressures and
application of numerical method is presented to allow
computation of the product composition. The only program inputs
are temperature, pressure, fuel species (CmHn) and mixture
composition. No initial estimates are required for the solution.

Thermodynamic analysis:
When a mixture of CmHn and air at or near room temperature is
heated to higher temperatures, the following gas species may be
evolved: C2H2 and higher hydrocarbons, CH4, CO, CO2, H2O, H2, O2,
N2, O, H, OH, NO and C (soot). In the range between soot
evolution and free oxygen, and below about 16000C, the species
C2H2 and higher hydrocarbons, O, H, OH, and NO never represent
more than 0.05% of the total pressure and they may be
neglected. The resulting error in the partial pressures of CO, CO 2,
H2 and H2O is less than 0.2% and is negligible. Thus, the gaseous
species considered here are CH4, CO, CO2, H2O, H2, and O2.
At equilibrium there are 6 gaseous species and 3 components (C,
H and O), so there are three independent equilibria. Reactions A,
B, and C are selected.

The following three equations can eventually be obtained from

the expressions for the equilibrium constants for these reactions:

It is convenient to choose a term Fi to be a function of

Combining equations 1, 2 and 3 with appropriate mass balance
equations we obtain:

Where, ni0 = number of moles in initial mixture at room

temperature.

Application of Newton-Raphson:
Since equations 4, 5 and 6 contain three unknowns raised to the
third power, they can only be solved numerically. The solution is
performed by computer using the Newton-Raphson method. To
use this method, it is required to supply reliable initial estimates
of
.These are then improved by iteration. The initial
estimates are determined from the following reactions, assuming
complete decomposition of CH4:

Linearity being assumed between the conditions for soot

evolution and complete combustion (Q2 < n0CmHn < Q1), for a given
value of n0CmHn , initial estimates are given by:

The values of nCH4 and nO2 are then computed using equilibrium
relationships for reactions A and B.

RESULTS

Calculated gas compositions determined by the present method

are compared with published data by the U.S. Bureau of Mines in
the following Table 1. The present results are in excellent
agreement with those data calculated using a much more
complicated and lengthy method.

Table 1: Comparison of calculated gas composition (atm) with the

published values
(1600K, 1atm)

REFERENCES

1) M. Nagamori and P.J. Mackey. technical note: Thermodynamic analysis and

generalized computer program for hydrocarbon(CmHn)- air mixtures.
2) R.W. Smith and E. B. Cook. The thermodynamics of combustion gases.
Computed compositions of methane-ar, propane-air and ethylene-air flames.
3) Robert T. DeHoff. Thermodynamics in Materials Science.