&EPA United States Environmental Protection Agency EPA-600/R-05/066 March 2005 Program PARAMS User's Guide Program Version: 1.0 Document Version: 1.0 •I" Diffusivity in Solids for Mixed Chemical Classes Correlation DS=A-B/H(V) where Df = difiusivity in solid (rrf/s), v = molar volume (g/mol), and A and B are constants. Material -1.536 -4.674 0.997 Oriented strand board 19.73 -8.401 0.973 Particle board 10.59 -6.970 0.785 Plywood -0.6787 -4.720 0.815 Vinyl tile •3.546 •4.286 0.917 Click on a material to select - Your selection Gypsum board Enter molar volume (cm3/mol) i Copy ------- ------- EPA-600/R-05/066 March 2005 Program PARAMS User's Guide Program Version: 1.0 Document Version: 1.0 by Zhishi Quo U.S. Environmental Protection Agency Office of Research & Development National Risk Management Research Laboratory Air Pollution Prevention & Control Division Research Triangle Park, NC 27711 U.S. Environmental Protection Agency Office of Research and Development Washington, DC 20460 ------- Abstract This Microsoft Windows-based computer program implements 30 methods for estimating the parameters in indoor emissions source models, which are an essential component of indoor air quality (IAQ) and exposure models. These methods fall into eight categories: (1) the properties of indoor air, (2) the first-order decay rate constants for solvent emissions from indoor coating materials, (3) gas-phase, liquid-phase, and overall mass transfer coefficients, (4) molar volume, (5) molecular diffusivity in air, liquid, and solid materials, (6) solid-air partition coefficient, (7) vapor pressure and volatility for pure organic compounds and petroleum-based solvents, and (8) the properties of water. Potential users include those who develop or use IAQ and exposure models and those who develop or use quantitative structure-activity relationship (QSAR) models. In addition, many calculations are useful to researchers in areas other than indoor air quality. Users can benefit from this program in two ways: first, it serves as a handy tool by putting commonly used parameter estimation methods in one place; second, it saves users time by taking over tedious calculations. It should be pointed out, however, that the methods implemented in this program cover only a fraction of the parameters that appear in the more than 50 indoor emission source models. Furthermore, the methods in the current version are mostly for gaseous pollutants; those for particulate matter are not included. ------- Foreword The U.S. Environmental Protection Agency (EPA) is charged by Congress with protecting the Nation's land, air, and water resources. Under a mandate of national environmental laws, the Agency strives to formulate and implement actions leading to a compatible balance between human activities and the ability of natural systems to support and nurture life. To meet this mandate, EPA's research program is providing data and technical support for solving environmental problems today and building a science knowledge base necessary to manage our ecological resources wisely, understand how pollutants affect our health, and prevent or reduce environmental risks in the future. The National Risk Management Research Laboratory (NRMRL) is the Agency's center for investigation of technological and management approaches for preventing and reducing risks from pollution that threaten human health and the environment. The focus of the Laboratory's research program is on methods and their cost-effectiveness for prevention and control of pollution to air, land, water, and subsurface resources; protection of water quality in public water systems; remediation of contaminated sites, sediments and ground water; prevention and control of indoor air pollution; and restoration of ecosystems. NRMRL collaborates with both public and private sector partners to foster technologies that reduce the cost of compliance and to anticipate emerging problems. NRMRL's research provides solutions to environmental problems by: developing and promoting technologies that protect and improve the environment; advancing scientific and engineering information to support regulatory and policy decisions; and providing the technical support and information transfer to ensure implementation of environmental regulations and strategies at the national, state, and community levels. This publication has been produced as part of the Laboratory's strategic long-term research plan. It is published and made available by EPA's Office of Research and Development to assist the user community and to link researchers with their clients. Sally Gutierrez, Acting Director National Risk Management Research Laboratory in ------- EPA Review Notice This report has been peer and administratively reviewed by the U.S. Environmental Protection Agency and approved for publication. Mention of trade names or commercial products does not constitute endorsement or recommendation for use. This document is available to the public through the National Technical Information Service, Springfield, Virginia 22161. IV ------- Table of Contents Section Page Abstract ii List of Figures vii List of Tables viii 1. Introduction 1 1.1 Purpose and Intended Users 1 1.2 Limitations 1 1.3 Parameter Estimation Methods Implemented 1 2. Installation and Technical Support 3 2.1 Minimum System Requirements 3 2.2 Installing PARAMS from Compact Disk 3 2.3 Installing PARAMS from Zip File 3 2.4 Installation Problems 3 2.5 Viewing and Printing the User's Guide 4 2.6 Technical Support 4 3. A Brief Tour of the Program 5 3.1 User Interface 5 3.2 Example 1: Calculating the density of air at 23 °C, 1 atm, and 65% RH 5 3.3 Example 2: Calculating the gas-phase mass transfer coefficient for n-decane (C10H22) at 23 °C and 50% RH 6 4. Method Descriptions 9 4.1 Properties of Air 9 4.1.1 Density of Dry and Moist Air 9 4.1.2 Moisture Content in Air 9 4.1.3 Viscosity of Air 10 4.2 First-Order Decay Rate Constant for Emissions from Paint 10 4.2.1 Methods for Petroleum-Based Paint 11 4.2.2 Methods for Latex Paint 14 ------- Table of Contents (concluded) Section Page 4.3 Mass Transfer Coefficient 15 4.3.1 Gas-Phase Mass Transfer Coefficient 15 4.3.2 Liquid-Phase Mass Transfer Coefficient 17 4.3.3 Overall Mass Transfer Coefficient 18 4.4 Molar Volume 19 4.4.1 Atomic and Structural Diffusion Volume Increments 20 4.4.2 Le Bas Molar Volume 20 4.5 Molecular Diffusivity 21 4.5.1 Diffusivity in Air 21 4.5.2 Diffusivity in Water 22 4.5.3 Diffusivity in Solids as a Function of Molecular Weight 24 4.5.4 Diffusivity in Solids as a Function of Molar Volume 24 4.6 Solid-air Partition Coefficient 26 4.6.1 Material and Chemical Specific Methods 26 4.6.2 Method for All Materials and Compound Classes 27 4.7 Volatility of Organic Compounds 27 4.7.1 Makar Method for Pure Organic Compounds 28 4.7.2 Total Vapor Pressure of Petroleum-Based Solvents 29 4.8 Properties of Water 29 4.8.1 Vapor Pressure of Water 29 4.8.2 Viscosity of Liquid Water 30 References 31 VI ------- List of Figures 1 Error Message Encountered When Trying to Install PARAMS to a Network Computer with Security Restrictions 3 2 Layout of Params' Main Screen, No Selected Method 5 3 Layout of the Main Window after the Method for Air Density Is Selected 6 4 Calculation Screen for Air Density 7 5 Calculation Screen for Gas-Phase Mass Transfer Coefficient Based on Sherwood Number. The Arrow Points to the Built-in Calculator for Air Density 7 6 Calculation Screen for Diffusivity in Air (FSG Method 1) 8 7 Calculation Screen for Moisture Content in Air 10 8 Calculation Screen for Air Viscosity 11 9 Calculation Screen for First-Order Decay Rate Constant with the Chinn Method . . 12 10 Calculation Screen for First-order Decay Rate Constant for TVOC Emissions from Oil-Based Indoor Coating Materials 13 11 Calculation Screen for k and E for Emissions of Individual VOCs from Oil-Based Coating Materials 14 12 Calculation Screen for Estimating the First-Order Decay Rate Constant for VOC Emissions from Alkyd Paint with the Koontz Method 15 13 Calculation Screens for Estimating the First-Order Decay Rate Constants for VOC Emissions Form Latex Paint. The Screen on Top Is for k, and the One on Bottom for k2 16 14 Calculation Screen for Gas-Phase Mass Transfer Coefficient 16 15 Calculation Screen for Liquid-Phase Mass Transfer Coefficient for Still Water .... 18 16 Calculation Screen for Liquid-Phase Mass Transfer Coefficient for Moving Water . 18 17 Calculation Screen for Overall Gas- and Liquid-Phase Mass Transfer Coefficients . 19 18 Calculation Screen for Overall Gas- and Liquid-Phase Mass Transfer Coefficients for Still Water Pools and Films 20 19 Calculation Screen for Molar Volume Based on Atomic and Structural Diffusion Volume Increments 21 20 Calculation Screen for Le Bas Volume 22 21 Calculation Screen for Diffusivity in Air with FSG Method 1, in Which the Molar Volume Is Estimated from Atomic and Structure Diffusion Volume Increments ... 23 vii ------- List of Figures (concluded) Figure Page 22 Calculation Screen for Diffusivity in Air with the FSG Method, in Which the Molar Volume Is Estimated from the Le Bas Volume 23 23 Calculation Screen for Molecular Diffusivity in Air with the WL Method 24 24 Calculation Screen for Molecular Diffusivity in Water 25 25 Calculation Screen for Diffusivity in Solid Material. This Method Is Specific to Given Material/Chemical Class Combinations 25 26 Calculation Screen for Molecular Diffusivity in Solid Materials. This Method Is Not Specific to a Particular Compound Class 26 27 Calculation Screen for Solid-air Partition Coefficient. This Method Is Material and Chemical Specific 27 28 Calculation Screen for Solid-air Partition Coefficient. This Method Is Not Specific to Compound Classes 27 29 Calculation Screen for Estimating the Vapor Pressure Based on Compound Class . 28 30 Calculation Screen for Total Vapor Pressure of Petroleum-Based Solvents 29 31 Calculation Screen for Water Vapor Pressure 30 32 Calculation Screen for Water Viscosity 30 List of Tables Table Page 1 List of Parameter Estimation Methods in PARAMS 2 2 Absolute Viscosity of Air from the Literature 10 Vlll ------- 1. Introduction 1.1 Purpose and Intended Users Although over 50 indoor emission source models have been developed (Guo, 2002a), few are widely used in indoor exposure assessment. This imbalance is partially caused by the fact that many source models contain one or more parameters that are difficult to determine. This program is a step toward alleviating this problem by providing 30 methods for estimating some of the parameters in those source models. It is useful to those who develop or use indoor air quality (IAQ) and exposure models, and those who develop or use quantitative structure- activity relationship (QSAR) models. In addition, many methods in this program are useful to research- ers in areas other than indoor air quality. Users can benefit from this program in two ways: (1) it serves as a handy tool by putting commonly used methods in one place, and (2) it saves users' time by taking over tedious calculations. This program was developed based on the devel- oper's review of existing parameter estimation methods for indoor emission source models (Guo, 2002b). Users are encouraged to read the review article for more detailed discussions and, more importantly, to consult with the original references. The name of this program, PARAMS, is an abbrevia- tion of parameters. 1.2 Limitations Overall, development of parameter estimation meth- ods has not progressed to the extent that IAQ model- ers would like to see. Users are reminded that the number of parameters that can be estimated with this program is only a fraction of the total number of parameters in the existing indoor source models. This program is intended to supplement, not to substitute for, experimentally determined model parameters. In other words, this program is most useful when experimentally determined values are not available. Most methods implemented in this program are for gaseous pollutants. Methods for particulate matter are not included in the current version. 1.3 Parameter Estimation Methods Implemented The methods implemented in this program are sum- marized in Table 1. Detailed discussions on each method is provided in Section 4. The References section gives a complete list of sources of these methods. ------- Program PARAMS Table 1. List of Parameter Estimation Methods in PARAMS. Method Group Subgroup Air properties First-order decay rate constant Mass transfer coefficient Molar volume Molecular diffusivity Solid-air partition coefficient Volatility Water properties Total Density Moisture content Viscosity Petroleum-based paint Latex paint Gas-phase Liquid-phase Overall N/A Gas-phase Liquid-phase Solid-phase N/A N/A Vapor pressure Viscosity No. of methods 1 1 1 4 2 3 2 2 2 3 1 2 2 2 1 1 30 ------- User's Guide 2. Installation and Technical Support 2.1 Minimum System Requirements • Intel Pentium 90 or equivalent, • Microsoft Windows 95 or later (see Section 2.4 for details), • 16 Mb of RAM, • 10 Mb free hard disk space, • CD-ROM drive (for installation from CD), • Software WinZip (for installation from zip file), Software Acrobat Reader 4.0 or later (for printing the User's Guide), • VGA or higher resolution monitor, and • Mouse or other pointing devices. 2.2 Installing PARAMS from Compact Disk • Insert the program CD; • If the installation program does not start automatically, use Windows Explorer to find the CD-ROM drive, then click on file Setup.EXE; and • Follow instructions to complete installation. 2.3 Installing PARAMS from Zip File • If you received the zip file as an e-mail at- tachment, save the file (PARAMS.txt) to a temporary folder in your hard drive; • Rename the file PARAMS.zip; • Unzip (i.e., extract) the zip file with WinZip and run program Setup.EXE; • Follow the instructions to complete installa- tion; and • Delete installation files. 2.4 Installation Problems This program has been tested for installation errors for Microsoft Windows 95, 98, 2000, ME, and XP Professional. It is not guaranteed that it will work under other versions of Windows. An independent quality assurance (QA) review revealed that this program could not be installed to Windows PC Home Edition. Also note that, if your computer has Windows XP Professional and is connected to a network, you may receive an error message similar to the one shown in Figure 1. It means that you are not authorized to install any software on your computer, and you must ask a computer support technician to install the software for you. Setup has detected that unlnstall5hield is in use. Please close unlnstallShield and restart setup. Error 432. OK Figure 1. Error Message Encountered When Trying to Install PARAMS to a Network Computer with Security Restrictions. ------- Program PARAMS 2.5 Viewing and Printing the User's Guide The User's Guide is provided in pdf file format, and requires Adobe Acrobat Reader (version 4 or higher) to read. There are two ways to access the document: From Windows Start menu: • Find the group name for program PARAMS by clicking on ------- User's Guide 3. A Brief Tour of the Program 3.1 User Interface To start the program, choose Start Q> Programs Q> Params 1.0 Q> Params. This program has a fairly simple user interface. Figure 2 shows the main screen after the user launches the program under Windows XP. Note that, for other Windows operating systems, the appearance of the start screen may be slightly different. As shown in Figure 2, all the methods are organized in a tree list, very similar to the file list in Windows Explorer. To view more details in the list, simply click one of the plus (+) signs. There are two small buttons under the tree list. Clicking the one on the left (with an open book icon) makes the tree list fully expand; clicking the one on the right (with a PARAMS -- Parameter Estimation for Indoor Source Models closed book icon) makes the list collapse. To select a parameter estimation method, click on one of the items in the tree list. The method selected will appear in the upper-right pane (Figure 3). The next step is to click the ------- Program PARAMS • T PARAMS -- Parameter Estimation for Indoor Source Models - n x Select a method moisture content viscosity + First-order decay rate constant + Mass transfer coefficient + Molar volume + Molecular diffusivity + Solid/air partition coefficient + Volatility + Water properties Your selection Air properties density Figure 3. Layout of the Main Window after the Method for Air Density Is Selected. corner (see Figure 3), click on the ------- User's Guide ••" Air density Air Temperature |23 Atmospheric Pressure mmHg Relative Humidity (RH) lelect one: Dry air 0 Moist air Air density = 0.0011843 (g/cnf) ? Help [BlCJjculate]] H^j Copy Figure 4. Calculation Screen for Air Density. Density of air (g/cm3) Viscosity of air (g/cm/s) Velocity of air (cm/s) Diffusivity in air (:ms/s) Characteristic length (cm) Close •r Gas-phase Mass Transfer Coefficient (kg) from Sherwood Number Help / Paste & Exit | H^ Copy Figure 5. Calculation Screen for Gas-Phase Mass Transfer Coefficient Based on Sherwood Number. The Arrow Points to the Built-in Calculator for Air Density. 7 ------- Program PARAMS Similarly, you can calculate the viscosity of air by clicking on the second calculator button. Air velocity inside a room varies from case to case. For this exercise, enter 5. For hints, click the button with a question mark. It will tell you that the typical range air velocity in the indoor environments is from 5 to 10 cm/s. To calculate the diffusivity of n-decane in air, click the calculator button next to the entry box for diffus- ivity; the program will ask you to select one from three available methods. If you are unfamiliar with these methods, click on the ------- User's Guide 4. Method Descriptions 4.1 Properties of Air The properties of air calculated by this program are density, moisture content, and viscosity. 4.1.1 Density of Dry and Moist Air The density of dry or moist air is calculated from Equations. 1 and 2 (Weast, 1973, page F-9), respec- tively. RH T, P - 0.3783 Pw 0 ji p (1) (2) where ddry = density of dry air at temperature T and pressure P, in grams per cubic meter, dmoisi = density of moist air at temperature T and pressure P, in grams per cubic meter, d0 = density of dry air at temperature T0 and pressure P0, in grams per cubic meter, T0 = standard temperature = 273.2 K, T = temperature of air in Kelvin, P0 = standard atmospheric pressure = 760 mm Hg, P = atmospheric pressure in millimeters mercury (Hg), and pw = partial pressure of moisture in air in millimeters Hg. In this program, d0 = 0.0012929 g/cm3 at 0 °C and 760 mmHg is from Weast (1973, page F-9). The user input for moisture content is in relative humidity, which is then converted to partial pressure (millimeters Hg) by using Equation 3. (3) where RH = relative humidity, and Pw0 = water vapor pressure at given temp- erature in millimeters Hg. The method used to estimate the water vapor pressure (Pw0) is described in Section 4.8.1. The calculation screen is shown in Figure 4 in the previous section. 4.1.2 Moisture Content in Air This program computes the moisture content in room air—either saturated or unsaturated—in parts per million and grams per cubic meter. Information required from the user includes room temperature, atmospheric pressure, and for unsaturated air, relative humidity. Figure 7 shows the calculation screen. Calculation of moisture content in air involves three steps: Step 1: Calculating water vapor pressure by using Equation 44 in Section 4.8.1; Step 2: Calculating the partial pressure by using Equations; Step 3: Converting partial pressure to concentration units by Equations 4 and 5. C = 106 P IP ^wl 1U J w ' J 0 (4) where Cw] = water content in air in parts per million, P0 = atmospheric pressure in millimeters Hg. where Cw2 is in grams per cubic meter, ------- Program PARAMS • I' Moisture content in air -Air Temperature Atmospheric Pressure mmH9 Relative Humidity (RH) oo lelect one:— 9 Saturated isaturated Help Calculate JL Close Figure 7. Calculation Screen for Moisture Content in Air. Mw = molecular weight for water in grams per mole, VT = molar volume of gas at temperature T in liters. 4.1.3 Viscosity of Air This program calculates the absolute viscosity of air between 0 and 74 °C by using experimental data found in the literature. Figure 8 shows the calculation screen, and Table 2 the viscosity data. Table 2. Absolute Viscosity of Airfrom the Litera- ture3 Temperature Viscosity (°Q 0 18 40 54 74 (l^Poise) 170.8 182.7 190.4 195.8 210.2 (g/s/cm) 1.708xlQ-4 1.827xlQ-4 1.904xlQ-4 1.958xlQ-4 2.102xlO-4 1 Source: Weast, 1973; page F-43. A third-order polynomial (Equation 6) is used to calculate the viscosity at any temperature between 0 and 74 °C under the standard atmospheric pressure. The coefficients in Equation 6 were determined by least square with r2 = 0.999999998, where r is the correlation coefficient. //= 170.80 1.60383 0.9154397-0.0170441 lO-4P (6) where //= absolute viscosity in microPoise (1 Poise = 1 gram per centimeters per second), and T= temperature in degrees Celsius. Note that some indoor source models require kine- matic viscosity, which is the ratio of the absolute viscosity and air density. Kinematic viscosity has the unit of Stokes or, equivalently, square centimeters per second. 4.2 First-Order Decay Rate Constant for Emissions from Paint The software contains methods for calculating the first-order decay rate constant for both latex and petroleum-based paints. The decay rate constant for petroleum-based paint can be calculated by four methods. 10 ------- User's Guide "I* Absolute viscosity of air - n x Enter air temperature (°C): i g Calculate I Figure 8. Calculation Screen for Air Viscosity. 4.2.1 Methods for Petroleum-Based Paint The first-order decay emission model has two forms (Equation 7), and they are equivalent because of the relationship in Equation 8 (Guo, 2000a). InlO I k (7) (8) where E = emission factor in milligrams per square meter per hour, E0 = initial emission rate in milligrams per square meter per hour, M0 = initial pollutant mass in the source in milligrams per square meter, k = first-order decay rate constant (h"1), and t = time in hours. When the initial pollutant mass (M0) is known, the decay constant (K) becomes the only parameter to be determined, and this program provides four methods for estimating k for emissions of volatile organic compounds (VOCs) and total VOCs (TVOCs) from petroleum-based paint. These methods are the Chinn- Evans and Guo methods for TVOCs and the Guo and Koontz methods for individual VOCs. Chirm-Evans Method Evans (1994) proposed to estimate k from the 90% drying time (t09) for solvent evaporations from petroleum-based paint (Equation 9). (9) 10.9 where tog is calculated from Equations 10 and 11 (Chinn, 1981). C = = 7.3698-0.95461og10C \6040mP T (10) (11) where Cv = solvent volatility in milligrams per cubic meter, m = molecular weight of solvent in grams per mole, P = vapor pressure of solvent in millimeters Hg, and T= temperature in Kelvin. Input parameters include vapor pressure, molecular weight, and temperature. Built-in calculators are available for the first two parameters (Figure 9). If this method is used to estimate & for TVOC emissions for a solvent mixture, parameter P in Equation 11 should be replaced by the total vapor pressure for the solvent. The total vapor pressure can be (1) experi- mentally determined, (2) estimated based on the contents of the major VOCs (see Section 4.7.2), or (3) approximated by the vapor pressure of the most abundant VOC in the mixture—a calculator is avail- 11 ------- Program PARAMS •T First-order decay rate constant from 90% drying time f- Ifnlfxl Enter parameters here Vapor pressure (mm Hg) molecular weight (g/mol) E = EO exp(-k t) Pastel Exit lift Copy Figure 9. Calculation Screen for First-Order Decay Rate Constant with the Chinn Method. ble in the data entry window. The average molecular weight for TVOCs can be (1) estimated based on the contents of the major VOCs (see Section 4.7.2) or (2) approximated by the molecular weight of the most abundant VOC in the mixture. This method tends to overestimate & for an individual VOC in a mixture. One should also be aware that the correlation (Equation 10) was found with the 90% evaporation time being determined on paper filters with dry air flowing through (ASTM, 1977). Appar- ently, the experimental conditions (e.g., film thick- ness and ventilation rate) are far from realistic. Besides, this method ignores the effect of film thick- ness. Despite these limitations, it is very useful for rough estimations because all the parameters in Equations. 10 and 11 are easily obtained. Guo Methodfor TVOCs This method (Equation 12) was obtained by simplify- ing a mass transfer model (Guo, 1999). It also pro- vides an estimate of the initial emission factor (Equa- tion 13). Information required from the user is shown in Figure 10. /C \^- f k = 9dy F = k C j^0 n. \^T (12) (13) where kis in h"1, kg = gas-phase mass transfer coefficient in meters per hour, Cr = TVOC saturation concentration con- verted from total vapor pressure in milli- grams per cubic meter, 6= thickness of paint film in meters, d= density of paint in grams per cubic meter, yr = TVOC content in paint in milligrams per gram, and 12 ------- User's Guide •I* 1st-order decay constant for TVOC in oil-based paint Total vapor pressure for TVOC (mm Hg) Solvent average molecular wt (g/mol) Wet paint film thickness (urn) Paint density (g/crri5) Gas-phase mass transfer coef (rn/h) TVOC content in paint (mg/g) 7 Help Model: E = EO exp(-k t) Copy Figure 10. Calculation Screen for First-order Decay Rate Constant for TVOC Emissions from Oil-Based Indoor Coating Materials. E0 = initial emission factor in milligrams per square meter per hour. If the user calculates the mass transfer coefficient (kg), the molecular formula of the most abundant component in the solvent should be used. As previ- ously described, the total vapor pressure (Cr) can be (1) experimentally determined, (2) estimated based on the contents of the major VOCs (see Section 4.7.2), or (3) approximated by the vapor pressure of the most abundant VOC in the mixture. The calcula- tor button next to the total vapor pressure in the data entry window is for option (2). The method described in Section 4.7.1 can be used for option (3) Guo Method for Individual VOCs Equations 14 and 15 (Guo, 1999) are used to estimate the first-order decay rate constant (K) and the initial emission rate (Eg) for individual VOCs from oil- based indoor coating materials. Seven input parame- ters are required from the user (Figure 11). K „ U,, fflT 9d yT mi , „ y,mr (14) (15) s yTm, where A: is in hr"1, Cv = VOC saturation concentration converted from vapor pressure in milligrams per cubic meter, yt = VOC content of the paint in milligrams per gram, mr = average molecular weight for TVOCs in grams per mole, and mt = molecular weight for the VOC of interest in grams per mole. Koontz Method for Individual VOCs The Koontz correlation (Equation 16) was found 13 ------- Program PARAMS •" 1st-order decay constant for individual VOC in oil-based paint VOC vapor pressure (mm Hg) Solvent average molecular wt (g/mol) Wet paint film thickness (urn) Paint density (g/crri5) Gas-phase mass transfer coef (rn/h) TVOC content in paint (mg/g) VOC content in paint (mg/g) 7 Help JJ Model: E = EO exp(-k t) @S Copy Close Figure 11. Calculation Screen for /rand Efor Emissions of Individual VOCs from Oil-Based Coating Materials. from experimentally determined k's for alkyd paint (Koontz, 2001), pO.27 '" " 06) k= 2.95 xlO9 ,4.02 ,30.58 ; (rz = 0.86) m where k is in h"1, P = vapor pressure in millimeters Hg, m = molecular weight in grams per mole, 6= thickness of paint film in mils, and r = correlation coefficient. User inputs are vapor pressure, molecular weight, and wet film thickness (Figure 12). 4.2.2 Methods for Latex Paint The dual exponential decay model (Equation 17) is often used for glycol emissions from latex paint. Wilkes, et al. (1996) proposed Equations 18 and 19 for estimating ^ and k2, respectively. This method does not estimate E1 and E2. T^ T^ — K i t i T^ — K o t fa — fa £ ~\~ fa Q £1 = 233.25 P; (r2 = 0.92) k2 = 5.839 x 10'X (r2 = 0.96) (17) (18) (19) where E, = initial emission factor for "fast" emis- sions in milligrams per square meter per hour, E2 = initial emission factor for "slow" emis- sions in milligrams per square meter per hour, kj = first-order decay rate constant for "fast" emissions (h"1), k2 = first-order decay rate constant for "slow" emissions (h"1), P = vapor pressure in millimeters Hg, m = molecular weight in grams per mole, and r = correlation coefficient. 14 ------- User's Guide •" 1st-order decay constant for VOC from alkyd paint f- Ifnlfxl Vapor pressure (mm Hg) Molecular wight (g/mol) Wet film thickness Model: E = EO exp(-k t) Figure 12. Calculation Screen for Estimating the First-Order Decay Rate Constant for VOC Emissions from Alkyd Paint with the Koontz Method. hese two parameters are calculated with two separate calculation screens (Figure 13). 4.3 Mass Transfer Coefficient The software can calculate the gas-phase mass transfer coefficient by either the Sherwood, the Sparks, or the Mackay-Matsugu method. The liquid- phase mass transfer coefficient can be calculated either for still water pools and films or for moving water. The overall mass transfer coefficient can be calculated on a generic basis or for still water pools and films. 4.3.1 Gas-Phase Mass Transfer Coefficient Three methods are provided for calculating the gas- phase mass transfer coefficient: Sherwood method, Sparks method, and Mackay-Matsugu method. Since all three methods require the same user input, they share the same calculation screen (Figure 14). Sherwood Method This method (Bennet and Myers, 1982) is based on correlations between three dimensionless numbers: Sherwood number (Sh), Schmidt number (Sc\ and Reynolds number (Re). k L Sh=-— (20) Lup S = (21) (22) where kg = gas-phase mass transfer coefficient in meters per hour, L = characteristic length of the source in meters, 15 ------- Program PARAMS 1st-order constant for latex paint (k1) Enter vapor pressure (mm Hg): - n x E = E1*exp(-k1 t) + E2*exp(-k21) H Calculate I I* 1st-order constant for latex paint (k2) Enter molecular weight (g/mol): E = E1*exp(-k1 t) + E2*exp(-k21) Figure 13. Calculation Screens for Estimating the First-Order Decay Rate Constants for VOC Emissions From Latex Paint. The Screen on Top Is for ^ and the One on Bottom for k2. •r Gas-phase Mass Transfer Coefficient (kg) from Sherwood Number Density of air (g/crn3) i Viscosity of air (g/cm/s) Velocity of air (cm/s) Diffusivity in air (crrvVs) Characteristic length (cm) Help X Close I ^^^^^^^^•^^^^^^J .^^^^^.^^^^^J 1 Figure 14. Calculation Screen for Gas-Phase Mass Transfer Coefficient. 16 ------- User's Guide Da = diffusivity in air in square meters per hour, u = air velocity in meters per hour, p = density of air in grams per cubic meter, and // = viscosity of air in grams per meter per hour. A series of correlations have been developed between Sh, Sc, andRe (Bennett & Myers, 1982; White, 1991). For example, Equation 23 applies to laminar flow conditions and is used in this program. (23) The calculation involves four steps. Step 1. Calculate the Reynolds number (Equation 21); Step 2. Calculate the Schmidt number (Equation 22); Step 3. Calculate the Sherwood number (Equation 23); and Step 4. Calculate the gas-phase mass transfer coeffi- cient (k) from Equation 20. Sparks Method Sparks, etal (1996) proposed a simpler method based on experimental data obtained from small chambers and a test house (Equation 24), and is used in several emission source models for interior paint. £„ = 0.33 D L'1 RJ (24) Mackay-Matsugu Method This method was based on experimental data for water evaporation (Mackay and Matsugu, 1973) and has been used mostly for solvent spills. 0.78 r-0.11 o -0.67 k - 0.0292 Ma/8rau S (25) where kg, u, and L are in meters per hour, meters per hour, and meters, respectively. These three methods require the same user input. Currently there are not sufficient experimental data to discriminate one method from the others. This devel- oper suggests the following "rules-of-thumb" for method selection: (1) choose the method that is recommended by the source model; (2) if the source model does not recommend a specific method, use the Sherwood method. 4.3.2 Liquid-Phase Mass Transfer Coefficient The software can calculate the liquid-phase mass transfer coefficient for still water pools and films and for moving water. Still Water Pools and Films For still, shallow water pools and films, Guo and Roache (2003) proposed to use Equation 26 to estimate the liquid-phase mass transfer coefficient. (26) where kL(X) = liquid-phase mass transfer coefficient for compound X in meters per hour, DL(X) = diffusivity of compound X in water in square meters per hour. A calculator is provided in the calculation screen for the diffusivity in water (Figure 15), and the method is discussed in Section 4.5.2. Moving Water This method (Equation 27) is for ambient water bodies (Southworth, 1992) and is included in this program because there are no similar methods for indoor conditions. User inputs are molecular weight, velocity of water flow, and water depth (Figure 16.). Use this method with caution. (27) where kL is in centimeters per hour, uc = velocity of water current in meters per second, Z = water depth in meters, and m = molecular weight in grams per mole. 17 ------- Program PARAMS • r Liquid-phase Mass Transfer Coefficient for Still Water (kL) Enter diffusivity in water (mz/h): i- n x I Calculate I Figure 15. Calculation Screen for Liquid-Phase Mass Transfer Coefficient for Still Water. •r Liquid-phase mass transfer coeff. for flowing water Enter parameters here Molecular weight (g/mol) Water flow velocity (m/s) Figure 16. Calculation Screen for Liquid-Phase Mass Transfer Coefficient for Moving Water. 4.3.3 Overall Mass Transfer Coefficient Generic Overall mass transfer coefficients are often used to estimate pollutant emissions from tap water and water-based consumer products. This generic method (Equations 28 and 29) is not a parameter estimation method per se. Rather, it gives the definition of overall mass transfer coefficient (Lyman, etal., 1990; ch 15, pi 1) and is used to calculate the overall mass 18 ------- User's Guide transfer coefficient from the gas- and liquid-phase mass transfer coefficients and Henry's constant. Figure 17 shows the calculation screen. 1 K. OL 1 H 1 kgH k (28) (29) where KOL = overall liquid-phase mass transfer coefficient in meters per hour, kL = liquid-phase mass transfer coefficient in meters per hour, kg = gas-phase mass transfer coefficient in meters per hour, H= dimensionless Henry's constant (i.e., air/water partition coefficient). Since the two overall mass transfer coefficients (KOL and KOG) are linked by Equation 30, one can be calculated from the other. (30) Still Water Pools and Films For still water pools and films, Guo and Roache (2003) proposed a three-step calculation method. Step 1. Use Equation 20 to estimate the gas-phase mass transfer coefficient (&g); Step 2. Use Equation 27 to estimate the liquid-phase mass transfer coefficient (kL); and Step 3. Use Equation 28 to calculate the liquid-phase overall mass transfer coefficient. Once the overall liquid-phase mass transfer coeffi- cient (KOI) is known, the overall gas-phase mass transfer coefficient (KOG) can be easily obtained from Equation 30. Calculators for kg and kL are provided in the calculation screen (Figure 18). 4.4 Molar Volume Molar volume (often in cubic centimeters per mole) is a measure of molecular size and is used to estimate «r Overall mass transfer coeff. (generic method) \- Ifnlfxl Gas-phase mass transfer coeff. (m/h) Liquid-phase mass transfer coeff. (m/h) r Dimensionless Henry's constant (air/water) I ® Convert | 7 Help Epi Copy X Close | Figure 17. Calculation Screen for Overall Gas- and Liquid-Phase Mass Transfer Coefficients. 19 ------- Program PARAMS «T Overall mass transfer coeff. for still water Gas-phase mass transfer coeff. (m/h) Diffusivity in water (m3/h) Dimensionless Henry's constant (air/water) I ® Convert | 7 Help Figure 18. Calculation Screen for Overall Gas- and Liquid-Phase Mass Transfer Coefficients for Still Water Pools and Films. the diffusion coefficient in air, water, and solids. Two methods are commonly used. One is based on atomic and structural diffusion volume increments and the other is known as the Le Bas molar volume, which is determined at the normal boiling point of the sub- stance. The relationship between these two parame- ters is shown in Equation 31. LB (31) where Vmol = molar volume of gas at normal temper- ature in cubic centimeters per mole, and VLB = Le Bas molar volume in cubic centi- meters per mole. 4.4.1 A tomic and Structural Diffusion Volume Increments In this method, the molar volume is the sum of the volume for each atom and structure (Fuller, et al., 1966). The data table used in this program is from Lyman, et al.(1990, ch 17, p 11). For instance, the diffusion volume increments for carbon, hydrogen, and the aromatic ring are, respectively, 16.5, 1.98, and -20.2 cmVmol. Thus, the molar volume for benzene (C6 H6) is Vmol = 6x16.5 + 6x 1.98 - 20.2 =110.9 (cmVmol) The drawback of this method is that the incremental molar volumes are only available for six atoms: C, H, O, N, Cl, and S. Furthermore, the values for N, Cl, and S are based on limited experimental data. The calculation screen for this method is shown in Figure 19. 4.4.2 Le Bas Molar Volume The Le Bas method estimates the molar volumes of liquids at their respective normal boiling points. Like the method described above, the Le Bas volume is also additive. The original data table is used in this program (Reid, et al., 1977 p 58; Lyman, et al., 1990, ch 17, p 11). This method pays more attention to the molecular structure than the previous method (Sec- tion 4.4.2). For instance, oxygen has five incremental 20 ------- User's Guide •' Diffusion Volume f- Ifnlfxl Chemical Formula & Structure Carbon (C) Hydrogen (H) Oxygen (0) Nitrogen (N) Chlorine (Cl) Sulfur (S) Rings * * Including aromatic and heterocyclic rings. ? Help Paste &Exit 18 Copy X Close Figure 19. Calculation Screen for Molar Volume Based on Atomic and Structural Diffusion Volume Increments. volumes depending on its bonding with other atoms (e.g., esters and acids). Incremental volumes are available for nine atoms: C, H, O, N, Br, Cl, F, I, and S . The calculation screen is shown in Figure 20. 4.5 Molecular Diffusivity The software contains algorithms for calculating diffusivity in solids as a function of either molecular weight or molar volume, in water, and in air by two methods. 4.5.1 Diffusivity in Air The method of Fuller-Schettler-Giddings (FSG) and the method of Wilke and Lee (WL) are the two most commonly used methods for estimating molecular diffusivity in air. Overall, the WL method is more accurate, but requires knowledge of the boiling point of the chemical of interest. FSG method This method is based on Equation 32 (Fuller, et al., 1966). It is most accurate for non-polar gases at low to moderate temperature and is less accurate for the polar acids and glycols. il.75 MAMB (32) (33) where DA = molecular diffusivity in square centi- meters per second, T= temperature in Kelvin, MA = molecular weight for air = 28.97 g/mole, MB = molecular weight for the chemical of interest in grams per mole, P = atmospheric pressure in atmospheres, 21 ------- Program PARAMS •r Le Bas Molar Volume Chemical Formula & Structure Carbon (C) Hydrogen (H) Oxygen (0), except below 0 in methyl esters/ethers 0 in ethyl esters/ethers 0 in higher estersfethers 0 in acids 0 joined to S, P, S Nitrogen (N), double bound Nitrogen (N), primary amines Nitrogene (N), 2nd amines n jo :] [5 ^j B ^J B ^j Bromine (Br) Chlorine (Cl) Fluorine (F) Iodine (I) Sulfur (S) 3-membered ring 4-membered ring 5-membered ring 6-membered ring Naphthalene Anthracene Help S; Paste & Exit Figure 20. Calculation Screen for Le Bas Volume. VA = molar volume for air (20.1 cmVmol), and VB = molar volume for the chemical of interest in cubic centimeters per mole. There are two methods for estimating VB: (1) from atomic and structure diffusion volume increments (see Section 4.4.1) and (2) from the Le Bas volume (see Section 4.4.2). This program implements both methods, which are assigned FSG method 1 andFSG method 2, respectively. In FSG method 2, a mean value of 0.875 is used for the constant in Equation 31 (seeLyman, etal., 1990, ch 17, p 13). The calculation screens for FSG methods 1 and 2 are shown in Figures 21 and 22, respectively. WL method This method (Equation 34) is usable for a wider range of compounds and temperatures than the FSG method (Wilke&Lee, 1955). D = • B'T 2/3 (34) where B' = a function of molecular weight of air and that of the chemical of interest, P0 = atmospheric pressure in atmospheres, OAB = characteristic length of the chemical of interest interacting with air, and Q = collision integral. Calculations of B', OAB, and Q are by no means difficult, but rather, are tedious. The user is encourag- ed to read the original paper for more details (Lyman, et al., 1990, ch. 17, pp!3-14). The calculation screen for the WL method is shown in Figure 23. 4.5.2 Diffusivitv in Water The Hayduk and Laudie method for estimating the diffusivity in water is based on Equation 35 (Hayduk and Laudie, 1974): 13.26X10"5 V 0.589 LB where DL = diffusivity in water in square centi- meters per second, 22 ------- User's Guide >r Diffusivity in Air - FSG Method (1) Chemical Formula & Structure Carbon (C) Hydrogen (H) Oxygen (O) Nitrogen (N) Chlorine (Cl) Sulfur (S) Rings * p F F !° lo" * Including aromatic and heterocyclic rings. Temperature (°C) |23.0 Pressure (atm) h Q ? Help tjt, Pastel Exit Figure 21. Calculation Screen for Diffusivity in Air with FSG Method 1, in Which the Molar Volume Is Estimated from Atomic and Structure Diffusion Volume Increments. • r Diffusivity in Air - FSG Method (2) Q@S _, . _ 1 o CU Carbon (C) |o ^f Hydrogen (H) 15 [|J Oxygen (0), except below lo 0 in methyl esters/ethers lo 0 in ethyl esters/ethers p 0 in higher esters/ethers p 0 in acids 0 0 joined to S, P, S [o Nitrogen (N), double bound p Nitrogen (N), primary amines p Nitrogene (N), 2nd amines 15 I I 3 I I I I I I Bromine (Br) [jfl ^1 Chlorine (Cl) 15 ^ Fluorine (F) 15 |^ Iodine (1) JO ^] Sulfur (S) |o *| 3-rnembered ring p |5 4-membered ring 0 ^| 5-membered ring p H 6-membered ring 0 * Naphthalene |o ^j Anthracene JO ^J ? Help Temperature ("C) |25.0 Pressure (atm) 1.0 '^^^^^^^^^^^^^^^^ r^g J|_ Close Figure 22. Calculation Screen for Diffusivity in Air with the FSG Method, in Which the Molar Volume Is Estimated from the Le Bas Volume. 23 ------- Program PARAMS Diffusivity in Air - WL Method Chemical Formula £ Structure Carbon (C) Hydrogen (H) Oxygen (0), except below 0 in methyl esters/ethers 0 in ethyl esterslethers 0 in higher esters/ethers 0 in acids 0 joined to S, P, S Nitrogen (N), double bounded Nitrogen (N), primary amines Nitrogen (N), 2nd amines O 0 * 0 t 0 v o C F3 F^ Bromine (Br) Chlorine (Cl) Fluorine (F) Iodine (1) Sulfur (S) 3-membered ring 4-membered ring 5-mernbered ring 6-mernbered ring Naphthalene Anthracene o If n Temperature (°C) o Boiling Point (°C) J80.1 Pressure (atm) H.O 7 Help Paste S: Exit Ii [Sa, .-. epjCopy | Figure 23. Calculation Screen for Molecular Diffusivity in Air with the WL Method. rjw = viscosity of water (centiPoise), and V^ = Le Bas volume in cubic centimeters per mole. The user needs to enter the molecular formula in the calculation screen (Figure 24), and the two parame- ters in Equation 35 (r/w and VL^) are calculated internally based on methods described in Sections 4.8.2 and 4.4.3, respectively. 4.5.3 Diffusivity in Solids as a Function of Molecular Weight For a given solid material and a class of chemicals, correlation exists between the diffusivity of a chemi- cal and its molecular weight (Bodalal, et al., 2001; Cox, et al., 2001). The two constants in Equation 36, A and w, are found from experimental data. Data for nine material/chemical class combinations are avail- able in this program. D = A m" (36) where Ds = diffusivity in solid in square meters per second, A = a coefficient specific to a material and a compound class, m = molecular weight in grams per mole, and n = an index specific to material and a com- pound class. Values of A and n for different materials are provided in the calculation screen (Figure 25). When the user clicks on a material in the table, the selected mate- rial/chemicals will be displayed at the upper-right corner. In Figure 25, gypsum board/aromatics are selected and, thus, A = 44.81 and n = 5.99. 4.5.4 Diffusivity in Solids as a Function of Molar Volume Correlations described in Section 4.5.3 are specific to 24 ------- User's Guide Diffusivity in Water - Hayduk ft Laudie Method Chemical Formula & Structure Carbon (C) Hydrogen (H) Oxygen (0), except below 0 in methyl esters/ethers 0 in ethyl esters/ethers 0 in higher esters/ethers 0 in acids 0 joined to S, P, S Nitrogen (N), double bound E j^j Nitrogen (N), primary amines D j^j Nitrogene (N), 2nd amines JO H F^ r^ F^ F^ m F^ Bromine (Br) Chlorine (Cl) Fluorine (F) Iodine (I) Sulfur (S) 3-rnembered ring 4-rnemberedring 5-rnembered ring 6-rnemberedring Naphthalene Anthracene F^ F^ F^ Temperature (°C) 7 Help Paste 8, Exit Figure 24. Calculation Screen for Molecular Diffusivity in Water. •T Diffusivity in Solids for Individual Chemical Classes Correlation Ds =A/H? Ds = diffusivity in solid (m2/s), m = molecular weight (g/mol), and A and n are constants. Material Chemicals nl Pf A Aiomatics Oriented strand board Alkanes Particle board Particle board 4.481 E1 5.99 0.9816 Your selection Gypsum board / Aromatics Enter molecular weight (g/mol) es atics ydes 1.450E7 1.692E7 8.355 0.9866 3.5 3.396E8 9.33 0.9618 0.8328 Click on a rnatenal to select 1& Copy Figure 25. Calculation Screen for Diffusivity in Solid Material. This Method Is Specific to Given Material/Chemical Class Combinations. 25 ------- Program PARAMS certain material/chemical class combinations. To loosen such restrictions, Guo (2002b) suggested that Ds be correlated to the molar volume. Equation 37 can be applied to mixed chemical classes. \n(Ds)=A+B\n(VJ (37) where Vm = molar volume in cubic centimeters per mole. Coefficients A and B for different materials are provided in the calculation screen (Figure 26). The user is expected to select a material, enter the molar volume and then click the ------- User's Guide screen (Figure 27). The square of correlation coeffi- cient (r2) ranged from 0.689 to 0.997. 4.6.2 Method for All Materials and Compound Classes By combining all experimental data (see Section 4.6.1), Guo (2002b) found a correlation for all materi- als and compound classes. Equation 40 («=56; r2= 0.734) is useful for roughly estimating the solid-air partition coefficient without any experimental data. Figure 28 shows the calculation screen. \D(KP) = 8.86- 0.785 ln(P) (40) 4.7 Volatility of Organic Compounds The software has algorithms for computing the vapor pressure of individual organic compounds and the total vapor pressure of petroleum-based solvents. •r Solid/Air Partition Coefficient for Individual Chemical Classes Correlation K = B/PH where K= solid/air partition coefficient (-), P = vapor pressure (mm Hg), and B and n are constants. Material Chemical class B aromatics Oriented strand board alkanes 1.069E+04 Particle board Particle board < aromatics aldehydes 1.073E+04 1.305E+04 1.037E+04 Click on a material to select bypsum board • aromatics Enter vapor pressure (mm Hg) Figure 27. Calculation Screen for Solid-Air Partition Coefficient. This Method Is Material and Chemical Specific. •r Solid/Air Partition Coeff. for All Chemicals/Materials - H X Enter vapor pressure (mm Hg): Figure 28. Calculation Screen for Solid-air Partition Coefficient. This Method Is Not Specific to Compound Classes. 27 ------- Program PARAMS 4.7.1 Makar Method for Pure Organic Com- pounds A method developed by Makar (2000) allows the user to estimate the vapor pressure for an organic com- pound by knowing (1) its compound class, (2) the carbon number in the molecule, and (3) the temp- erature of interest. In doing so, Makar divided or- ganic compounds into 39 classes (e.g., n-alcohols, n- alkanes, and polyaromatics). For each compound class, the 12 coefficients in Equation 41 were found based on available experimental data and are given in a table. Iog10 P = a0 al T+ a2 T2 a (41) where P is in millimeters Hg and Tis in Kelvins. In general, the correlations are good. This method is very useful in the absence of experimental data at room temperature. It is the user's responsibility, how- ever, to determine the class to which a given com- pound belongs. In other words, the user must know the molecular structure of the compound. Coefficients for different compound classes are stored in a database table, invisible to the user. The user is expected to select a compound class from the list, select the carbon number, and enter the tempera- ture (Figure 29). Note that the range of allowable carbon numbers for each compound class is defined by the method developer. -I* Vapor Pressure by Compound Class I Select .1 Compound Class Acetate; n-Alcohols Aldehydes n-Alkyl-Cyclopentanes n-Alkyl-Cyclohexanes Dimethyl-Cycloalkanes Unsubstituted Cycloalkanes Multiple-lso-Bran:hed Alkanes Single-lso-Bran:hed Alkanes n-Alkanes Single-Tert-Branched Alkanes Tert-and-lso-Di-Branched Alkanes Di-Tert- Alkanes 2-Alkyl-1-Alkenes 3+Alkyl-1-Alkenes Internal Alkenes n-1-Alkenes 1-Alkynes n-An hydrides n-Amines Bromoalkanes You selected: Acetates Carbon number Temperature (°C) 25 Figure 29. Calculation Screen for Estimating the Vapor Pressure Based on Compound Class. 28 ------- User's Guide 4.7.2 Total Vapor Pressure of Petroleum- Based Solvents Predicting the emissions of TVOCs from petroleum- based paint or solvents requires knowledge of the total vapor pressure for TVOC. Assuming ideal solution, the total vapor pressure is the sum of the partial pressures for all compounds in the solvent mixture, but it is difficult to quantify all the compo- nents of a petroleum-based solvent, which contains hundreds of compounds. Guo, et al. (1999) suggested that total vapor pressure be approximated by that of an imaginary solvent consisting of the known major components in the mixture (Equation 42). Knowledge of the contents of about a dozen major components in the solvent—normally achieved by GC analysis—is sufficient for a reasonable estimate of the total vapor pressure. (42) To simplify the calculations, this program contains a mini-database for the properties of common VOCs in petroleum solvents (Figure 30). The user is expected to enter the contents of individual VOCs in the coating materials in the last column. The user can, of course, add new VOCs to the table. This method also calculates the average molecular weight based on Equation 43. m = (43) 4.8 Properties of Water The software has algorithms for calculating the vapor pressure and viscosity of water. 4.8.1 Vapor Pressure of Water The vapor pressure for water is calculated from Equation 44 (Yaws, 1994a, page 345) •!' Total vapor pressure for petroleum solvent Enter VOC contents here: Compound Formula MW octane nonane decane undecane dodecane toluene ethyl benzene 0-nylene rn-xylene p-xylene o-ethjil toluene C8H18 C8H20 C10H22 C11 H24 C12H26 rn-phhnl hnli ipn C7H8 C8H10 C8H10 C8H10 C8H10 C9H12 114 128 142 156 170 92 106 106 106 106 120 7 Help VP (mm Hg) Content (rng/g) 12.324 20 4.144 1.575 0.616 0.253 24.473 8.850 5.887 7.240 7.710 2.526 50 125 60 10 ; Paste & Exit A Figure 30. Calculation Screen for Total Vapor Pressure of Petroleum-Based Solvents. 29 ------- Program PARAMS + DT+ET2 (44) where Pw0 = water vapor pressure in millimeters Hg, T= temperature in Kelvins, ,4 = 29.8605, J8 = -3.1522xl03, C =-7.3037, £> = 2.4247xlQ-9, and E= 1.8090X1Q-6. Temperature is the only user input (Figure 31). 4.8.2 Viscosity of Liquid Water The absolute viscosity of liquid water is calculated from Equation 45 (Yaws, 1994b). log10/7= A+B/T+CT+DT2 (45) where 77 = liquid viscosity (centiPoise), T= temperature in Kelvins and 273 K < T < 642 K, ,4 = -10.2158, B= 1.7925X10'3, C=1.7730xlO-2, and £> = -1.2631xlO-5. Temperature is the only user input in the calculation screen (Figure 32). Note that 1 centiPoise = 0.01 Poise = 0.01 (g/s/cm). Vapor Pressure for Water - n x Enter indoor temperature (°C): i Figure 31. Calculation Screen for Water Vapor Pressure. Viscosity for Water Enter indoor temperature (°C): Figure 32. Calculation Screen for Water Viscosity. 30 ------- User's Guide References ASTM (1977) Standard methods for evaporation rates of volatile liquids. In: Annual Book of ASTM Standards, Part 27, American Society of Testing and Materials, Philadelphia, PA, pp. 716-726. Bennet, C.O. and Myers, I.E. (1982) Momentum, Heat, and Mass Transfer, 3rd ed., McGraw-Hill, New York, NY, p 504. Bodalal, A., Zhang, J.S., Plett, E.G., and Shaw, C.Y. (2001) Correlations between the internal diffusion and equilibrium partition coefficients of volatile organic compounds (VOCs) in building materials and the VOC properties, ASHRAE Transactions, Vol. 107, pp 789-800. Chinn,K.S.K. (1981)^4SimpleMethodforPredicting Chemical Agent Evaporation. U.S. Army Dugway Proving Ground, Dugway, UT, DPG-TR-401, p 4. Cox, S.S., Zhao, D., and Little, J.C. (2001) Measur- ing partition and diffusion coefficients for volatile organic compounds in vinyl flooring, Atmospheric Environment, Vol. 35, pp 3823-3830. Evans, W.C. (1994) Development of continuous- application source terms and analytical solution for one- and two-compartment systems. In: Tichenor, B. A. (Ed), Characterizing Sources of Indoor Air Pollu- tion and Related Sink Effects, ASTM STP 1287, American Society of Testing and Materials, Philadel- phia, PA, pp. 279-293 Fuller, E.N., Schettler, P.O., and Giddings, J.C. (1966) A new method for prediction of binary gas- phase diffusion coefficients, Industrial and Engineer- ing Chemistry, Vol. 58, pp!9-27. Guo, Z., Chang, J.C.S., Sparks, L.E., andFortmann, R.C. (1999) Estimation of the rate of VOC emissions from solvent-based indoor coating materials based on product formul ati on, A tmospheric Environment, Vol. 33, pp 1205-1215. Guo, Z. (2002a) Review of indoor emission source models-part 1. overview, Environmental Pollution, Vol. 120, pp 533-549. Guo, Z. (2002b) Review of indoor emission source models - part 2. parameter estimation, Environmental Pollution, Vol. 120, pp 551-564. Guo, Z. and Roache, N. F. (2003) Overall mass transfer coefficient for pollutant emissions from small water pools under simulated indoor environmental conditions, The Annals of Occupational Hygiene, Vol. 47, pp 279-286. Hayduk, W. and Laudie, H. (1974) Prediction of diffusion coefficient for non-electrolysis in dilute aqueous solution, American Institute of Chemical Engineers Journal, Vol .2,611-615.Cited by Lyman, etal. (1990). Koontz, M. (2001) Wall Paint Exposure Model (WPEM) Version 3.2 User's Guide, developed by Geomet Technologies, Inc., Germantown, MD, for U.S. EPA Office of Pollution Prevention and Toxics, Washington, DC, and National Paint and Coatings Association, Washington, DC. http://www.epa.gov/opptintr/exposure/docs/wpem. htm (accessed on June, 2005). 31 ------- Program PARAMS Lyman, W.L., Reehl, W.F., and Rosenblatt, D.H. (1990) Handbook of Chemical Property Estimation Methods: Environmental Behavior of Organic Compounds, American Chemical Society, Washing- ton, DC. Mackay, D. and Matsugu, R. (1973) Evaporation rates of liquid hydrocarbon spills on land and water, The Canadian Journal of Chemical Engineering., Vol. 5l,pp 434-439. Makar, P. A. (2000) The estimation of organic gas vapor pressure, Atmospheric Environment, Vol. 35, pp 961-974. Reid, R.C., Prausnitz, J.M., and Sherwood, T.K. (1977) The Properties of Gases and Liquids, 3rd ed., McGraw-Hill, New York, NY, pp 58-59. Southworth, G.R. (1979) The role of volatilization in removing polyaromatic hydrocarbons from aquatic environments, Bulletin of Environmental Contamina- tion & Toxicology, Vol. 21, pp 507-514. Cited by Lyman, etal. (1990). Sparks, L., Tichenor, B., Chang, J., and Guo, Z. (1996) Gas-phase mass transfer model for predicting volatile organic compound (VOC) emission rates from indoor pollutant sources, Indoor Air Vol. 6, pp 31-40. Weast, R.C. (Ed.) (1973)Handbookof'Chemistry and Physics, 53th Ed., The Chemical Rubber Co., Cleve- land, OH. White, P.M. (1991) Heat and Mass Transfer, Addison-Wesley, New York, NY. Wilke, C.R. and Lee, C.Y. (1955) Estimation of diffusion coefficients for gases and vapors, Industrial Engineering Chemistry, Vol. 47, pp 1253-1257. Cited by Lyman, et al. (1990). Wilkes, C., Koontz, M., Rayn, M., and Cinalli, C. (1996) Estimation of emission profiles from interior latex paints. In: Indoor Air '96, Proceedings of the 7th International Conference of Indoor Air Quality and Climate, SEEC Ishibashi, Inc., Japan, Vol. 2, pp. 55- 60. Yaws, C.L. (1994a) Handbook of Vapor Pressure, Vol 4. Inorganic Compounds and Elements, Gulf Publishing Company, Houston, TX, p-354 Yaws, C.L. (1994b) Handbook of Viscosity, Gulf Publishing Company, Houston, TX, Vol. 4, p 350. Zhao, D.Y., Cox, S.S., and Little, J.C. (1999) Source/sink characterization of diffusion-controlled building materials. In: Indoor Air 99: Proceedings of the 8th International Conference on Indoor Air Quality and Climate, Construct on Research Commu- nications Ltd., London, UK, Vol. 1, pp. 408-413. 32 ------- TECHNICAL REPORT DATA (Please read Instructions on the reverse before completing) 1. REPORT NO. EPA-600/R-05/066 2. 3. RECIPIENT'S ACCESSION NO. 4. TITLE AND SUBTITLE Program PARAMS User's Guide, Program Version: 1.0, Document Version: 1.0 5. REPORT DATE March 2005 6. PERFORMING ORGANIZATION CODE 7. AUTHORS 8. PERFORMING ORGANIZATION REPORT NO. Z. Quo (U.S. EPA) 9. PERFORMING ORGANIZATION NAME AND ADDRESS See Block 12 10. PROGRAM ELEMENT NO. 11. CONTRACT/GRANT NO. In-house 12. SPONSORING AGENCY NAME AND ADDRESS U. S. EPA, Office of Research and Development Air Pollution Prevention and Control Division Research Triangle Park, North Carolina 27711 13. TYPE OF REPORT AND PERIOD COVERED User's Guide, 2003-2004 14. SPONSORING AGENCY CODE EPA/600/13 15. SUPPLEMENTARY NOTES The EPA Principle Investigator is Zhishi Quo, Mail Code E305-03, Phone (919) 541-0185, e-mail guo.zhishi@epa.gov 16. ABSTRACT The report describes a Microsoft Windows-based computer program that implements 30 methods for estimating the parameters in indoor emissions source models, which are an essential component of indoor air quality (IAQ) and exposure models. These methods fall into eight categories: (1) the properties of indoor air, (2) the first-order decay rate constants for solvent emissions from indoor coating materials, (3) gas- phase, liquid-phase, and overall mass transfer coefficients, (4) molar volume, (5) molecular diffusivity in air, liquid, and solid materials, (6) solid-air partition coefficient, (7) vapor pressure and volatility for pure organic compounds and petroleum-based solvents, and (8) the properties of water. Potential users include those who develop or use IAQ and exposure models and those who develop or use quantitative structure-activity relationship (QSAR) models. In addition, many calculations are useful to researchers in areas other than indoor air quality. Users can benefit from this program in two ways: first, it serves as a handy tool by putting commonly used parameter estimation methods in one place; second, it saves users time by taking over tedious calculations. It should be pointed out, however, that the methods implemented in this program cover only a fraction of the parameters that appear in the more than 50 indoor emission source models. Furthermore, the methods in the current version are mostly for gaseous pollutants; those for particulate matter are not included. 17. KEYWORDS AND DOCUMENT ANALYSIS DESCRIPTORS b. IDENTIFIERS/OPEN ENDED TERMS c. COSATI Field/Group Air Pollution Atmosphere Contamination Control Mathematical Models Computation Paints Mass Transfer Diffusion Volatility Water Pollution Control Stationary Sources 13B 14G 20M 06K 07B 12A 11C, 13C 18. DISTRIBUTION STATEMENT 19. SECURITY CLASS (This Report) Unclassified 21. NO. OF PAGES 40 Release to Public 20. SECURITY CLASS (This Page) Unclassified 22. PRICE EPA Form 2220-1 (Rev. 4-77 ) PREVIOUS EDITION IS OBSOLETE forms/admin/techrpt.frm 7/8/99 pad ------- |