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Reactivity and kinetics of 1,3-butadiene under ultraviolet irradiation at 254nm

Reactivity and kinetics of 1,3-butadiene under ultraviolet irradiation at 254nm The reaction process of gaseous 1,3-butadiene following ultraviolet irradiation at the temperature range from 298 to 323 K under nitrogen atmosphere was monitored by UV–vis spectrophotometry. A gaseous mini-reactor was used as a reaction vessel and could be directly monitored in a UV–vis spectrophotometer. We investigated the reactivity and kinetics of 1,3-butadiene under non-UV and UV irradiation to evaluate its photochemical stability. A second-order –1 kinetic model with 50.48 kJ·mol activation energy fitted the reaction data for non-UV irradiation, whereas a first- –1 order kinetic model was appropriate in the case of UV irradiation with activation energies of 19.92–43.65 kJ mol . This indicates that ultraviolet light could accelerate the photolysis reaction rate of 1,3-butadiene. In addition, the reaction products were determined using gas chromatography-mass spectrometry (GC–MS), and the reaction pathways were identified. The photolysis of 1,3-butadiene gave rise to various volatile products by cleavage and rearrangement of single C–C bonds. The differences between dimerization and dissociation of 1,3-butadiene under ultraviolet irradia- tion were elucidated by combining experimental and theoretical methods. The present findings provide fundamental insight into the photochemistry of 1,3-butadiene compounds. Keywords: 1,3-butadiene, Photolysis, Reaction kinetics, Ultraviolet irradiation determine the sensitivity of 1,3-butadiene polyperoxides Introduction using the standard drop weight method [13]. The results As an important organic precursor, 1,3-butadiene is showed that a low-energy shock could cause rapid com- widely used in the production of polybutadiene and bustion, while a high-energy shock would produce a ther- other copolymers, such as cis-polybutadiene rubber [1, mal explosion. Various types of calorimeters were used 2], neoprene, and styrene-butadiene polymers [3–5]. to study the thermal polymerization of 1,3-butadiene. Owing to conjugation effects [6], 1,3-butadiene is prone The thermal characteristics and hazards associated with to polymerize to form polymers and polyperoxides upon 1,3-butadiene were studied using an accelerated calorim- contact with light, heat, and oxygen in air [7], resulting eter (ARC) [14]. The thermal dimerization and polym - in reduced performance and limiting its applications. erization reactions of 1,3-butadiene in the presence and Polyperoxides were reported to be impact-sensitive and absence of oxygen were evaluated to assess its thermal thermally unstable, and slow deposition over some time reactivity and runaway behavior using theoretical com- can lead to highly hazardous conditions in 1,3-buta- putational models and thermal analysis techniques [15]. diene plants [8]. Many serious explosion accidents An automated pressure-tracking adiabatic calorimeter have occurred during the production of 1,3-butadiene (APTAC ) was used for measuring the overall thermo- [9–12]. Hendry et  al. conducted impact experiments to dynamic and kinetic parameters. In addition to thermal polymerization, the UV-based photopolymerization processes of 1,3-butadiene have *Correspondence: gxumali@126.com; xmliu1@gxu.edu.cn School of Chemistry and Chemical Engineering, Guangxi University, also been extensively studied in the past decades. Earlier Nanning 530004, China © The Author(s) 2022. Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http:// creat iveco mmons. org/ licen ses/ by/4. 0/. The Creative Commons Public Domain Dedication waiver (http:// creat iveco mmons. org/ publi cdoma in/ zero/1. 0/) applies to the data made available in this article, unless otherwise stated in a credit line to the data. Liang et al. BMC Chemistry (2022) 16:4 Page 2 of 12 reports [16–19] showed that irradiation of solutions obtained from Guangxi Guoxin Gas Research Co., Ltd., containing conjugated dienes and various photosensi- China. tizers led to the formation of dimers of the dienes. The photochemistry of 1,3-butadiene in solution yielded Photochemistry of 1,3‑butadiene none of the main volatile products that were observed A sealed threaded quartz colorimetric dish (volume in the vapor phase but produced only cyclobutene, bicy- 3.5  mL, Yixing Spectral Analysis Optical Components clo[1.1.0]butane, dimers, and a polymer [20]. In addition Co., Ltd., China) was used both as a gaseous ultraviolet to the photopolymerization products, some decompo- mini-reactor and sample cell, which could be analyzed sition products, such as ethylene and acetylene were directly to avoid the errors associated with intermediate also detected the above study. However, photopolym- extraction. Before each experimental measurement, the erization and photolysis reactions involve two different reactor was first evacuated and simultaneously passed mechanisms. The origin of the coexistence of these two through fresh nitrogen for not less than 5  min to flush competing mechanisms under ultraviolet light irradiation out all oxygen. The required trace amount of gaseous is worthy of further investigation by a combination theo- 1,3-butadiene was injected into the reactor using a gas retical and experimental methods. However, the specific micro-sampling syringe. Homogeneous mixing of the requirements and testing procedures make the experi- reactants in the reactor was carried out before starting mental analysis tedious and expensive. A more practi- the experiment. For quantitative analysis of 1,3-butadi- cal and simpler experimental analysis method should be ene, the reactor was placed into a UV–vis spectropho- employed, such as UV–vis spectrophotometry. On the tometer (UV-2550, Shimadzu Instruments Co., Ltd., other hand, the importance of the reaction rate in chemi- Japan) at preselected time intervals. Then, the reactor cal production is self-evident. Understanding the effects was transferred into a constant-temperature box to main- of various factors on the reaction rate facilitates the tain the temperature at the desired value (other than selection of the conditions required to make the chemi- room temperature). A schematic diagram of the experi- cal reaction proceed at the desired rate. This highlights ment is shown in Fig. 1. The photochemical reaction was the crucial importance of investigating the kinetics of the performed at different temperatures (298, 303, 308, 313, photochemical reactions of gaseous 1,3-butadiene. 318, 323  K) for 5  h. The light source was a low-pressure In this work, the reactions of gaseous 1,3-butadiene UV lamp (Philips, TUV G6T5, 6  W) with maximum under UV irradiation in nitrogen atmosphere at low tem- emission at 254  nm, which was placed on the top of the perature were carried out in a gaseous ultraviolet mini- constant-temperature box. The light intensity of the UV −2 reactor. A UV–vis spectrophotometer was employed to lamp was between 25 and 500  μW  cm , as measured monitor the reaction process. In order to clarify the influ - by a UV-C ultraviolet radiometer (Shanghai Baoshan ence of 254  nm UV light on the 1,3-butadiene reaction Gucun Optic Instrument Factory, Shanghai, China) in rate constants during the photochemical reaction, the air. The intensity of the ultraviolet radiation was varied by reaction rate constants and activation energy obtained adjusting the distance between the lamp and the reactor. in absence of irradiation were used as reference. To Dynamic data processing was carried out using the itera- understand the reactivity of 1,3-butadiene under ultra- tive method (Additional file 1). violet irradiation, we studied the relationship between UV intensities and reaction rate constants. In addition, Qualitative analysis of reaction products the reaction products were analyzed by gas chromatog- The main products of the thermal and photochemi - raphy–mass spectrometry (GC–MS), and the possible cal reactions of 1,3-butadiene were qualitatively ana- mechanisms of the photochemical reaction of 1,3-buta- lyzed by GC–MS (GC/MS-QP2010 Ultra, SHIMADZU, diene were systematically examined. The results were Japan) using an Agilent J&W advanced capillary column compared with the reaction mechanisms reported in the (30  m × 0.25  mm × 5.00  μm) and an electron impact previous studies. The differences between the photolysis ionization detector (EID, 70  eV). The analytical proce - and photodimerization pathways for 1,3-butadiene under dures were as follows: the temperature was maintained 254 nm irradiation are also discussed in detail. at 333  K for 1  min, then increased to 373  K at a rate of −1 3 K  min , and kept for 3 min. The carrier gas was ultra - −1 high pure helium at a constant flow rate of 4.0 mL  min . The injection temperature and volume were maintained Material and methods at 373 K and 1.0 mL, respectively; the split ratio was 30:1, Materials while the interface and ion source temperatures were set 1,3-Butadiene (mass purity > 99.90%, molecular weight –1 at 473 and 493  K, respectively. A quadrupole mass filter 54.09 g  mol ) was obtained from Guangdong Walter was used with a m/z range of 18–300 in full-scan mode. Gas Co., Ltd., China. N gas (mass purity > 99.99%) was 2 Liang  et al. BMC Chemistry (2022) 16:4 Page 3 of 12 Fig. 1 Schematic diagram of the research The detected peaks were identified based on the National Institute of Standards and Technology 2011 library of mass spectra. Qualitative analysis of the products was based on the cracking patterns and retention times observed in the mass spectrometry and gas chromatogra- phy analyses, respectively. Results and discussion Quantitative analysis of 1,3‑butadiene by UV–vis spectrophotometry UV–vis spectrophotometry is widely employed for the quantitative determination of the concentration of liq- uids [21, 22]; however, it has rarely been applied to the analysis of other states of matter, such as gas. Therefore, in this study we aimed to fill this gap by using UV–vis Fig. 2 UV spectra of 1,3-butadiene reaction process. a 1,3-butadiene; b thermal products of 1,3-butadiene; c photoreaction products of spectrophotometry for the quantitative analysis of gase- 1,3-butadiene; d blank reactor ous 1,3-butadiene. The experimental results are shown in Fig.  2. 1,3-Butadiene showed an obvious absorption peak with a maximum at 209  nm, due to the ultraviolet Thermal reaction kinetics of 1,3‑butadiene absorption of conjugated double bonds. Figure 2d shows In order to clarify the influence of ultraviolet light on that the reactor cell did not affect the process under the reaction constants during the photochemical pro- experimental conditions. Therefore, quantitative analy - cess, we first analysed the reaction in absence of ultra - sis was performed spectrophotometrically by monitoring violet illumination, that is, the thermal reaction. A the decay of the strong absorbance peak of 1,3-butadiene detailed kinetic analysis was performed to assess the at 209 nm. Figure 2b, c suggest that the absorption of the effect of the temperature on the rate of the thermal thermal and photoreaction products of 1,3-butadiene reaction of 1,3-butadiene. To simplify the kinetic equa- was negligible, because they showed almost no absorb- tions and the calculation of the related parameters, ance within the same wavelength range. The working gaseous 1,3-butadiene was considered to be uniformly equation for the quantitative analysis of 1,3-butadiene, distributed in the reactor. as determined by the external standard method, was 4 2 The thermal reaction of 1,3-butadiene was assumed to y = 0.4672 × 10 x + 0.1026 (R = 0.9996), where y and x proceed as follows: represent the absorbance and amount (mol) of 1,3-buta- diene, respectively. Then, the molar amount of 1,3-buta - α CH = CH−CH = CH k products 2 2 1 −→ diene was calculated from the working curve equation. This approach provides a new route for the quantitative The reaction rate (r ) of 1,3-butadiene could be analysis of other gases as well. expressed as Liang et al. BMC Chemistry (2022) 16:4 Page 4 of 12 suitable for describing the 1,3-butadiene thermal reac- dn BD r =− = k n (1) 1 1 BD tion than the first-order model, suggesting that the ther - dt mal reaction of 1,3-butadiene is more like a second-order where k represents the kinetic rate constant of the ther- reaction. This is consistent with previous research [23]. It mal reaction, t is the reaction time (h), n is the amount BD was suggested that the dimerization process followed a of 1,3-butadiene (mol) at time t, and α denotes the ther- second-order kinetics in the temperature range from 298 mal reaction order. Based on Eq.  (1), the calculated val- to 323 K. ues were fitted to different models via a trial-and-error The activation energies (E ) could be estimated using method: i.e., a is first-order [Eq.  (2)] or second-order the Arrhenius equation: [Eq.  (3)]. We compared the correlation coefficient R to k = A exp(−E /RT ) 0 a (4) confirm the reaction order: where k is the rate constant, R is the gas constant ln n =−k t + C (2) BD 1 −1 [8.314  J·(mol  K) ], A is the frequency factor, and T is the absolute temperature. Taking the natural logarithm of =−k t + C (3) both sides of Eq. (4), we obtain BD where C is a constant. ln k =− + ln A (5) RT The experimental ln n vs. t or 1/n vs. t plots show a −1 linear relationship, corresponding to the correct rate Plots of ln k vs. T consisted of a straight line (Fig. 4), equation, and the rate constant was thus obtained from whose slope was used to calculate the activation energy the slope of the regression line. The results are shown in of the thermal reaction of 1,3-butadiene, which was esti- −1 Fig. 3 and the kinetic parameters are displayed in Table 1. mated to be 50.48 kJ  mol . It is indicating that the second-order model was more Fig. 3 Correlation plots for the 1,3-butadiene thermal reaction, a first-order model; b second-order model Table 1 Kinetic parameters for the 1,3-butadiene thermal reaction T/K First order model Second order model –3 −1 2 −1 2 k × 10 /h Kinetic equation R k /(mol h) Kinetic equation R 1 1 −3 298 0.7504 ln n = − 0.7504 × 10 t − 9.106 0.9812 6.771 1/n = 6.771 t + 9007 0.9813 −3 303 1.055 ln n = − 1.055 × 10 t − 9.154 0.9186 9.999 1/n = 9.999 t + 9457 0.9190 −3 308 1.493 ln n = − 1.493 × 10 t − 9.156 0.9565 14.19 1/n = 14.19 t + 9469 0.9569 −3 313 2.149 ln n = − 2.149 × 10 t − 9.190 0.9599 19.98 1/n = 19.98 t + 9799 0.9689 −3 318 2.727 ln n = − 2.727 × 10 t − 9.215 0.9596 27.58 1/n = 27.58 t + 10,048 0.9602 −3 323 3.449 ln n = − 3.449 × 10 t − 9.098 0.9716 31.12 1/n = 31.12 t + 8938 0.9708 Liang  et al. BMC Chemistry (2022) 16:4 Page 5 of 12 β CH = CH−CH = CH hv, k products 2 2 2 −−−→ The general photolysis reaction rate expression (r ) could be written as dn BD β r =− = k n (6) 2 2 BD dt where k and β denote the rate constant and order of the photolysis reaction. Similar to the thermal reaction kinetics of 1,3-buta- diene, two kinds of kinetics model were plot in Fig.  5. The kinetic parameters of the 1,3-butadiene photo - reaction are shown in Table  2. It can be inferred from this data that the photolysis reaction follows a first- order kinetics. Rauchenwald et  al. reported a new −1 method of destroying waste anesthetic gases by using Fig. 4 The plot of ln k vs. T gas-phase photochemistry and the photochemistry exhaust gas destruction system exhibits a constant first-order removal rate [24]. Hu et  al. investigated the Photolysis kinetics of 1,3‑butadiene under ultraviolet VUV/UV photodegradation of three iodinated disin- irradiation fection byproducts followed pseudo-first-order kinet - The photochemical reaction of 1,3-butadiene can be rep - ics [25]. The 1,3-butadiene photolysis under 254  nm resented as follows: Fig. 5 Curves of 1,3-butadiene photolysis, a first-order model; b second-order model Table 2 Kinetic parameters of 1,3-butadiene photolysis T/K First order model Second order model –2 −1 2 −1 2 k × 10 /h Kinetic equation R k /(mol h) Kinetic equation R 2 2 –2 298 1.102 ln n = − 1.102 × 10 t − 7.394 0.9599 147.6 1/n = 147.6 t + 9460 0.9596 –2 303 1.282 ln n = − 1.282 × 10 t − 7.352 0.9714 160.2 1/n = 160.2 t + 8943 0.9706 –2 308 1.436 ln n = − 1.436 × 10 t − 7.412 0.9902 201.2 1/n = 201.2 t + 9686 0.9898 –2 313 1.574 ln n = − 1.574 × 10 t − 7.703 0.9729 170.4 1/n = 170.4 t + 7123 0.9650 –2 318 1.794 ln n = − 1.794 × 10 t − 7.526 0.9950 386.6 1/n = 386.6 t + 14,729 0.9792 –2 323 1.847 ln n = − 1.847 × 10 t − 7.175 0.9973 342.2 1/n = 342.2 t + 11,313 0.9857 Liang et al. BMC Chemistry (2022) 16:4 Page 6 of 12 Quantum yield of 1,3‑butadiene UV is well fitted by first-order kinetics. The activation The quantum yield (Φ) is the ratio of the amount of reac - energy of the photolysis process was calculated to be −1 tant to the number of Einstein absorbed in a certain time, 19.92 kJ  mol . which reflects the efficiency of a photochemical reaction In the photochemistry system, 1,3-butadiene simul- [32, 33]. The number of Einstein absorbed is defined as: taneously undergoes both thermal and photolysis reactions, under the combined action of the system (I − I )S 0 1 temperature and ultraviolet light intensity. However, R(t) = (7) N hV the rates of the thermal and photolysis reactions were different, according to the data in Tables  1 and 2: the where S is the irradiated area of 1,3-butadiene (3.5  cm ), thermal activation energy is approximately three times I and I denote the incident and transmitted light inten- 0 1 −2 larger than the photolysis one., so the rate of pho- sity (μW  cm ), respectively, N is the Avogadro’s num- tochemistry should be much greater than thermo- ber (6.023 × 10 ), V is the volume of 1,3-butadiene 3 −34 chemistry in theory [26]. The ultraviolet illumination (3.5  cm ), h is the Planck’s constant (6.63 × 10  J s), and efficiently promotes the 1,3-butadiene photoreaction. ν is the frequency of the UV light (ν = c/λ, with c = veloc- This could indicate that the photolysis would predomi - ity of light and λ = 254 nm). The amount of reactant was nate in the photochemistry system, and the thermal calculated according to the chemical reaction kinetics, reaction could thus be neglected in the kinetic calcula- giving tions. Therefore, we studied the 1,3-butadiene photoly - −dn /dt −k n sis under different ultraviolet intensities at 254 nm and BD 2 BD � = = (8) various temperatures. R(t) R(t) Quantum yield measurements were carried out at 303 K in nitrogen atmosphere. The initial quantum yield Eec ff t of light intensity on 1,3‑butadiene photoreaction of 1,3-butadiene is shown in Table  4; the data show that The irradiation intensity is an important factor that influ - Φ did not vary with the UV light intensity after the ini- ences the photoreaction activity of organic chemicals tial reaction stage, and its average value was 31.46. It [27]. Owing to their low cost and accessibility, 254 nm UV could be inferred that a radical produced by an activated lamp plays an important role in daily life and are widely 1,3-butadiene molecule may cause several molecules to used in disinfection [28] and degradation of organic spe- react, rather than only one molecule [34]. cies [29]. The maximum ultraviolet intensity of outdoor solar radiation at 254 nm was detected as approximately −2 30 μW  cm . Therefore, the effect of the light intensity Reaction products and pathways of 1,3‑butadiene on the 1,3-butadiene photoreaction was studied in the Another basic task in chemical kinetics is the study of temperature and light intensity ranges of 298–323 K and −2 the reaction process. This analysis can reveal the rela - 25–500 μW  cm , respectively. The effect of temperature tionship between the structure of a compound and its and ultraviolet intensity on the rate constant of the pho- ability to react, thereby providing a deeper understand- tochemical reactions is illustrated in Fig. 6. −2 ing of its chemical transformations. The comparison of The rate constant increased from 0.635 × 10 to −2 −1 the observed mass fragments with the GC–MS library 1.501 × 10  h when the ultraviolet intensity was −2 revealed the main products of the dimerization and pho- changed from 25 to 500  μW  cm at 298  K (Table  3). tolysis reaction of 1,3-butadiene (Figure S1). The relative The increase of the 1,3-butadiene rate constant with the content of the product was calculated by the peak area ultraviolet intensity is related to the fact that a higher normalization method. intensity enables the reactant molecules to gain suffi - As shown in Table  5, 1,2-divinylcyclobutane and cient energy to cross the energy barrier. As a result, an 4-vinylcyclohexene were the main products of the ther- enhanced reaction rate was obtained. The activation mal reaction of 1,3-butadiene under nitrogen atmos- energies for the 1,3-butadiene photoreaction calculated −1 phere. This result supports the findings of a previous from the Arrhenius Eq.  (5) were 19.92–43.65  kJ  mol , work [15]. 1,3-Butadiene was mainly dimerised at the ini- and decreased with increasing ultraviolet irradiation tial stage of the reaction, and the dimerization proceeded (Fig. 7a). A linear relationship was observed between the via the Diels–Alder reaction. The proposed reaction activation energy and the logarithm of the light intensity pathways shown in Fig. 8 are based on the present experi- (Fig. 7b); the corresponding equation could be expressed 2 mental results and previous studies [14, 15]. It should be as E = − 7.294·lnI + 66.15 (R = 0.9886). This shows that −1 noted that a rotational barrier of 20.10 kJ  mol separates the ultraviolet light intensity can be controlled to make the trans and cis isomers of 1,3-butadiene, which enables the reaction proceed in the preferred direction [30, 31]. Liang  et al. BMC Chemistry (2022) 16:4 Page 7 of 12 Fig. 6 Correlation plots of ln n vs. t for the photoreaction of 1,3-butadiene at different temperatures their rapid conversion [35]. In the dimerization pathway, radical intermediate [15]. The concerted mechanism sug - trans- and cis-butadiene will dimerise into 1,2-divinylcy- gests that the 1,3-butadiene monomers would directly clobutane and 4-vinylcyclohexene. These reactions pro - dimerise into the final product through an activated tran - ceed through the formation of the octa-1,7-diene-3,6-diyl sition state [36]. Liang et al. BMC Chemistry (2022) 16:4 Page 8 of 12 Table 3 Kinetic parameters for the photoreaction of 1,3-butadiene −2 –2 −1 −1 2 I/(μW  cm ) k × 10 /h E/(kJ  mol ) R 2 a 298 K 303 K 308 K 313 K 318 K 323 K 25 0.1635 0.2187 0.2973 0.4333 0.5333 0.5962 43.65 0.9821 50 0.2605 0.3112 0.3958 0.5642 0.6391 0.7764 36.49 0.9865 100 0.3879 0.4088 0.5113 0.6420 0.8020 1.004 31.96 0.9744 200 0.5395 0.6232 0.8182 0.9311 1.064 1.273 27.59 0.9901 300 0.7516 0.9006 1.038 1.146 1.501 1.638 25.26 0.9836 400 1.009 1.077 1.302 1.450 1.739 2.056 21.57 0.9863 500 1.501 1.721 1.974 2.260 2.477 2.804 19.92 0.9815 Fig. 7 Relationship curve for the activation energy with ultraviolet intensity. a E vs. I; b E vs. ln I a a irradiation time, in agreement with the kinetics analysis Table 4 The effect of varying ultraviolet intensity on the of the photolysis reaction (Figure S2). quantum yield (Φ) of 1,3-butadiene The photolysis reaction pathways are illustrated in −2 −1 Fig.  9. As discussed above, the variety of products that I/(μW  cm ) k /h I / I / I –I / Φ 2 0 1 0 1 −2 −2 −2 (μW  cm ) (μW  cm ) (μW  cm ) are formed in the direct photolysis originate from the subsequent photochemical processes. The absorption 25 0.001670 20 18.7 1.3 37.19 of ultraviolet irradiation by 1,3-butadiene would lead 50 0.002417 38 35.2 2.8 24.99 to the formation of an excited 1,3-butadiene molecule, 100 0.003418 72 69 3 32.99 which may be followed by collisional deactivation to the 200 0.005297 133 127 6 25.56 ground-state molecule, or rearrangement to an excited 300 0.007364 207 198 9 23.69 1,2-butadiene molecule. The latter may either decom - 400 0.009555 280 272 8 34.58 pose or be deactivated to a stable  1,2-butadiene mole- 500 0.01282 351 342 9 41.24 cule through a collision. The main sources for acetylene and ethylene appear to be the excited 1,3-butadiene and 1,2-butadiene molecules. Furthermore, the excited In contrast, 1,3-butadiene yielded widely differ - 1,2-butadiene molecule would decompose into CH • and ent products under ultraviolet irradiation at 254  nm, C H • radicals [37]. The secondary reactions of CH • rad- 3 3 3 including ethylene, acetylene, cyclobutene, 1-butyne, icals may include recombination to yield ethane [38, 39]. and 1,2-butadiene, as shown in Table  6. The yields The reaction of the C H • radical is slightly more com- 3 3 of the various volatile products increased with the plicated, due to its uncertain structure. In particular, this Liang  et al. BMC Chemistry (2022) 16:4 Page 9 of 12 Table 5 Main identified products of 1,3-butadiene in the thermal reaction No. Name Molecular formula Relative amount/% Similarity/% 1 1,3-butadiene CH = CH–CH = CH 79.84 98 2 2 2 1,2-divinylcyclobutane 0.66 94 3 4-vinycyclohexene 19.50 97 cyclobutene molecule. And then it would be deactivated to a stable cyclobutene molecule through a collision [40]. Photolysis and photodimerization reactions of 1,3‑butadiene We also observed that the photolysis of 1,3-butadiene at 254  nm in the absence of any photosensitizer was markedly different from the 1,3-butadiene dimeriza - tion at 254  nm and from the dimerization initiated by a triplet sensitizer. A possible explanation for this differ - Fig. 8 Thermal reaction pathways of 1,3-butadiene ence might be that the ultraviolet light acted directly on 1,3-butadiene in the gas phase, causing it to undergo a decomposition reaction [20, 41]. According to the first law of photochemistry, only light absorption by mol- radical can adopt two types of structures, C H = C = CH• ecules can effectively lead to photochemical changes and •CH –C≡CH, whose reaction with CH • radicals 2 3 [42]. A photochemical reaction can only proceed when would yield 1,2-butadiene and 1-butyne, respectively. the energy required for the molecule to jump from the Although both products have been detected in our meas- ground to the excited state matches the energy of the urements, only the presence of the •CH –C≡CH struc- photon [43]. 1,3-Butadiene has four π molecular orbitals: ture could be confirmed, while that of the CH = C = CH• the lowest two are full, while the other two, with higher structure was uncertain, because the source of 1,2-buta- energies, are empty. The lowest-energy electron transi - diene could be the collision-induced deactivation of the tion of 1,3-butadiene occurs from the π to π * orbital 2 3 excited 1,2-butadiene molecules [38]. In addition, the at 220  nm, which means that a minimum energy of photolysis of 1,3-butadiene in the gas phase also leads to −1 544 kJ  mol is required for the electron transition [44]. the formation of an isomeric product, i.e., cyclobutene. Compared with this energy, the transition energy corre- The excited 1,3-butadiene molecule are scrambled by sponding to the 254  nm irradiation is not high enough, structural isomerization reactions leading to an excited but the energy difference between the two wavelengths is Table 6 Main identified products of 1,3-butadiene in the photolysis reaction No. Name Molecular formula Relative amount/% Similarity/% Irradiation time (h) 1 2 3 4 5 1 Ethylene H C = CH 1.72 1.82 2.23 3.18 4.35 99 2 2 2 Acetylene HC≡CH 1.07 1.23 1.80 2.45 99 3 Cyclobutene 2.63 3.69 4.50 6.56 7.91 92 4 1-Butyne CH –CH –HC≡CH 0.37 0.45 0.68 0.78 89 3 2 5 1,2-Butadiene CH –CH = C = CH 7.33 7.86 10.28 17.44 18.11 98 3 2 6 1,3-Butadiene CH = CH–CH = CH 88.31 85.19 81.31 70.34 66.40 98 2 2 Liang et al. BMC Chemistry (2022) 16:4 Page 10 of 12 Fig. 9 Photolysis reaction pathways of 1,3-butadiene −1 ethylene involved 1,3-hydrogen migration from the ter- only 73 kJ  mol . Thus, when the irradiation time is long minal CH group via a transition state, followed by C–C enough, the absorbed light can also break the chemical bond cleavage. The energy of the transition state calcu - bonds in the 1,3-butadiene backbone to trigger the pho- −1 lated at the G2M level of theory was 366.1 kJ  mol . The tolysis reaction. The generation of photolysis products −1 C H + C H products reside ~ 167.36  kJ  mol above also proves that gaseous 1,3-butadiene is expected to 2 2 2 4 1,3-butadiene. Li et al. carried out ab initio CASSCF cal- absorb light at 254 nm, and the reduction in light inten- culations to locate transition structures for the dimeriza- sity is not caused by surface reflections of the container. tion of 1,3-butadiene [47]. 1,3-Butadiene was found to In addition, the photochemistry of 1,3-butadiene in solu- undergo a Diels–Alder reaction to form 4-vinylcyclohex- tion, which corresponds to the reaction at very high pres- ene via a transition structure, with a measured activation sures, yielded none of the main volatile products. An –1 energy of 422.17 kJ  mol . The comparison of the activa - increase in the gas pressure led to a decreased yield of all tion energies indicated that photodecomposition is more volatile products; these yields would drop to zero at suf- likely to occur than photodimerization. ficiently high pressures [20]. Sensitizers have been employed to provide an excited triplet state for 1,3-butadiene to form ring compounds Conclusions instead of cracking [17]. The presence of the sensitizers We investigated the reactions and kinetics of gaseous makes the cycloaddition reaction easier than the pho- 1,3-butadiene under 254  nm ultraviolet irradiation in tolysis. At an optimum concentration, photodimerization nitrogen atmosphere at the temperature range from accounted for less than 10% of the butadiene consump- 298 to 323  K. We demonstrated a conceptually differ - tion, and the yield of dimers in the triplet-sensitised ent and practical approach for the quantitative analysis reaction was nearly 75%. The main photodimerization of gaseous 1,3-butadiene by UV–vis spectrophotometry products were 1,2-divinylcyclobutane, 4-vinylcyclohex- in a closed gaseous mini–reactor. Kinetic experiments ene, and 2-vinylbicyclo[3.1.0]hexane. Approximately 8% were performed both without and with UV irradiation of the products consisted of 1,5-cyclooctadiene, which of 1,3-butadiene, yielding activation energies of 50.48 has been reported as a product of the triplet-sensitised −1 and 19.92–43.65 kJ  mol , respectively, which indicated reaction [45]. that UV irradiation could accelerate the reaction rate of Accurate ab initio calculations of potential energy sur- 1,3-butadiene. Moreover, the possible reaction pathways faces for the dissociation and dimerization pathways of for the photolysis process were discussed in combination 1,3-butadiene are highly complementary to experimen- with the identified products. The differences between the tal studies of the photodissociation dynamics, because dimerization and dissociation processes of 1,3-butadiene they provide insight into possible reaction products and under ultraviolet irradiation were elucidated by combin their energies, as well as into various reaction mecha- ing experimental and theoretical methods. In summary, nisms leading to these products. Lee et al. used high-level this study provides a feasible approach for the analysis of ab  initio calculations to investigate the reaction mecha- gaseous products by UV–vis spectrophotometry, paving nism of the photodissociation of 1,3-butadiene [46]. the way for a more complete understanding of the photo- The photodissociation of 1,3-butadiene to acetylene and chemical reactions of 1,3-butadiene. Liang  et al. BMC Chemistry (2022) 16:4 Page 11 of 12 7. Ricci G, Forni A, Boglia A. New chromium(II) bidentate phosphine com- Supplementary Information plexes: synthesis, characterization, and behavior in the polymerization of The online version contains supplementary material available at https:// doi. 1,3-butadiene. Organometallics. 2004;23(15):3727–32. org/ 10. 1186/ s13065- 022- 00800-6. 8. Braithwaite B, Penketh GE. Iodometric determination of butadiene pol- yperoxide. Anal Chem. 1967;39(12):1470–1. 9. Alexander DS. Explosions in butadiene systems. Ind Eng Chem. Additional file 1: Figure S1. Total ion flow diagram of 1,3-butadiene 1959;51(6):733–8. thermal reaction products measured by GC-MS. Figure S2. Total ion flow 10. Klais O. Hydrogen peroxide decomposition in the presence of organic diagram of 1,3-butadiene photolysis reaction products measured by material: a case study. Thermochim Acta. 1993;225(2):213–22. GC-MS. 11. Goncalves LC, Gonzalez-Aguilar G, Frazao O, Baptista JM, Jorge P. Chemi- cal sensing by differential thermal analysis with a digitally controlled fiber optic interferometer. Rev Sci Instrum. 2013;84(1):662–8. Acknowledgements 12. Zhang CX, Lu GB, Chen LP, Chen WH, Peng MJ, Lv JY. Two decoupling This work was supported by the National Natural Science Foundation of China methods for non-isothermal DSC results of AIBN decomposition. J Hazard (21776050), National Institute of Advanced Industrial Science and Technology Mater. 2015;285:61–8. Fellowship of Japan, Major Science and Technology Special Project in Guangxi 13. Hendry DG, Mayo FR, Jones DA, Schuetzle D. Stability of butadiene (AA17204087-20), Innovation training program of Guangxi Zhuang Autono- polyperoxide. Ind Eng Chem Prod Res Dev. 1968;7(2):145–51. mous Region (R2030042001). 14. Liu P, Liu X, Saburi T, Kubota S, Wada Y. Thermal characteristics and hazard of 1,3-butadiene (BD) polymerization and oxidation. Thermochim Acta. Authors’ contributions 2020; 691:178713. https:// doi. org/ 10. 1016/j. tca. 2020. 178713. CY, FL and GL contributed to the method design and equipment improve- 15. Aldeeb AA, Rogers WJ, Mannan MS. Evaluation of 1,3-butadiene dimeriza- ment. ML, SD and HC performed the experiments and collected data. ML, LM tion and secondary reactions in the presence and absence of oxygen. J and XL coordinated the study and wrote the manuscript. All authors read and Hazard Mater. 2004;115(1/3):51–6. approved the final manuscript. 16. Hammond GS, Liu R. Stereoisomeric triplet states of conjugated dienes. J Am Chem Soc. 1963;85(4):477–8. Funding 17. Hammond GS, Turro NJ, Liu R. Mechanisms of photochemical reactions in Major Science and Technology Special Project in Guangxi, AA17204087-20. solution. XVI.1 Photosensitized dimerization of conjugated dienes. J Org National Natural Science Foundation of China, 21776050. National Institute of Chem. 1963;28(12):3297–303. Advanced Industrial Science and Technology Fellowship of Japan. 18. Hammond GS, Turro NJ, Fischer A. Photosensitized cycloaddition reac- tions. J Am Chem Soc. 1961;83(22):4674–5. Availability of data and materials 19. Turro NJ, Hammond GS. The photosensitited dimerization of cyclopenta- All data generated or analysed during this study are included in this published diene. J Am Chem Soc. 2002;84(14):2841–2. article (and its Additional files). 20. Haller I, Srinivasan R. Photochemistry of 1,3-butadiene: details of the primary processes and mechanism of photopolymerization. J Chem Phys. Declarations 1964;40(7):1992–7. 21. Panchapornpon D, Pengon S, Chinatangkul N, Chevadisaikul T. Validation Ethics approval and consent to participate of UV-Vis spectrophotometric method for stability evaluation of 5% Not applicable. extemporaneous vancomycin eye drops in various vehicles. Key Eng Mater. 2020;859:277–82. Consent for publication 22. Shi Z, Chow C, Fabris R, Liu J, Jin B. 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Reactivity and kinetics of 1,3-butadiene under ultraviolet irradiation at 254nm

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Abstract

The reaction process of gaseous 1,3-butadiene following ultraviolet irradiation at the temperature range from 298 to 323 K under nitrogen atmosphere was monitored by UV–vis spectrophotometry. A gaseous mini-reactor was used as a reaction vessel and could be directly monitored in a UV–vis spectrophotometer. We investigated the reactivity and kinetics of 1,3-butadiene under non-UV and UV irradiation to evaluate its photochemical stability. A second-order –1 kinetic model with 50.48 kJ·mol activation energy fitted the reaction data for non-UV irradiation, whereas a first- –1 order kinetic model was appropriate in the case of UV irradiation with activation energies of 19.92–43.65 kJ mol . This indicates that ultraviolet light could accelerate the photolysis reaction rate of 1,3-butadiene. In addition, the reaction products were determined using gas chromatography-mass spectrometry (GC–MS), and the reaction pathways were identified. The photolysis of 1,3-butadiene gave rise to various volatile products by cleavage and rearrangement of single C–C bonds. The differences between dimerization and dissociation of 1,3-butadiene under ultraviolet irradia- tion were elucidated by combining experimental and theoretical methods. The present findings provide fundamental insight into the photochemistry of 1,3-butadiene compounds. Keywords: 1,3-butadiene, Photolysis, Reaction kinetics, Ultraviolet irradiation determine the sensitivity of 1,3-butadiene polyperoxides Introduction using the standard drop weight method [13]. The results As an important organic precursor, 1,3-butadiene is showed that a low-energy shock could cause rapid com- widely used in the production of polybutadiene and bustion, while a high-energy shock would produce a ther- other copolymers, such as cis-polybutadiene rubber [1, mal explosion. Various types of calorimeters were used 2], neoprene, and styrene-butadiene polymers [3–5]. to study the thermal polymerization of 1,3-butadiene. Owing to conjugation effects [6], 1,3-butadiene is prone The thermal characteristics and hazards associated with to polymerize to form polymers and polyperoxides upon 1,3-butadiene were studied using an accelerated calorim- contact with light, heat, and oxygen in air [7], resulting eter (ARC) [14]. The thermal dimerization and polym - in reduced performance and limiting its applications. erization reactions of 1,3-butadiene in the presence and Polyperoxides were reported to be impact-sensitive and absence of oxygen were evaluated to assess its thermal thermally unstable, and slow deposition over some time reactivity and runaway behavior using theoretical com- can lead to highly hazardous conditions in 1,3-buta- putational models and thermal analysis techniques [15]. diene plants [8]. Many serious explosion accidents An automated pressure-tracking adiabatic calorimeter have occurred during the production of 1,3-butadiene (APTAC ) was used for measuring the overall thermo- [9–12]. Hendry et  al. conducted impact experiments to dynamic and kinetic parameters. In addition to thermal polymerization, the UV-based photopolymerization processes of 1,3-butadiene have *Correspondence: gxumali@126.com; xmliu1@gxu.edu.cn School of Chemistry and Chemical Engineering, Guangxi University, also been extensively studied in the past decades. Earlier Nanning 530004, China © The Author(s) 2022. Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http:// creat iveco mmons. org/ licen ses/ by/4. 0/. The Creative Commons Public Domain Dedication waiver (http:// creat iveco mmons. org/ publi cdoma in/ zero/1. 0/) applies to the data made available in this article, unless otherwise stated in a credit line to the data. Liang et al. BMC Chemistry (2022) 16:4 Page 2 of 12 reports [16–19] showed that irradiation of solutions obtained from Guangxi Guoxin Gas Research Co., Ltd., containing conjugated dienes and various photosensi- China. tizers led to the formation of dimers of the dienes. The photochemistry of 1,3-butadiene in solution yielded Photochemistry of 1,3‑butadiene none of the main volatile products that were observed A sealed threaded quartz colorimetric dish (volume in the vapor phase but produced only cyclobutene, bicy- 3.5  mL, Yixing Spectral Analysis Optical Components clo[1.1.0]butane, dimers, and a polymer [20]. In addition Co., Ltd., China) was used both as a gaseous ultraviolet to the photopolymerization products, some decompo- mini-reactor and sample cell, which could be analyzed sition products, such as ethylene and acetylene were directly to avoid the errors associated with intermediate also detected the above study. However, photopolym- extraction. Before each experimental measurement, the erization and photolysis reactions involve two different reactor was first evacuated and simultaneously passed mechanisms. The origin of the coexistence of these two through fresh nitrogen for not less than 5  min to flush competing mechanisms under ultraviolet light irradiation out all oxygen. The required trace amount of gaseous is worthy of further investigation by a combination theo- 1,3-butadiene was injected into the reactor using a gas retical and experimental methods. However, the specific micro-sampling syringe. Homogeneous mixing of the requirements and testing procedures make the experi- reactants in the reactor was carried out before starting mental analysis tedious and expensive. A more practi- the experiment. For quantitative analysis of 1,3-butadi- cal and simpler experimental analysis method should be ene, the reactor was placed into a UV–vis spectropho- employed, such as UV–vis spectrophotometry. On the tometer (UV-2550, Shimadzu Instruments Co., Ltd., other hand, the importance of the reaction rate in chemi- Japan) at preselected time intervals. Then, the reactor cal production is self-evident. Understanding the effects was transferred into a constant-temperature box to main- of various factors on the reaction rate facilitates the tain the temperature at the desired value (other than selection of the conditions required to make the chemi- room temperature). A schematic diagram of the experi- cal reaction proceed at the desired rate. This highlights ment is shown in Fig. 1. The photochemical reaction was the crucial importance of investigating the kinetics of the performed at different temperatures (298, 303, 308, 313, photochemical reactions of gaseous 1,3-butadiene. 318, 323  K) for 5  h. The light source was a low-pressure In this work, the reactions of gaseous 1,3-butadiene UV lamp (Philips, TUV G6T5, 6  W) with maximum under UV irradiation in nitrogen atmosphere at low tem- emission at 254  nm, which was placed on the top of the perature were carried out in a gaseous ultraviolet mini- constant-temperature box. The light intensity of the UV −2 reactor. A UV–vis spectrophotometer was employed to lamp was between 25 and 500  μW  cm , as measured monitor the reaction process. In order to clarify the influ - by a UV-C ultraviolet radiometer (Shanghai Baoshan ence of 254  nm UV light on the 1,3-butadiene reaction Gucun Optic Instrument Factory, Shanghai, China) in rate constants during the photochemical reaction, the air. The intensity of the ultraviolet radiation was varied by reaction rate constants and activation energy obtained adjusting the distance between the lamp and the reactor. in absence of irradiation were used as reference. To Dynamic data processing was carried out using the itera- understand the reactivity of 1,3-butadiene under ultra- tive method (Additional file 1). violet irradiation, we studied the relationship between UV intensities and reaction rate constants. In addition, Qualitative analysis of reaction products the reaction products were analyzed by gas chromatog- The main products of the thermal and photochemi - raphy–mass spectrometry (GC–MS), and the possible cal reactions of 1,3-butadiene were qualitatively ana- mechanisms of the photochemical reaction of 1,3-buta- lyzed by GC–MS (GC/MS-QP2010 Ultra, SHIMADZU, diene were systematically examined. The results were Japan) using an Agilent J&W advanced capillary column compared with the reaction mechanisms reported in the (30  m × 0.25  mm × 5.00  μm) and an electron impact previous studies. The differences between the photolysis ionization detector (EID, 70  eV). The analytical proce - and photodimerization pathways for 1,3-butadiene under dures were as follows: the temperature was maintained 254 nm irradiation are also discussed in detail. at 333  K for 1  min, then increased to 373  K at a rate of −1 3 K  min , and kept for 3 min. The carrier gas was ultra - −1 high pure helium at a constant flow rate of 4.0 mL  min . The injection temperature and volume were maintained Material and methods at 373 K and 1.0 mL, respectively; the split ratio was 30:1, Materials while the interface and ion source temperatures were set 1,3-Butadiene (mass purity > 99.90%, molecular weight –1 at 473 and 493  K, respectively. A quadrupole mass filter 54.09 g  mol ) was obtained from Guangdong Walter was used with a m/z range of 18–300 in full-scan mode. Gas Co., Ltd., China. N gas (mass purity > 99.99%) was 2 Liang  et al. BMC Chemistry (2022) 16:4 Page 3 of 12 Fig. 1 Schematic diagram of the research The detected peaks were identified based on the National Institute of Standards and Technology 2011 library of mass spectra. Qualitative analysis of the products was based on the cracking patterns and retention times observed in the mass spectrometry and gas chromatogra- phy analyses, respectively. Results and discussion Quantitative analysis of 1,3‑butadiene by UV–vis spectrophotometry UV–vis spectrophotometry is widely employed for the quantitative determination of the concentration of liq- uids [21, 22]; however, it has rarely been applied to the analysis of other states of matter, such as gas. Therefore, in this study we aimed to fill this gap by using UV–vis Fig. 2 UV spectra of 1,3-butadiene reaction process. a 1,3-butadiene; b thermal products of 1,3-butadiene; c photoreaction products of spectrophotometry for the quantitative analysis of gase- 1,3-butadiene; d blank reactor ous 1,3-butadiene. The experimental results are shown in Fig.  2. 1,3-Butadiene showed an obvious absorption peak with a maximum at 209  nm, due to the ultraviolet Thermal reaction kinetics of 1,3‑butadiene absorption of conjugated double bonds. Figure 2d shows In order to clarify the influence of ultraviolet light on that the reactor cell did not affect the process under the reaction constants during the photochemical pro- experimental conditions. Therefore, quantitative analy - cess, we first analysed the reaction in absence of ultra - sis was performed spectrophotometrically by monitoring violet illumination, that is, the thermal reaction. A the decay of the strong absorbance peak of 1,3-butadiene detailed kinetic analysis was performed to assess the at 209 nm. Figure 2b, c suggest that the absorption of the effect of the temperature on the rate of the thermal thermal and photoreaction products of 1,3-butadiene reaction of 1,3-butadiene. To simplify the kinetic equa- was negligible, because they showed almost no absorb- tions and the calculation of the related parameters, ance within the same wavelength range. The working gaseous 1,3-butadiene was considered to be uniformly equation for the quantitative analysis of 1,3-butadiene, distributed in the reactor. as determined by the external standard method, was 4 2 The thermal reaction of 1,3-butadiene was assumed to y = 0.4672 × 10 x + 0.1026 (R = 0.9996), where y and x proceed as follows: represent the absorbance and amount (mol) of 1,3-buta- diene, respectively. Then, the molar amount of 1,3-buta - α CH = CH−CH = CH k products 2 2 1 −→ diene was calculated from the working curve equation. This approach provides a new route for the quantitative The reaction rate (r ) of 1,3-butadiene could be analysis of other gases as well. expressed as Liang et al. BMC Chemistry (2022) 16:4 Page 4 of 12 suitable for describing the 1,3-butadiene thermal reac- dn BD r =− = k n (1) 1 1 BD tion than the first-order model, suggesting that the ther - dt mal reaction of 1,3-butadiene is more like a second-order where k represents the kinetic rate constant of the ther- reaction. This is consistent with previous research [23]. It mal reaction, t is the reaction time (h), n is the amount BD was suggested that the dimerization process followed a of 1,3-butadiene (mol) at time t, and α denotes the ther- second-order kinetics in the temperature range from 298 mal reaction order. Based on Eq.  (1), the calculated val- to 323 K. ues were fitted to different models via a trial-and-error The activation energies (E ) could be estimated using method: i.e., a is first-order [Eq.  (2)] or second-order the Arrhenius equation: [Eq.  (3)]. We compared the correlation coefficient R to k = A exp(−E /RT ) 0 a (4) confirm the reaction order: where k is the rate constant, R is the gas constant ln n =−k t + C (2) BD 1 −1 [8.314  J·(mol  K) ], A is the frequency factor, and T is the absolute temperature. Taking the natural logarithm of =−k t + C (3) both sides of Eq. (4), we obtain BD where C is a constant. ln k =− + ln A (5) RT The experimental ln n vs. t or 1/n vs. t plots show a −1 linear relationship, corresponding to the correct rate Plots of ln k vs. T consisted of a straight line (Fig. 4), equation, and the rate constant was thus obtained from whose slope was used to calculate the activation energy the slope of the regression line. The results are shown in of the thermal reaction of 1,3-butadiene, which was esti- −1 Fig. 3 and the kinetic parameters are displayed in Table 1. mated to be 50.48 kJ  mol . It is indicating that the second-order model was more Fig. 3 Correlation plots for the 1,3-butadiene thermal reaction, a first-order model; b second-order model Table 1 Kinetic parameters for the 1,3-butadiene thermal reaction T/K First order model Second order model –3 −1 2 −1 2 k × 10 /h Kinetic equation R k /(mol h) Kinetic equation R 1 1 −3 298 0.7504 ln n = − 0.7504 × 10 t − 9.106 0.9812 6.771 1/n = 6.771 t + 9007 0.9813 −3 303 1.055 ln n = − 1.055 × 10 t − 9.154 0.9186 9.999 1/n = 9.999 t + 9457 0.9190 −3 308 1.493 ln n = − 1.493 × 10 t − 9.156 0.9565 14.19 1/n = 14.19 t + 9469 0.9569 −3 313 2.149 ln n = − 2.149 × 10 t − 9.190 0.9599 19.98 1/n = 19.98 t + 9799 0.9689 −3 318 2.727 ln n = − 2.727 × 10 t − 9.215 0.9596 27.58 1/n = 27.58 t + 10,048 0.9602 −3 323 3.449 ln n = − 3.449 × 10 t − 9.098 0.9716 31.12 1/n = 31.12 t + 8938 0.9708 Liang  et al. BMC Chemistry (2022) 16:4 Page 5 of 12 β CH = CH−CH = CH hv, k products 2 2 2 −−−→ The general photolysis reaction rate expression (r ) could be written as dn BD β r =− = k n (6) 2 2 BD dt where k and β denote the rate constant and order of the photolysis reaction. Similar to the thermal reaction kinetics of 1,3-buta- diene, two kinds of kinetics model were plot in Fig.  5. The kinetic parameters of the 1,3-butadiene photo - reaction are shown in Table  2. It can be inferred from this data that the photolysis reaction follows a first- order kinetics. Rauchenwald et  al. reported a new −1 method of destroying waste anesthetic gases by using Fig. 4 The plot of ln k vs. T gas-phase photochemistry and the photochemistry exhaust gas destruction system exhibits a constant first-order removal rate [24]. Hu et  al. investigated the Photolysis kinetics of 1,3‑butadiene under ultraviolet VUV/UV photodegradation of three iodinated disin- irradiation fection byproducts followed pseudo-first-order kinet - The photochemical reaction of 1,3-butadiene can be rep - ics [25]. The 1,3-butadiene photolysis under 254  nm resented as follows: Fig. 5 Curves of 1,3-butadiene photolysis, a first-order model; b second-order model Table 2 Kinetic parameters of 1,3-butadiene photolysis T/K First order model Second order model –2 −1 2 −1 2 k × 10 /h Kinetic equation R k /(mol h) Kinetic equation R 2 2 –2 298 1.102 ln n = − 1.102 × 10 t − 7.394 0.9599 147.6 1/n = 147.6 t + 9460 0.9596 –2 303 1.282 ln n = − 1.282 × 10 t − 7.352 0.9714 160.2 1/n = 160.2 t + 8943 0.9706 –2 308 1.436 ln n = − 1.436 × 10 t − 7.412 0.9902 201.2 1/n = 201.2 t + 9686 0.9898 –2 313 1.574 ln n = − 1.574 × 10 t − 7.703 0.9729 170.4 1/n = 170.4 t + 7123 0.9650 –2 318 1.794 ln n = − 1.794 × 10 t − 7.526 0.9950 386.6 1/n = 386.6 t + 14,729 0.9792 –2 323 1.847 ln n = − 1.847 × 10 t − 7.175 0.9973 342.2 1/n = 342.2 t + 11,313 0.9857 Liang et al. BMC Chemistry (2022) 16:4 Page 6 of 12 Quantum yield of 1,3‑butadiene UV is well fitted by first-order kinetics. The activation The quantum yield (Φ) is the ratio of the amount of reac - energy of the photolysis process was calculated to be −1 tant to the number of Einstein absorbed in a certain time, 19.92 kJ  mol . which reflects the efficiency of a photochemical reaction In the photochemistry system, 1,3-butadiene simul- [32, 33]. The number of Einstein absorbed is defined as: taneously undergoes both thermal and photolysis reactions, under the combined action of the system (I − I )S 0 1 temperature and ultraviolet light intensity. However, R(t) = (7) N hV the rates of the thermal and photolysis reactions were different, according to the data in Tables  1 and 2: the where S is the irradiated area of 1,3-butadiene (3.5  cm ), thermal activation energy is approximately three times I and I denote the incident and transmitted light inten- 0 1 −2 larger than the photolysis one., so the rate of pho- sity (μW  cm ), respectively, N is the Avogadro’s num- tochemistry should be much greater than thermo- ber (6.023 × 10 ), V is the volume of 1,3-butadiene 3 −34 chemistry in theory [26]. The ultraviolet illumination (3.5  cm ), h is the Planck’s constant (6.63 × 10  J s), and efficiently promotes the 1,3-butadiene photoreaction. ν is the frequency of the UV light (ν = c/λ, with c = veloc- This could indicate that the photolysis would predomi - ity of light and λ = 254 nm). The amount of reactant was nate in the photochemistry system, and the thermal calculated according to the chemical reaction kinetics, reaction could thus be neglected in the kinetic calcula- giving tions. Therefore, we studied the 1,3-butadiene photoly - −dn /dt −k n sis under different ultraviolet intensities at 254 nm and BD 2 BD � = = (8) various temperatures. R(t) R(t) Quantum yield measurements were carried out at 303 K in nitrogen atmosphere. The initial quantum yield Eec ff t of light intensity on 1,3‑butadiene photoreaction of 1,3-butadiene is shown in Table  4; the data show that The irradiation intensity is an important factor that influ - Φ did not vary with the UV light intensity after the ini- ences the photoreaction activity of organic chemicals tial reaction stage, and its average value was 31.46. It [27]. Owing to their low cost and accessibility, 254 nm UV could be inferred that a radical produced by an activated lamp plays an important role in daily life and are widely 1,3-butadiene molecule may cause several molecules to used in disinfection [28] and degradation of organic spe- react, rather than only one molecule [34]. cies [29]. The maximum ultraviolet intensity of outdoor solar radiation at 254 nm was detected as approximately −2 30 μW  cm . Therefore, the effect of the light intensity Reaction products and pathways of 1,3‑butadiene on the 1,3-butadiene photoreaction was studied in the Another basic task in chemical kinetics is the study of temperature and light intensity ranges of 298–323 K and −2 the reaction process. This analysis can reveal the rela - 25–500 μW  cm , respectively. The effect of temperature tionship between the structure of a compound and its and ultraviolet intensity on the rate constant of the pho- ability to react, thereby providing a deeper understand- tochemical reactions is illustrated in Fig. 6. −2 ing of its chemical transformations. The comparison of The rate constant increased from 0.635 × 10 to −2 −1 the observed mass fragments with the GC–MS library 1.501 × 10  h when the ultraviolet intensity was −2 revealed the main products of the dimerization and pho- changed from 25 to 500  μW  cm at 298  K (Table  3). tolysis reaction of 1,3-butadiene (Figure S1). The relative The increase of the 1,3-butadiene rate constant with the content of the product was calculated by the peak area ultraviolet intensity is related to the fact that a higher normalization method. intensity enables the reactant molecules to gain suffi - As shown in Table  5, 1,2-divinylcyclobutane and cient energy to cross the energy barrier. As a result, an 4-vinylcyclohexene were the main products of the ther- enhanced reaction rate was obtained. The activation mal reaction of 1,3-butadiene under nitrogen atmos- energies for the 1,3-butadiene photoreaction calculated −1 phere. This result supports the findings of a previous from the Arrhenius Eq.  (5) were 19.92–43.65  kJ  mol , work [15]. 1,3-Butadiene was mainly dimerised at the ini- and decreased with increasing ultraviolet irradiation tial stage of the reaction, and the dimerization proceeded (Fig. 7a). A linear relationship was observed between the via the Diels–Alder reaction. The proposed reaction activation energy and the logarithm of the light intensity pathways shown in Fig. 8 are based on the present experi- (Fig. 7b); the corresponding equation could be expressed 2 mental results and previous studies [14, 15]. It should be as E = − 7.294·lnI + 66.15 (R = 0.9886). This shows that −1 noted that a rotational barrier of 20.10 kJ  mol separates the ultraviolet light intensity can be controlled to make the trans and cis isomers of 1,3-butadiene, which enables the reaction proceed in the preferred direction [30, 31]. Liang  et al. BMC Chemistry (2022) 16:4 Page 7 of 12 Fig. 6 Correlation plots of ln n vs. t for the photoreaction of 1,3-butadiene at different temperatures their rapid conversion [35]. In the dimerization pathway, radical intermediate [15]. The concerted mechanism sug - trans- and cis-butadiene will dimerise into 1,2-divinylcy- gests that the 1,3-butadiene monomers would directly clobutane and 4-vinylcyclohexene. These reactions pro - dimerise into the final product through an activated tran - ceed through the formation of the octa-1,7-diene-3,6-diyl sition state [36]. Liang et al. BMC Chemistry (2022) 16:4 Page 8 of 12 Table 3 Kinetic parameters for the photoreaction of 1,3-butadiene −2 –2 −1 −1 2 I/(μW  cm ) k × 10 /h E/(kJ  mol ) R 2 a 298 K 303 K 308 K 313 K 318 K 323 K 25 0.1635 0.2187 0.2973 0.4333 0.5333 0.5962 43.65 0.9821 50 0.2605 0.3112 0.3958 0.5642 0.6391 0.7764 36.49 0.9865 100 0.3879 0.4088 0.5113 0.6420 0.8020 1.004 31.96 0.9744 200 0.5395 0.6232 0.8182 0.9311 1.064 1.273 27.59 0.9901 300 0.7516 0.9006 1.038 1.146 1.501 1.638 25.26 0.9836 400 1.009 1.077 1.302 1.450 1.739 2.056 21.57 0.9863 500 1.501 1.721 1.974 2.260 2.477 2.804 19.92 0.9815 Fig. 7 Relationship curve for the activation energy with ultraviolet intensity. a E vs. I; b E vs. ln I a a irradiation time, in agreement with the kinetics analysis Table 4 The effect of varying ultraviolet intensity on the of the photolysis reaction (Figure S2). quantum yield (Φ) of 1,3-butadiene The photolysis reaction pathways are illustrated in −2 −1 Fig.  9. As discussed above, the variety of products that I/(μW  cm ) k /h I / I / I –I / Φ 2 0 1 0 1 −2 −2 −2 (μW  cm ) (μW  cm ) (μW  cm ) are formed in the direct photolysis originate from the subsequent photochemical processes. The absorption 25 0.001670 20 18.7 1.3 37.19 of ultraviolet irradiation by 1,3-butadiene would lead 50 0.002417 38 35.2 2.8 24.99 to the formation of an excited 1,3-butadiene molecule, 100 0.003418 72 69 3 32.99 which may be followed by collisional deactivation to the 200 0.005297 133 127 6 25.56 ground-state molecule, or rearrangement to an excited 300 0.007364 207 198 9 23.69 1,2-butadiene molecule. The latter may either decom - 400 0.009555 280 272 8 34.58 pose or be deactivated to a stable  1,2-butadiene mole- 500 0.01282 351 342 9 41.24 cule through a collision. The main sources for acetylene and ethylene appear to be the excited 1,3-butadiene and 1,2-butadiene molecules. Furthermore, the excited In contrast, 1,3-butadiene yielded widely differ - 1,2-butadiene molecule would decompose into CH • and ent products under ultraviolet irradiation at 254  nm, C H • radicals [37]. The secondary reactions of CH • rad- 3 3 3 including ethylene, acetylene, cyclobutene, 1-butyne, icals may include recombination to yield ethane [38, 39]. and 1,2-butadiene, as shown in Table  6. The yields The reaction of the C H • radical is slightly more com- 3 3 of the various volatile products increased with the plicated, due to its uncertain structure. In particular, this Liang  et al. BMC Chemistry (2022) 16:4 Page 9 of 12 Table 5 Main identified products of 1,3-butadiene in the thermal reaction No. Name Molecular formula Relative amount/% Similarity/% 1 1,3-butadiene CH = CH–CH = CH 79.84 98 2 2 2 1,2-divinylcyclobutane 0.66 94 3 4-vinycyclohexene 19.50 97 cyclobutene molecule. And then it would be deactivated to a stable cyclobutene molecule through a collision [40]. Photolysis and photodimerization reactions of 1,3‑butadiene We also observed that the photolysis of 1,3-butadiene at 254  nm in the absence of any photosensitizer was markedly different from the 1,3-butadiene dimeriza - tion at 254  nm and from the dimerization initiated by a triplet sensitizer. A possible explanation for this differ - Fig. 8 Thermal reaction pathways of 1,3-butadiene ence might be that the ultraviolet light acted directly on 1,3-butadiene in the gas phase, causing it to undergo a decomposition reaction [20, 41]. According to the first law of photochemistry, only light absorption by mol- radical can adopt two types of structures, C H = C = CH• ecules can effectively lead to photochemical changes and •CH –C≡CH, whose reaction with CH • radicals 2 3 [42]. A photochemical reaction can only proceed when would yield 1,2-butadiene and 1-butyne, respectively. the energy required for the molecule to jump from the Although both products have been detected in our meas- ground to the excited state matches the energy of the urements, only the presence of the •CH –C≡CH struc- photon [43]. 1,3-Butadiene has four π molecular orbitals: ture could be confirmed, while that of the CH = C = CH• the lowest two are full, while the other two, with higher structure was uncertain, because the source of 1,2-buta- energies, are empty. The lowest-energy electron transi - diene could be the collision-induced deactivation of the tion of 1,3-butadiene occurs from the π to π * orbital 2 3 excited 1,2-butadiene molecules [38]. In addition, the at 220  nm, which means that a minimum energy of photolysis of 1,3-butadiene in the gas phase also leads to −1 544 kJ  mol is required for the electron transition [44]. the formation of an isomeric product, i.e., cyclobutene. Compared with this energy, the transition energy corre- The excited 1,3-butadiene molecule are scrambled by sponding to the 254  nm irradiation is not high enough, structural isomerization reactions leading to an excited but the energy difference between the two wavelengths is Table 6 Main identified products of 1,3-butadiene in the photolysis reaction No. Name Molecular formula Relative amount/% Similarity/% Irradiation time (h) 1 2 3 4 5 1 Ethylene H C = CH 1.72 1.82 2.23 3.18 4.35 99 2 2 2 Acetylene HC≡CH 1.07 1.23 1.80 2.45 99 3 Cyclobutene 2.63 3.69 4.50 6.56 7.91 92 4 1-Butyne CH –CH –HC≡CH 0.37 0.45 0.68 0.78 89 3 2 5 1,2-Butadiene CH –CH = C = CH 7.33 7.86 10.28 17.44 18.11 98 3 2 6 1,3-Butadiene CH = CH–CH = CH 88.31 85.19 81.31 70.34 66.40 98 2 2 Liang et al. BMC Chemistry (2022) 16:4 Page 10 of 12 Fig. 9 Photolysis reaction pathways of 1,3-butadiene −1 ethylene involved 1,3-hydrogen migration from the ter- only 73 kJ  mol . Thus, when the irradiation time is long minal CH group via a transition state, followed by C–C enough, the absorbed light can also break the chemical bond cleavage. The energy of the transition state calcu - bonds in the 1,3-butadiene backbone to trigger the pho- −1 lated at the G2M level of theory was 366.1 kJ  mol . The tolysis reaction. The generation of photolysis products −1 C H + C H products reside ~ 167.36  kJ  mol above also proves that gaseous 1,3-butadiene is expected to 2 2 2 4 1,3-butadiene. Li et al. carried out ab initio CASSCF cal- absorb light at 254 nm, and the reduction in light inten- culations to locate transition structures for the dimeriza- sity is not caused by surface reflections of the container. tion of 1,3-butadiene [47]. 1,3-Butadiene was found to In addition, the photochemistry of 1,3-butadiene in solu- undergo a Diels–Alder reaction to form 4-vinylcyclohex- tion, which corresponds to the reaction at very high pres- ene via a transition structure, with a measured activation sures, yielded none of the main volatile products. An –1 energy of 422.17 kJ  mol . The comparison of the activa - increase in the gas pressure led to a decreased yield of all tion energies indicated that photodecomposition is more volatile products; these yields would drop to zero at suf- likely to occur than photodimerization. ficiently high pressures [20]. Sensitizers have been employed to provide an excited triplet state for 1,3-butadiene to form ring compounds Conclusions instead of cracking [17]. The presence of the sensitizers We investigated the reactions and kinetics of gaseous makes the cycloaddition reaction easier than the pho- 1,3-butadiene under 254  nm ultraviolet irradiation in tolysis. At an optimum concentration, photodimerization nitrogen atmosphere at the temperature range from accounted for less than 10% of the butadiene consump- 298 to 323  K. We demonstrated a conceptually differ - tion, and the yield of dimers in the triplet-sensitised ent and practical approach for the quantitative analysis reaction was nearly 75%. The main photodimerization of gaseous 1,3-butadiene by UV–vis spectrophotometry products were 1,2-divinylcyclobutane, 4-vinylcyclohex- in a closed gaseous mini–reactor. Kinetic experiments ene, and 2-vinylbicyclo[3.1.0]hexane. Approximately 8% were performed both without and with UV irradiation of the products consisted of 1,5-cyclooctadiene, which of 1,3-butadiene, yielding activation energies of 50.48 has been reported as a product of the triplet-sensitised −1 and 19.92–43.65 kJ  mol , respectively, which indicated reaction [45]. that UV irradiation could accelerate the reaction rate of Accurate ab initio calculations of potential energy sur- 1,3-butadiene. Moreover, the possible reaction pathways faces for the dissociation and dimerization pathways of for the photolysis process were discussed in combination 1,3-butadiene are highly complementary to experimen- with the identified products. The differences between the tal studies of the photodissociation dynamics, because dimerization and dissociation processes of 1,3-butadiene they provide insight into possible reaction products and under ultraviolet irradiation were elucidated by combin their energies, as well as into various reaction mecha- ing experimental and theoretical methods. In summary, nisms leading to these products. Lee et al. used high-level this study provides a feasible approach for the analysis of ab  initio calculations to investigate the reaction mecha- gaseous products by UV–vis spectrophotometry, paving nism of the photodissociation of 1,3-butadiene [46]. the way for a more complete understanding of the photo- The photodissociation of 1,3-butadiene to acetylene and chemical reactions of 1,3-butadiene. Liang  et al. BMC Chemistry (2022) 16:4 Page 11 of 12 7. Ricci G, Forni A, Boglia A. 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BMC ChemistrySpringer Journals

Published: Feb 18, 2022

Keywords: 1,3-butadiene; Photolysis; Reaction kinetics; Ultraviolet irradiation

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