Document B5x8ORdGmNVbOwy2GYaGZO4qE

March 22, 1949 Dr. George Culingaert, Ethyl Corporation, 1600 . Eight Mile Road, Ferndale 20, Detroit, Mich. Dear 0*1: I am sending you herewith a report'sent to me by Mr. VanHartesveldt of Thompson Products, Incorporated. The report will be self explanatory, I believe, but,in intent, it represents an attempt on the part of Mr. VanRartesveldt and his associates to appraise the practical significance of the evaporation of tetraethyl lead from their product. The data and their interpretation should be considered against the background of the work done in your Laboratory on this problem. I should appreciate it very m u c h if you would look this over critically and let me have your considered judgment as to its validity in relation to tiie practical problem p resented. Sincerely yours, RAK ef Enc. RoB'ert ''A . liehoe , 'M . D ^ 0020627 N21961 . T. C O l W i U , P r e s i d e n t J O H N N. C O L E , V i c e P r e s i d e n t C. H. V A N H A R T E S V E I O T , V i c . P u t i d i Thompson "Vita-Meter Corporation A W H O l l Y- O W NSD SU BSI D I A R Y O F T H O M P SO N P RO DUCTS, INC. P LEA SC DIRECT REP LY TO C. H. V A N HARESVELDT 6 4 0 2 CEDAR AVENUE C LEV E LA N D 3. OH IO 23555 EU CLI D AV EN U E Cleveland 17, Ohio March 13, 194-9 Robert A. Kehoe, M. D. ' University of Cincinnati Kettering Laboratory of Applied Physiology Eden Avenue Cincinnati 19, Ohio . Dear Dr. Kehoe: Enclosed are two copies of a report on relative evaporation rates of tetraethyl lead from gasoline and Vital. At rates of evaporation comparable to that expected from open containers and transfer from one container to another, tetraethyl lead evaporates from Vitol between 1.1 and 2.3 tunes as fast as from gasoline. This comparison was determined for the amount of tetraethyl lead evaporated with the first 10 to 23% of gasoline evaporated. As additional gasoline and Vitol evaporated, the rate of lead evaporation from Vitol increased to 3*5 to 5 times as fast as gasoline. However these latter rates are through a range of total evaporation less significant because attendant waste and fire hazard bring a correction of the condition for commercial reasons. I will appreciate your sending one of 'the copies to the proper person at the Ethyl Laboratories because I do not consider realistic their report showing lead evaporation from Vitol to be one hundred times faster than from gasoline. Their report has been made available to other oil companies who have asked my viewpoint but I would prefer to have an interpretation of all the data come from you. As we prepare for the Cincinnati effort it will be helpful to have the area in which Viiametsrs and Vitol will be sold defined precisely. I would like to call in Cincinnati at your convenience to discuss this matter along with a general consideration of tentative schedules for subsequent expansion of our sales area in the event that all results continue to be favorable. I could come on Friday, March 25th and will await your advice on whether or not this date suits you. If it does not, I will be glad to have you suggest a time. "With all best wishes, j Cordially yours, CHV:sg ce: A. T-. Colwell C. H. Van Hartesveldt ii -STUDY CF THY FXLATIVF. EVAPORATION E&IE5 OF TETRAETHYL HEAD FKCLS C-ASOLINE ANL VITOL a study of the relative evaporation rates of tetraethyl lead from gaso line ana Vitol "as undertaken in. an atter.pt to determine the relative amounts of lead vapors given off during constant exposure of the solutions to the air. It is known that the evaporation .rate of tetraethyl lead from gasoline is relatively low until approximately 1/2 of the gasoline evaporates with a grad ual though not sharp increase thereafter. For a homogeneous single phase solution with one component of relatively Ion vapor pressure, this would be true as the molar concentration of the low vapor pressure component must be increased to cause an in crease in its relative evaporation rate. The presence of two insoluble, immiscible liquids in Vitol presented the questions applicable to a two-phase solution, fince the individual or combined vapor pressures of alcohol and water in the molar concentrations of Vitol were less than that of gasoline, it seemed feasible to investigate the evaporation of tetra ethyl lead from Vitol curing the early stages of exposure. If the individual or combined vapor pressures were low, relative to the vapor pressure of tetraethyl lead the initial evaporation rate of tetraethyl lead would be high regardless of the phases. If there were a suitable balance between the vapor pressures, evaporation of the tetraethyl lead could, quite possibly, bo gradual enough to eliminate the possibility of a large concentration of tetraethyl lead vapors at any point during the evaporation of Vitol. In order to determine the amounts of liquid and tetraethyl lead evaporaiing curing given time intervals and under similar conditions, samples of Blue funocc gasoline and Vitol with 3 cc. per gallon oftetraethyl lead were placed in 600 ml. beakers and set side by side in a standard laboratory fume hood. At the time inter vals indicated in the data, the volume of the solution was measured and a 50 ml. sample withdrawn for tetraethyl lead analysis. The volumes anu time intervals usee were optional, but preliminary investigation had indicated that satisfactory curves could be prepared. . All percentage calculations are based on the use of 500 ml. of solution with 3 cc. per gallon ox tetraethyl lead (i.e. of solution evaporated'* is that per cent of total -solution which has evaporated, and of tetraethyl lead evaporate is that per cent of the total tetraethyl lead content which has evaporated). He 0020630 ( ( -2 The data for test "a" v;as collected by evaporating in a fume hood with two exhaust vents ocen. The volume of the solution at each time interval was ob tained by weighing the solution in the container and determining the specific gravity of the solution with a Festphal balance. The tetraethyl lead analysis for this and all subsequent tests was run in strict accordance vdth A.S.T.M. resignation: L526-42 a.l.T..;. tanoards, 1946. The data for test ,rb" was collected in order to obtain some information not available in the first test and to determine the effect of some procedure vari ations on who final conclusions. In order to more nearly simulate actual evaporat ing conditions in the field, one of the exhaust vents of the fume hood was closed, thus greatly reducing the air circulation and accounting for the lower evaporation rates. The volume of the solution was obtained by passing the solution into a graduate calibrated in one ml. intervals. The temperature, taken at each time interval, vass 25..:5 C. eSO The purpose of the tests used to prepare Graph 4 ras to amplify that portion of the curve between the start of the evaporation and the 2-1/2 hour reading, i. O 1C " t jT X ethyl lean ueterminations were mace since the rate of tetraethyl lead evaporation v;1th respect to solution evaporation can be determined frorn the preceding Graphs. Blue funoco gasoline used in these tests was obtained from the Thompson Froaucts lynamometer laboratory and is covered by the attached certificate of analy sis. The Vitol used was that currently being used in the field. The Gulfpride gasoline used in the test for Graph 4 was obtained from the Thompson Products dyna mometer laboratory ana was found to contain 2.37 ml. per gallon of tetraethyl lead. Conclusions A. Under the more rapid evaporating conditions -- 1) Gasoline evaporates from approximately 3.2 times as fast as Vitol in 2-1/2 hours to approximately 1.4 times as fast in 22 hours. 2) Initially, for every one per cent of liquid evaporated, approximately 1.4 times as much lead volatilizes from Vitol as from gasoline under the same conditions. 3) Lead evaporates approximately 1.1 times as fast from Vitol as from gasoline in 2-1/2 hours anc approx-imately 3.5 times as fast . in 22 hours. Mi 0020631 ' h i- o - Under the slower evaporating conditions -- 1) Gasoline- evaporates from approximately 1.9 times as fast as Vitol in 2-1/2 hours to ap proximately the same rate in 22 hours. 2) Initially, for every-one per cent of liquid evaporated, approximately 2.S times as much lead volatilizes from Vitol as from gasoline. ;) Lead evaporates approximately 2.3 times as fast from Vitol as from gasoline in 2-1/2 hours and approximately 5 times as fast in 22 hours. Re spectfully submitted, THQ'PfON FEOLUCTf, INC. APPROVED BY: /y -- C. C. Clark Assistant Chief Chemist KE" 0020632 # Table 1 late of lead Tetraethyl Evaporation m l . of lead tetraetevi ml. of y of lead tetraethyl lead tetraethyl evaporated evaporated \ritol (test "a") Start .212 2-1/2 .040 18.S 5-1/2 22 Vitol (test "`b'1) .050 .110 23.6 55.7 Start .262 2-1/2 5-1/2 22 Blue Sunoco (tost !,a") .021 r>oo *n-o r i c.O 12.2 n^ zy .2c Start 2-1/2 5-1/2 22 Blue Sunoco (test "b") .370 .054 .059 .059 14.6 16.0 16.0 Start 2- 1/2 5-1/2 22 .375 .013 analysis lost in procs; .027 3.5 7.2 K 0020633 ( Table 2 Rate f Solution Evaporation ml . o f solutlon m l . of solu- /i of solu- tion evaporated tlon evaporateo Vifol (test "a") 'Tj^ A. **j*-//^O 5-1/2 Vii.ol (test "b") 435 32 7.3 bS 1--^>0 jz 15.6 35.2 Start 450 ?-l/2 2o y -1k- .V 1 H "to .f C. rusC Blue Sunoco (test "a") 44 9.8 127 28.2 Start 2-1/?. 5-1/2 22 Blue Sunoco -(test "b*) 433 100 23.1 141 31. S 212 49.0 Start 2-1/2 5-1/2 22 450 42 9.3 62 13.S 124 27.6 0020634 Per Cent Liquid Evaporation Cc Rate of Liquid lgyaporation Curve Time in Hours - KE" 0020635 Cc Per Cent Tetraethyl Lead Evaporation vs. Per Cent of Liquid Evaporation Curve c $ , 3 Per Cent Total Tetraethyl Lead Evaporation K 0020636 fC Tetraethyl Lead Evaporation fresa Vitol and Gasoline f Per Cent,Total Tetraethyl Lead Evaporation 0020637 . ! c ,"- C' '- \ Rate of Liquid Evaporation Curve #2 A: c -V? ;-i ^ :v. M Per Cent Liquid Evaporation K& 0020633 SUNOCO DYNAFUEL Specifications 6 0Gravity - A.P.I./ O F. Distillation A.S.T.M. 10$ Evaporated 50$ Evaporated 90$ Evaporated Recovery Residue Sulphur - A.S.T.M. Gum - Copper Dish Gum - A.S.T.M. Copper Strip - A.S.T.M. Color Cetane F-l Octane F-2 Reid Vapor Pressure / 100 F. Induction Period WINTER GRADE Authority CKTjAYM 11/18/48 63Approx. 56.0 - .0 105 - 125 F. 205 - 235 F. 365 F. Max. 95.0$ Min. 2.0$ Max. 0.08% Max. 8 mgs. Max. 2.0 mgs. Max. Pass Blue 84.0 - 86.0 76.5 Min. 13.5 Max. 6 hours Min. Effective December 1 to February 28 HZ 0020639