ResearchGate Gas phase kinetics of the reaction system of 2NO(2)<-> N204 and simple alcohols between 293-358 K = @ rns eomentotoning ns page wns ued 00 We ass on 1 Rebuy 221Polish J. Chem., 79, 1301-1313 (2005) PHYSICAL CHEMISTRY Gas Phase Kinetics of the Reaction System of 2NO, © N20, and Simple Alcohols Between 293-358 K by D. Wojeik-Pastuszka’, A. Gola and E. Ratajezak Department of Physical Chemisry, Wroctaw Medical University, PL. Nankiera I, 50-140 Wroclaw, Poland (Received January 18th, 2005; revised manuscript April 13th, 2005) “The reversible reactions between nitrogen dioxide and alcohols (CH,OH, CH,CH.OH, (CH,CH.CH,OH, CH,CHOHCH) have been studied inthe gas phase, using the spectro- ‘Photometric method. RONO (R= CHs, CHjCHs, CH)CHsCH, CHyCHCHs) were identi- fied by UV spectra. The equilibrium constants aswell asthe bimolecular rte constants ‘were determined by computer modeling, using the programme MINICHEM. We ealeu- lated the following values for the forward rate constants KY: (3.040.9)x10™", .082.4)x10", (5.481.610, (2.080.6)x10"" em? molec” sand the equi ‘constants Ky 100230, £012, 109253, 312 21298 K forthe reactions with methanol, ethanol, I-propanol and 2-propanol, respectively. The temperature dependence ofthe rate constants and the equilibrium constants were studied and itallowed to obtain the tivation energy forthe forward and forthe reverse reaction, as well as thermochemical parameters. The equilibrium constants and the rate constants suggest that symmettical 1N40« i the reactive species. Key words: nitrogen dioxide, dinitrogen tetroxide, simple alcohols fogen oxides play an important role in the atmospheric chemistry. The major source of NO; in polluted atmosphere is human activity, such as combustion fuels. Smaller amounts of this gas are produced by oxidation of NO [1].NO and NO3 con- centrations have an influence on the ozone distribution and on the atmospheric ozone formation rates. Both oxides lead to photochemical ozone production in the tropo- sphere and ozone destruction in the stratosphere. It is possible, that in lower strato- sphere a huge amount of nitrogen oxides may appear asnitric acid (NO; ean react with OH to form HNO) [2] to contribute to acid rain and fogs. Nitrogen dioxide is always present in the equilibrium with NO, (2NO3 + N20.) and the equilibrium constant equals 5.2x10™ exp (6643/T) cm’ molec” [3]. NOz can undergo self-association leading to significant amounts of NzO¢ifthe NO: concentra- tions are large and/or the temperatures are low. The rate constants for the forward (k:) and reverse (kz) reaction are [4]: k, = 1.010™" em’ molee™ s and ky = 1.15x10"%exp_ (6460/T) cm’ molec" s"', 1871 7840233, fax: +48 71 7840230, erail: dorotaw@bf.uni.wroe.pl "Corresponding author;1302 D.Wéjeik-Pastuscka, A. Gola and E Ratajezak Dinitrogen tetroxide has a set of isomers and apart from very well known symme- trical O:N-NOz, an asymmetrical: trans — NO-NO; and cis - ONO-NO; were also identified at low temperature matrices by infrared spectroscopy [5,6]. Itisalso intere- sting to note, that another two asymmetrical isomers of NOs: frans -ONO-ONO and cis - ONO-ONO have been found by ab initio calculations at the MP2 level 7), al- though no experimental information has been reported on these molecule structures. Nitrogen dioxide can be involved in the reaction with alcohols, which are present in the atmosphere too [8,9]. They are produced by forested rural sites and in sea water. In the lower troposphere methanol and ethanol can be synthesized via hydrocarbon oxidation. Another important source of alcohols in the atmosphere is anthropogenic emission [10]. Alcohols are used as an alternative energy source. In recent years met- hanol and ethanol have been added to gasoline to achieve cleaner combustion and to reduce by half the concentration of oxidants and particulates of gasoline [11,12]. ‘The study of the reaction between methanol and nitrogen dioxide began Harris, and Siegel (13]. It was observed, that NO: is consumed in the reaction at room tempe- rature, Inalater study Yoffe and Gray [14] analyzed products of the reaction between di- nitrogen tetroxide and methanol and ethanol, both in the gas and liquid phase, atroom temperature. CH;ONO for methanol and C3HsONO for ethanol were identified by their UV absorption spectra. CH;ONO; was not observed under these conditions. It indicated that the reaction proceeds through esterification, and not through oxidation ‘by NOs. The authors considered also the equilibrium 2NO; ¢+ N04. The mechanism of the reaction involving symmetrical 0;N-NO; and not asymmetrical ONO-NO2 was proposed: CH,OH + N:0, > CH;ONO + HNOs. twas suggested, that at higher temperatures (623 K) the reaction may proceed via ox- {dation by nitrogen dioxide to produce CH,ONO;. ‘As the temperature increases, the mechanism of the reaction between NO: and (CH,OH changes. Anastasi and Hancock [15] reported that between 639-713 K there- action proceeds through H atom abstraction: NO; + CH;OH > HONO + CH,OH and the next step is followed by the reaction: ‘NO; + CH,OH - HONO + CH,O. Fairlie et al. [16] observed the third order of the reaction of NO; with alcohols be- tween 273~298 K with apparent negative temperature coefficient (E, =-67 kI mol).Gas phase kinetics ofthe reaction. 1303 -—————Saaelinticn fthermnction-_ 1308 ae anomalous temperature effects and the improbability of termolecular collisions dicated, that the rate determining step is a bimolecular reaction of NzOs. These ai ors predicted the activation energy about a few kilocalories. The obtained value of £termolecular rate constant for the forward reaction keat 298 K was: k;=4.8x1077, 7x10”, 3.010%, 5.110 cm® molec™ +” for the reaction with methanol, etha. 31,1-propanol and 2-propanol, respectively. In this work an equilibrium was obse- {edand the equilibrium constant at 298 K was calculated to be: 1379.2, 650.2, 808.5, 4.5 atm" for the reaction with methanol, ethanol, I-propanol and 2-propanol, re. fectively. Subsequently Silverwood and Thomas [17] studied the reaction between meth: 1 and nitrogen dioxide below 460 K. The equilibrium constant of the reaction (K )97 atm at 298 K) was calculated using the equilibrium pressures of NO, CH,OH, HONO and HNO; and assuming that two molecules of NO; and one molecule of HOH take part in the stechiometric reaction. From the van't Hoff plot the enthalpy ange for this reaction was derived (AH, = -66.5 kI mol”), ‘Niki etal. [18), using FTIR method, studied the reaction between nitrogen dioxi- bandmethanol and ethanol. The concentration of reactants and products was measu- ‘and the equilibrium constant (K = 1033.6 and 418.0 atm”' for the reaction with ‘ethanol and ethanol, respectively) as well as the termolecular rate constant for the ‘rward reaction at 298 K (in both cases ky= 5.710” em molec” s") were obtain- i. twas proposed, that the reaction proceeds with the second power of NO; and first dwer of methanol concentration, In this work the material balance for the reaction {as determined. The authors suggested, that the mechanism of the reaction might \wolve NO, with an estimated bi alecular rate constant k= 2.0x10~"* em? molec”! * at298 K for the forward reaction: NO, + CH,OH > CHONO + HNO}, The obta- ted equilibrium constant was K = 182 at 298 K. Koda eral. [19] confirmed the kinetics proposed by Niki eral. [18]. In this work tey found, thatthe reaction of NO; and CH OHis of second order with respect to the pacentration of NO; and depends on the first power of the methanol concentration, {though gradually becomes independent of the alcohol concentration with the incre. fe ofits concentration. The value ofthe termolecular rate constant was calculated to £ 1.810 cm* molec™*s™ at 294 K. The authors suggested that the reaction proce- 4s through an asymmetrical NO dimer, which reacts with methanol bimolecularly $ the rate determining step. Inthis work we confirmed that the main products ofthe reaction between nitrogen foxide and simple alcohols in the gas phase are RONO and HNO. Using computer jodeling we proposed the mechanism of the reaction, which involves symmetrical (50s. Assuming the bimolecular mechanism of the reaction, the rate constants for the drward and reverse reaction as well as the equilibrium constant were calculated. The fivation energy for the forward and reverse reaction and the enthalpy change of the faction were obtained too.1304 D. Wéjeik-Pastuszka, A. Gola and E. Ratajezak 304. Weajetk-Pastussha, A. Gola and E Reiafeso —_ EXPERIMENTAL “The experiment was performed using vacuum system connected withthe spectrophotometer JASCO 'v-530 with an optical pathlength of 10cm and resolution! nm, The kinetics of the stechiometrcreac- 12NO; + ROH € RONO + HNO) «vas studied using the inital concentration of NO: inthe range of 1.6x10'*-9.6x10""molec cm". The ini Tal concentration of alcohol was adjusted inthe most of experiments tobe atleast times greater than that ‘SENO: to obtain pecudo-first-order conditions for intial step of the reaction. Most ofthe measurements syere carried out at total pressure of 500 mbar, between 291-361 K. The temperature was controled 9 Within! K by thermostated water in an outer jacket, surrounding the reaction cell Nitrogen, as the bath as. was added to nitrogen dioxide and to alcoho o prepare NON; and ROH/N: mixtures, The pari fresoures were read with a Cole-Parmer Instrument Company absolute membrane manometer model Bg801-43, Gas mixture composed of NO3/N; was admitted into the reaction cell and after the stabilization CGamos experiment after 3605) ROH/N; mixture was added. The measurements were provided in 3600s, "The system was equipped with an optical glass reaction cel, having an approximate surface (S)t0 ‘volume (V) ratio of SV =2.3 em’. The results for the reaction with CH,OH obtained for this cell were ‘Tompared with measurements, which were performed using a 1 spherical stanles steal cell with S/V = (0.48 em It enabled to test the effect of surface on the reaction. Nz (99.9998) was provided by BOC GAZY and used without purification. The purification ofleo- hols and NO; was carried ou by freezing and bulb-to-bulb distillation in vacuum. Methanol was supplied fom Chempur, ethanol from Polmos, I-propanol and 2-propanol from Fluka. Nitrogen dioxide was obta- ined ffom Merck. RESULTS AND DISCUSSION ‘The final products of the reaction system NO,/ROH were identified by UV ab- sorption spectroscopy, and together with literature spectra [14,22], FTIR spectra [18] and MS [20] give strong evidence, thatthe end products ofthe reaction are RONO and HNO, No HONO and NO have been found. Characteristic nitrite esters absorption spectta were observed in the range of 300400 nm. They are shifted to short wave- Tength direction in comparison with HONO [21]. For the strongest band of HONO, lo- ‘cated at 354.2 nm, an absolute absorption cross section has been determined to be 6 = 5,02x10- em? molec”, The strongest band of CH,OH is located at 340 nm. Its ab- sorption cross section, derived from this experiment, was estimated to be 6 = 5.5x10" em? molec", base e, what is ina good agreement with literature data [22] (6 =3,0x10" em? molec”, base e). The second reaction product - HNO —has not been detected, probably due to its susceptibility to heterogeneous loss processes. Gaseous HINO) is known to present gas-handling problems, due to adsorption on the glass sur- face [18]. ‘Considering the equilibrium 2NO. ¢» NOs, the characteristic absorption feature at 450 nm was chosen for monitoring the NO; decay. Gierczak et al. [23] recorded NO; and N:O, spectra between 280 and 420 nm. In the range of 280-380 nm these spectra overlap. However, at the wavelength of 450 nm the contribution of N2Os canGas phase kinetics ofthe reaction 1305 bbeneglected and the NO; absorption cross section has fair value, Moreover, the pho- tolysis of NO; was avoided and RONO is not visible at this wavelength. Fig. presents a series of kinetic curves monitored at 450 nm, obtained at diffe- rent temperatures at a constant total pressure of S00 mbar. In the absence of alcohol, the concentration of NO; remained constant ina time seale of 360's. Inthe presence of alcohol NO: was consumed in the reversible reaction. The rate of NO, decay is depen- ed on temperature (Fig. 1) and the initial concentration of NO>. Athigher initial con- centration of NO; the reaction was faster. It is interesting to note, that the consumption of NO; at higher temperature was slower. The possible explanation, su- gested before [16,18-19], is that the reactive species is rather N20, and not NO3. The concentration of NO, decreases with the increase of temperature. The same pheno- menon was observed in the reaction between nitrogen dioxide and ammonia [24). In this case, the authors proposed, that the reaction proceeded through an intermediate adduct involving asymmetrical NzOs. 018 on Absorbance, base 10 ° eo 4000 50009200 Sono tis ' Figure 1. The NO; decay inthe presence of CH,OH at diferent temperatures, (a ~ 294 K, b~320 K, €-333 K, d~ 343 K, ©~ 358 K), [NOz]_= 8:0«10" molec cm”, Pu = $00 mbar, The insert shows the simulation kinetic curve for'NO; decay (solid line) together with experimental points; initial conditions: [NOs], = 3.2x10"* molec em”, [CHOH], = 1.6x10" molec em? T=298 K, Pai = $00 mbar. ‘We employed the programme MINICHEM [25] to investigate the mechanism of the reaction. This computer modeling allows a direct fitting of model curves to the experimental decay and formation curves of reactants and produets (sce the insert in Fig. 1). The system of four reactions: NO; +NO: N20. (1) N:0,-9NO; +NOz Q) N,0,+ROH—+RONO+HNO; (3) RONO+HNO;>N:0,+ROH (4)1306 D. Wéjelk-Pastuszka, A. Gola and F. Ratajcoak with theirrate constants, as well as the initial concentrations of NO; and aleohol were input to this programme. The theoretical curves were fitted to the experimental data by changing the rate constants ofthe reaction (3) and (4). Therate constants for there- action (1) and (2) are well known [4]. From these fittings we obtained the bimolecular rate constants for the forward (ks) and for the reverse reaction (k,). It was noticed that both of the rate constants were dependent on the input values, although the rate constant k, was much more sensitive than the rate constant k, to changes ofits value during fitting, The results together al conditions are summarized in Table 1. The estimated error of ks and ky was “Table 1 Kinetic data and equilibrium constant for ROH ~ NO» mixtures at 500 mbar Ns. CHOH cucH.0H | CH,CH,CH.OH | _CH,CHOHICH, | al wo ® By Sey | i “ a ui “ “ | 5 5 ts | os [a0 [31 las| - | -[-[-]-[-[-T-T- 22[11}a9{ai|us| - | - [-[-|-T-]-T-T- aifar{ia tai tas | ol -[-[-|-[-[-t-]-1- 32| 16 | 3a [31 [aol - | - [-]-]-]-T-]-|- 2 | 21 [as] 29 [wl - [| T- -T PtT 1s [os [as |a2lin| - | -|-{-[-[-]-1-1- 22[11|a2|a6] | -|-[-[-|-T-[-[-T- 27114 | 34 [29 la| - | - | - |= |=] -T-T-T- 32 [1s [2e[2s{m{-|-[- [=| 20 | s3 | 39 28 42 | 21 | 24] 22 [| -|-]-]-]-]-[-[-]- 4 [27 [19 [as {| -|-|-[-|-[-[-|-]- so[so|-|-|-|-|-|-|ss|{soluol - | - | - os|as|—|-|-|-|-| =| sa] sol re] - | - | - 22/14 [oz |iso[ s{-|-[-|-]- =| | | [ar Tua [or fiso [s [== [TTT -T-T-T- sos[32|16|os|n0| 7|-|-[-|[-[-[-[-|-|- 42[21 [oso] 7|-|-[-]-]-[-]-|-]- sa[27[os{ ool 9[-|-1-]-T- =a)‘Table 1 (continuation) 32] 16fosfno[ s|-]-[-[-[-]- Jas [as] read Ea rc ca ee | | | ees PT sos[4s [24 [or | sof 9 | - [= |= T= T= fis [as ts ss|29fo7[as| 9 -|-[-[-[-]- 7-1-1. 4[s2fo7{eo| s|-|-[-[- [= [-- Tete satus [- | - | |---| 20| oo | 2 [= [| - as[ oa] -[-T-T=T eT is [ so [os PT sol ea] s2 [| - | -T- t= 1 = fistoof | - | T- so ao | — | TT TT as [0 fa [= estas | [| - 1-1 - T= Tos[ sols | - [= T- 22{aifeslaslwl-|-[-|-|-[-|-|-|- 27{ia fotos wl -|-[-[-|-]-f-t-t- sz[s2] 16 fo2 tor [ sf - [=| - = [-{- 1 T_T 42 {21 fo2fae | o[—-|-[- [=] T eft s4| 27 forfas| s{-|-|-[-|-|-[-[-[- 32 [16 [rato] efartartal =| - = fi7[ oo | s2{is | - | -[-1-]-{-1-]--fisfaln axle | - [TTT TT as tno fe 32 {32 [-[- [= [=] T- T= -T fistale vo[aaos|-{|-|-|[-|-|-|-|-]|-|2s|n [am as | 24 [12 | 62] [22 [ool as] -|-[-[-[-[- 64 | 32 [roles |is [16 [se] | - | [P= t= - ao] so [i2[a9 | [rofaato | =| - |= 1 - [1 96 | 4s [11 | ao [ar [is] a2 [os] = | - -|-|- Sal figs [sa [ea | | ewes | eal = 19 | 80 | 24 42 | 21 [155] 60 | 26 [13 fo [|= | T-7- 7-7 aa | 24 [ss] 70 | 22 [13 [iso [ao | - |= |= [-T 64 | 32 [12 | 60 | 20 | 10 | 100] 10 | 18 | 20 | 26 | 1s | 53 | 29 a 8.0 | 40 | 135) 40 | 34 | 1.7] 7.7] 22 | 15 | 55 | 27 | 1.2 | 54} 23 96 135| 40 [34 [12 | as] 16 [13 [ss] oe] = [= [= 2 - |= T-tree} is [7 -- TTT 28 = |= Te Tio [oe Fis =P 32 as [ssf [-[-[- [2 t=] - ft. 32 195| 995] 20 | - | = | = lessfos| a | - | | - e 32 26 | 60 | 43 | - | - | - | -|-|-/|-)|-/ - 32 | 32 |2e [asf | -[-[-1-1-[-1[-T-1-1308, D. Wojetk-Pastusska, A. Gola and E. Ratajezak Table 1 (continuation) 45 eo | 30 [is] 90] 1 [sasluo] a | - | - | - ss| 29 |i2 | o2[9 | -[-[-]-]-[-[-[-[-] 33[64 | 32 [13 | s3 | 25 [10 [no] 9 | 24 | 90 | 27 | 18 | 73 | 2s qatar | | - | [iz] sof an | = TT = fiz [a [2s so | 40 [13 | 53 | 25 [16 | 9a] 18 | 29 | 50] se | 1a | 63 | 96 | 48 |16 | 56 | 29 | 13 | 80] 16 | 18) 3s} si | - | - | - | [estes] - TT - Tas [no fs | - [- T- T- TeT 64 | 32 | 185] so | 23 | 31 [of a8 | - | - | - 30 | 40 | 2s | 70 | 36 | 26 [100 | 26 | 18 | 80 | 22 358 1 96 | 48 | 19 [no] 7 | 23 [uo [ a [or | 6 | 6 u2| so | 19 | so | 24 | 19 [roo | a9 | - | | ns | uss] 6s | 28 [1s [io [is | - [- | “total pressure 250 mbar The obtained average value of the rate constant for the forward reaction with met- hanol k}’ is 3.0x10""* cm’ molec” s“ at 298 K, what is in a good agreement with the value suggested by Niki er al. [18] (approximately 2x10"'* cm? molec” s). In the case of the rate constant for the reverse reaction ks, Niki ef al. [18], using the equili- brium constant K and the rate constant for the forward reaction k;, calculated ke = 1.1x10 em? molec” s", what agrees with the average value derived by us kt’ 3.0x10 em? molec” s". ‘We used Niki’s etal [18] experimental data together with the computer modeling of the reaction employed in this work. The obtained value ofks for the reaction with methanol is: k; =3.2x10"'* cm’ molec” s“' at 298, The same procedure was employed for Koda’s er al. [19] experimental data. This yields the value of k; = 1.2x10~* em? molec”! s“', These values are in a good agreement with the average value derived from this work (k}* = 3.0x10"* cm? molec” s“). Most of the measurements were performed at total pressure of $00 mbar. Experi- ‘ments were also carried out at lower total pressure (250 mbar) in ordertotest, whether the reaction depends on the pressure. In both cases (500 mbar and 250 mbar) for the reaction of NO; with CH;OH the values of ks were similar (see Table 1). The same re- sults were also obtained for the reaction with other alcohols. In orderto determine the alcohol influence on the rate constant ks, measurements using 2.5, 5 and 10-fold excess of alcohol compared to NO; have been conducted. No ‘much difference in ky values in the case of 5 and 10-fold excess of alcohol was noti- ced. This suggests, thatthe reaction is independent of the alcohol concentration. Ho- wever, when the alcohol concentration was only 2.5 times larger than the NOs concentration, the value of ky was different, what might suggest that 2.5-fold excess of alcohol was not sufficient for pseudo-first-order conditions. In this case the reac-Gas phase kinetics ofthe reaction. 1309 tion depends on the alcohol concentration. In conclusion we decided to provide expe- iments, using the initial concentration of alcohol 5 times larger than the NOz concentration. ‘A fow experiments with different reactors were performed totest the effect of sur- face on the reaction. The average value of the rate constant of the forward reaction of NOs with methanol based on measurements in the optical glass cell (S/V =2.3 cm”) ‘at 298 K has a similar value (k}* = 3.0x10~'* cm’ molec obtained in the case of the stainless steal cell (k}” =2.4x10""* em? molec" s')(S/V=0.48 em”). Mo- reover, they agree well with the values of ks obtained using Niki's er al. [18] (ks = 3.2107 em? molec” s“) and Koda’s ef al. [19] (ks = 1.2x10~"* cm* molec” s“) experimental data together with the computer modeling, where S/V = 2.0 em” (the gold-coated Wilks cell) and S/V=0.9 em" (the reaction cell made of Pyrex glass), re- spectively. However, we observed a different value of the rate constant forthe reverse reaction ks. Using the optical glass cell (S/V = 2.3 cm”), the average value of kT = 3.0x10* cm? molec” s, which is one order of magnitude lower than derived from Niki’s etal. [18] (S/V = 2.0 mr, the gold-coated Wilks cell) and Koda’s etal. [19] (S/V=0.9 cm" the reaction cell made of Pyrex glass) measurements (in both cases ky = 17x10" cm? molec s“), Much larger discrepancy was noticed, when the stain- less steal reactor with S/V = 0.48 cm” was used. The obtained average value of the rate constant for the reverse reaction is ki’ = 9.8x10 cm’ molec” s"'. The value of k. accounts for losses of HNOs by diffusion to the walls and possible removal by ir- reversible processes. The most reliable values were obtained for the forward rate con- stant (ks). Fairlie eral. 16] have reported, that he surface ofthe reaction cell had an influen- ce on the rate constant of the reaction. However, it does not appear that initial rates were directly proportional to $/V ratio as would be the case ifthe reaction were com- pletely surface catalyzed. ‘The temperature dependence of the bimolecular rate constants ks and ks was stu- ied between 293-358 K and the results are presented in Fig. 2. From these Archenius plots the positive activation energy for the forward (Es) and forthe reverse reaction (E.) were derived. Fairlie etal. [16] predicted, thatthe activation energy for the reac- tion can be at most only a few kilocalories, what is in a good agreement with our re- sults (E, = 3.9 kJ mol" and E,~ 7.6 kJ mol" for the reaction with methanol). The values of the activation energy for the reaction of NO; with other alcohols, together with thermochemical data, are listed in Table 2. The uncertainty in the values of the activation energy E, and E, was estimated by Student's test (95% confidence level). Using the rate constants ks and ka, we calculated the equilibrium constants (K) of the reaction from the expression: K = ky/ky. Measurements were conducted between 1293-358 K, under conditions, where the equilibrium was clearly observable and the kinetic observations supported the proposed reaction mechanism, used for analysis of the experimental data. In the case of ethanol no equilibrium was observed at lower temperatures and the measurements were performed between 320-358 K. The values1310 D, Wéjetk-Pastuscka, A. Gola and E. Ratajezak & a a i P+ a S . te a : 10007T (K") Figure 2, Inks, 1000/7 obtained from NO; decay inthe presence of CH,OH for the forward (A. and mt) and forthe reverse (@) reaction using different reaction cells(@ and @ optical glass cel, S/V= 2.3 em, A stainless steal cell, IV = 0.48 cm. ofky' andk’ in Table? for the reaction of NO; with ethanol were derived by extrapo- lating the plot of InK against 1000/T to 298 K. “Table 2. Kinetic parameters and thermochemical data forthe reactions between NO; and alcohols inthe gas phase ] Alcohols | | Kinetic CHLOH | CHLCHLOH | CHICHLCHLOH | CHCHOHCH parameters and) | termoebemical data | | 7 1 [a0 | maser | aarayio* | Gationae | aoinoxae F280, | cosmo | corooan® | gouspae® | gasien0® | K, 298 §) 100250 aout 109853 sesi2 ait 2 re 42 96 eae | ast | [smart Ba ar | 49Gas phase kinetics ofthe reaction. Bu ‘Table 2 (continuation) & x mot* B ky mor 6? AH; ~ Das; i mot 8G} =-RTInKy, ki mol" ‘aH mor based on literature “19 2172 4 50 ermachemical data 3.9887 55850 12873 3.6827 7629 103834 37328 losti9 a “85 “85 90 us 91 6 4 ‘The second law analysis of the equilibrium constants (Fig. 3) enabled to obtain the values of the enthalpy change of the reaction (AH,) with four alcohols studied. ‘These results agree within +6 kJ mot” with the enthalpy change calculated, using the ‘known values for the heat of formation of reactants [26-30]. ‘The calculations and computer modeling were based only on the thermochemical data and kinetic parameters for symmetrical NzO,. The thermochemical and kinetic, data for asymmetrical isomers of NO, are not available, although they may be involved in the mechanism of the title reaction too. 5 Figure 3. Van'tHoffplot ofthe measured equilibrium constant (K) forthe reaction of NO; with CH,OH.ees pes poe 1312 . Wejetk-Pastuscka, A. Gola and E.Ratajecak ‘The proposed mechanism, involving different isomers of N2Os,might be used for the reaction of NO; with all alcohols studied. Considering the obtained values of ki- netic parameters and thermochemical data listed in Table 2, we have noticed that the ‘values seem to be almost the same forall alcohols, ie. the values of k}’ are in the ran- ge from 2.010" to 8.0x10™ cm’ molec“ sand the enthalpy change of the reac~ tions derived from the van't Hoff plots are between -10.1 and—4.2 kJ mot *, Itshould bbe noticed that the bond dissociation energies D (R-OH) are almost the same forall alcohols investigated in this work (382.8 k/' mol” for methanol, ethanol and 1-propa- nol and 384.9 kJ mol for 2-propanol) [31]. Acknowledgments ‘We thank the Nordic Academy for Advanced Study (NorPA) for supporting the kinetic studs through "Network for Chemical Kinetics (NoNeCK), REFERENCES 1 .Finlayson-Pitts BJ and Pits IN., Atmospheric Chemistry, Wiley, NY 1986 2.Cratzen PJ, Quart JR Met. Soc., 96, 320 (1970). 3 Dentore WB, Sander P., Golden DM. Hampson RF. Kurylo MJ, HowardC.J~.Ravishankara A.R Rall CE. and Molina M., Chemical Kinetice and Photochemical Data for Use in Stratospheric ‘Modeling, Evaluation No, 12, Jet Propulsion Laboratory, Pasadena, CA 1997. 4, Atkinson R, Baulch DL, CoxR.A., Hampson RF. J, KerrJ.A,,RossiM.J-and TroeJ.J. Pls. Chem. Ref, Data, 26, 1329 (1997). 45. Louis RAISE and Crawford B. Jc, J. Chem. Pips. 42, 857 (1965) {6 Melen F and Herman M, J. Piys. Chem. Ref Data, 21,964 (1992). 43, Wang X, Qin Q-Z. and Fan K,, J. Molec Siract. Theochem), 432, $5 (1998). EiNgupen HLT, Takenaka N, Bandow H., Maeda Y, de Oliva ST, Botelho MMF. and Tavares TM, “Aim. Environ 38,3075 (2001). 49. SinghHL, Chen Y, Tabazadeh A..Fuku . Bey .,YantoscaR., Jacob D., Amold F,Wobifrom K. Atlas Er Flocks F, lake D., Blake N, Hikes B, Snow J, Talbot R., Gregory G., Sate G., Vay 8. and Kondo ¥, J. Geophys. Res, 105, 3795 (2000) 10.Singh HB, Kanakidou M, Crutzen PJ. and Jacob D1, Nature, 378, $0 (1995). 1-Barinaga M., Nature, 327, 36 (1987). [2iLynd LR, Cushman J4H,, Nichols RJ. and Wyman ChE. Science, 251, 1318 (1991) 13, Haris Land Siegel BM, J. Am. Chem, Soe, 68,2520 (1941). 14, Yolfe AD. and Gray PJ! Cem: Soc, 1412 (1951). 15-Anastasi Ch and Hancock D.U, J. Chem. Soe, Farad. Trans. 2,84, 1697 (1988) te.Paitie AM, Je, Carbery JJ. and Treacy 1.C, J. Am Chem. Soc, 78,3786 (1953). 17:Silverwood R. and Thomss JH. Trans. Farad. Soc, 68,2476 (1967). 18-Niki H, Maker PD., Savage CM. and Breitenbach LP, In J. Chem. Kinet, 14, 1199 (1982) 19.Roda , Yoshikawa K., Okada J. and Akita K., Environ. Sel. Technol, 19,262 (1988). 30-RetjerakE, Stuba B.Brudnik K., Fagersttm K, Mahmoud G,Lund A, PagsbergP. and Slleen A. ‘Kinnic and snechaniatic studies of NOs reactions with NH, H,O, CH,OH, CH)SH and CH,CHO, 13" Intemational Symposium on Gas Kinetics, University College Dublin, Abstracts 1994, p. 287 21 Pagberg P, Bjergbakke E., RaajezakE, and Sillesen A. Chem. Pls: Let, 272, 383 (1997). 22.Calvert 1G. and Pitts IN i, Photochemistry, Wiley, NY 1966, 235. Giewszak T, Burkholder 1B, and Ravishankara AR, J. Phys. Chem. A, 103, 877 (1999) 34, PagabergP, Sillesen A, Brudnik K. and RatajezakE., Bull Pol. Acad. Sct. Chem, 48,299 2001)Gas phase kinetics ofthe reaction. 1313 25 Kater, Belt and Ran 01, MINICHEM Veron OCT 202 Rn Nan 26 DeMlore WB, Sander SP, Golden DM, Molin MJ, Hampson RE, Kuro M1, Howard CJ. and Ravishankara A.R., Chemical Kintles and Photochemical Data for Use in Stratospheric Modeling, Evaluation No.9, Jet Propulsion Laboratory, Pasadena, CA 1990. 27. Rebbert RE. and Laidier K.1, J. Chem. Pps. 20, $74 (1982). 28.Connett E, J. Chem. Thermodyn. 4, 233 (1972). 29.BattL., Christie K, Milne RT. and Summers AJ, Int J. Chem: Kinet, 6,877 (1974). 30. Buckely . and Herington E..G., Trans. Farad So. 61, 1618 (1965). 531. Benson §.W,, Thermochemical Kinetic, Wiley, NY 1968,