PROGRESS REPORT NO. 7 KINETICS OF OXIDATION AND QUENCHING OF COMBUSTIBLES IN EXHAUST SYSTEMS OF GASOLINE ENGINES D. Jo PATTERSON PERIOD: SEPTEMBER 1, 1969 to.SEPTEMBER 30, 1969 SEPTEMBER 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 No0 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 Additional engine tests were run in order to check out procedures and equipment, and determine emission levels from the standard 350 CID Chevrolet engine. In some of this work aldehyde measurements were made at the wye using the DNPH Method. The following figure shows DNPH aldehydes as formaldehyde and hydrocarbons as hexane measured by a flame ionization detector. The hydrocarbon measurement was made at the muffler outlet. The engine was run at 1200 rpm, 50 percent full load with a lean mixture. The measured

400 350 CID V-8 INDOLENE CLEAR FUEL 1200 RPM 350 50% FULL LOAD 300 E 250 a. aX A TOTAL FID HYDROCARBONS o 200 AS HEXANE c20 0 TOTAL ALDEHYDES AS FORMALDEHYDE 1J1 16.9 A/F 17.2 1.2 % O2 100 - 17.1.9% 17.1 50 1% MBT,I.. I I I I I I0 20 30 40 50 DEGREES BTOC

air-fuel ratio is indicated on the curve. More data will be taken on the standard engine. The subtractive column analyzer has been completed. Next an evaluation will be made with known calibration gases. PHASE II PROGRESS Preliminary studies aimed toward developing a first generation reactor model continue. The literature search continues. A trip to Mobil Scientific Laboratory was made to discuss their modeling approach. PHASE III PROGRESS Studies of both timed and continuous sampling techniques continue, The electronic control for the timed sampler is still being debugged. Some preliminary timed sampling measurements have been made at the port of a single cylinder CFR engine using the breaker point control system. Work is in progress to restore the Perkin-Elmer 800 gas chromatograph in our laboratory to good operating conditions. It is hoped this unit will suffice for the G. C. analyses required.

CRC CAPE 8-68 PROGRAM OVERALL FINANCIAL SUMMARY Program Total: February 24, 1969 - February 23, 1970 $106,455 Cumulative Expenditures through August 24, 1969 44,784 Balance $ 64,671 110 100 L Labor - - - Projected * - K( Actual Total Projected' Actual 90 80 70 60 Dollars Thousands 50 40 _ 30 20 / /,t~' 10 - F M A M 3 Ju A S 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. Wilrmington, 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