Volatility (Chemistry)
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Determining Volatile Organic Carbon by Differential Scanning Calorimetry
DETERMINING VOLATILE ORGANIC CARBON BY DIFFERENTIAL SCANNING CALORIMETRY By Roger L. Blaine TA Instrument, Inc. Volatile Organic Carbons (VOCs) are known to have serious environmental effects. Because of these deleterious effects, large scale attempts are being made to measure, reduce and regulate VOC use and emission. The California EPA, for example, requires characterization of the total volatility of pesticides based upon a TGA loss-on-drying test method [1, 2]. In another move, countries of the European market have reached a protocol agreement to reduce and stabilize VOC emissions by the year 2000 to 70% of the 1991 values [3]. And recently the Swiss Federal Government has imposed a tax on the amount of VOC [4]. Such regulatory agreements require qualitative and quantitative tools to assess what is a VOC and how much is present in a given formulation. Chief targets for VOC action include the paints and coatings industries, agricultural pesticides and solvent cleaning processes. VOC’s are defined as those organic materials having a vapor pressure greater than 10 Pa at 20 °C or having corresponding volatility at other operating temperatures associated with industrial processes [3]. Differential scanning calorimetry (DSC) is a useful tool for screening for potential VOC candidates as well as the actual determination of vapor pressure of suspect materials. Both of these measurements are based on the determination of the boiling (or sublimation) temperature; the former under atmospheric conditions, the latter under reduced pressures. Figure 1 725 ° exo 180 C µ size: 10 l 580 prog: 10°C / min atm: N2 Heat Flow Heat Flow 2.25mPa 435 (326 psi) [ ----] Pressure (psi) endo 290 50 100 150 200 250 300 Temperature (°C) TA250 Nielson and co-workers [5] have observed that: • All organic solvents with boiling temperatures below 170 °C are classified as VOCs, and • No organics solvents with boiling temperatures greater than 260 °C are VOCs. -
Chapter 3 Equations of State
Chapter 3 Equations of State The simplest way to derive the Helmholtz function of a fluid is to directly integrate the equation of state with respect to volume (Sadus, 1992a, 1994). An equation of state can be applied to either vapour-liquid or supercritical phenomena without any conceptual difficulties. Therefore, in addition to liquid-liquid and vapour -liquid properties, it is also possible to determine transitions between these phenomena from the same inputs. All of the physical properties of the fluid except ideal gas are also simultaneously calculated. Many equations of state have been proposed in the literature with either an empirical, semi- empirical or theoretical basis. Comprehensive reviews can be found in the works of Martin (1979), Gubbins (1983), Anderko (1990), Sandler (1994), Economou and Donohue (1996), Wei and Sadus (2000) and Sengers et al. (2000). The van der Waals equation of state (1873) was the first equation to predict vapour-liquid coexistence. Later, the Redlich-Kwong equation of state (Redlich and Kwong, 1949) improved the accuracy of the van der Waals equation by proposing a temperature dependence for the attractive term. Soave (1972) and Peng and Robinson (1976) proposed additional modifications of the Redlich-Kwong equation to more accurately predict the vapour pressure, liquid density, and equilibria ratios. Guggenheim (1965) and Carnahan and Starling (1969) modified the repulsive term of van der Waals equation of state and obtained more accurate expressions for hard sphere systems. Christoforakos and Franck (1986) modified both the attractive and repulsive terms of van der Waals equation of state. Boublik (1981) extended the Carnahan-Starling hard sphere term to obtain an accurate equation for hard convex geometries. -
Molecular Corridors and Parameterizations of Volatility in the Chemical Evolution of Organic Aerosols
Atmos. Chem. Phys., 16, 3327–3344, 2016 www.atmos-chem-phys.net/16/3327/2016/ doi:10.5194/acp-16-3327-2016 © Author(s) 2016. CC Attribution 3.0 License. Molecular corridors and parameterizations of volatility in the chemical evolution of organic aerosols Ying Li1,2, Ulrich Pöschl1, and Manabu Shiraiwa1 1Multiphase Chemistry Department, Max Planck Institute for Chemistry, Mainz, Germany 2State Key Laboratory of Atmospheric Boundary Layer Physics and Atmospheric Chemistry (LAPC), Institute of Atmospheric Physics, Chinese Academy of Sciences, Beijing, China Correspondence to: Manabu Shiraiwa ([email protected]) Received: 23 September 2015 – Published in Atmos. Chem. Phys. Discuss.: 15 October 2015 Revised: 1 March 2016 – Accepted: 3 March 2016 – Published: 14 March 2016 Abstract. The formation and aging of organic aerosols (OA) 1 Introduction proceed through multiple steps of chemical reaction and mass transport in the gas and particle phases, which is chal- lenging for the interpretation of field measurements and lab- Organic aerosols (OA) consist of a myriad of chemical oratory experiments as well as accurate representation of species and account for a substantial mass fraction (20–90 %) OA evolution in atmospheric aerosol models. Based on data of the total submicron particles in the troposphere (Jimenez from over 30 000 compounds, we show that organic com- et al., 2009; Nizkorodov et al., 2011). They influence regional pounds with a wide variety of functional groups fall into and global climate by affecting radiative budget of the at- molecular corridors, characterized by a tight inverse cor- mosphere and serving as nuclei for cloud droplets and ice relation between molar mass and volatility. -
Liquid-Vapor Equilibrium in a Binary System
Liquid-Vapor Equilibria in Binary Systems1 Purpose The purpose of this experiment is to study a binary liquid-vapor equilibrium of chloroform and acetone. Measurements of liquid and vapor compositions will be made by refractometry. The data will be treated according to equilibrium thermodynamic considerations, which are developed in the theory section. Theory Consider a liquid-gas equilibrium involving more than one species. By definition, an ideal solution is one in which the vapor pressure of a particular component is proportional to the mole fraction of that component in the liquid phase over the entire range of mole fractions. Note that no distinction is made between solute and solvent. The proportionality constant is the vapor pressure of the pure material. Empirically it has been found that in very dilute solutions the vapor pressure of solvent (major component) is proportional to the mole fraction X of the solvent. The proportionality constant is the vapor pressure, po, of the pure solvent. This rule is called Raoult's law: o (1) psolvent = p solvent Xsolvent for Xsolvent = 1 For a truly ideal solution, this law should apply over the entire range of compositions. However, as Xsolvent decreases, a point will generally be reached where the vapor pressure no longer follows the ideal relationship. Similarly, if we consider the solute in an ideal solution, then Eq.(1) should be valid. Experimentally, it is generally found that for dilute real solutions the following relationship is obeyed: psolute=K Xsolute for Xsolute<< 1 (2) where K is a constant but not equal to the vapor pressure of pure solute. -
Distillation Theory
Chapter 2 Distillation Theory by Ivar J. Halvorsen and Sigurd Skogestad Norwegian University of Science and Technology Department of Chemical Engineering 7491 Trondheim, Norway This is a revised version of an article published in the Encyclopedia of Separation Science by Aca- demic Press Ltd. (2000). The article gives some of the basics of distillation theory and its purpose is to provide basic understanding and some tools for simple hand calculations of distillation col- umns. The methods presented here can be used to obtain simple estimates and to check more rigorous computations. NTNU Dr. ing. Thesis 2001:43 Ivar J. Halvorsen 28 2.1 Introduction Distillation is a very old separation technology for separating liquid mixtures that can be traced back to the chemists in Alexandria in the first century A.D. Today distillation is the most important industrial separation technology. It is particu- larly well suited for high purity separations since any degree of separation can be obtained with a fixed energy consumption by increasing the number of equilib- rium stages. To describe the degree of separation between two components in a column or in a column section, we introduce the separation factor: ()⁄ xL xH S = ------------------------T (2.1) ()x ⁄ x L H B where x denotes mole fraction of a component, subscript L denotes light compo- nent, H heavy component, T denotes the top of the section, and B the bottom. It is relatively straightforward to derive models of distillation columns based on almost any degree of detail, and also to use such models to simulate the behaviour on a computer. -
Effect of Pressure on Distillation Separation Operation
Solutions for R&D to Design PreFEED Effect of Pressure on Distillation Separation Operation April 30, 2012 PreFEED Corporation Hiromasa Taguchi Solutions for R&D to Design 1 PreFEED Introduction Generally, it is known that, for distillation, separation tends to be enhanced by lower pressures. For two components, the ease of distillation separation can be judged from the value of the relative volatility (α). Here, we will take typical substances as examples and examine the effect of pressure changes on their relative volatilities. Solutions for R&D to Design 2 PreFEED Ideal Solution System The relative volatility (α) is a ratio of vapor-liquid equilibrium ratios and can be expressed by the following equation: K1 y1 y2 K1 , K2 K2 x1 x2 In the case of an ideal solution system , using Raoult’s law, the relative volatility can be expressed as a ratio of vapor pressures. Py x Po 1 1 1 Raoult’s law Py x Po o 2 2 2 K1 P1 y Po o K 1 1 K2 P2 1 x1 P o y2 P2 K2 x2 P Solutions for R&D to Design 3 PreFEED Methanol-Ethanol System As an example of an ideal solution system , let’s consider a methanol-ethanol binary system. α is calculated by obtaining vapor pressures from the Antoine constants in the table below. 0 B 2.8 ln(Pi [Pa]) A 2.6 C T[K] 2.4 ABC 2.2 Methanol 23.4803 3626.55 -34.29 2 Ethanol 23.8047 3803.98 -41.68 1.8 As the temperature (saturated 1.6 pressure) decreases, the value of 1.4 α increases. -
Understanding Vapor Diffusion and Condensation
uilding enclosure assemblies temperature is the temperature at which the moisture content, age, temperature, and serve a variety of functions RH of the air would be 100%. This is also other factors. Vapor resistance is commonly to deliver long-lasting sepa- the temperature at which condensation will expressed using the inverse term “vapor ration of the interior building begin to occur. permeance,” which is the relative ease of environment from the exteri- The direction of vapor diffusion flow vapor diffusion through a material. or, one of which is the control through an assembly is always from the Vapor-retarding materials are often Bof vapor diffusion. Resistance to vapor diffu- high vapor pressure side to the low vapor grouped into classes (Classes I, II, III) sion is part of the environmental separation; pressure side, which is often also from the depending on their vapor permeance values. however, vapor diffusion control is often warm side to the cold side, because warm Class I (<0.1 US perm) and Class II (0.1 to primarily provided to avoid potentially dam- air can hold more water than cold air (see 1.0 US perm) vapor retarder materials are aging moisture accumulation within build- Figure 2). Importantly, this means it is not considered impermeable to near-imperme- ing enclosure assemblies. While resistance always from the higher RH side to the lower able, respectively, and are known within to vapor diffusion in wall assemblies has RH side. the industry as “vapor barriers.” Some long been understood, ever-increasing ener- The direction of the vapor drive has materials that fall into this category include gy code requirements have led to increased important ramifications with respect to the polyethylene sheet, sheet metal, aluminum insulation levels, which in turn have altered placement of materials within an assembly, foil, some foam plastic insulations (depend- the way assemblies perform with respect to and what works in one climate may not work ing on thickness), and self-adhered (peel- vapor diffusion and condensation control. -
Sub-Slab Vapor Sampling Procedures
Sub-Slab Vapor Sampling Procedures RR-986 July 2014 Table of Contents I. Introduction .......................................................................................................................... 2 II. Sub-Slab Sample Ports .......................................................................................................... 2 A. Distribution of sub-slab probes ...................................................................................... 3 B. Permanent vs. temporary sub-slab probes .................................................................... 4 C. Tubing used in the sample train ..................................................................................... 4 D. Abandonment of sub-slab probes .................................................................................. 4 E. Sub-slab vapor samples collected from a sump pit ....................................................... 4 III. Leak Testing and Collecting a Sub-slab Sample .................................................................... 5 A. Shut-in test ..................................................................................................................... 6 B. Helium shroud ................................................................................................................ 7 C. Other leak detection methods for probe seals .............................................................. 7 D. Sample collection after leak testing ............................................................................... 8 -
Condensation Information October 2016
Sun Windows General Information Section 1 Condensation Information October 2016 Condensation Every year, with the arrival of cold, winter weather, questions about condensation arise. The moisture that forms on window glass, obscuring the view, freezing or even collecting in puddles on the window sill, can be irritating and possibly even damaging. The first reaction may be to blame the windows for this problem, yet windows do not cause condensation. Excessive water vapor in the air, the temperature of the air and air circulation or movement are the three factors involved in the formation of condensation. Today’s modern homes are built very “air-tight” for energy efficiency. They provide better insulating properties and a cleaner, more comfortable living environment than older homes. These improvements in home design and construction have created some new problems as well. The more “air-tight” a home is the less fresh air that home circulates. A typical central air and heat system only circulates the air already within the home. This air becomes saturated with by-products of normal living. One of these is water vapor. Excessive water vapor in the home will most likely show up as condensation on windows. Condensation on your windows is a warning sign that the relative humidity (the measure of water vapor in the air) in your home is too high. You may see it develop on your windows, but it may be damaging the structural components and finishes through-out your home. It can also be damaging to your health. The following review should answer many questions concerning condensation and provide good information that will help in controlling condensation. -
Commodity Volatility
SPRING/SUMMER 2011 POINTTO THE BOARDROOM BUZZ: Commodity Volatility Dodd-Frank How to prepare now Growth in Europe Gartner Names Triple Point Leader Key Customers Answer What keeps them up at night? The Dodd-Frank Wall Street Reform “ The landmark Dodd-Frank Wall Street Reform and Consumer Protection Act will fundamentally change the fi nancial regulatory framework in the United States. As transparency remains a key regulatory theme, real-time access to data across multiple risk centers will be vital.” — Mike Zadoroznyj, VP, Treasury and Regulatory Compliance, Triple Point DODD-FRANK CHANGES THE DERIVATIVES LANDSCAPE Weighing in at more than 800 pages and signed into law in July of 2010, the Dodd-Frank Act (DFA) has been described as the most sweeping set of banking reforms since the Great Depression. Unquestionably it will change the landscape of derivatives trading in signifi cant ways. Peter F. Armstrong Dodd-Frank requires swap counterparties to report transaction data to SDRs (Swap Data Repositories) or, Founder and CEO if no SDR will accept the information, to the CFTC oorr Triple Point Technology SEC as appropriate for the type of swap. Even if an organization is armed with an end-user exemption, Rapidly rising and volatile commodity it may still be required to report this activity prices can harm profi tability, depending on the classifi cation of its counterparty. shareholder value, and credibility Continued on pagee 1616 with analysts. These challenges — historically a Purchasing Department purview — are now getting the attention of CEOs and CFOs. • PepsiCo, Kraft Foods, and Campbell There are other options than raising The traditional methods of handling Soup Company have already lowered prices and cutting costs; it’s time rising raw material and energy earnings guidance for 2011 due to for manufacturing companies to costs, such as substituting cheaper rising costs. -
VAPOR-LIQUID EQUILIBRIA Using the Gibbs Energy and the Common Tangent Plane Criterion
ChE curriculum VAPOR-LIQUID EQUILIBRIA Using the Gibbs Energy and the Common Tangent Plane Criterion MARÍA DEL MAR OLAYA, JUAN A. REYES-LABARTA, MARÍA DOLORES SERRANO, ANTONIO MARCILLA University of Alicante • Apdo. 99, Alicante 03080, Spain hase thermodynamics is often perceived as a difficult overall composition. This is the case with the binary system subject with which many students never become fully in Figure 1(a); it is homogeneous for all compositions. The gM comfortable. It is our opinion that the Gibbsian geo- vs. composition curve is concave down, meaning that no split Pmetrical framework, which can be easily represented in Excel occurs in the global mixture composition to give two liquid spreadsheets, can help students to gain a better understanding phases. Geometrically, this implies that it is impossible to find of phase equilibria using only elementary concepts of high two different points on the gM curve sharing a common tangent school geometry. line. In contrast, the change of curvature in the gM function Phase equilibrium calculations are essential to the simula- as shown in Figure 1(b) permits the existence of two conju- tion and optimization of chemical processes. The task with gated points (I and II) that do share a common tangent line these calculations is to accurately predict the correct number and which, in turn, lead to the formation of two equilibrium of phases at equilibrium present in the system and their com- liquid phases (LL). Any initial mixture, as for example zi in positions. Methods for these calculations can be divided into Figure 1(b), located between the inflection points s on the M 2 M dx2 two main categories: the equation-solving approach (K-value g curve, is intrinsically unstable (d g / i <0) and splits method) and minimization of the Gibbs free energy. -
Redefining Volatile for Vocs
South Coast Air Quality Management District 21865 Copley Drive, Diamond Bar, CA 91765-4182 (909) 396-2000 • http://www.aqmd.gov Non-Volatile, Semi-Volatile, or Volatile: Redefining Volatile for Volatile Organic Compounds Uyên-Uyên T. Võ, Michael P. Morris ABSTRACT The term volatile organic compound (VOC) is poorly defined because measuring volatility is subjective. There are numerous standardized tests designed to determine VOC content, each with an implied method to determine volatility. The parameters (time, temperature, reference material, column polarity, etc.) used in the definitions and the associated test methods were created without a significant evaluation of volatilization characteristics in real world settings. Not only do these differences lead to varying VOC content results, but occasionally they conflict with one another. An ambient evaporation study of selected analytes and a few formulated products was conducted and the results were compared to several current VOC test methodologies, as follows: SCAQMD Method 313 (M313), ASTM Standard Test Method E 1868-10 (E1868) and U.S. EPA Reference Method 24 (M24). The ambient evaporation study showed a definite distinction between non-volatile, semi-volatile and volatile compounds. Some low vapor pressure (LVP) solvents, currently considered exempt as a VOC by some methods, volatilize at ambient conditions nearly as rapidly as the traditional high volatility solvents they are meant to replace. Conversely, bio-based and heavy hydrocarbons did not readily volatilize, though they often are calculated as VOCs in some traditional test methods. The study suggests that regulatory standards should be reevaluated to better reflect these findings to more accurately reflect real world emission from the use of VOC containing products.