Rate of Sulfonation of Alpha-Olef1n by Gaseous So3 Using Pulse Method

Miyauchi, Terukatsu; Kikuchi, Tetsuji; Ogoshi, Toshiaki; Susuki, Rinnosuke; Kataoka, Hiroshi

doi:10.1252/jcej.4.44

Cited by 4 publications

(3 citation statements)

References 3 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Figure 1 shows one of these plots (for the run at 200°C), and Table 2 lists the k obs values with their 95% confidence limits and statistical data. Figure 2 shows the Arrhenius plot of ln k vs. 1/T (T in deg K and k in s −1 has the following equation: [3] This equation can be rearranged, with some rounding off, to [4] where T is in °C and k is in s −1 . Equation 4 enables k to be calculated for any temperature and makes it possible to estimate N(SO 2 ,t), the number of moles of SO 2 evolved when N(LASH 0 ) moles of LASH are heated for t s at T (°C):…”

Section: Resultsmentioning

confidence: 99%

Chemistry and kinetics of LAS acid thermal decomposition

Roberts

Lejeune

2002

J Surfact & Detergents

View full text Add to dashboard Cite

The emission of sulfur dioxide (SO 2 ) from linear alkylbenzene sulfonate (LAS) acid (LASH) at high temperatures has been studied. Rate constants and Arrhenius parameters have been determined, enabling estimation of the amount of SO 2 evolved under any time/temperature combination for risk assessment purposes. Further analysis of the kinetic data and comparison with earlier molecular modeling work on the mechanism of sulfonation of linear alkyl benzene (LAB) to make LASH provide insight into the reaction pathway of SO 2 formation by thermal decomposition of LASH. For risk assessment purposes, the calculation is as follows: Estimate k from k = 3.9 × 10 7 ·e −13,000/(273+T) where T is in degrees C and k is in s −1 . Estimate N(SO 2 ,t), the number of moles of SO 2 evolved when N(LASH 0 ) moles of LASH are heated for t s at T°C, from:Paper no. S1254 in JSD 5, 111-115 (April 2002).KEY WORDS: Color formation, sulfonation, sulfur dioxide, sulfur trioxide.When working with linear alkylbenzene sulfonate (LAS) acid (LASH) we have often observed an odor of sulfur dioxide (SO 2 ), particularly at high temperatures. Formation of SO 2 from LASH does not appear to have been investigated previously. We therefore carried out kinetic studies to understand the nature of the chemical reactions involved and to enable the prediction of the SO 2 emission for any LASH heating situation.In the present work a series of experiments was carried out to measure the amounts of SO 2 released on heating LASH at temperatures between 170 and 220°C. MATERIALS AND METHODSLASH was obtained from the sulfonation plant at the Lever Fabergé factory in Port Sunlight (Wirral, United Kingdom). LASH (ca. 3.5 g) was heated in a two-necked flask at a fixed temperature (ranging from 180 to 220°C). A continuous stream of nitrogen was passed into the flask, and the exiting gas was passed through a Drechsel bottle containing 100 mL 0.1 M NaOH, to collect any SO 2 and convert it to sodium sulfite. At various time intervals the Drechsel bottle was replaced and the contents analyzed for sodium sulfite by addition of excess iodine followed by back-titration with sodium thiosulfate solution. RESULTSThe results from kinetic experiments in which LASH was heated at temperatures ranging from 180 to 220°C are presented in Table 1.The nature of the organic reactions was not known when the work started. The two most likely possibilities were:NMR and IR spectra of the nonvolatile residue after the reaction showed no evidence of phenolic OH groups and indicated that the major component was LAB, i.e., the reaction occurring is shown in Equation 1, desulfonation.First-order kinetic analysis. The simplest way to analyze data of the type shown in Table 1 is by first-order rate plots, for which in this case ln(100 − %SO 2 ) is the appropriate function to be plotted against time. These plots give reasonably straight lines whose slopes are the first-order or pseudo firstorder rate constants k obs . Figure 1 shows one of these plots (for the run at 200°C), and Table 2 lists the k obs ...

show abstract

Section: Resultsmentioning

confidence: 99%

Chemistry and kinetics of LAS acid thermal decomposition

Roberts

Lejeune

2002

J Surfact & Detergents

View full text Add to dashboard Cite

show abstract

“…This could be an indication that the RHF geometries are, in this case, quite different from the MP2 optimized geometries. The gas phase results clearly do not match the experimental data, particularly for the closely related reaction of octadec-1-ene with sulfur trioxide to form the corresponding octadecane sultone, 28 which has an experimentally determined activation energy of 6.22 kcal mol Ϫ1 .…”

Section: Mechanism Of the Addition Reactionmentioning

confidence: 89%

“…These results are now more consistent with the experimentally determined activation energy of 6.22 kcal mol Ϫ1 for the related reaction of octadec-1-ene with sulfur trioxide. 28 However, solvent appears to have a smaller effect on the energy of the corresponding transition state derived from the reaction of tetrafluoroethene with sulfur trioxide, as the transition state is only stabilized by 2.04 and 4.93 kcal mol Ϫ1 on moving from a relative permittivity of 1.48 to 3.11 (Table 6), possibly because the van der Waals radius of fluorine is larger than that of hydrogen (1.35 versus 1.20 Å), 14 resulting in a smaller stabilizing interaction energy at the surface.…”

Section: Mechanism Of the Addition Reactionmentioning

confidence: 99%