Calculating the partition coefficients of organic solvents in octanol/water and octanol/air

Partition coefficients define how a solute is distributed between two immiscible phases at equilibrium. The experimental estimation of partition coefficients in a complex system can be an expensive, difficult, and time-consuming process. Here a computational strategy to predict the distributions of a set of solutes in two relevant phase equilibria is presented. The octanol/water and octanol/air partition coefficients are predicted for a group of polar solvents using density functional theory (DFT) calculations in combination with a solvation model based on density (SMD) and are in excellent agreement with experimental data. Thus, the use of quantum-chemical calculations to predict partition coefficients from free energies should be a valuable alternative for unknown solvents. The obtained results indicate that the SMD continuum model in conjunction with any of the three DFT functionals (B3LYP, M06-2X, and M11) agrees with the observed experimental values. The ighest correlation to experimental data for the octanol/water partition coefficients was reached by the M11 functional; for the octanol/air partition coefficient, the M06-2X functional yielded the best performance. To the best of our knowledge, this is the first computational approach for the rediction of octanol/air partition coefficients by DFT calculations, which has remarkable accuracy and precision

Searching for solvents with an increased carbon dioxide solubility using multivariate statistics

Ionic liquids (ILs) are used in various fields of chemistry. One of them is CO2 capture, a process that is quite well described. The solubility of CO2 in ILs can be used as a model to investigate gas absorption processes. The aim is to find the relationships between the solubility of CO2 and other variables—physicochemical properties and parameters related to greenness. In this study, 12 variables are used to describe a dataset consisting of 26 ILs and 16 molecular solvents. We used a cluster analysis, a principal component analysis, and a K-means hierarchical clustering to find the patterns in the dataset and the discriminators between the clusters of compounds. The results showed that ILs and molecular solvents form two well-separated groups, and the variables were well separated into greenness-related and physicochemical properties. Such patterns suggest that the modeling of greenness properties and of the solubility of CO2 on physicochemical properties can be difficult

How to evaluate methods used in chemical laboratories in terms of the total chemical risk? : a ChlorTox Scale

Reliable assessment of the health and environmental risk associated with the use of chemicals is critical to objectively evaluate the greenness and whiteness of an analytical method. An objective and useful way of risk assessment should take into account all the relevant properties of used substances, their actual amounts needed for application of the method, and quantify the assessment result using a standardized unit. This article presents a relatively simple approach to meet the above requirements, which we call the Chloroform-oriented Toxicity Estimation Scale (ChlorTox Scale). The risk posed by a given substance is expressed by the ChlorTox value, and the sum of the values obtained for all reagents is the overall risk posed by the method (Total ChlorTox). The ChlorTox value is calculated by comparing the hazards for the substance being assessed to the standard – chloroform, using the approach selected by the user as optimal, taking into account the amount of a pure substance needed for single analysis. The ChlorTox unit is the equivalent mass of chloroform which reflects the estimated degree of predicted risk. This tool can be used for risk assessment in laboratories of various profiles

Overview of the three multicriteria approaches applied to a global assessment of analytical methods

[EN] Critical and global evaluation of analytical methods should be one of the primary goals in analytical chemistry. A holistic approach, however, requires a look at the varied features: commonly discussed validation criteria, often underrated practical and economic aspects, and typically overlooked compliance with the principles of green analytical chemistry. Carrying out such an assessment in a critical and transparent way is extremely difficult without special tools. The purpose of this work is to discuss and compare the three different approaches that seem to be potential candidates: multi-criteria decision analysis methods (MCDA), HEXAGON, and RGB model. The basic principles of each methodology, individual possibilities offered, and the results of the assessment of selected model methods will be presented. Ultimately, the potential compatibility of assessing the same group of methods using different tools will be examined. This contribution can help to select optimal tool and conduct more thorough and insightful assessments

Tools and techniques for solvent selection: green solvent selection guides

Driven by legislation and evolving attitudes towards environmental issues, establishing green solvents for extractions, separations, formulations and reaction chemistry has become an increasingly important area of research. Several general purpose solvent selection guides have now been published with the aim to reduce use of the most hazardous solvents. This review serves the purpose of explaining the role of these guides, highlighting their similarities and differences. How they can be used most effectively to enhance the greenness of chemical processes, particularly in laboratory organic synthesis and the pharmaceutical industry, is addressed in detail

River water quality assessment using environmentric techniques : case study of Jakara River Basin.

akara River Basin has been extensively studied to assess the overall water quality and to identify the major variables responsible for water quality variations in the basin. A total of 27 sampling points were selected in the riverine network of the Upper Jakara River Basin. Water samples were collected in triplicate and analyzed for physicochemical variables. Pearson product-moment correlation analysis was conducted to evaluate the relationship of water quality parameters and revealed a significant relationship between salinity, conductivity with dissolved solids (DS) and 5-day biochemical oxygen demand (BOD5), chemical oxygen demand (COD), and nitrogen in form of ammonia (NH4). Partial correlation analysis (r p) results showed that there is a strong relationship between salinity and turbidity (r p = 0.930, p = 0.001) and BOD5 and COD (r p = 0.839, p = 0.001) controlling for the linear effects of conductivity and NH4, respectively. Principal component analysis and or factor analysis was used to investigate the origin of each water quality parameter in the Jakara Basin and identified three major factors explaining 68.11 % of the total variance in water quality. The major variations are related to anthropogenic activities (irrigation agricultural, construction activities, clearing of land, and domestic waste disposal) and natural processes (erosion of river bank and runoff). Discriminant analysis (DA) was applied on the dataset to maximize the similarities between group relative to within-group variance of the parameters. DA provided better results with great discriminatory ability using eight variables (DO, BOD5, COD, SS, NH4, conductivity, salinity, and DS) as the most statistically significantly responsible for surface water quality variation in the area. The present study, however, makes several noteworthy contributions to the existing knowledge on the spatial variations of surface water quality and is believed to serve as a baseline data for further studies. Future research should therefore concentrate on the investigation of temporal variations of water quality in the basin

Novel Desorber for Online Drilling Mud Gas Logging

This work presents the construction solution and experimental results of a novel desorber for online drilling mud gas logging. The traditional desorbers use mechanical mixing of the liquid to stimulate transfer of hydrocarbons to the gaseous phase that is further analyzed. The presented approach is based on transfer of hydrocarbons from the liquid to the gas bubbles flowing through it and further gas analysis. The desorber was checked for gas logging from four different drilling muds collected from Polish boreholes. The results of optimization studies are also presented in this study. The comparison of the novel desorber with a commercial one reveals strong advantages of the novel one. It is characterized by much better hydrocarbons recovery efficiency and allows reaching lower limits of detection of the whole analytical system. The presented desorber seems to be very attractive alternative over widely used mechanical desorbers

Determination of chlorinated solvents in industrial water and wastewater by DAI–GC–ECD

A very simple and quick analytical method, based on direct aqueous injection, for determination of halogenated solvents in refinery water and wastewater, is described. There is a need to determine halogenated solvents in refinery water streams, because they may originate from several processes. There is also a need to develop methods enabling VOX to be determined in samples containing oil fractions. The method described enables simultaneous determination of 26 compounds with low detection limits (sub-μg L−1) and excellent precision, especially for highly halogenated solvents. The matrix effects of four types of sample were evaluated—the method seemed to be relatively insensitive to variations in matrix composition. Deuterated 1,2-dichloroethane was used as internal standard and surrogate compound in quantitative analysis; application of isotopically labelled compounds is rarely reported when non-mass spectrometric detectors are used for analysis. Analysis of real samples showed that the most frequently detected compounds were dichloromethane and 1,2-dichloroethane

Pre-selection and assessment of green organic solvents by clustering chemometric tools

The study presents the result of the application of chemometric tools for selection of physicochemical parameters of solvents for predicting missing variables - bioconcentration factors, water-octanol and octanol-air partitioning constants. EPI Suite software was successfully applied to predict missing values for solvents commonly considered as 'green'. Values for logBCF, logKOW and logKOA were modelled for 43 rather nonpolar solvents and 69 polar ones. Application of multivariate statistics was also proved to be useful in the assessment of the obtained modelling results. The presented approach can be one of the first steps and support tools in the assessment of chemicals in terms of their greenness