Increased flammability hazard when ionic liquid [C6mim][Cl] is exposed to high temperatures.

Industrial use of ionic liquids may require exposure to high temperatures. We demonstrate that such applications may result in an increase in flammability hazard due to chemical decomposition. The ionic liquid, 1-hexyl-3-methylimidazolium chloride ([C6mim][Cl]), was selected as the study sample. The flash point and other properties were measured using a commercially available flash point analyzer, a thermogravimetric analyzer (TGA), Fourier transform infrared spectroscopy (FTIR), an integrated TGA-FTIR system, and pyrolysis-gas chromatography-mass spectrometer. We found that thermal decomposition occurred with the release of chloromethane, 1-chlorohexane, 1-hexene, 1-methylimidazole, and 1-hexylimidazole as [C6mim][Cl] was heated. Such decomposition changed the components of the residual liquid phase. Vaporization of the [C6mim][Cl] decomposition products increased the mass loss rate on TGA as [C6mim][Cl] was heated to high temperatures, resulting in a high concentration of flammable gases and a decrease in the flash point, which increased the flammability hazard.

Effect of stirring on the safety of flammable liquid mixtures.

Flash point is the most important variable employed to characterize fire and explosion hazard of liquids. The models developed for predicting the flash point of partially miscible mixtures in the literature to date are all based on the assumption of liquid-liquid equilibrium. In real-world environments, however, the liquid-liquid equilibrium assumption does not always hold, such as the collection or accumulation of waste solvents without stirring, where complete stirring for a period of time is usually used to ensure the liquid phases being in equilibrium. This study investigated the effect of stirring on the flash-point behavior of binary partially miscible mixtures. Two series of partially miscible binary mixtures were employed to elucidate the effect of stirring. The first series was aqueous-organic mixtures, including water+1-butanol, water+2-butanol, water+isobutanol, water+1-pentanol, and water+octane; the second series was the mixtures of two flammable solvents, which included methanol+decane, methanol+2,2,4-trimethylpentane, and methanol+octane. Results reveal that for binary aqueous-organic solutions the flash-point values of unstirred mixtures were located between those of the completely stirred mixtures and those of the flammable component. Therefore, risk assessment could be done based on the flammable component flash-point value. However, for the assurance of safety, it is suggested to completely stir those mixtures before handling to reduce the risk.

Nitrogen dilution effect on the flammability limits for hydrocarbons.

Theoretical models to predict the upper/lower flammability limits of hydrocarbons diluted with inert nitrogen gas are proposed in this study. It is found that there are linear relations between the reciprocal of the upper/lower flammability limits and the reciprocal of the molar fraction of hydrocarbon in the hydrocarbon/inert nitrogen mixture. Such linearity is examined by experimental data reported in the literature, which include the cases of methane, propane, ethylene and propylene. The R-squared values (R(2)) of the regression lines of the cases explored are all greater than 0.989 for upper flammability limit (UFL). The theoretical slope of the predictive line for lower flammability limit (LFL) is found to be very close to zero for all explored cases; and this result successfully explains the experimental fact that adding inert nitrogen to a flammable material has very limited effect on LFL. Because limit oxygen concentration (LOC) could be taken as the intersectional point of the UFL curve and LFL curve, a LOC-based method is proposed to predict the slope of the UFL curve when experimental data of UFL are not available. This LOC-based method predicts the UFL with average error ranging from 2.17% to 5.84% and maximum error ranging from 8.58% to 12.18% for the cases explored. The predictive models for inert gas of nitrogen are also extended to the case of inert gas other than nitrogen. Through the extended models, it was found that the inert ability of an inert gas depends on its mean molar heat capacity at the adiabatic flame temperature. Theoretical calculation shows that the inert abilities of carbon dioxide, steam, nitrogen and helium are in the following order: carbon dioxide>steam>nitrogen>helium; and this sequence conforms to the existing experimental data reported in the literature.

Prediction of autoignition temperatures of organic compounds by the structural group contribution approach.

A model to predict the autoignition temperatures (AIT) of organic compounds is proposed based on the structural group contribution (SGC) approach. This model has been built up using a 400-compound training set; the fitting ability for these training data is 0.8474, with an average error of 32K and an average error percentage of 4.9%. The predictive capability of the proposed model has been demonstrated on an 83-compound validation set; the predictive capability for these validation data is about 0.5361, with an average error of 70K and an average error percentage of 11.0%. The proposed model is shown to be more accurate than those of other published works. This improvement is largely attributed to the modifications of the group definitions for estimating the AIT instead of the type of empirical model chosen. Through the Q(2) value and hypothesis testing, it was found that the empirical model should be chosen as a polynomial of degree 3. As compared to the known errors in experimentally determining the AIT, the proposed method offers a reasonable estimate of the AIT for the organic compounds in the training set, and can also approximate the AIT for compounds whose AIT is as yet unknown or not readily available to within a reasonable accuracy.

Carbon dioxide dilution effect on flammability limits for hydrocarbons.

Theoretical models to predict the upper/lower flammability limits of a mixture composed of hydrocarbon and inert carbon dioxide are proposed in this study. It is found theoretically that there are linear relations between the reciprocal of the upper/lower flammability limits and the reciprocal of the molar fraction of hydrocarbon in the hydrocarbon/inert gas mixture. These theoretical linear relations are examined by existing experimental results reported in the literature, which include the cases of methane, propane, ethylene, and propylene. The coefficients of determination (R(2)) of the regression lines are found to be larger than 0.959 for all aforementioned cases. Thus, the proposed models are highly supported by existing experimental results. A preliminary study also shows the conclusions in present work have the possibility to extend to non-hydrocarbon flammable materials or to inert gas other than carbon dioxide. It is coincident that the theoretical model for the lower flammability limit (LFL) in present work is the same as the empirical model conjectured by Kondo et al.

Flash-point prediction for binary partially miscible mixtures of flammable solvents.

Flash point is the most important variable used to characterize fire and explosion hazard of liquids. Herein, partially miscible mixtures are presented within the context of liquid-liquid extraction processes. This paper describes development of a model for predicting the flash point of binary partially miscible mixtures of flammable solvents. To confirm the predictive efficacy of the derived flash points, the model was verified by comparing the predicted values with the experimental data for the studied mixtures: methanol+octane; methanol+decane; acetone+decane; methanol+2,2,4-trimethylpentane; and, ethanol+tetradecane. Our results reveal that immiscibility in the two liquid phases should not be ignored in the prediction of flash point. Overall, the predictive results of this proposed model describe the experimental data well. Based on this evidence, therefore, it appears reasonable to suggest potential application for our model in assessment of fire and explosion hazards, and development of inherently safer designs for chemical processes containing binary partially miscible mixtures of flammable solvents.

Binary mixtures exhibiting maximum flash-point behavior.

This study has demonstrated the existence of maximum flash-point solutions, where the maximum flash-point value is larger than those of the individual components. The behavior of such a solution has potential application in hazard reduction. The sufficient condition for a binary mixture to form such a maximum flash-point solution, and the equations to determine its composition and maximum flash point are proposed here, as these may be important in terms of hazard reduction. The sufficient condition and associated equations were verified by comparison with the experimental data. Our results reveal that this derived condition is satisfactory to establish that a liquid mixture is a maximum flash-point solution. The proposed equations may be successfully applied to estimate the composition and maximum flash-point value of such a mixture.

A non-ideal model for predicting the effect of dissolved salt on the flash point of solvent mixtures.

Flash point is one of the major quantities used to characterize the fire and explosion hazard of liquids. Herein, a liquid with dissolved salt is presented in a salt-distillation process for separating close-boiling or azeotropic systems. The addition of salts to a liquid may reduce fire and explosion hazard. In this study, we have modified a previously proposed model for predicting the flash point of miscible mixtures to extend its application to solvent/salt mixtures. This modified model was verified by comparison with the experimental data for organic solvent/salt and aqueous-organic solvent/salt mixtures to confirm its efficacy in terms of prediction of the flash points of these mixtures. The experimental results confirm marked increases in liquid flash point increment with addition of inorganic salts relative to supplementation with equivalent quantities of water. Based on this evidence, it appears reasonable to suggest potential application for the model in assessment of the fire and explosion hazard for solvent/salt mixtures and, further, that addition of inorganic salts may prove useful for hazard reduction in flammable liquids.

A general model for predicting the flash point of miscible mixtures.

A mathematical model is presented for predicting the flash point of miscible mixtures. This model is reducible and adequate for some specified systems as proposed previously. Except for multiple aqueous-organic solutions, the predictive capability of the reduced form for other miscible mixtures, including binary aqueous-organic solutions and flammables-only analogues, has been verified previously. The model was validated using the ternary aqueous-organic solutions, water+methanol+ethanol/isopropanol. The results of the study confirm that the model predicts the flash points of these solutions by utilizing the flash points of the individual components. Further, if the binary interaction parameters for a ternary aqueous-organic solution are not accessible, a model based upon the binary interaction parameters of the binary solutions may provide a very acceptable means of predicting the flash point for such a ternary solution through comparison of the predicted and experimental data, as demonstrated in this study.

The prediction of the flash point for binary aqueous-organic solutions.

A mathematical model, which may be used for predicting the flash point of aqueous-organic solutions, has been proposed and subsequently verified by experimentally-derived data. The results reveal that this model is able to precisely predict the flash point over the entire composition range of binary aqueous-organic solutions by way of utilizing the flash point data pertaining to the flammable component. The derivative of flash point with respect to composition (solution composition effect upon flash point) can be applied to process safety design/operation in order to identify as to whether the dilution of a flammable liquid solution with water is effective in reducing the fire and explosion hazard of the solution at a specified composition. Such a derivative equation was thus derived based upon the flash point prediction model referred to above and then verified by the application of experimentally-derived data.