Fire and explosion hazards of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide.

Ionic liquids (ILs) have very low volatility and are consequently considered as a green replacement to the organic solvents that have been widely used to date. The fire and explosion hazards of traditional organic solvents primarily depend on the combustibility of their vapors; therefore, ILs have been regarded as nonflammable for a long time because of their low volatility. However, recent studies have shown that ILs are flammable due to their thermal stability and consequently, the fire and explosion hazards of ILs limit their practical applications. The compound 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (abbreviated as [EMIM][Tf2N]) has been considered a potential candidate solvent for surfactant systems, but studies about the fire and explosion hazards of this IL are rare in the literature. In this study, the fire and explosion hazards of [EMIM][Tf2N] were explored in terms of different aspects. The auto-ignition temperature of [EMIM][Tf2N] was found to be 478 °C with an ignition delay time of 12.6 s. It was observed with the TGA/DSC system that the decomposition of [EMIM][Tf2N] was endothermic in a nitrogen atmosphere but exothermic in an air atmosphere. The dynamic TGA curves showed that the apparent activation energies were the same in both nitrogen and air atmospheres, but the dynamic DSC curves showed that the apparent activation energies were different in nitrogen and air atmospheres. The apparent activation energy inferred from the DSC curve in an air atmosphere was found to be the same as the apparent activation energy estimated by the Semenov theory of thermal ignition. Analysis of the gaseous decomposition products of [EMIM][Tf2N] by the TGA-FTIR system indicated that the exothermal effect in the air atmosphere was caused by the auto-ignition of acetylene (which is one of the gaseous decomposition products) and not by decomposition itself.

Evaluating Molecular Properties Involved in Transport of Small Molecules in Stratum Corneum: A Quantitative Structure-Activity Relationship for Skin Permeability.

The skin permeability (Kp) defines the rate of a chemical penetrating across the stratum corneum. This value is widely used to quantitatively describe the transport of molecules in the outermost layer of epidermal skin and indicate the significance of skin absorption. This study defined a Kp quantitative structure-activity relationship (QSAR) based on 106 chemical substances of Kp measured using human skin and interpreted the molecular interactions underlying transport behavior of small molecules in the stratum corneum. The Kp QSAR developed in this study identified four molecular descriptors that described the molecular cyclicity in the molecule reflecting local geometrical environments, topological distances between pairs of oxygen and chlorine atoms, lipophilicity, and similarity to antineoplastics in molecular properties. This Kp QSAR considered the octanol-water partition coefficient to be a direct influence on transdermal movement of molecules. Moreover, the Kp QSAR identified a sub-domain of molecular properties initially defined to describe the antineoplastic resemblance of a compound as a significant factor in affecting transdermal permeation of solutes. This finding suggests that the influence of molecular size on the chemical's skin-permeating capability should be interpreted with other relevant physicochemical properties rather than being represented by molecular weight alone.

Effect of joint mobilization techniques for primary total knee arthroplasty: Study protocol for a randomized controlled trial.

BACKGROUND: Total knee arthroplasty (TKA) has become the most preferred procedure by patients for the relief of pain caused by knee osteoarthritis. TKA patients aim a speedy recovery after the surgery. Joint mobilization techniques for rehabilitation have been widely used to relieve pain and improve joint mobility. However, relevant randomized controlled trials showing the curative effect of these techniques remain lacking to date. Accordingly, this study aims to investigate whether joint mobilization techniques are valid for primary TKA. METHODS/DESIGN: We will manage a single-blind, prospective, randomized, controlled trial of 120 patients with unilateral TKA. Patients will be randomized into an intervention group, a physical modality therapy group, and a usual care group. The intervention group will undergo joint mobilization manipulation treatment once a day and regular training twice a day for a month. The physical modality therapy group will undergo physical therapy once a day and regular training twice a day for a month. The usual care group will perform regular training twice a day for a month. Primary outcome measures will be based on the visual analog scale, the knee joint Hospital for Special Surgery score, range of motion, surrounded degree, and adverse effect. Secondary indicators will include manual muscle testing, 36-Item Short Form Health Survey, Berg Balance Scale function evaluation, Pittsburgh Sleep Quality Index, proprioception, and muscle morphology. We will direct intention-to-treat analysis if a subject withdraws from the trial. DISCUSSION: The important features of this trial for joint mobilization techniques in primary TKA are randomization procedures, single-blind, large sample size, and standardized protocol. This study aims to investigate whether joint mobilization techniques are effective for early TKA patients. The result of this study may serve as a guide for TKA patients, medical personnel, and healthcare decision makers. TRIAL REGISTRATION: It has been registered at http://www.chictr.org.cn/showproj.aspx?proj=15262 (Identifier:ChiCTR-IOR-16009192), Registered 11 September 2016. We also could provide the correct URL of the online registry in the WHO Trial Registration. http://apps.who.int/trialsearch/Trial2.aspx?TrialID=ChiCTR-IOR-16009192.

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.