PROGRESS REPORT NO. 5 KINETICS OF OXIDATION AND QUENCHING OF COMBUSTIBLES IN EXHAUST SYSTEMS OF GASOLINE ENGINES D. J. PATTERSON PERIOD: JULY 1, 1969 to JULY 31, 1969 July 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 Initial emission tests were run on the production 350 CID Chevrolet engine. Speed was set at 1200 rpm and load at a calculated road value. Spark timing was varied from TDC to 50~ BTC and air-fuel ratio from rich to lean misfire limits C02, CO, and HC were measured by NDIR. HC emissions were measured by FID simultaneously. Further tests will include load and speed effects. A computer data reduction program has been written. Upon completion of baseline tests on the production engine, similar tests will be run using the DuPont reactor~ 1

Wet chemical techniques are being set up for aldehyde measurements. Most of the equipment is now on hand to analyze for total aldehydes and ketones by the DNPH method and formaldehyde for a Chromotropic Acid method. A Bausch and Lomb Spectronic 20 Colorimeter has been obtained for the calorimetric comparison. Several calibration tests have been run using standard formalin solution as the formaldehyde source. All necessary parts have been ordered for the subtractive column set up. It is anticipated that construction will begin next month. PHASE II PROGRESS Work has begun on the computer modeling phase. Initial efforts will be toward a relatively simple model based on overall rate data obtained from the literature. A trip to Mobil Scientific Laboratory is anticipated in the near future for the purpose of discussing their modeling approach. PHASE III PROGRESS Studies of both timed and continuous sampling techniques continue. An electronic control is being built up for the Cox timed sampler.

CRC CAPE 8-68 PROGRAM OVERALL FINANCIAL SUMMARY Program Total: February 24, 1969 - February 23, 1970 $106,455 Cumulative Expenditures through June 24, 1969 25,257 Balance $ 81,218 110 100 Labor - - - Projected )- K Actual Total - Projected' -— Actual 90 80 70 60 Dollar s / rhousands50 40 30 20 10 _ 10F M A M J Ju A S 0 N 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 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