Document 5LnXb0zpqeLB9X3R7YX9jaM5z

5 December 7, 1973 it f=_ *. -i fe, u RCff-ARS? i--y V. MENt JUN12 1974 W. M. sm*--: ^3 Cohimbuv UhorAiotics SOS King Avenue ColumbuK Ohio 43201 Telephone 1614} 200-3151 lvU* ?4 *5454 Mr. W. R. Taylor Diamond Shamrock Chemical Company * 1100 Superior Avenue Cleveland, Ohio 44114 Dear Mr. Taylor: The Smog Reactivity of Vinyl Chloride Monomer ____- _______ _______ _____ Tills letter.will serve as Battolle's Columbua laboratories report on the jL study conducted for Diamond Shamrock Chemical Company of the photochemical?- - .smog reactivity of vinyl chloride monomer- (VCM). Photochemical smog re- U` activity can be stated in a number of ways, l.e., in terms of ozone formation, eye irritation, nitric oxide photo-oxidation, aerosol formation, etc. In the present study attention is focused on ozone formation, tha prinicpnl photochemical smog manifestation from a regulatory point Of view. Several other smog parameters have also been obtained and are discussed in this report, principally to present a more complete description of the. reactivity of VCM. Within, the limited framework of the experiments carried out in this pro gram the smog reactivity of VCH la not clearly defined. At the higher concentration studied it appears to be less reactive with respect to ozone production and .eye irritation, while at the lower concentration studied # It appears to- be very* definitely more reactive than toluene with respect to ozone prOduction^^s.-^- An absolute, definition- of smog reactivity does not exist; reactivities of VCM are therefore presented relative to smog profiles of toluene under similar chamber conditions. Profiles of smog-chamber runs with VCM and toluene are included with, this report. Initial conditions and reactivity parameters are listed in Table 1. A tun using dlethylamine as a potential low reactivity hydrocarbon reactant waa also carried out (Run 3) but was of questionable accuracy and has therefore been excluded from the overall analysis. Hydrocarbon values are reported as parts per million of carbon (ppmC). All other concentrations are reported ae parts per million (ppm) on e volume basis. AP00018340 Mr. U. K. Taylor 2 December 7, All runs were carried out at 90 + 2* F and at 40 + 5 percent relative humidity.. Illumination intensity as* measured by photodecomposition was kj * 0.45 min"*, slightly greater than noon-day sunlight intensity* Total hydrocarbon was determined by flainc ionization, K0 and NO* continu ous Saltnman techniques, ozone by chemiluminescence, total aldehyde by the codi.unt bisulfite procedure,, and aerosol by broad band integrated ncphclbaetry. Eye irritation measurements ware made by two seven-member eye panels* The overall average eye irritation index for the two panels Is reported for the fifth hour of irradiation* The eye irritation index is defined as ^ * indexj where t is the arithmetic mc;m time, in seconds, for panel response. On this basis zero in the lowest possible irritation index value and ten the highest. Eye irritation claim arc obvi ously subjective data* In general an index of seven or more is fairly irritating while on index of five or less is mild-to-non-fcrritating* Vinvl Chloride Monomer - The initial VCM experiment, Run 1 in Table 1, was carried out at the reltfr tively high hydrocarbon loading of 4 ppm (by volume) VCM. The HC/N0s ratio was approximately 2. This experiment should be compared with Run 4 which consists of toluene under the same volume loading and HC/N'0X conditions. Overall, the VCM run was slower than the toluene experiment* The time to NO maximum was about an hour slower for the VCM run* Ozone: peaked at 0.24 ppm in the toluene*run and was only 0.04 ppm although.sell], increasing after six hours' in the VCM experiment. Total aldehyde levels at the fifth hour of irradiation were similar for both toluene and VCM. Aerosol values as measured by light scattering were much higher in the toluene run* Eye Irritation was also higher for the toluene experiment*. Comparing now VCM (Runs 2 and 6) and toluene (Run 5) at a lower hydrocar bon.. loading and higher*HC/KO^, we.see in Table 1 that the time to KO2 maximum Is.now similar, for VCM and toluene and that VCM yields an ozone maximum which: is considerably higher than that ftom toluene (Run 5)* Once again; toluene resulted in much higher aerosol yields than VCM. Eye Irritation' and total aldehyde values for the duplicate VCM experiments were scattered and bracketed the toluene values for these smog manifestations. Aerosol reactivity is often reported in terms of light scattering* There was no evidence of any marked aerosol production In these studies for VCM. AP00018341 TABLE X. INACTIVITY EXPERIMENTS 50 I- so Cuwl o V c* cm CM CM V\ rCMt oO' oCM ooo * ? * HCM O ot/Yv vrOt . Ka ICY m Hooc5 * fH* CM CM N H CM rCOt oo o CoM O VCOM o U"| oH Q rt ' V99 a N in CM. CKM . oco CM t4 oCM o ovO o C4M* *CO-O*r O vCO*4 Ort ft O* s CM H Vo S if *5-3 ^.-6 <r cm CM CM VO n HcO o ooft o vO o M> rt O VClOOM VO CM to CMft oOV <=> . o COft CCMO OY o o 'CtrMt CtoM rt , oa oUvYJ -o O a >> u >H ov stf P*- o OCO COM vCP&k O N -< o * Msor vOo A CO O CCMM u"t :/ X So fss ss w9 I ' > > "Hc2* ft)* <*. v . - <93 coi- es ft a& u2u2-.*** O J ti > J*ooj oJ3 la-l "os*a* 5&3 OSi 5* Sr Cfe l Ot X I eft X CB s 1 u n. CU * H mO Xn o > tfrt)t o. o Si S3 cf* O ft) rct*' Or> 5 U4r Q JJ rt M. b W es (>4* S | <3 t'rWt) oe Mo o W trt Aftt aa> y% o *n Cc3 rt <o -8 f<t9* rBt O O X0 B on *>? 1 cT o*1 $ ffHwrttt POS AP00018342 Ur. W,, K Tayloc ' December 7, mV*, Summary Hie photochemical smog reactivity of VGM as observed in these .experiments is qualitatively summarised in the following tabulation. The reactivity of VCM is somewhat in question in that, low o/.onc and eye irritation re activity is. observed at the high concentration loading, and high reactivity is observed at the low concentration loading, . Wa appreciate the opportunity to work with Diamond Shamrock on this study. Please call me if you would like further amplification on the results presented here. Arthur Levy, (1 Senior Research Leader Atmospheric*Chemistry and Combustion Systems Section AL:mb Duplicate Enc. / 1 1 AP00018343 Run No. 1 VCM 4 ppm (V/v ) APOOO18344 IRRADIATION TIHE, HOURS QUALITATIVE COMPARISON WITH TOLUENE *t fot.5pe cs so ( O' O CM KO A58 ^ J= t * 0> w Kw 5 rt.rf. Hp P T4 W *- s n if '5 25 ^ tuf u C o * oCM ocm HCl 5 wM a ^3 O MU PU01 4ft 01 *ta 3 8 M & ikUJ JoS 3 O 'IJ a tC g s> * 5 Ww s I t fe + O AP000I8345 IRRADIATION TIME, HOURS ineJd `^0 *"2 ** O AP00018346 Run No* 2 VCM 1,1 ppm (v/v ) APOOOf8347 IRRADIATION TIME, HOURS IRRADIATION TIME, !!OURS Toluene 3.9 ppm (v /v ) 1 ,Z0M + O..t.f i .) f I t I i i l Sso HOc...H **Ho ?. CsO. M*m '. CCM o odd E0 rt N# H% o Oudd *0U I050I o Pi VI N o C4 VHI 3 o Run So. 4 APOOOI8348 ! I S O SB g M H SO5 t-< <TJ Toluene 1,8 ppm (v/v ) Run No. 5 o^w.-'on t.wx S APOOO18349 (A/ ) odd JOAf t 9 'o s nnB AP00018350 IRRADIATION TIMS, HOURS