Chapter 2

The Chemistry of Spark-Ignition Engine Combustion

and Emission Formation

J. B. Edwards
Department of Chemical Engineering
The University of Detroit
Detroit, Michigan and
Chrysler Corporation
Highland Park, Michigan

I. INTRODUCTION

The ability of the spark-ignition engine to release chemical energy via

combustion reactions and transform this energy into mechanical energy is
well known. The engine may be visualized as a combination of parallel but
out of phase batch reactors. These are commonly called the combustion
chambers. Four-, six-, or eight-batch reactors are arranged in parallel. The
effluent from these batch reactors is combined in one or two pulsating-flow
reactors, called the exhaust system.
Many different types of chemical reactions occur within these batch
and flow reactors. Some result in the production of motive power. Other
reactions are inconsequential with respect to the production of motive power
but make major contributions to the chemical species found in the engine
exhaust.
In this chapter the various chemical phenomena occurring within the
engine will be examined in detail. In addition to examining each of these
processes singularly, the engine will be viewed as a complex system involving
parallel and sequential processes as well as feedback paths. This is necessary
because changes in one process may alter the nature of other processes and
complicate the assertainment of causal relationships.
Particular attention is paid to those chemical processes which result in
the synthesis of molecules such as reactive hydrocarbons, oxygenated hydro-

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G. S. Springer et al. (eds.), Engine Emissions

© Plenum Press New York 1973
34 Chapter 2

carbon derivatives, carbon monoxide, nitric oxide, and particulate matter.

The design of the engine, the composition of the fuel injected, and the main-
tenance of the engine all may significantly influence the chemical phenomena
which occur within the engine and ultimately the compounds exhausted into
the atmosphere.
In a previous paper(\) the author discussed the basic principles of
chemical phenomena occurring in a spark-ignition engine. This present
discussion will update the previous one in two ways. First, the results of
recent publications are included in this discussion. Recent investigations
have led to a better understanding of many phenomena, particularly the
generation of nitric oxide in spark-ignition engines. Secondly, the subject
matter of the present discussion is broadened to include consideration of the
relationship between chemical phenomena in spark-ignition engines and the
production of chemical species of recent interest, such as aldehydes and
particulate matter.

II. ENGINE PROCESSES

A. Inputs

The substances in the first four boxes shown in Fig. 1, the fuel, the oil,
and the additives present in both, as well as the components of the air are
rather obvious candidates for a variety of reactions which occur within the
engine. Traditionally the materials of which the engine and exhaust system
are constructed have not been considered to be consumable reactants; however,
these materials are potential inputs for the production of particulates. Ac-

MOTOR
OIL So FUEL FUEL AIR (METALS So
AOOITIVES ADDITIVES CERAMICS)

PROCESS
INPUTS

ENGINE
PROCESSES

Fig. 1. Inputs to and physical and chemical processes within a spark-ignition engine.