PROGRESS REPORT NO. 4 KINETICS OF OXIDATION AND QUENCHING OF COMBUSTIBLES IN EXHAUST SYSTEMS OF GASOLINE ENGINES D. J. PATTERSON PERIOD: JUNE 1, 1969 to JUNE 30, 1969 June 1969 This project is under the technical supervision of the: Coordinating Research Council APRAC-Cape. 8-68 Steering Committee and. is work performed by the: Department of Mechanical Engineering The University of Michigan Ann Arbor, Michigan Under Contract No. CAPE-8-68(1-68)-CRC and Contract No. CPA-22-69-51-HEW

LONG-RANGE OBJECTIVES It is well-known that a significant amount of CO and unburned fuel may be consumed in the exhaust system of gasoline engines. Such combustion phenomena in exhaust reactors may be used to advantage to reduce the emission of these undesirable constituents. This process is the basis of exhaust air injection systems currently installed on some automobiles. The overall objectives of this three-year research program are:'To determine the chemical and physical processes which affect the emission characteristics of exhaust reactors installed on selected typical engines operating at various conditions on a dynamometer test stand. To identify the chemical species and significant chemical reactions present before, within, and after the reactor. To obtain information which will be helpful in predicting the design of the next generation of gasoline engine exhaust reactors. PHASE I PROGRESS The Beckman NDIR analyzer cart (CO, C02, and HC) has been completed and checked out. Calibrating gases (CO, C02, NO, and hexane) have been received. Some preliminary emission testing has been done. Next cross-sectional engine and emission data will be recorded. Initially the effect of spark timing, airfuel ratio, speed and load will be studied with the standard engine exhaust system. Then the du Pont reactor will be installed and evaluated in similar tests

A Kistler 601A pressure transducer has been installed in the Number 1 cylinder of the engine. This is the cylinder to be used for the single cylinder reactor. Design work is still in progress to install a see-through quartz window in the exhaust port. The speed of sound technique for measuring instantaneous exhaust temperature appears to be too expensive and poses a major development problem in itself. A thin film resistance thermometer technique will be explored instead. A decision has been made to measure aldehydes by the DNPH method. This method is essentially that proposed by Oberdorfer. In addition a decision has been made to analyze hydrocarbon emissions in more detail by using the class analysis technique proposed by Sigsby. For the present detailed GC analysis has been de-emphasized. Next these two wet chemical techniques will be set up. An initial single cylinder exhaust reactor design has been completed. Parts have been ordered. This reactor will be used to obtain design information for successive generations of reactors. PHASE II PROGRESS Dr. Kadlec has indicated that work will begin next month —July, 1969. 1. Oberdorfer, P. E., "Determination of Aldehydes in Automobile Exhaust Gas," SAE Preprint 670123, Jan. 1967. 2. Sigsby, J. E., Environmental Science and Technology, 1, No. 4, April 1967, p. 309.

PHASE III PROGRESS Construction of subtrative columns for class analysis will begin next month as reported in Phase I. Studies of both timed and continuous sampling techniques are in progress. OTHER A meeting of the CAPE-8 technical subcommittee with University of Michigan personnel was held on June 27, 1969, in the conference room of the Automotive Laboratory. The overall project was reviewed. The next project meeting was set for October 7, 1969, in Ann Arbor.

CRC CAPE 8-68 PROGRAM OVERALL FINANCIAL SUMMARY Program Total: February 24, 1969 - February 23, 1970 $106, 455 Cumulative Expenditures through May 24, 1969 11, 785 Balance $ 94, 670 110 100 Labor - - - Projected,- -'( Actual Total Projected - Actual 90 80 70 60 _ Dollars | Thousands 50 40 / 30 20 10 u F M A M J Ju A S 0 D J F Months 1969 1970

DISTRIBUTION LIST No. of Contract Distribution copies Mr. Alan E. Zengel 3 Assistant Project Manager Coordinating Research Council, Inc. 30 Rockefeller Plaza New York, New York 10020 Dr. P. R. Ryason 1 Chevron Research Company 576 Standard Avenue Richmond, California 94802 Mr. R. L. Bradow, Senior Chemist 1 Research and Technical Department Texaco, Inc. P. O. Box 509 Beacon, New York 12508 Dr. E. N. Cantwell 1 Automotive Emissions Division Petroleum Laboratory E. I. DuPont de Nemours and Company, Inc. Wilmington, Delaware 19898 Dr. J. B. Edwards 1 Research Section Chrysler Corporation 12800 Oakland Avenue Detroit, Michigan 48203 Mr. G. D. Kittredge 15 Motor Vehicle Research and Development Bell Tower Hotel 300 South Thayer Street Ann Arbor, Michigan 48104 Dr. C. H. Ruof 1 Scientific Laboratory Ford Motor Company P. O. Box 2053 Dearborn, Michigan 48121

DISTRIBUTION LIST (Concluded) No. of Contract Distribution copies Mr. R. C. Schwing 1 Research Center Laboratories Fuels and Lubricants Department General Motors Corporation General Motors Technical Center 12 Mile and Mound Roads Warren, Michigan 48090 Mrs. Mary Englehart 1 Department of Health, Education, and Welfare National Air Pollution Control Administration 411 W. Chapel Hill Street Durham, North Carolina 27701 Internal Distribution Professor J. A. Bolt, Dept. of Mech. Eng., Auto. Lab., N.C. 1 Professor B. Carnahan, Dept. of Chem. Eng., East Eng. Bldg. 1 Professor J. A. Clark, Dept. of Mech. Eng., West Eng. Bldg. 1 Professor D. E. Cole, Dept. of Mech. Eng., Auto. Lab., N.C. 1 Professor N. A. Henein, Dept. of Mech. Eng., Auto. Lab., N.C. 1 Professor R. Kadlec, Dept. of Chem. Eng., East Eng. Bldg. 1 Professor J. J. Martin, Dept. of Chem. Eng., East Eng. Bldg. 1 Professor W. Mirsky, Dept. of Mech. Eng., Auto. Lab., N.C. 1 Professor D. J. Patterson, Dept. of Mech. Eng., Auto. Lab., N.C. 2 Project File 15